8-o3-g. kostov - seventh national conference on chemistry
TRANSCRIPT
1
Department of Organic Chemical Technologies Prof As Zlatarov University of Burgas Bulgaria e-mail gkostovbtubg
Recent Advances in the Synthesis and Properties of Functionalized
Fluoropolymers as Engineering Materials
GKostov
VII National Conference on Chemistry 26-29 May 2011 Sofia Bulgaria
2
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
33
1 FEATURES BENEFITS ADVANTAGES of F POLYMERS
LOW REFRACTIVE INDEX
OPTICAL FIBRES AND COATINGS
LOW SURFACE ENERGY
LUBRICITY RELEASE
VERY LOW SURFACE TENSION
SPECIALITY SURFACTANTS amp FIRE FIGHTING AGENTS
VERY STRONG ORGANIC ACIDS
CATALYSTS amp PROTON EXCHANGE MEMBRANES
4
HIGH CHEMICAL THERMAL AND OXIDATIVE STABILITY
PROTECTIVE COATINGS
INSULATION
WIRE AND CABLE INDUSTRIES
HIGH OIL WATER AND SOIL REPELLENCY
TEXTILES LEATHER PAPER WOOD GLASS CONCRETESTONE METALS PROTECTION
5
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
6
21 Advantages of polymer opticalmaterials over conventional glasses
High optical transparency at transmission wavelengths
Potential to tune their optical properties by tailoringthe molecular structure
Lightweight
Flexibility even at large diameters
Good processability
Easy handling
Low cost
7
23Disadvantages of POWs
POWs reveal optical losses much higher than silica
PMMA (visible region) ndash 100 dBkm
Silica fibres ndash 03 dBkm
Transmission on short distances
Develop partial crystallinity and low Tg
Organic polymers are prone to oxidative degradation
22Applications of POWs
Short-haul communication links
Data systems in aircrafts automobiles
Local area networks
Inter- and intra- office network systems
8
SOLUTION
Substitution of F (or D) atoms for H atoms
- low overtone band strength
- less scattering
- low nD
Lower attenuation
Amorphous fluorinated polymers
Cytop trade(Asahi Glass)
Teflonreg AF(Du Pont)
9
24 OBJECTIVES
1 Synthesis of novel amorphous hydroxy functionalfluoropolymer resins and their acrylation Photocrosslinking and optical materials
2 New perfluorovinyl dioxolane monomers andcopolymer and optical materials
10
25 STRATEGY OF SYNTHESIS OF OPTICAL POLYMERS
Requirements for optical polymers
Optical transparency in the visible and NIR regions
amorphous with high Tg nD ndash14-15 Td gt150degC
Good processability to fibers films and tapes (Mn=2000-4000 gmol)
Photocrosslinkable (preferably acrylic and fluorinatedresins)
Homogenous network with good mechanical properties
11
Scheme 1 General scheme of fluoroacrylate synthesis
Fluoroolefin
-+ +
cyclicmonomer
termonomerX X OH
OH OH
OH
OCOCH=CH2
OCOCH=CH2
OCOCH=CH2
CF2=CFCl (CTFE)
CF2=CF(CF3) (HFP)
O O
O
Vinylenecarbonate
X=O(CH2)n
n=2 or n=4
Kostov G et al EP 1479 702 A1(2005) (Assigned to Atofina)
Kostov G Rousseau A Boutevin B Pascal T Journal of Fluorine Chem (2005) 126(2) 231-240
1212
261) Fluorooligomers CTFEVCA-basedcopolymers
Length limit of polymer
Chain-transfer agent or suitable solvent
Photocrosslinkable reactive functions
Reactive diluents fluorinated function monomers precise adjustement of resinsrsquo refractive index
2) Photocrosslinking
UV
Reactive diluent(s) Amorphous crosslinked network
26 CTFEVCAhydroxy VE copolymers
13
Main characteristics of CTFEVCA copolymers
Table 1 Selected monomercopolymer compositions of CTFEVCA copolymers and their main characteristics
CTFE inmonommixture(mol )
CTFEa
incopolym
(mol )
Yield
(wt )
Mnd
(gmol-1)
PDIb Tg
(degC)
Td10
(degC)
NC-Hcm3
(10-3)
nD
(23degC)
8070605040
603518459398346
640641658706722
28002500225020001800
2220252520
7090
100110120
274295289246254
5484115148162
14379143581435714459
-
Polar organic solvents acetone THF EtOAc DMF DMSO
Reactive diluents HDDA NVP and the couple HDDAATRIFESolubility
14
262 STUDY OF CTFEVCAHFP TERPOLYMERIZATION
Objective to improve the solubility in reactivediluents and fluorine content in copolymers
Reaction conditions
CTFEVCA = 067 = const
HFP in monomer mixture ndash from 5 to 20 mol (21to 10 mol in copolymer composition ndash 19F NMR
Characterization of CTFEVCAHFP terpolymers
- solubility in reactive diluents
- Tg ~ 120degCTd ~ 250degC
- NC-Hcm3 (nD resp)
15
n(C C lF C F 2 )x (C H 2 C H )y (C H C H )z
O
(C H 2 )n
O H
OOCO
O(C H 2 )n
O H
4 0 0 0 g m o l-1M n lt o ligo m e riza tio n
n = 2 o r 4+C = CF
C l
F
F
C HH C
OC
O
O
+
Scheme 3 CTFE VCA hydroxy VE terpolymerization
263 SYNTHESIS OF CTFEVCAHYDROXY VINYL ETHER TERPOLYMERS
16
OCH2 =CH C
O(CH2)n
O
R]nCH)z(CHCH)y(CH2CF2)x(CClFH[
acrylation
O H
(CH2)n
O
R]nCH)z(CHCH)y(CH2CF2)x(CClFH[
OC
OO
OC
OO
Function polymerizableunder UV
Scheme 6 Acrylation of ndashOH functionalized CTFEVCA co-polymers
27ACRYLATION OF HYDROXY FUNCTIONALIZED CO-POLYMERS
CH2=CHCOCl
CH2=C(CH3)COCl
17
28 Characterization of UV-cured materialsDMA analysis
Tg of acrylated CTFEVCAHBVE compositions ~90degC
E ndash modulus 1 GPa at 20degC 50 MPa at 120degC
Taird10 ~ 200ndash220degC
DSC analysis
Tg of acrylated CTFEVCA-CH2OH compositions ~ 100ndash105degC
Taird10 ~ 230ndash240degC
1
2
2
3
18
29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber
291 Monomer synthesis
F3CCF2FC
O O
F F
CF3F3CCFFC
O O
F F
CF2
CF2F2C
CFFCO O
F F
F2C CF2
CF2CF2
CFFCO O
F F
A B DC
Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives
Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA
1919
292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)
F 2C CXY +
FC CFO
CO
F2CCF2
CF2
CF2TBPPi 75oC
C4F5H5
FC CF
OC
O
F2CCF2
CF2
F2C
CXY
F 2C
n
n
m
m
zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)
Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578
20
Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)
Run Monomer M2 Monomers in the feed(mol )
F-Ox M2
Copolym compsby microanal
(mol)F-Ox M2
Copolym compsby NMR(mol )
F-Ox M2
Conv(wt)
Tg(degC)
Td10(degC)
1 F2C=CFCl 20 80 35 65 374 626 63 105 322
2 F2C=CFCl 40 60 62 38 615 385 70 148 354
3 F2C=CFOC3F7
64 36 874 126 852 148 82 144 342
4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359
5 F2C=CH2 14 86 382 618 378 622 65 108 370
6 F2C=CH2 35 65 584 416 579 421 67 138 356
nR lt 135
21
210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP
CTFEVCAHVE) oligomers in good yield and high Tg were synthesized
2 Successful acrylation of hydroxy functionalized cooligomers
3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties
4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties
dArr
Suitable for waveguides applications
22
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
2323
31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to
hydrogenated analogues
Lower interfacial tension and CMC
Excellent chemical and thermal stability
Oleophobicity oil and fat repellants
Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc
Traditional commercial fluorosurfactants
Long fluorocarbon chain C6ltRFltC12
Perfluorooctane sulphonate (PFOS)
Perfluooctanoic acid ( PFOA)
their derivatives
2424
32 DRAWBACKS OF FLUORINATED SURFACTANTS
Bioaccumulable
Toxic and persistent
Wide-spread in the environment
3M company suggested perfluorinated chain le C4
bull Low bioconcentration factor
bull Low toxicity
bull Still high product performance
2525
General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4
Hydrophobic
G G GF- blockRF
Hydrophobic Hydrophilic
a ) for RF (CF3)2CF
b) for fluorinated monomer CH2=CH (TFP)
CF3
nCH2=CH + (CF3)2CFI RF - hydrophobic - I
CF3 CF3CF3
G
CF3
CF3CF-CH2-CH-CH2-CH Hydrophilic
CF3 CF3
Degradation
33 Synthesis of different end products as fluorinated surfactants
26
CF I + n nCFI
CF3
CF3
O
O
nCFCF3 I
O
O
Rad
nCFCF3
Zn
HSOH
O
nCFCF3
SOH
O
HOO
p
nCFCF3
SO
OO p
H2C CH2
nCFCF3
I
NNEt3
nCFCF3
NEt3nCF
CF3
N
I I
Surfactant C Surfactant B
Surfactant A
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants
Anionic surfactant
27
Surfactant Appearance Fluoroalkyl
10 decomp temperature a
(oC)
Tg and melting point b (oC)
(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC
(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145
(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175
Table 1 Properties of synthesized fluorinated surfactants
a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin
b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin
G Kostov et al USP 0027349 (2007)
28
Conditions Weight losses ()
Surfactant A Surfactant B Surfactant C
(1) Base-acid resistance
98 H2SO4 25 oC 7 days 00 lt12 00
60 HNO3 25 oC 7 days - gt400 lt20
37 HCl 25 oC 7 days 00 gt150 00
40 NaOH 25 oC 7 days 00 00 00
(2) Solubility in selected solvents Solubility (g100mL)
Water 25oC 72 hrs gt10 gt10 gt10
Methanol 25oC 72 hrs gt10 gt10 gt10
Diethyl ether 25oC 72 hrs lt1 lt1 lt1
Benzene 25oC 72 hrs lt2 lt2 lt2
Acetone 25oC 72 hrs lt10 lt10 lt10
Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-
Conclusions
The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6
29
Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA
30
Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis
34 Phosphorous containing TFP surfactants
31
3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate
Hydrolysis
Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)
32
Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to
those of PFOA (white)
33
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated Surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
34
Main characteristics of themembrane
To separate oxygen from hydrogen
To insure a good protonic conductivity
To be chemically physically andmechanically stable in acid media andat high temperatures
Rеasonable cost applications
No electronic conductivity
41 FUEL CELL MEMBRANES
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
2
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
33
1 FEATURES BENEFITS ADVANTAGES of F POLYMERS
LOW REFRACTIVE INDEX
OPTICAL FIBRES AND COATINGS
LOW SURFACE ENERGY
LUBRICITY RELEASE
VERY LOW SURFACE TENSION
SPECIALITY SURFACTANTS amp FIRE FIGHTING AGENTS
VERY STRONG ORGANIC ACIDS
CATALYSTS amp PROTON EXCHANGE MEMBRANES
4
HIGH CHEMICAL THERMAL AND OXIDATIVE STABILITY
PROTECTIVE COATINGS
INSULATION
WIRE AND CABLE INDUSTRIES
HIGH OIL WATER AND SOIL REPELLENCY
TEXTILES LEATHER PAPER WOOD GLASS CONCRETESTONE METALS PROTECTION
5
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
6
21 Advantages of polymer opticalmaterials over conventional glasses
High optical transparency at transmission wavelengths
Potential to tune their optical properties by tailoringthe molecular structure
Lightweight
Flexibility even at large diameters
Good processability
Easy handling
Low cost
7
23Disadvantages of POWs
POWs reveal optical losses much higher than silica
PMMA (visible region) ndash 100 dBkm
Silica fibres ndash 03 dBkm
Transmission on short distances
Develop partial crystallinity and low Tg
Organic polymers are prone to oxidative degradation
22Applications of POWs
Short-haul communication links
Data systems in aircrafts automobiles
Local area networks
Inter- and intra- office network systems
8
SOLUTION
Substitution of F (or D) atoms for H atoms
- low overtone band strength
- less scattering
- low nD
Lower attenuation
Amorphous fluorinated polymers
Cytop trade(Asahi Glass)
Teflonreg AF(Du Pont)
9
24 OBJECTIVES
1 Synthesis of novel amorphous hydroxy functionalfluoropolymer resins and their acrylation Photocrosslinking and optical materials
2 New perfluorovinyl dioxolane monomers andcopolymer and optical materials
10
25 STRATEGY OF SYNTHESIS OF OPTICAL POLYMERS
Requirements for optical polymers
Optical transparency in the visible and NIR regions
amorphous with high Tg nD ndash14-15 Td gt150degC
Good processability to fibers films and tapes (Mn=2000-4000 gmol)
Photocrosslinkable (preferably acrylic and fluorinatedresins)
Homogenous network with good mechanical properties
11
Scheme 1 General scheme of fluoroacrylate synthesis
Fluoroolefin
-+ +
cyclicmonomer
termonomerX X OH
OH OH
OH
OCOCH=CH2
OCOCH=CH2
OCOCH=CH2
CF2=CFCl (CTFE)
CF2=CF(CF3) (HFP)
O O
O
Vinylenecarbonate
X=O(CH2)n
n=2 or n=4
Kostov G et al EP 1479 702 A1(2005) (Assigned to Atofina)
Kostov G Rousseau A Boutevin B Pascal T Journal of Fluorine Chem (2005) 126(2) 231-240
1212
261) Fluorooligomers CTFEVCA-basedcopolymers
Length limit of polymer
Chain-transfer agent or suitable solvent
Photocrosslinkable reactive functions
Reactive diluents fluorinated function monomers precise adjustement of resinsrsquo refractive index
2) Photocrosslinking
UV
Reactive diluent(s) Amorphous crosslinked network
26 CTFEVCAhydroxy VE copolymers
13
Main characteristics of CTFEVCA copolymers
Table 1 Selected monomercopolymer compositions of CTFEVCA copolymers and their main characteristics
CTFE inmonommixture(mol )
CTFEa
incopolym
(mol )
Yield
(wt )
Mnd
(gmol-1)
PDIb Tg
(degC)
Td10
(degC)
NC-Hcm3
(10-3)
nD
(23degC)
8070605040
603518459398346
640641658706722
28002500225020001800
2220252520
7090
100110120
274295289246254
5484115148162
14379143581435714459
-
Polar organic solvents acetone THF EtOAc DMF DMSO
Reactive diluents HDDA NVP and the couple HDDAATRIFESolubility
14
262 STUDY OF CTFEVCAHFP TERPOLYMERIZATION
Objective to improve the solubility in reactivediluents and fluorine content in copolymers
Reaction conditions
CTFEVCA = 067 = const
HFP in monomer mixture ndash from 5 to 20 mol (21to 10 mol in copolymer composition ndash 19F NMR
Characterization of CTFEVCAHFP terpolymers
- solubility in reactive diluents
- Tg ~ 120degCTd ~ 250degC
- NC-Hcm3 (nD resp)
15
n(C C lF C F 2 )x (C H 2 C H )y (C H C H )z
O
(C H 2 )n
O H
OOCO
O(C H 2 )n
O H
4 0 0 0 g m o l-1M n lt o ligo m e riza tio n
n = 2 o r 4+C = CF
C l
F
F
C HH C
OC
O
O
+
Scheme 3 CTFE VCA hydroxy VE terpolymerization
263 SYNTHESIS OF CTFEVCAHYDROXY VINYL ETHER TERPOLYMERS
16
OCH2 =CH C
O(CH2)n
O
R]nCH)z(CHCH)y(CH2CF2)x(CClFH[
acrylation
O H
(CH2)n
O
R]nCH)z(CHCH)y(CH2CF2)x(CClFH[
OC
OO
OC
OO
Function polymerizableunder UV
Scheme 6 Acrylation of ndashOH functionalized CTFEVCA co-polymers
27ACRYLATION OF HYDROXY FUNCTIONALIZED CO-POLYMERS
CH2=CHCOCl
CH2=C(CH3)COCl
17
28 Characterization of UV-cured materialsDMA analysis
Tg of acrylated CTFEVCAHBVE compositions ~90degC
E ndash modulus 1 GPa at 20degC 50 MPa at 120degC
Taird10 ~ 200ndash220degC
DSC analysis
Tg of acrylated CTFEVCA-CH2OH compositions ~ 100ndash105degC
Taird10 ~ 230ndash240degC
1
2
2
3
18
29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber
291 Monomer synthesis
F3CCF2FC
O O
F F
CF3F3CCFFC
O O
F F
CF2
CF2F2C
CFFCO O
F F
F2C CF2
CF2CF2
CFFCO O
F F
A B DC
Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives
Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA
1919
292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)
F 2C CXY +
FC CFO
CO
F2CCF2
CF2
CF2TBPPi 75oC
C4F5H5
FC CF
OC
O
F2CCF2
CF2
F2C
CXY
F 2C
n
n
m
m
zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)
Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578
20
Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)
Run Monomer M2 Monomers in the feed(mol )
F-Ox M2
Copolym compsby microanal
(mol)F-Ox M2
Copolym compsby NMR(mol )
F-Ox M2
Conv(wt)
Tg(degC)
Td10(degC)
1 F2C=CFCl 20 80 35 65 374 626 63 105 322
2 F2C=CFCl 40 60 62 38 615 385 70 148 354
3 F2C=CFOC3F7
64 36 874 126 852 148 82 144 342
4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359
5 F2C=CH2 14 86 382 618 378 622 65 108 370
6 F2C=CH2 35 65 584 416 579 421 67 138 356
nR lt 135
21
210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP
CTFEVCAHVE) oligomers in good yield and high Tg were synthesized
2 Successful acrylation of hydroxy functionalized cooligomers
3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties
4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties
dArr
Suitable for waveguides applications
22
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
2323
31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to
hydrogenated analogues
Lower interfacial tension and CMC
Excellent chemical and thermal stability
Oleophobicity oil and fat repellants
Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc
Traditional commercial fluorosurfactants
Long fluorocarbon chain C6ltRFltC12
Perfluorooctane sulphonate (PFOS)
Perfluooctanoic acid ( PFOA)
their derivatives
2424
32 DRAWBACKS OF FLUORINATED SURFACTANTS
Bioaccumulable
Toxic and persistent
Wide-spread in the environment
3M company suggested perfluorinated chain le C4
bull Low bioconcentration factor
bull Low toxicity
bull Still high product performance
2525
General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4
Hydrophobic
G G GF- blockRF
Hydrophobic Hydrophilic
a ) for RF (CF3)2CF
b) for fluorinated monomer CH2=CH (TFP)
CF3
nCH2=CH + (CF3)2CFI RF - hydrophobic - I
CF3 CF3CF3
G
CF3
CF3CF-CH2-CH-CH2-CH Hydrophilic
CF3 CF3
Degradation
33 Synthesis of different end products as fluorinated surfactants
26
CF I + n nCFI
CF3
CF3
O
O
nCFCF3 I
O
O
Rad
nCFCF3
Zn
HSOH
O
nCFCF3
SOH
O
HOO
p
nCFCF3
SO
OO p
H2C CH2
nCFCF3
I
NNEt3
nCFCF3
NEt3nCF
CF3
N
I I
Surfactant C Surfactant B
Surfactant A
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants
Anionic surfactant
27
Surfactant Appearance Fluoroalkyl
10 decomp temperature a
(oC)
Tg and melting point b (oC)
(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC
(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145
(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175
Table 1 Properties of synthesized fluorinated surfactants
a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin
b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin
G Kostov et al USP 0027349 (2007)
28
Conditions Weight losses ()
Surfactant A Surfactant B Surfactant C
(1) Base-acid resistance
98 H2SO4 25 oC 7 days 00 lt12 00
60 HNO3 25 oC 7 days - gt400 lt20
37 HCl 25 oC 7 days 00 gt150 00
40 NaOH 25 oC 7 days 00 00 00
(2) Solubility in selected solvents Solubility (g100mL)
Water 25oC 72 hrs gt10 gt10 gt10
Methanol 25oC 72 hrs gt10 gt10 gt10
Diethyl ether 25oC 72 hrs lt1 lt1 lt1
Benzene 25oC 72 hrs lt2 lt2 lt2
Acetone 25oC 72 hrs lt10 lt10 lt10
Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-
Conclusions
The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6
29
Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA
30
Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis
34 Phosphorous containing TFP surfactants
31
3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate
Hydrolysis
Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)
32
Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to
those of PFOA (white)
33
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated Surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
34
Main characteristics of themembrane
To separate oxygen from hydrogen
To insure a good protonic conductivity
To be chemically physically andmechanically stable in acid media andat high temperatures
Rеasonable cost applications
No electronic conductivity
41 FUEL CELL MEMBRANES
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
33
1 FEATURES BENEFITS ADVANTAGES of F POLYMERS
LOW REFRACTIVE INDEX
OPTICAL FIBRES AND COATINGS
LOW SURFACE ENERGY
LUBRICITY RELEASE
VERY LOW SURFACE TENSION
SPECIALITY SURFACTANTS amp FIRE FIGHTING AGENTS
VERY STRONG ORGANIC ACIDS
CATALYSTS amp PROTON EXCHANGE MEMBRANES
4
HIGH CHEMICAL THERMAL AND OXIDATIVE STABILITY
PROTECTIVE COATINGS
INSULATION
WIRE AND CABLE INDUSTRIES
HIGH OIL WATER AND SOIL REPELLENCY
TEXTILES LEATHER PAPER WOOD GLASS CONCRETESTONE METALS PROTECTION
5
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
6
21 Advantages of polymer opticalmaterials over conventional glasses
High optical transparency at transmission wavelengths
Potential to tune their optical properties by tailoringthe molecular structure
Lightweight
Flexibility even at large diameters
Good processability
Easy handling
Low cost
7
23Disadvantages of POWs
POWs reveal optical losses much higher than silica
PMMA (visible region) ndash 100 dBkm
Silica fibres ndash 03 dBkm
Transmission on short distances
Develop partial crystallinity and low Tg
Organic polymers are prone to oxidative degradation
22Applications of POWs
Short-haul communication links
Data systems in aircrafts automobiles
Local area networks
Inter- and intra- office network systems
8
SOLUTION
Substitution of F (or D) atoms for H atoms
- low overtone band strength
- less scattering
- low nD
Lower attenuation
Amorphous fluorinated polymers
Cytop trade(Asahi Glass)
Teflonreg AF(Du Pont)
9
24 OBJECTIVES
1 Synthesis of novel amorphous hydroxy functionalfluoropolymer resins and their acrylation Photocrosslinking and optical materials
2 New perfluorovinyl dioxolane monomers andcopolymer and optical materials
10
25 STRATEGY OF SYNTHESIS OF OPTICAL POLYMERS
Requirements for optical polymers
Optical transparency in the visible and NIR regions
amorphous with high Tg nD ndash14-15 Td gt150degC
Good processability to fibers films and tapes (Mn=2000-4000 gmol)
Photocrosslinkable (preferably acrylic and fluorinatedresins)
Homogenous network with good mechanical properties
11
Scheme 1 General scheme of fluoroacrylate synthesis
Fluoroolefin
-+ +
cyclicmonomer
termonomerX X OH
OH OH
OH
OCOCH=CH2
OCOCH=CH2
OCOCH=CH2
CF2=CFCl (CTFE)
CF2=CF(CF3) (HFP)
O O
O
Vinylenecarbonate
X=O(CH2)n
n=2 or n=4
Kostov G et al EP 1479 702 A1(2005) (Assigned to Atofina)
Kostov G Rousseau A Boutevin B Pascal T Journal of Fluorine Chem (2005) 126(2) 231-240
1212
261) Fluorooligomers CTFEVCA-basedcopolymers
Length limit of polymer
Chain-transfer agent or suitable solvent
Photocrosslinkable reactive functions
Reactive diluents fluorinated function monomers precise adjustement of resinsrsquo refractive index
2) Photocrosslinking
UV
Reactive diluent(s) Amorphous crosslinked network
26 CTFEVCAhydroxy VE copolymers
13
Main characteristics of CTFEVCA copolymers
Table 1 Selected monomercopolymer compositions of CTFEVCA copolymers and their main characteristics
CTFE inmonommixture(mol )
CTFEa
incopolym
(mol )
Yield
(wt )
Mnd
(gmol-1)
PDIb Tg
(degC)
Td10
(degC)
NC-Hcm3
(10-3)
nD
(23degC)
8070605040
603518459398346
640641658706722
28002500225020001800
2220252520
7090
100110120
274295289246254
5484115148162
14379143581435714459
-
Polar organic solvents acetone THF EtOAc DMF DMSO
Reactive diluents HDDA NVP and the couple HDDAATRIFESolubility
14
262 STUDY OF CTFEVCAHFP TERPOLYMERIZATION
Objective to improve the solubility in reactivediluents and fluorine content in copolymers
Reaction conditions
CTFEVCA = 067 = const
HFP in monomer mixture ndash from 5 to 20 mol (21to 10 mol in copolymer composition ndash 19F NMR
Characterization of CTFEVCAHFP terpolymers
- solubility in reactive diluents
- Tg ~ 120degCTd ~ 250degC
- NC-Hcm3 (nD resp)
15
n(C C lF C F 2 )x (C H 2 C H )y (C H C H )z
O
(C H 2 )n
O H
OOCO
O(C H 2 )n
O H
4 0 0 0 g m o l-1M n lt o ligo m e riza tio n
n = 2 o r 4+C = CF
C l
F
F
C HH C
OC
O
O
+
Scheme 3 CTFE VCA hydroxy VE terpolymerization
263 SYNTHESIS OF CTFEVCAHYDROXY VINYL ETHER TERPOLYMERS
16
OCH2 =CH C
O(CH2)n
O
R]nCH)z(CHCH)y(CH2CF2)x(CClFH[
acrylation
O H
(CH2)n
O
R]nCH)z(CHCH)y(CH2CF2)x(CClFH[
OC
OO
OC
OO
Function polymerizableunder UV
Scheme 6 Acrylation of ndashOH functionalized CTFEVCA co-polymers
27ACRYLATION OF HYDROXY FUNCTIONALIZED CO-POLYMERS
CH2=CHCOCl
CH2=C(CH3)COCl
17
28 Characterization of UV-cured materialsDMA analysis
Tg of acrylated CTFEVCAHBVE compositions ~90degC
E ndash modulus 1 GPa at 20degC 50 MPa at 120degC
Taird10 ~ 200ndash220degC
DSC analysis
Tg of acrylated CTFEVCA-CH2OH compositions ~ 100ndash105degC
Taird10 ~ 230ndash240degC
1
2
2
3
18
29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber
291 Monomer synthesis
F3CCF2FC
O O
F F
CF3F3CCFFC
O O
F F
CF2
CF2F2C
CFFCO O
F F
F2C CF2
CF2CF2
CFFCO O
F F
A B DC
Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives
Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA
1919
292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)
F 2C CXY +
FC CFO
CO
F2CCF2
CF2
CF2TBPPi 75oC
C4F5H5
FC CF
OC
O
F2CCF2
CF2
F2C
CXY
F 2C
n
n
m
m
zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)
Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578
20
Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)
Run Monomer M2 Monomers in the feed(mol )
F-Ox M2
Copolym compsby microanal
(mol)F-Ox M2
Copolym compsby NMR(mol )
F-Ox M2
Conv(wt)
Tg(degC)
Td10(degC)
1 F2C=CFCl 20 80 35 65 374 626 63 105 322
2 F2C=CFCl 40 60 62 38 615 385 70 148 354
3 F2C=CFOC3F7
64 36 874 126 852 148 82 144 342
4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359
5 F2C=CH2 14 86 382 618 378 622 65 108 370
6 F2C=CH2 35 65 584 416 579 421 67 138 356
nR lt 135
21
210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP
CTFEVCAHVE) oligomers in good yield and high Tg were synthesized
2 Successful acrylation of hydroxy functionalized cooligomers
3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties
4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties
dArr
Suitable for waveguides applications
22
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
2323
31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to
hydrogenated analogues
Lower interfacial tension and CMC
Excellent chemical and thermal stability
Oleophobicity oil and fat repellants
Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc
Traditional commercial fluorosurfactants
Long fluorocarbon chain C6ltRFltC12
Perfluorooctane sulphonate (PFOS)
Perfluooctanoic acid ( PFOA)
their derivatives
2424
32 DRAWBACKS OF FLUORINATED SURFACTANTS
Bioaccumulable
Toxic and persistent
Wide-spread in the environment
3M company suggested perfluorinated chain le C4
bull Low bioconcentration factor
bull Low toxicity
bull Still high product performance
2525
General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4
Hydrophobic
G G GF- blockRF
Hydrophobic Hydrophilic
a ) for RF (CF3)2CF
b) for fluorinated monomer CH2=CH (TFP)
CF3
nCH2=CH + (CF3)2CFI RF - hydrophobic - I
CF3 CF3CF3
G
CF3
CF3CF-CH2-CH-CH2-CH Hydrophilic
CF3 CF3
Degradation
33 Synthesis of different end products as fluorinated surfactants
26
CF I + n nCFI
CF3
CF3
O
O
nCFCF3 I
O
O
Rad
nCFCF3
Zn
HSOH
O
nCFCF3
SOH
O
HOO
p
nCFCF3
SO
OO p
H2C CH2
nCFCF3
I
NNEt3
nCFCF3
NEt3nCF
CF3
N
I I
Surfactant C Surfactant B
Surfactant A
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants
Anionic surfactant
27
Surfactant Appearance Fluoroalkyl
10 decomp temperature a
(oC)
Tg and melting point b (oC)
(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC
(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145
(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175
Table 1 Properties of synthesized fluorinated surfactants
a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin
b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin
G Kostov et al USP 0027349 (2007)
28
Conditions Weight losses ()
Surfactant A Surfactant B Surfactant C
(1) Base-acid resistance
98 H2SO4 25 oC 7 days 00 lt12 00
60 HNO3 25 oC 7 days - gt400 lt20
37 HCl 25 oC 7 days 00 gt150 00
40 NaOH 25 oC 7 days 00 00 00
(2) Solubility in selected solvents Solubility (g100mL)
Water 25oC 72 hrs gt10 gt10 gt10
Methanol 25oC 72 hrs gt10 gt10 gt10
Diethyl ether 25oC 72 hrs lt1 lt1 lt1
Benzene 25oC 72 hrs lt2 lt2 lt2
Acetone 25oC 72 hrs lt10 lt10 lt10
Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-
Conclusions
The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6
29
Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA
30
Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis
34 Phosphorous containing TFP surfactants
31
3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate
Hydrolysis
Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)
32
Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to
those of PFOA (white)
33
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated Surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
34
Main characteristics of themembrane
To separate oxygen from hydrogen
To insure a good protonic conductivity
To be chemically physically andmechanically stable in acid media andat high temperatures
Rеasonable cost applications
No electronic conductivity
41 FUEL CELL MEMBRANES
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
4
HIGH CHEMICAL THERMAL AND OXIDATIVE STABILITY
PROTECTIVE COATINGS
INSULATION
WIRE AND CABLE INDUSTRIES
HIGH OIL WATER AND SOIL REPELLENCY
TEXTILES LEATHER PAPER WOOD GLASS CONCRETESTONE METALS PROTECTION
5
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
6
21 Advantages of polymer opticalmaterials over conventional glasses
High optical transparency at transmission wavelengths
Potential to tune their optical properties by tailoringthe molecular structure
Lightweight
Flexibility even at large diameters
Good processability
Easy handling
Low cost
7
23Disadvantages of POWs
POWs reveal optical losses much higher than silica
PMMA (visible region) ndash 100 dBkm
Silica fibres ndash 03 dBkm
Transmission on short distances
Develop partial crystallinity and low Tg
Organic polymers are prone to oxidative degradation
22Applications of POWs
Short-haul communication links
Data systems in aircrafts automobiles
Local area networks
Inter- and intra- office network systems
8
SOLUTION
Substitution of F (or D) atoms for H atoms
- low overtone band strength
- less scattering
- low nD
Lower attenuation
Amorphous fluorinated polymers
Cytop trade(Asahi Glass)
Teflonreg AF(Du Pont)
9
24 OBJECTIVES
1 Synthesis of novel amorphous hydroxy functionalfluoropolymer resins and their acrylation Photocrosslinking and optical materials
2 New perfluorovinyl dioxolane monomers andcopolymer and optical materials
10
25 STRATEGY OF SYNTHESIS OF OPTICAL POLYMERS
Requirements for optical polymers
Optical transparency in the visible and NIR regions
amorphous with high Tg nD ndash14-15 Td gt150degC
Good processability to fibers films and tapes (Mn=2000-4000 gmol)
Photocrosslinkable (preferably acrylic and fluorinatedresins)
Homogenous network with good mechanical properties
11
Scheme 1 General scheme of fluoroacrylate synthesis
Fluoroolefin
-+ +
cyclicmonomer
termonomerX X OH
OH OH
OH
OCOCH=CH2
OCOCH=CH2
OCOCH=CH2
CF2=CFCl (CTFE)
CF2=CF(CF3) (HFP)
O O
O
Vinylenecarbonate
X=O(CH2)n
n=2 or n=4
Kostov G et al EP 1479 702 A1(2005) (Assigned to Atofina)
Kostov G Rousseau A Boutevin B Pascal T Journal of Fluorine Chem (2005) 126(2) 231-240
1212
261) Fluorooligomers CTFEVCA-basedcopolymers
Length limit of polymer
Chain-transfer agent or suitable solvent
Photocrosslinkable reactive functions
Reactive diluents fluorinated function monomers precise adjustement of resinsrsquo refractive index
2) Photocrosslinking
UV
Reactive diluent(s) Amorphous crosslinked network
26 CTFEVCAhydroxy VE copolymers
13
Main characteristics of CTFEVCA copolymers
Table 1 Selected monomercopolymer compositions of CTFEVCA copolymers and their main characteristics
CTFE inmonommixture(mol )
CTFEa
incopolym
(mol )
Yield
(wt )
Mnd
(gmol-1)
PDIb Tg
(degC)
Td10
(degC)
NC-Hcm3
(10-3)
nD
(23degC)
8070605040
603518459398346
640641658706722
28002500225020001800
2220252520
7090
100110120
274295289246254
5484115148162
14379143581435714459
-
Polar organic solvents acetone THF EtOAc DMF DMSO
Reactive diluents HDDA NVP and the couple HDDAATRIFESolubility
14
262 STUDY OF CTFEVCAHFP TERPOLYMERIZATION
Objective to improve the solubility in reactivediluents and fluorine content in copolymers
Reaction conditions
CTFEVCA = 067 = const
HFP in monomer mixture ndash from 5 to 20 mol (21to 10 mol in copolymer composition ndash 19F NMR
Characterization of CTFEVCAHFP terpolymers
- solubility in reactive diluents
- Tg ~ 120degCTd ~ 250degC
- NC-Hcm3 (nD resp)
15
n(C C lF C F 2 )x (C H 2 C H )y (C H C H )z
O
(C H 2 )n
O H
OOCO
O(C H 2 )n
O H
4 0 0 0 g m o l-1M n lt o ligo m e riza tio n
n = 2 o r 4+C = CF
C l
F
F
C HH C
OC
O
O
+
Scheme 3 CTFE VCA hydroxy VE terpolymerization
263 SYNTHESIS OF CTFEVCAHYDROXY VINYL ETHER TERPOLYMERS
16
OCH2 =CH C
O(CH2)n
O
R]nCH)z(CHCH)y(CH2CF2)x(CClFH[
acrylation
O H
(CH2)n
O
R]nCH)z(CHCH)y(CH2CF2)x(CClFH[
OC
OO
OC
OO
Function polymerizableunder UV
Scheme 6 Acrylation of ndashOH functionalized CTFEVCA co-polymers
27ACRYLATION OF HYDROXY FUNCTIONALIZED CO-POLYMERS
CH2=CHCOCl
CH2=C(CH3)COCl
17
28 Characterization of UV-cured materialsDMA analysis
Tg of acrylated CTFEVCAHBVE compositions ~90degC
E ndash modulus 1 GPa at 20degC 50 MPa at 120degC
Taird10 ~ 200ndash220degC
DSC analysis
Tg of acrylated CTFEVCA-CH2OH compositions ~ 100ndash105degC
Taird10 ~ 230ndash240degC
1
2
2
3
18
29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber
291 Monomer synthesis
F3CCF2FC
O O
F F
CF3F3CCFFC
O O
F F
CF2
CF2F2C
CFFCO O
F F
F2C CF2
CF2CF2
CFFCO O
F F
A B DC
Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives
Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA
1919
292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)
F 2C CXY +
FC CFO
CO
F2CCF2
CF2
CF2TBPPi 75oC
C4F5H5
FC CF
OC
O
F2CCF2
CF2
F2C
CXY
F 2C
n
n
m
m
zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)
Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578
20
Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)
Run Monomer M2 Monomers in the feed(mol )
F-Ox M2
Copolym compsby microanal
(mol)F-Ox M2
Copolym compsby NMR(mol )
F-Ox M2
Conv(wt)
Tg(degC)
Td10(degC)
1 F2C=CFCl 20 80 35 65 374 626 63 105 322
2 F2C=CFCl 40 60 62 38 615 385 70 148 354
3 F2C=CFOC3F7
64 36 874 126 852 148 82 144 342
4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359
5 F2C=CH2 14 86 382 618 378 622 65 108 370
6 F2C=CH2 35 65 584 416 579 421 67 138 356
nR lt 135
21
210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP
CTFEVCAHVE) oligomers in good yield and high Tg were synthesized
2 Successful acrylation of hydroxy functionalized cooligomers
3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties
4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties
dArr
Suitable for waveguides applications
22
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
2323
31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to
hydrogenated analogues
Lower interfacial tension and CMC
Excellent chemical and thermal stability
Oleophobicity oil and fat repellants
Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc
Traditional commercial fluorosurfactants
Long fluorocarbon chain C6ltRFltC12
Perfluorooctane sulphonate (PFOS)
Perfluooctanoic acid ( PFOA)
their derivatives
2424
32 DRAWBACKS OF FLUORINATED SURFACTANTS
Bioaccumulable
Toxic and persistent
Wide-spread in the environment
3M company suggested perfluorinated chain le C4
bull Low bioconcentration factor
bull Low toxicity
bull Still high product performance
2525
General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4
Hydrophobic
G G GF- blockRF
Hydrophobic Hydrophilic
a ) for RF (CF3)2CF
b) for fluorinated monomer CH2=CH (TFP)
CF3
nCH2=CH + (CF3)2CFI RF - hydrophobic - I
CF3 CF3CF3
G
CF3
CF3CF-CH2-CH-CH2-CH Hydrophilic
CF3 CF3
Degradation
33 Synthesis of different end products as fluorinated surfactants
26
CF I + n nCFI
CF3
CF3
O
O
nCFCF3 I
O
O
Rad
nCFCF3
Zn
HSOH
O
nCFCF3
SOH
O
HOO
p
nCFCF3
SO
OO p
H2C CH2
nCFCF3
I
NNEt3
nCFCF3
NEt3nCF
CF3
N
I I
Surfactant C Surfactant B
Surfactant A
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants
Anionic surfactant
27
Surfactant Appearance Fluoroalkyl
10 decomp temperature a
(oC)
Tg and melting point b (oC)
(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC
(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145
(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175
Table 1 Properties of synthesized fluorinated surfactants
a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin
b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin
G Kostov et al USP 0027349 (2007)
28
Conditions Weight losses ()
Surfactant A Surfactant B Surfactant C
(1) Base-acid resistance
98 H2SO4 25 oC 7 days 00 lt12 00
60 HNO3 25 oC 7 days - gt400 lt20
37 HCl 25 oC 7 days 00 gt150 00
40 NaOH 25 oC 7 days 00 00 00
(2) Solubility in selected solvents Solubility (g100mL)
Water 25oC 72 hrs gt10 gt10 gt10
Methanol 25oC 72 hrs gt10 gt10 gt10
Diethyl ether 25oC 72 hrs lt1 lt1 lt1
Benzene 25oC 72 hrs lt2 lt2 lt2
Acetone 25oC 72 hrs lt10 lt10 lt10
Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-
Conclusions
The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6
29
Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA
30
Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis
34 Phosphorous containing TFP surfactants
31
3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate
Hydrolysis
Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)
32
Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to
those of PFOA (white)
33
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated Surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
34
Main characteristics of themembrane
To separate oxygen from hydrogen
To insure a good protonic conductivity
To be chemically physically andmechanically stable in acid media andat high temperatures
Rеasonable cost applications
No electronic conductivity
41 FUEL CELL MEMBRANES
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
5
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
6
21 Advantages of polymer opticalmaterials over conventional glasses
High optical transparency at transmission wavelengths
Potential to tune their optical properties by tailoringthe molecular structure
Lightweight
Flexibility even at large diameters
Good processability
Easy handling
Low cost
7
23Disadvantages of POWs
POWs reveal optical losses much higher than silica
PMMA (visible region) ndash 100 dBkm
Silica fibres ndash 03 dBkm
Transmission on short distances
Develop partial crystallinity and low Tg
Organic polymers are prone to oxidative degradation
22Applications of POWs
Short-haul communication links
Data systems in aircrafts automobiles
Local area networks
Inter- and intra- office network systems
8
SOLUTION
Substitution of F (or D) atoms for H atoms
- low overtone band strength
- less scattering
- low nD
Lower attenuation
Amorphous fluorinated polymers
Cytop trade(Asahi Glass)
Teflonreg AF(Du Pont)
9
24 OBJECTIVES
1 Synthesis of novel amorphous hydroxy functionalfluoropolymer resins and their acrylation Photocrosslinking and optical materials
2 New perfluorovinyl dioxolane monomers andcopolymer and optical materials
10
25 STRATEGY OF SYNTHESIS OF OPTICAL POLYMERS
Requirements for optical polymers
Optical transparency in the visible and NIR regions
amorphous with high Tg nD ndash14-15 Td gt150degC
Good processability to fibers films and tapes (Mn=2000-4000 gmol)
Photocrosslinkable (preferably acrylic and fluorinatedresins)
Homogenous network with good mechanical properties
11
Scheme 1 General scheme of fluoroacrylate synthesis
Fluoroolefin
-+ +
cyclicmonomer
termonomerX X OH
OH OH
OH
OCOCH=CH2
OCOCH=CH2
OCOCH=CH2
CF2=CFCl (CTFE)
CF2=CF(CF3) (HFP)
O O
O
Vinylenecarbonate
X=O(CH2)n
n=2 or n=4
Kostov G et al EP 1479 702 A1(2005) (Assigned to Atofina)
Kostov G Rousseau A Boutevin B Pascal T Journal of Fluorine Chem (2005) 126(2) 231-240
1212
261) Fluorooligomers CTFEVCA-basedcopolymers
Length limit of polymer
Chain-transfer agent or suitable solvent
Photocrosslinkable reactive functions
Reactive diluents fluorinated function monomers precise adjustement of resinsrsquo refractive index
2) Photocrosslinking
UV
Reactive diluent(s) Amorphous crosslinked network
26 CTFEVCAhydroxy VE copolymers
13
Main characteristics of CTFEVCA copolymers
Table 1 Selected monomercopolymer compositions of CTFEVCA copolymers and their main characteristics
CTFE inmonommixture(mol )
CTFEa
incopolym
(mol )
Yield
(wt )
Mnd
(gmol-1)
PDIb Tg
(degC)
Td10
(degC)
NC-Hcm3
(10-3)
nD
(23degC)
8070605040
603518459398346
640641658706722
28002500225020001800
2220252520
7090
100110120
274295289246254
5484115148162
14379143581435714459
-
Polar organic solvents acetone THF EtOAc DMF DMSO
Reactive diluents HDDA NVP and the couple HDDAATRIFESolubility
14
262 STUDY OF CTFEVCAHFP TERPOLYMERIZATION
Objective to improve the solubility in reactivediluents and fluorine content in copolymers
Reaction conditions
CTFEVCA = 067 = const
HFP in monomer mixture ndash from 5 to 20 mol (21to 10 mol in copolymer composition ndash 19F NMR
Characterization of CTFEVCAHFP terpolymers
- solubility in reactive diluents
- Tg ~ 120degCTd ~ 250degC
- NC-Hcm3 (nD resp)
15
n(C C lF C F 2 )x (C H 2 C H )y (C H C H )z
O
(C H 2 )n
O H
OOCO
O(C H 2 )n
O H
4 0 0 0 g m o l-1M n lt o ligo m e riza tio n
n = 2 o r 4+C = CF
C l
F
F
C HH C
OC
O
O
+
Scheme 3 CTFE VCA hydroxy VE terpolymerization
263 SYNTHESIS OF CTFEVCAHYDROXY VINYL ETHER TERPOLYMERS
16
OCH2 =CH C
O(CH2)n
O
R]nCH)z(CHCH)y(CH2CF2)x(CClFH[
acrylation
O H
(CH2)n
O
R]nCH)z(CHCH)y(CH2CF2)x(CClFH[
OC
OO
OC
OO
Function polymerizableunder UV
Scheme 6 Acrylation of ndashOH functionalized CTFEVCA co-polymers
27ACRYLATION OF HYDROXY FUNCTIONALIZED CO-POLYMERS
CH2=CHCOCl
CH2=C(CH3)COCl
17
28 Characterization of UV-cured materialsDMA analysis
Tg of acrylated CTFEVCAHBVE compositions ~90degC
E ndash modulus 1 GPa at 20degC 50 MPa at 120degC
Taird10 ~ 200ndash220degC
DSC analysis
Tg of acrylated CTFEVCA-CH2OH compositions ~ 100ndash105degC
Taird10 ~ 230ndash240degC
1
2
2
3
18
29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber
291 Monomer synthesis
F3CCF2FC
O O
F F
CF3F3CCFFC
O O
F F
CF2
CF2F2C
CFFCO O
F F
F2C CF2
CF2CF2
CFFCO O
F F
A B DC
Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives
Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA
1919
292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)
F 2C CXY +
FC CFO
CO
F2CCF2
CF2
CF2TBPPi 75oC
C4F5H5
FC CF
OC
O
F2CCF2
CF2
F2C
CXY
F 2C
n
n
m
m
zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)
Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578
20
Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)
Run Monomer M2 Monomers in the feed(mol )
F-Ox M2
Copolym compsby microanal
(mol)F-Ox M2
Copolym compsby NMR(mol )
F-Ox M2
Conv(wt)
Tg(degC)
Td10(degC)
1 F2C=CFCl 20 80 35 65 374 626 63 105 322
2 F2C=CFCl 40 60 62 38 615 385 70 148 354
3 F2C=CFOC3F7
64 36 874 126 852 148 82 144 342
4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359
5 F2C=CH2 14 86 382 618 378 622 65 108 370
6 F2C=CH2 35 65 584 416 579 421 67 138 356
nR lt 135
21
210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP
CTFEVCAHVE) oligomers in good yield and high Tg were synthesized
2 Successful acrylation of hydroxy functionalized cooligomers
3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties
4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties
dArr
Suitable for waveguides applications
22
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
2323
31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to
hydrogenated analogues
Lower interfacial tension and CMC
Excellent chemical and thermal stability
Oleophobicity oil and fat repellants
Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc
Traditional commercial fluorosurfactants
Long fluorocarbon chain C6ltRFltC12
Perfluorooctane sulphonate (PFOS)
Perfluooctanoic acid ( PFOA)
their derivatives
2424
32 DRAWBACKS OF FLUORINATED SURFACTANTS
Bioaccumulable
Toxic and persistent
Wide-spread in the environment
3M company suggested perfluorinated chain le C4
bull Low bioconcentration factor
bull Low toxicity
bull Still high product performance
2525
General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4
Hydrophobic
G G GF- blockRF
Hydrophobic Hydrophilic
a ) for RF (CF3)2CF
b) for fluorinated monomer CH2=CH (TFP)
CF3
nCH2=CH + (CF3)2CFI RF - hydrophobic - I
CF3 CF3CF3
G
CF3
CF3CF-CH2-CH-CH2-CH Hydrophilic
CF3 CF3
Degradation
33 Synthesis of different end products as fluorinated surfactants
26
CF I + n nCFI
CF3
CF3
O
O
nCFCF3 I
O
O
Rad
nCFCF3
Zn
HSOH
O
nCFCF3
SOH
O
HOO
p
nCFCF3
SO
OO p
H2C CH2
nCFCF3
I
NNEt3
nCFCF3
NEt3nCF
CF3
N
I I
Surfactant C Surfactant B
Surfactant A
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants
Anionic surfactant
27
Surfactant Appearance Fluoroalkyl
10 decomp temperature a
(oC)
Tg and melting point b (oC)
(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC
(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145
(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175
Table 1 Properties of synthesized fluorinated surfactants
a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin
b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin
G Kostov et al USP 0027349 (2007)
28
Conditions Weight losses ()
Surfactant A Surfactant B Surfactant C
(1) Base-acid resistance
98 H2SO4 25 oC 7 days 00 lt12 00
60 HNO3 25 oC 7 days - gt400 lt20
37 HCl 25 oC 7 days 00 gt150 00
40 NaOH 25 oC 7 days 00 00 00
(2) Solubility in selected solvents Solubility (g100mL)
Water 25oC 72 hrs gt10 gt10 gt10
Methanol 25oC 72 hrs gt10 gt10 gt10
Diethyl ether 25oC 72 hrs lt1 lt1 lt1
Benzene 25oC 72 hrs lt2 lt2 lt2
Acetone 25oC 72 hrs lt10 lt10 lt10
Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-
Conclusions
The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6
29
Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA
30
Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis
34 Phosphorous containing TFP surfactants
31
3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate
Hydrolysis
Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)
32
Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to
those of PFOA (white)
33
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated Surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
34
Main characteristics of themembrane
To separate oxygen from hydrogen
To insure a good protonic conductivity
To be chemically physically andmechanically stable in acid media andat high temperatures
Rеasonable cost applications
No electronic conductivity
41 FUEL CELL MEMBRANES
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
6
21 Advantages of polymer opticalmaterials over conventional glasses
High optical transparency at transmission wavelengths
Potential to tune their optical properties by tailoringthe molecular structure
Lightweight
Flexibility even at large diameters
Good processability
Easy handling
Low cost
7
23Disadvantages of POWs
POWs reveal optical losses much higher than silica
PMMA (visible region) ndash 100 dBkm
Silica fibres ndash 03 dBkm
Transmission on short distances
Develop partial crystallinity and low Tg
Organic polymers are prone to oxidative degradation
22Applications of POWs
Short-haul communication links
Data systems in aircrafts automobiles
Local area networks
Inter- and intra- office network systems
8
SOLUTION
Substitution of F (or D) atoms for H atoms
- low overtone band strength
- less scattering
- low nD
Lower attenuation
Amorphous fluorinated polymers
Cytop trade(Asahi Glass)
Teflonreg AF(Du Pont)
9
24 OBJECTIVES
1 Synthesis of novel amorphous hydroxy functionalfluoropolymer resins and their acrylation Photocrosslinking and optical materials
2 New perfluorovinyl dioxolane monomers andcopolymer and optical materials
10
25 STRATEGY OF SYNTHESIS OF OPTICAL POLYMERS
Requirements for optical polymers
Optical transparency in the visible and NIR regions
amorphous with high Tg nD ndash14-15 Td gt150degC
Good processability to fibers films and tapes (Mn=2000-4000 gmol)
Photocrosslinkable (preferably acrylic and fluorinatedresins)
Homogenous network with good mechanical properties
11
Scheme 1 General scheme of fluoroacrylate synthesis
Fluoroolefin
-+ +
cyclicmonomer
termonomerX X OH
OH OH
OH
OCOCH=CH2
OCOCH=CH2
OCOCH=CH2
CF2=CFCl (CTFE)
CF2=CF(CF3) (HFP)
O O
O
Vinylenecarbonate
X=O(CH2)n
n=2 or n=4
Kostov G et al EP 1479 702 A1(2005) (Assigned to Atofina)
Kostov G Rousseau A Boutevin B Pascal T Journal of Fluorine Chem (2005) 126(2) 231-240
1212
261) Fluorooligomers CTFEVCA-basedcopolymers
Length limit of polymer
Chain-transfer agent or suitable solvent
Photocrosslinkable reactive functions
Reactive diluents fluorinated function monomers precise adjustement of resinsrsquo refractive index
2) Photocrosslinking
UV
Reactive diluent(s) Amorphous crosslinked network
26 CTFEVCAhydroxy VE copolymers
13
Main characteristics of CTFEVCA copolymers
Table 1 Selected monomercopolymer compositions of CTFEVCA copolymers and their main characteristics
CTFE inmonommixture(mol )
CTFEa
incopolym
(mol )
Yield
(wt )
Mnd
(gmol-1)
PDIb Tg
(degC)
Td10
(degC)
NC-Hcm3
(10-3)
nD
(23degC)
8070605040
603518459398346
640641658706722
28002500225020001800
2220252520
7090
100110120
274295289246254
5484115148162
14379143581435714459
-
Polar organic solvents acetone THF EtOAc DMF DMSO
Reactive diluents HDDA NVP and the couple HDDAATRIFESolubility
14
262 STUDY OF CTFEVCAHFP TERPOLYMERIZATION
Objective to improve the solubility in reactivediluents and fluorine content in copolymers
Reaction conditions
CTFEVCA = 067 = const
HFP in monomer mixture ndash from 5 to 20 mol (21to 10 mol in copolymer composition ndash 19F NMR
Characterization of CTFEVCAHFP terpolymers
- solubility in reactive diluents
- Tg ~ 120degCTd ~ 250degC
- NC-Hcm3 (nD resp)
15
n(C C lF C F 2 )x (C H 2 C H )y (C H C H )z
O
(C H 2 )n
O H
OOCO
O(C H 2 )n
O H
4 0 0 0 g m o l-1M n lt o ligo m e riza tio n
n = 2 o r 4+C = CF
C l
F
F
C HH C
OC
O
O
+
Scheme 3 CTFE VCA hydroxy VE terpolymerization
263 SYNTHESIS OF CTFEVCAHYDROXY VINYL ETHER TERPOLYMERS
16
OCH2 =CH C
O(CH2)n
O
R]nCH)z(CHCH)y(CH2CF2)x(CClFH[
acrylation
O H
(CH2)n
O
R]nCH)z(CHCH)y(CH2CF2)x(CClFH[
OC
OO
OC
OO
Function polymerizableunder UV
Scheme 6 Acrylation of ndashOH functionalized CTFEVCA co-polymers
27ACRYLATION OF HYDROXY FUNCTIONALIZED CO-POLYMERS
CH2=CHCOCl
CH2=C(CH3)COCl
17
28 Characterization of UV-cured materialsDMA analysis
Tg of acrylated CTFEVCAHBVE compositions ~90degC
E ndash modulus 1 GPa at 20degC 50 MPa at 120degC
Taird10 ~ 200ndash220degC
DSC analysis
Tg of acrylated CTFEVCA-CH2OH compositions ~ 100ndash105degC
Taird10 ~ 230ndash240degC
1
2
2
3
18
29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber
291 Monomer synthesis
F3CCF2FC
O O
F F
CF3F3CCFFC
O O
F F
CF2
CF2F2C
CFFCO O
F F
F2C CF2
CF2CF2
CFFCO O
F F
A B DC
Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives
Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA
1919
292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)
F 2C CXY +
FC CFO
CO
F2CCF2
CF2
CF2TBPPi 75oC
C4F5H5
FC CF
OC
O
F2CCF2
CF2
F2C
CXY
F 2C
n
n
m
m
zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)
Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578
20
Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)
Run Monomer M2 Monomers in the feed(mol )
F-Ox M2
Copolym compsby microanal
(mol)F-Ox M2
Copolym compsby NMR(mol )
F-Ox M2
Conv(wt)
Tg(degC)
Td10(degC)
1 F2C=CFCl 20 80 35 65 374 626 63 105 322
2 F2C=CFCl 40 60 62 38 615 385 70 148 354
3 F2C=CFOC3F7
64 36 874 126 852 148 82 144 342
4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359
5 F2C=CH2 14 86 382 618 378 622 65 108 370
6 F2C=CH2 35 65 584 416 579 421 67 138 356
nR lt 135
21
210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP
CTFEVCAHVE) oligomers in good yield and high Tg were synthesized
2 Successful acrylation of hydroxy functionalized cooligomers
3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties
4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties
dArr
Suitable for waveguides applications
22
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
2323
31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to
hydrogenated analogues
Lower interfacial tension and CMC
Excellent chemical and thermal stability
Oleophobicity oil and fat repellants
Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc
Traditional commercial fluorosurfactants
Long fluorocarbon chain C6ltRFltC12
Perfluorooctane sulphonate (PFOS)
Perfluooctanoic acid ( PFOA)
their derivatives
2424
32 DRAWBACKS OF FLUORINATED SURFACTANTS
Bioaccumulable
Toxic and persistent
Wide-spread in the environment
3M company suggested perfluorinated chain le C4
bull Low bioconcentration factor
bull Low toxicity
bull Still high product performance
2525
General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4
Hydrophobic
G G GF- blockRF
Hydrophobic Hydrophilic
a ) for RF (CF3)2CF
b) for fluorinated monomer CH2=CH (TFP)
CF3
nCH2=CH + (CF3)2CFI RF - hydrophobic - I
CF3 CF3CF3
G
CF3
CF3CF-CH2-CH-CH2-CH Hydrophilic
CF3 CF3
Degradation
33 Synthesis of different end products as fluorinated surfactants
26
CF I + n nCFI
CF3
CF3
O
O
nCFCF3 I
O
O
Rad
nCFCF3
Zn
HSOH
O
nCFCF3
SOH
O
HOO
p
nCFCF3
SO
OO p
H2C CH2
nCFCF3
I
NNEt3
nCFCF3
NEt3nCF
CF3
N
I I
Surfactant C Surfactant B
Surfactant A
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants
Anionic surfactant
27
Surfactant Appearance Fluoroalkyl
10 decomp temperature a
(oC)
Tg and melting point b (oC)
(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC
(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145
(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175
Table 1 Properties of synthesized fluorinated surfactants
a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin
b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin
G Kostov et al USP 0027349 (2007)
28
Conditions Weight losses ()
Surfactant A Surfactant B Surfactant C
(1) Base-acid resistance
98 H2SO4 25 oC 7 days 00 lt12 00
60 HNO3 25 oC 7 days - gt400 lt20
37 HCl 25 oC 7 days 00 gt150 00
40 NaOH 25 oC 7 days 00 00 00
(2) Solubility in selected solvents Solubility (g100mL)
Water 25oC 72 hrs gt10 gt10 gt10
Methanol 25oC 72 hrs gt10 gt10 gt10
Diethyl ether 25oC 72 hrs lt1 lt1 lt1
Benzene 25oC 72 hrs lt2 lt2 lt2
Acetone 25oC 72 hrs lt10 lt10 lt10
Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-
Conclusions
The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6
29
Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA
30
Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis
34 Phosphorous containing TFP surfactants
31
3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate
Hydrolysis
Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)
32
Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to
those of PFOA (white)
33
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated Surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
34
Main characteristics of themembrane
To separate oxygen from hydrogen
To insure a good protonic conductivity
To be chemically physically andmechanically stable in acid media andat high temperatures
Rеasonable cost applications
No electronic conductivity
41 FUEL CELL MEMBRANES
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
7
23Disadvantages of POWs
POWs reveal optical losses much higher than silica
PMMA (visible region) ndash 100 dBkm
Silica fibres ndash 03 dBkm
Transmission on short distances
Develop partial crystallinity and low Tg
Organic polymers are prone to oxidative degradation
22Applications of POWs
Short-haul communication links
Data systems in aircrafts automobiles
Local area networks
Inter- and intra- office network systems
8
SOLUTION
Substitution of F (or D) atoms for H atoms
- low overtone band strength
- less scattering
- low nD
Lower attenuation
Amorphous fluorinated polymers
Cytop trade(Asahi Glass)
Teflonreg AF(Du Pont)
9
24 OBJECTIVES
1 Synthesis of novel amorphous hydroxy functionalfluoropolymer resins and their acrylation Photocrosslinking and optical materials
2 New perfluorovinyl dioxolane monomers andcopolymer and optical materials
10
25 STRATEGY OF SYNTHESIS OF OPTICAL POLYMERS
Requirements for optical polymers
Optical transparency in the visible and NIR regions
amorphous with high Tg nD ndash14-15 Td gt150degC
Good processability to fibers films and tapes (Mn=2000-4000 gmol)
Photocrosslinkable (preferably acrylic and fluorinatedresins)
Homogenous network with good mechanical properties
11
Scheme 1 General scheme of fluoroacrylate synthesis
Fluoroolefin
-+ +
cyclicmonomer
termonomerX X OH
OH OH
OH
OCOCH=CH2
OCOCH=CH2
OCOCH=CH2
CF2=CFCl (CTFE)
CF2=CF(CF3) (HFP)
O O
O
Vinylenecarbonate
X=O(CH2)n
n=2 or n=4
Kostov G et al EP 1479 702 A1(2005) (Assigned to Atofina)
Kostov G Rousseau A Boutevin B Pascal T Journal of Fluorine Chem (2005) 126(2) 231-240
1212
261) Fluorooligomers CTFEVCA-basedcopolymers
Length limit of polymer
Chain-transfer agent or suitable solvent
Photocrosslinkable reactive functions
Reactive diluents fluorinated function monomers precise adjustement of resinsrsquo refractive index
2) Photocrosslinking
UV
Reactive diluent(s) Amorphous crosslinked network
26 CTFEVCAhydroxy VE copolymers
13
Main characteristics of CTFEVCA copolymers
Table 1 Selected monomercopolymer compositions of CTFEVCA copolymers and their main characteristics
CTFE inmonommixture(mol )
CTFEa
incopolym
(mol )
Yield
(wt )
Mnd
(gmol-1)
PDIb Tg
(degC)
Td10
(degC)
NC-Hcm3
(10-3)
nD
(23degC)
8070605040
603518459398346
640641658706722
28002500225020001800
2220252520
7090
100110120
274295289246254
5484115148162
14379143581435714459
-
Polar organic solvents acetone THF EtOAc DMF DMSO
Reactive diluents HDDA NVP and the couple HDDAATRIFESolubility
14
262 STUDY OF CTFEVCAHFP TERPOLYMERIZATION
Objective to improve the solubility in reactivediluents and fluorine content in copolymers
Reaction conditions
CTFEVCA = 067 = const
HFP in monomer mixture ndash from 5 to 20 mol (21to 10 mol in copolymer composition ndash 19F NMR
Characterization of CTFEVCAHFP terpolymers
- solubility in reactive diluents
- Tg ~ 120degCTd ~ 250degC
- NC-Hcm3 (nD resp)
15
n(C C lF C F 2 )x (C H 2 C H )y (C H C H )z
O
(C H 2 )n
O H
OOCO
O(C H 2 )n
O H
4 0 0 0 g m o l-1M n lt o ligo m e riza tio n
n = 2 o r 4+C = CF
C l
F
F
C HH C
OC
O
O
+
Scheme 3 CTFE VCA hydroxy VE terpolymerization
263 SYNTHESIS OF CTFEVCAHYDROXY VINYL ETHER TERPOLYMERS
16
OCH2 =CH C
O(CH2)n
O
R]nCH)z(CHCH)y(CH2CF2)x(CClFH[
acrylation
O H
(CH2)n
O
R]nCH)z(CHCH)y(CH2CF2)x(CClFH[
OC
OO
OC
OO
Function polymerizableunder UV
Scheme 6 Acrylation of ndashOH functionalized CTFEVCA co-polymers
27ACRYLATION OF HYDROXY FUNCTIONALIZED CO-POLYMERS
CH2=CHCOCl
CH2=C(CH3)COCl
17
28 Characterization of UV-cured materialsDMA analysis
Tg of acrylated CTFEVCAHBVE compositions ~90degC
E ndash modulus 1 GPa at 20degC 50 MPa at 120degC
Taird10 ~ 200ndash220degC
DSC analysis
Tg of acrylated CTFEVCA-CH2OH compositions ~ 100ndash105degC
Taird10 ~ 230ndash240degC
1
2
2
3
18
29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber
291 Monomer synthesis
F3CCF2FC
O O
F F
CF3F3CCFFC
O O
F F
CF2
CF2F2C
CFFCO O
F F
F2C CF2
CF2CF2
CFFCO O
F F
A B DC
Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives
Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA
1919
292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)
F 2C CXY +
FC CFO
CO
F2CCF2
CF2
CF2TBPPi 75oC
C4F5H5
FC CF
OC
O
F2CCF2
CF2
F2C
CXY
F 2C
n
n
m
m
zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)
Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578
20
Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)
Run Monomer M2 Monomers in the feed(mol )
F-Ox M2
Copolym compsby microanal
(mol)F-Ox M2
Copolym compsby NMR(mol )
F-Ox M2
Conv(wt)
Tg(degC)
Td10(degC)
1 F2C=CFCl 20 80 35 65 374 626 63 105 322
2 F2C=CFCl 40 60 62 38 615 385 70 148 354
3 F2C=CFOC3F7
64 36 874 126 852 148 82 144 342
4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359
5 F2C=CH2 14 86 382 618 378 622 65 108 370
6 F2C=CH2 35 65 584 416 579 421 67 138 356
nR lt 135
21
210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP
CTFEVCAHVE) oligomers in good yield and high Tg were synthesized
2 Successful acrylation of hydroxy functionalized cooligomers
3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties
4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties
dArr
Suitable for waveguides applications
22
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
2323
31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to
hydrogenated analogues
Lower interfacial tension and CMC
Excellent chemical and thermal stability
Oleophobicity oil and fat repellants
Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc
Traditional commercial fluorosurfactants
Long fluorocarbon chain C6ltRFltC12
Perfluorooctane sulphonate (PFOS)
Perfluooctanoic acid ( PFOA)
their derivatives
2424
32 DRAWBACKS OF FLUORINATED SURFACTANTS
Bioaccumulable
Toxic and persistent
Wide-spread in the environment
3M company suggested perfluorinated chain le C4
bull Low bioconcentration factor
bull Low toxicity
bull Still high product performance
2525
General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4
Hydrophobic
G G GF- blockRF
Hydrophobic Hydrophilic
a ) for RF (CF3)2CF
b) for fluorinated monomer CH2=CH (TFP)
CF3
nCH2=CH + (CF3)2CFI RF - hydrophobic - I
CF3 CF3CF3
G
CF3
CF3CF-CH2-CH-CH2-CH Hydrophilic
CF3 CF3
Degradation
33 Synthesis of different end products as fluorinated surfactants
26
CF I + n nCFI
CF3
CF3
O
O
nCFCF3 I
O
O
Rad
nCFCF3
Zn
HSOH
O
nCFCF3
SOH
O
HOO
p
nCFCF3
SO
OO p
H2C CH2
nCFCF3
I
NNEt3
nCFCF3
NEt3nCF
CF3
N
I I
Surfactant C Surfactant B
Surfactant A
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants
Anionic surfactant
27
Surfactant Appearance Fluoroalkyl
10 decomp temperature a
(oC)
Tg and melting point b (oC)
(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC
(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145
(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175
Table 1 Properties of synthesized fluorinated surfactants
a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin
b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin
G Kostov et al USP 0027349 (2007)
28
Conditions Weight losses ()
Surfactant A Surfactant B Surfactant C
(1) Base-acid resistance
98 H2SO4 25 oC 7 days 00 lt12 00
60 HNO3 25 oC 7 days - gt400 lt20
37 HCl 25 oC 7 days 00 gt150 00
40 NaOH 25 oC 7 days 00 00 00
(2) Solubility in selected solvents Solubility (g100mL)
Water 25oC 72 hrs gt10 gt10 gt10
Methanol 25oC 72 hrs gt10 gt10 gt10
Diethyl ether 25oC 72 hrs lt1 lt1 lt1
Benzene 25oC 72 hrs lt2 lt2 lt2
Acetone 25oC 72 hrs lt10 lt10 lt10
Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-
Conclusions
The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6
29
Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA
30
Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis
34 Phosphorous containing TFP surfactants
31
3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate
Hydrolysis
Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)
32
Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to
those of PFOA (white)
33
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated Surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
34
Main characteristics of themembrane
To separate oxygen from hydrogen
To insure a good protonic conductivity
To be chemically physically andmechanically stable in acid media andat high temperatures
Rеasonable cost applications
No electronic conductivity
41 FUEL CELL MEMBRANES
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
8
SOLUTION
Substitution of F (or D) atoms for H atoms
- low overtone band strength
- less scattering
- low nD
Lower attenuation
Amorphous fluorinated polymers
Cytop trade(Asahi Glass)
Teflonreg AF(Du Pont)
9
24 OBJECTIVES
1 Synthesis of novel amorphous hydroxy functionalfluoropolymer resins and their acrylation Photocrosslinking and optical materials
2 New perfluorovinyl dioxolane monomers andcopolymer and optical materials
10
25 STRATEGY OF SYNTHESIS OF OPTICAL POLYMERS
Requirements for optical polymers
Optical transparency in the visible and NIR regions
amorphous with high Tg nD ndash14-15 Td gt150degC
Good processability to fibers films and tapes (Mn=2000-4000 gmol)
Photocrosslinkable (preferably acrylic and fluorinatedresins)
Homogenous network with good mechanical properties
11
Scheme 1 General scheme of fluoroacrylate synthesis
Fluoroolefin
-+ +
cyclicmonomer
termonomerX X OH
OH OH
OH
OCOCH=CH2
OCOCH=CH2
OCOCH=CH2
CF2=CFCl (CTFE)
CF2=CF(CF3) (HFP)
O O
O
Vinylenecarbonate
X=O(CH2)n
n=2 or n=4
Kostov G et al EP 1479 702 A1(2005) (Assigned to Atofina)
Kostov G Rousseau A Boutevin B Pascal T Journal of Fluorine Chem (2005) 126(2) 231-240
1212
261) Fluorooligomers CTFEVCA-basedcopolymers
Length limit of polymer
Chain-transfer agent or suitable solvent
Photocrosslinkable reactive functions
Reactive diluents fluorinated function monomers precise adjustement of resinsrsquo refractive index
2) Photocrosslinking
UV
Reactive diluent(s) Amorphous crosslinked network
26 CTFEVCAhydroxy VE copolymers
13
Main characteristics of CTFEVCA copolymers
Table 1 Selected monomercopolymer compositions of CTFEVCA copolymers and their main characteristics
CTFE inmonommixture(mol )
CTFEa
incopolym
(mol )
Yield
(wt )
Mnd
(gmol-1)
PDIb Tg
(degC)
Td10
(degC)
NC-Hcm3
(10-3)
nD
(23degC)
8070605040
603518459398346
640641658706722
28002500225020001800
2220252520
7090
100110120
274295289246254
5484115148162
14379143581435714459
-
Polar organic solvents acetone THF EtOAc DMF DMSO
Reactive diluents HDDA NVP and the couple HDDAATRIFESolubility
14
262 STUDY OF CTFEVCAHFP TERPOLYMERIZATION
Objective to improve the solubility in reactivediluents and fluorine content in copolymers
Reaction conditions
CTFEVCA = 067 = const
HFP in monomer mixture ndash from 5 to 20 mol (21to 10 mol in copolymer composition ndash 19F NMR
Characterization of CTFEVCAHFP terpolymers
- solubility in reactive diluents
- Tg ~ 120degCTd ~ 250degC
- NC-Hcm3 (nD resp)
15
n(C C lF C F 2 )x (C H 2 C H )y (C H C H )z
O
(C H 2 )n
O H
OOCO
O(C H 2 )n
O H
4 0 0 0 g m o l-1M n lt o ligo m e riza tio n
n = 2 o r 4+C = CF
C l
F
F
C HH C
OC
O
O
+
Scheme 3 CTFE VCA hydroxy VE terpolymerization
263 SYNTHESIS OF CTFEVCAHYDROXY VINYL ETHER TERPOLYMERS
16
OCH2 =CH C
O(CH2)n
O
R]nCH)z(CHCH)y(CH2CF2)x(CClFH[
acrylation
O H
(CH2)n
O
R]nCH)z(CHCH)y(CH2CF2)x(CClFH[
OC
OO
OC
OO
Function polymerizableunder UV
Scheme 6 Acrylation of ndashOH functionalized CTFEVCA co-polymers
27ACRYLATION OF HYDROXY FUNCTIONALIZED CO-POLYMERS
CH2=CHCOCl
CH2=C(CH3)COCl
17
28 Characterization of UV-cured materialsDMA analysis
Tg of acrylated CTFEVCAHBVE compositions ~90degC
E ndash modulus 1 GPa at 20degC 50 MPa at 120degC
Taird10 ~ 200ndash220degC
DSC analysis
Tg of acrylated CTFEVCA-CH2OH compositions ~ 100ndash105degC
Taird10 ~ 230ndash240degC
1
2
2
3
18
29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber
291 Monomer synthesis
F3CCF2FC
O O
F F
CF3F3CCFFC
O O
F F
CF2
CF2F2C
CFFCO O
F F
F2C CF2
CF2CF2
CFFCO O
F F
A B DC
Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives
Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA
1919
292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)
F 2C CXY +
FC CFO
CO
F2CCF2
CF2
CF2TBPPi 75oC
C4F5H5
FC CF
OC
O
F2CCF2
CF2
F2C
CXY
F 2C
n
n
m
m
zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)
Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578
20
Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)
Run Monomer M2 Monomers in the feed(mol )
F-Ox M2
Copolym compsby microanal
(mol)F-Ox M2
Copolym compsby NMR(mol )
F-Ox M2
Conv(wt)
Tg(degC)
Td10(degC)
1 F2C=CFCl 20 80 35 65 374 626 63 105 322
2 F2C=CFCl 40 60 62 38 615 385 70 148 354
3 F2C=CFOC3F7
64 36 874 126 852 148 82 144 342
4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359
5 F2C=CH2 14 86 382 618 378 622 65 108 370
6 F2C=CH2 35 65 584 416 579 421 67 138 356
nR lt 135
21
210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP
CTFEVCAHVE) oligomers in good yield and high Tg were synthesized
2 Successful acrylation of hydroxy functionalized cooligomers
3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties
4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties
dArr
Suitable for waveguides applications
22
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
2323
31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to
hydrogenated analogues
Lower interfacial tension and CMC
Excellent chemical and thermal stability
Oleophobicity oil and fat repellants
Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc
Traditional commercial fluorosurfactants
Long fluorocarbon chain C6ltRFltC12
Perfluorooctane sulphonate (PFOS)
Perfluooctanoic acid ( PFOA)
their derivatives
2424
32 DRAWBACKS OF FLUORINATED SURFACTANTS
Bioaccumulable
Toxic and persistent
Wide-spread in the environment
3M company suggested perfluorinated chain le C4
bull Low bioconcentration factor
bull Low toxicity
bull Still high product performance
2525
General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4
Hydrophobic
G G GF- blockRF
Hydrophobic Hydrophilic
a ) for RF (CF3)2CF
b) for fluorinated monomer CH2=CH (TFP)
CF3
nCH2=CH + (CF3)2CFI RF - hydrophobic - I
CF3 CF3CF3
G
CF3
CF3CF-CH2-CH-CH2-CH Hydrophilic
CF3 CF3
Degradation
33 Synthesis of different end products as fluorinated surfactants
26
CF I + n nCFI
CF3
CF3
O
O
nCFCF3 I
O
O
Rad
nCFCF3
Zn
HSOH
O
nCFCF3
SOH
O
HOO
p
nCFCF3
SO
OO p
H2C CH2
nCFCF3
I
NNEt3
nCFCF3
NEt3nCF
CF3
N
I I
Surfactant C Surfactant B
Surfactant A
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants
Anionic surfactant
27
Surfactant Appearance Fluoroalkyl
10 decomp temperature a
(oC)
Tg and melting point b (oC)
(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC
(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145
(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175
Table 1 Properties of synthesized fluorinated surfactants
a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin
b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin
G Kostov et al USP 0027349 (2007)
28
Conditions Weight losses ()
Surfactant A Surfactant B Surfactant C
(1) Base-acid resistance
98 H2SO4 25 oC 7 days 00 lt12 00
60 HNO3 25 oC 7 days - gt400 lt20
37 HCl 25 oC 7 days 00 gt150 00
40 NaOH 25 oC 7 days 00 00 00
(2) Solubility in selected solvents Solubility (g100mL)
Water 25oC 72 hrs gt10 gt10 gt10
Methanol 25oC 72 hrs gt10 gt10 gt10
Diethyl ether 25oC 72 hrs lt1 lt1 lt1
Benzene 25oC 72 hrs lt2 lt2 lt2
Acetone 25oC 72 hrs lt10 lt10 lt10
Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-
Conclusions
The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6
29
Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA
30
Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis
34 Phosphorous containing TFP surfactants
31
3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate
Hydrolysis
Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)
32
Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to
those of PFOA (white)
33
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated Surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
34
Main characteristics of themembrane
To separate oxygen from hydrogen
To insure a good protonic conductivity
To be chemically physically andmechanically stable in acid media andat high temperatures
Rеasonable cost applications
No electronic conductivity
41 FUEL CELL MEMBRANES
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
9
24 OBJECTIVES
1 Synthesis of novel amorphous hydroxy functionalfluoropolymer resins and their acrylation Photocrosslinking and optical materials
2 New perfluorovinyl dioxolane monomers andcopolymer and optical materials
10
25 STRATEGY OF SYNTHESIS OF OPTICAL POLYMERS
Requirements for optical polymers
Optical transparency in the visible and NIR regions
amorphous with high Tg nD ndash14-15 Td gt150degC
Good processability to fibers films and tapes (Mn=2000-4000 gmol)
Photocrosslinkable (preferably acrylic and fluorinatedresins)
Homogenous network with good mechanical properties
11
Scheme 1 General scheme of fluoroacrylate synthesis
Fluoroolefin
-+ +
cyclicmonomer
termonomerX X OH
OH OH
OH
OCOCH=CH2
OCOCH=CH2
OCOCH=CH2
CF2=CFCl (CTFE)
CF2=CF(CF3) (HFP)
O O
O
Vinylenecarbonate
X=O(CH2)n
n=2 or n=4
Kostov G et al EP 1479 702 A1(2005) (Assigned to Atofina)
Kostov G Rousseau A Boutevin B Pascal T Journal of Fluorine Chem (2005) 126(2) 231-240
1212
261) Fluorooligomers CTFEVCA-basedcopolymers
Length limit of polymer
Chain-transfer agent or suitable solvent
Photocrosslinkable reactive functions
Reactive diluents fluorinated function monomers precise adjustement of resinsrsquo refractive index
2) Photocrosslinking
UV
Reactive diluent(s) Amorphous crosslinked network
26 CTFEVCAhydroxy VE copolymers
13
Main characteristics of CTFEVCA copolymers
Table 1 Selected monomercopolymer compositions of CTFEVCA copolymers and their main characteristics
CTFE inmonommixture(mol )
CTFEa
incopolym
(mol )
Yield
(wt )
Mnd
(gmol-1)
PDIb Tg
(degC)
Td10
(degC)
NC-Hcm3
(10-3)
nD
(23degC)
8070605040
603518459398346
640641658706722
28002500225020001800
2220252520
7090
100110120
274295289246254
5484115148162
14379143581435714459
-
Polar organic solvents acetone THF EtOAc DMF DMSO
Reactive diluents HDDA NVP and the couple HDDAATRIFESolubility
14
262 STUDY OF CTFEVCAHFP TERPOLYMERIZATION
Objective to improve the solubility in reactivediluents and fluorine content in copolymers
Reaction conditions
CTFEVCA = 067 = const
HFP in monomer mixture ndash from 5 to 20 mol (21to 10 mol in copolymer composition ndash 19F NMR
Characterization of CTFEVCAHFP terpolymers
- solubility in reactive diluents
- Tg ~ 120degCTd ~ 250degC
- NC-Hcm3 (nD resp)
15
n(C C lF C F 2 )x (C H 2 C H )y (C H C H )z
O
(C H 2 )n
O H
OOCO
O(C H 2 )n
O H
4 0 0 0 g m o l-1M n lt o ligo m e riza tio n
n = 2 o r 4+C = CF
C l
F
F
C HH C
OC
O
O
+
Scheme 3 CTFE VCA hydroxy VE terpolymerization
263 SYNTHESIS OF CTFEVCAHYDROXY VINYL ETHER TERPOLYMERS
16
OCH2 =CH C
O(CH2)n
O
R]nCH)z(CHCH)y(CH2CF2)x(CClFH[
acrylation
O H
(CH2)n
O
R]nCH)z(CHCH)y(CH2CF2)x(CClFH[
OC
OO
OC
OO
Function polymerizableunder UV
Scheme 6 Acrylation of ndashOH functionalized CTFEVCA co-polymers
27ACRYLATION OF HYDROXY FUNCTIONALIZED CO-POLYMERS
CH2=CHCOCl
CH2=C(CH3)COCl
17
28 Characterization of UV-cured materialsDMA analysis
Tg of acrylated CTFEVCAHBVE compositions ~90degC
E ndash modulus 1 GPa at 20degC 50 MPa at 120degC
Taird10 ~ 200ndash220degC
DSC analysis
Tg of acrylated CTFEVCA-CH2OH compositions ~ 100ndash105degC
Taird10 ~ 230ndash240degC
1
2
2
3
18
29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber
291 Monomer synthesis
F3CCF2FC
O O
F F
CF3F3CCFFC
O O
F F
CF2
CF2F2C
CFFCO O
F F
F2C CF2
CF2CF2
CFFCO O
F F
A B DC
Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives
Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA
1919
292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)
F 2C CXY +
FC CFO
CO
F2CCF2
CF2
CF2TBPPi 75oC
C4F5H5
FC CF
OC
O
F2CCF2
CF2
F2C
CXY
F 2C
n
n
m
m
zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)
Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578
20
Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)
Run Monomer M2 Monomers in the feed(mol )
F-Ox M2
Copolym compsby microanal
(mol)F-Ox M2
Copolym compsby NMR(mol )
F-Ox M2
Conv(wt)
Tg(degC)
Td10(degC)
1 F2C=CFCl 20 80 35 65 374 626 63 105 322
2 F2C=CFCl 40 60 62 38 615 385 70 148 354
3 F2C=CFOC3F7
64 36 874 126 852 148 82 144 342
4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359
5 F2C=CH2 14 86 382 618 378 622 65 108 370
6 F2C=CH2 35 65 584 416 579 421 67 138 356
nR lt 135
21
210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP
CTFEVCAHVE) oligomers in good yield and high Tg were synthesized
2 Successful acrylation of hydroxy functionalized cooligomers
3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties
4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties
dArr
Suitable for waveguides applications
22
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
2323
31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to
hydrogenated analogues
Lower interfacial tension and CMC
Excellent chemical and thermal stability
Oleophobicity oil and fat repellants
Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc
Traditional commercial fluorosurfactants
Long fluorocarbon chain C6ltRFltC12
Perfluorooctane sulphonate (PFOS)
Perfluooctanoic acid ( PFOA)
their derivatives
2424
32 DRAWBACKS OF FLUORINATED SURFACTANTS
Bioaccumulable
Toxic and persistent
Wide-spread in the environment
3M company suggested perfluorinated chain le C4
bull Low bioconcentration factor
bull Low toxicity
bull Still high product performance
2525
General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4
Hydrophobic
G G GF- blockRF
Hydrophobic Hydrophilic
a ) for RF (CF3)2CF
b) for fluorinated monomer CH2=CH (TFP)
CF3
nCH2=CH + (CF3)2CFI RF - hydrophobic - I
CF3 CF3CF3
G
CF3
CF3CF-CH2-CH-CH2-CH Hydrophilic
CF3 CF3
Degradation
33 Synthesis of different end products as fluorinated surfactants
26
CF I + n nCFI
CF3
CF3
O
O
nCFCF3 I
O
O
Rad
nCFCF3
Zn
HSOH
O
nCFCF3
SOH
O
HOO
p
nCFCF3
SO
OO p
H2C CH2
nCFCF3
I
NNEt3
nCFCF3
NEt3nCF
CF3
N
I I
Surfactant C Surfactant B
Surfactant A
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants
Anionic surfactant
27
Surfactant Appearance Fluoroalkyl
10 decomp temperature a
(oC)
Tg and melting point b (oC)
(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC
(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145
(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175
Table 1 Properties of synthesized fluorinated surfactants
a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin
b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin
G Kostov et al USP 0027349 (2007)
28
Conditions Weight losses ()
Surfactant A Surfactant B Surfactant C
(1) Base-acid resistance
98 H2SO4 25 oC 7 days 00 lt12 00
60 HNO3 25 oC 7 days - gt400 lt20
37 HCl 25 oC 7 days 00 gt150 00
40 NaOH 25 oC 7 days 00 00 00
(2) Solubility in selected solvents Solubility (g100mL)
Water 25oC 72 hrs gt10 gt10 gt10
Methanol 25oC 72 hrs gt10 gt10 gt10
Diethyl ether 25oC 72 hrs lt1 lt1 lt1
Benzene 25oC 72 hrs lt2 lt2 lt2
Acetone 25oC 72 hrs lt10 lt10 lt10
Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-
Conclusions
The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6
29
Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA
30
Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis
34 Phosphorous containing TFP surfactants
31
3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate
Hydrolysis
Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)
32
Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to
those of PFOA (white)
33
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated Surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
34
Main characteristics of themembrane
To separate oxygen from hydrogen
To insure a good protonic conductivity
To be chemically physically andmechanically stable in acid media andat high temperatures
Rеasonable cost applications
No electronic conductivity
41 FUEL CELL MEMBRANES
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
10
25 STRATEGY OF SYNTHESIS OF OPTICAL POLYMERS
Requirements for optical polymers
Optical transparency in the visible and NIR regions
amorphous with high Tg nD ndash14-15 Td gt150degC
Good processability to fibers films and tapes (Mn=2000-4000 gmol)
Photocrosslinkable (preferably acrylic and fluorinatedresins)
Homogenous network with good mechanical properties
11
Scheme 1 General scheme of fluoroacrylate synthesis
Fluoroolefin
-+ +
cyclicmonomer
termonomerX X OH
OH OH
OH
OCOCH=CH2
OCOCH=CH2
OCOCH=CH2
CF2=CFCl (CTFE)
CF2=CF(CF3) (HFP)
O O
O
Vinylenecarbonate
X=O(CH2)n
n=2 or n=4
Kostov G et al EP 1479 702 A1(2005) (Assigned to Atofina)
Kostov G Rousseau A Boutevin B Pascal T Journal of Fluorine Chem (2005) 126(2) 231-240
1212
261) Fluorooligomers CTFEVCA-basedcopolymers
Length limit of polymer
Chain-transfer agent or suitable solvent
Photocrosslinkable reactive functions
Reactive diluents fluorinated function monomers precise adjustement of resinsrsquo refractive index
2) Photocrosslinking
UV
Reactive diluent(s) Amorphous crosslinked network
26 CTFEVCAhydroxy VE copolymers
13
Main characteristics of CTFEVCA copolymers
Table 1 Selected monomercopolymer compositions of CTFEVCA copolymers and their main characteristics
CTFE inmonommixture(mol )
CTFEa
incopolym
(mol )
Yield
(wt )
Mnd
(gmol-1)
PDIb Tg
(degC)
Td10
(degC)
NC-Hcm3
(10-3)
nD
(23degC)
8070605040
603518459398346
640641658706722
28002500225020001800
2220252520
7090
100110120
274295289246254
5484115148162
14379143581435714459
-
Polar organic solvents acetone THF EtOAc DMF DMSO
Reactive diluents HDDA NVP and the couple HDDAATRIFESolubility
14
262 STUDY OF CTFEVCAHFP TERPOLYMERIZATION
Objective to improve the solubility in reactivediluents and fluorine content in copolymers
Reaction conditions
CTFEVCA = 067 = const
HFP in monomer mixture ndash from 5 to 20 mol (21to 10 mol in copolymer composition ndash 19F NMR
Characterization of CTFEVCAHFP terpolymers
- solubility in reactive diluents
- Tg ~ 120degCTd ~ 250degC
- NC-Hcm3 (nD resp)
15
n(C C lF C F 2 )x (C H 2 C H )y (C H C H )z
O
(C H 2 )n
O H
OOCO
O(C H 2 )n
O H
4 0 0 0 g m o l-1M n lt o ligo m e riza tio n
n = 2 o r 4+C = CF
C l
F
F
C HH C
OC
O
O
+
Scheme 3 CTFE VCA hydroxy VE terpolymerization
263 SYNTHESIS OF CTFEVCAHYDROXY VINYL ETHER TERPOLYMERS
16
OCH2 =CH C
O(CH2)n
O
R]nCH)z(CHCH)y(CH2CF2)x(CClFH[
acrylation
O H
(CH2)n
O
R]nCH)z(CHCH)y(CH2CF2)x(CClFH[
OC
OO
OC
OO
Function polymerizableunder UV
Scheme 6 Acrylation of ndashOH functionalized CTFEVCA co-polymers
27ACRYLATION OF HYDROXY FUNCTIONALIZED CO-POLYMERS
CH2=CHCOCl
CH2=C(CH3)COCl
17
28 Characterization of UV-cured materialsDMA analysis
Tg of acrylated CTFEVCAHBVE compositions ~90degC
E ndash modulus 1 GPa at 20degC 50 MPa at 120degC
Taird10 ~ 200ndash220degC
DSC analysis
Tg of acrylated CTFEVCA-CH2OH compositions ~ 100ndash105degC
Taird10 ~ 230ndash240degC
1
2
2
3
18
29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber
291 Monomer synthesis
F3CCF2FC
O O
F F
CF3F3CCFFC
O O
F F
CF2
CF2F2C
CFFCO O
F F
F2C CF2
CF2CF2
CFFCO O
F F
A B DC
Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives
Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA
1919
292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)
F 2C CXY +
FC CFO
CO
F2CCF2
CF2
CF2TBPPi 75oC
C4F5H5
FC CF
OC
O
F2CCF2
CF2
F2C
CXY
F 2C
n
n
m
m
zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)
Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578
20
Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)
Run Monomer M2 Monomers in the feed(mol )
F-Ox M2
Copolym compsby microanal
(mol)F-Ox M2
Copolym compsby NMR(mol )
F-Ox M2
Conv(wt)
Tg(degC)
Td10(degC)
1 F2C=CFCl 20 80 35 65 374 626 63 105 322
2 F2C=CFCl 40 60 62 38 615 385 70 148 354
3 F2C=CFOC3F7
64 36 874 126 852 148 82 144 342
4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359
5 F2C=CH2 14 86 382 618 378 622 65 108 370
6 F2C=CH2 35 65 584 416 579 421 67 138 356
nR lt 135
21
210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP
CTFEVCAHVE) oligomers in good yield and high Tg were synthesized
2 Successful acrylation of hydroxy functionalized cooligomers
3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties
4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties
dArr
Suitable for waveguides applications
22
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
2323
31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to
hydrogenated analogues
Lower interfacial tension and CMC
Excellent chemical and thermal stability
Oleophobicity oil and fat repellants
Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc
Traditional commercial fluorosurfactants
Long fluorocarbon chain C6ltRFltC12
Perfluorooctane sulphonate (PFOS)
Perfluooctanoic acid ( PFOA)
their derivatives
2424
32 DRAWBACKS OF FLUORINATED SURFACTANTS
Bioaccumulable
Toxic and persistent
Wide-spread in the environment
3M company suggested perfluorinated chain le C4
bull Low bioconcentration factor
bull Low toxicity
bull Still high product performance
2525
General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4
Hydrophobic
G G GF- blockRF
Hydrophobic Hydrophilic
a ) for RF (CF3)2CF
b) for fluorinated monomer CH2=CH (TFP)
CF3
nCH2=CH + (CF3)2CFI RF - hydrophobic - I
CF3 CF3CF3
G
CF3
CF3CF-CH2-CH-CH2-CH Hydrophilic
CF3 CF3
Degradation
33 Synthesis of different end products as fluorinated surfactants
26
CF I + n nCFI
CF3
CF3
O
O
nCFCF3 I
O
O
Rad
nCFCF3
Zn
HSOH
O
nCFCF3
SOH
O
HOO
p
nCFCF3
SO
OO p
H2C CH2
nCFCF3
I
NNEt3
nCFCF3
NEt3nCF
CF3
N
I I
Surfactant C Surfactant B
Surfactant A
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants
Anionic surfactant
27
Surfactant Appearance Fluoroalkyl
10 decomp temperature a
(oC)
Tg and melting point b (oC)
(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC
(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145
(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175
Table 1 Properties of synthesized fluorinated surfactants
a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin
b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin
G Kostov et al USP 0027349 (2007)
28
Conditions Weight losses ()
Surfactant A Surfactant B Surfactant C
(1) Base-acid resistance
98 H2SO4 25 oC 7 days 00 lt12 00
60 HNO3 25 oC 7 days - gt400 lt20
37 HCl 25 oC 7 days 00 gt150 00
40 NaOH 25 oC 7 days 00 00 00
(2) Solubility in selected solvents Solubility (g100mL)
Water 25oC 72 hrs gt10 gt10 gt10
Methanol 25oC 72 hrs gt10 gt10 gt10
Diethyl ether 25oC 72 hrs lt1 lt1 lt1
Benzene 25oC 72 hrs lt2 lt2 lt2
Acetone 25oC 72 hrs lt10 lt10 lt10
Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-
Conclusions
The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6
29
Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA
30
Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis
34 Phosphorous containing TFP surfactants
31
3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate
Hydrolysis
Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)
32
Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to
those of PFOA (white)
33
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated Surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
34
Main characteristics of themembrane
To separate oxygen from hydrogen
To insure a good protonic conductivity
To be chemically physically andmechanically stable in acid media andat high temperatures
Rеasonable cost applications
No electronic conductivity
41 FUEL CELL MEMBRANES
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
11
Scheme 1 General scheme of fluoroacrylate synthesis
Fluoroolefin
-+ +
cyclicmonomer
termonomerX X OH
OH OH
OH
OCOCH=CH2
OCOCH=CH2
OCOCH=CH2
CF2=CFCl (CTFE)
CF2=CF(CF3) (HFP)
O O
O
Vinylenecarbonate
X=O(CH2)n
n=2 or n=4
Kostov G et al EP 1479 702 A1(2005) (Assigned to Atofina)
Kostov G Rousseau A Boutevin B Pascal T Journal of Fluorine Chem (2005) 126(2) 231-240
1212
261) Fluorooligomers CTFEVCA-basedcopolymers
Length limit of polymer
Chain-transfer agent or suitable solvent
Photocrosslinkable reactive functions
Reactive diluents fluorinated function monomers precise adjustement of resinsrsquo refractive index
2) Photocrosslinking
UV
Reactive diluent(s) Amorphous crosslinked network
26 CTFEVCAhydroxy VE copolymers
13
Main characteristics of CTFEVCA copolymers
Table 1 Selected monomercopolymer compositions of CTFEVCA copolymers and their main characteristics
CTFE inmonommixture(mol )
CTFEa
incopolym
(mol )
Yield
(wt )
Mnd
(gmol-1)
PDIb Tg
(degC)
Td10
(degC)
NC-Hcm3
(10-3)
nD
(23degC)
8070605040
603518459398346
640641658706722
28002500225020001800
2220252520
7090
100110120
274295289246254
5484115148162
14379143581435714459
-
Polar organic solvents acetone THF EtOAc DMF DMSO
Reactive diluents HDDA NVP and the couple HDDAATRIFESolubility
14
262 STUDY OF CTFEVCAHFP TERPOLYMERIZATION
Objective to improve the solubility in reactivediluents and fluorine content in copolymers
Reaction conditions
CTFEVCA = 067 = const
HFP in monomer mixture ndash from 5 to 20 mol (21to 10 mol in copolymer composition ndash 19F NMR
Characterization of CTFEVCAHFP terpolymers
- solubility in reactive diluents
- Tg ~ 120degCTd ~ 250degC
- NC-Hcm3 (nD resp)
15
n(C C lF C F 2 )x (C H 2 C H )y (C H C H )z
O
(C H 2 )n
O H
OOCO
O(C H 2 )n
O H
4 0 0 0 g m o l-1M n lt o ligo m e riza tio n
n = 2 o r 4+C = CF
C l
F
F
C HH C
OC
O
O
+
Scheme 3 CTFE VCA hydroxy VE terpolymerization
263 SYNTHESIS OF CTFEVCAHYDROXY VINYL ETHER TERPOLYMERS
16
OCH2 =CH C
O(CH2)n
O
R]nCH)z(CHCH)y(CH2CF2)x(CClFH[
acrylation
O H
(CH2)n
O
R]nCH)z(CHCH)y(CH2CF2)x(CClFH[
OC
OO
OC
OO
Function polymerizableunder UV
Scheme 6 Acrylation of ndashOH functionalized CTFEVCA co-polymers
27ACRYLATION OF HYDROXY FUNCTIONALIZED CO-POLYMERS
CH2=CHCOCl
CH2=C(CH3)COCl
17
28 Characterization of UV-cured materialsDMA analysis
Tg of acrylated CTFEVCAHBVE compositions ~90degC
E ndash modulus 1 GPa at 20degC 50 MPa at 120degC
Taird10 ~ 200ndash220degC
DSC analysis
Tg of acrylated CTFEVCA-CH2OH compositions ~ 100ndash105degC
Taird10 ~ 230ndash240degC
1
2
2
3
18
29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber
291 Monomer synthesis
F3CCF2FC
O O
F F
CF3F3CCFFC
O O
F F
CF2
CF2F2C
CFFCO O
F F
F2C CF2
CF2CF2
CFFCO O
F F
A B DC
Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives
Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA
1919
292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)
F 2C CXY +
FC CFO
CO
F2CCF2
CF2
CF2TBPPi 75oC
C4F5H5
FC CF
OC
O
F2CCF2
CF2
F2C
CXY
F 2C
n
n
m
m
zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)
Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578
20
Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)
Run Monomer M2 Monomers in the feed(mol )
F-Ox M2
Copolym compsby microanal
(mol)F-Ox M2
Copolym compsby NMR(mol )
F-Ox M2
Conv(wt)
Tg(degC)
Td10(degC)
1 F2C=CFCl 20 80 35 65 374 626 63 105 322
2 F2C=CFCl 40 60 62 38 615 385 70 148 354
3 F2C=CFOC3F7
64 36 874 126 852 148 82 144 342
4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359
5 F2C=CH2 14 86 382 618 378 622 65 108 370
6 F2C=CH2 35 65 584 416 579 421 67 138 356
nR lt 135
21
210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP
CTFEVCAHVE) oligomers in good yield and high Tg were synthesized
2 Successful acrylation of hydroxy functionalized cooligomers
3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties
4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties
dArr
Suitable for waveguides applications
22
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
2323
31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to
hydrogenated analogues
Lower interfacial tension and CMC
Excellent chemical and thermal stability
Oleophobicity oil and fat repellants
Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc
Traditional commercial fluorosurfactants
Long fluorocarbon chain C6ltRFltC12
Perfluorooctane sulphonate (PFOS)
Perfluooctanoic acid ( PFOA)
their derivatives
2424
32 DRAWBACKS OF FLUORINATED SURFACTANTS
Bioaccumulable
Toxic and persistent
Wide-spread in the environment
3M company suggested perfluorinated chain le C4
bull Low bioconcentration factor
bull Low toxicity
bull Still high product performance
2525
General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4
Hydrophobic
G G GF- blockRF
Hydrophobic Hydrophilic
a ) for RF (CF3)2CF
b) for fluorinated monomer CH2=CH (TFP)
CF3
nCH2=CH + (CF3)2CFI RF - hydrophobic - I
CF3 CF3CF3
G
CF3
CF3CF-CH2-CH-CH2-CH Hydrophilic
CF3 CF3
Degradation
33 Synthesis of different end products as fluorinated surfactants
26
CF I + n nCFI
CF3
CF3
O
O
nCFCF3 I
O
O
Rad
nCFCF3
Zn
HSOH
O
nCFCF3
SOH
O
HOO
p
nCFCF3
SO
OO p
H2C CH2
nCFCF3
I
NNEt3
nCFCF3
NEt3nCF
CF3
N
I I
Surfactant C Surfactant B
Surfactant A
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants
Anionic surfactant
27
Surfactant Appearance Fluoroalkyl
10 decomp temperature a
(oC)
Tg and melting point b (oC)
(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC
(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145
(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175
Table 1 Properties of synthesized fluorinated surfactants
a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin
b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin
G Kostov et al USP 0027349 (2007)
28
Conditions Weight losses ()
Surfactant A Surfactant B Surfactant C
(1) Base-acid resistance
98 H2SO4 25 oC 7 days 00 lt12 00
60 HNO3 25 oC 7 days - gt400 lt20
37 HCl 25 oC 7 days 00 gt150 00
40 NaOH 25 oC 7 days 00 00 00
(2) Solubility in selected solvents Solubility (g100mL)
Water 25oC 72 hrs gt10 gt10 gt10
Methanol 25oC 72 hrs gt10 gt10 gt10
Diethyl ether 25oC 72 hrs lt1 lt1 lt1
Benzene 25oC 72 hrs lt2 lt2 lt2
Acetone 25oC 72 hrs lt10 lt10 lt10
Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-
Conclusions
The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6
29
Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA
30
Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis
34 Phosphorous containing TFP surfactants
31
3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate
Hydrolysis
Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)
32
Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to
those of PFOA (white)
33
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated Surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
34
Main characteristics of themembrane
To separate oxygen from hydrogen
To insure a good protonic conductivity
To be chemically physically andmechanically stable in acid media andat high temperatures
Rеasonable cost applications
No electronic conductivity
41 FUEL CELL MEMBRANES
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
1212
261) Fluorooligomers CTFEVCA-basedcopolymers
Length limit of polymer
Chain-transfer agent or suitable solvent
Photocrosslinkable reactive functions
Reactive diluents fluorinated function monomers precise adjustement of resinsrsquo refractive index
2) Photocrosslinking
UV
Reactive diluent(s) Amorphous crosslinked network
26 CTFEVCAhydroxy VE copolymers
13
Main characteristics of CTFEVCA copolymers
Table 1 Selected monomercopolymer compositions of CTFEVCA copolymers and their main characteristics
CTFE inmonommixture(mol )
CTFEa
incopolym
(mol )
Yield
(wt )
Mnd
(gmol-1)
PDIb Tg
(degC)
Td10
(degC)
NC-Hcm3
(10-3)
nD
(23degC)
8070605040
603518459398346
640641658706722
28002500225020001800
2220252520
7090
100110120
274295289246254
5484115148162
14379143581435714459
-
Polar organic solvents acetone THF EtOAc DMF DMSO
Reactive diluents HDDA NVP and the couple HDDAATRIFESolubility
14
262 STUDY OF CTFEVCAHFP TERPOLYMERIZATION
Objective to improve the solubility in reactivediluents and fluorine content in copolymers
Reaction conditions
CTFEVCA = 067 = const
HFP in monomer mixture ndash from 5 to 20 mol (21to 10 mol in copolymer composition ndash 19F NMR
Characterization of CTFEVCAHFP terpolymers
- solubility in reactive diluents
- Tg ~ 120degCTd ~ 250degC
- NC-Hcm3 (nD resp)
15
n(C C lF C F 2 )x (C H 2 C H )y (C H C H )z
O
(C H 2 )n
O H
OOCO
O(C H 2 )n
O H
4 0 0 0 g m o l-1M n lt o ligo m e riza tio n
n = 2 o r 4+C = CF
C l
F
F
C HH C
OC
O
O
+
Scheme 3 CTFE VCA hydroxy VE terpolymerization
263 SYNTHESIS OF CTFEVCAHYDROXY VINYL ETHER TERPOLYMERS
16
OCH2 =CH C
O(CH2)n
O
R]nCH)z(CHCH)y(CH2CF2)x(CClFH[
acrylation
O H
(CH2)n
O
R]nCH)z(CHCH)y(CH2CF2)x(CClFH[
OC
OO
OC
OO
Function polymerizableunder UV
Scheme 6 Acrylation of ndashOH functionalized CTFEVCA co-polymers
27ACRYLATION OF HYDROXY FUNCTIONALIZED CO-POLYMERS
CH2=CHCOCl
CH2=C(CH3)COCl
17
28 Characterization of UV-cured materialsDMA analysis
Tg of acrylated CTFEVCAHBVE compositions ~90degC
E ndash modulus 1 GPa at 20degC 50 MPa at 120degC
Taird10 ~ 200ndash220degC
DSC analysis
Tg of acrylated CTFEVCA-CH2OH compositions ~ 100ndash105degC
Taird10 ~ 230ndash240degC
1
2
2
3
18
29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber
291 Monomer synthesis
F3CCF2FC
O O
F F
CF3F3CCFFC
O O
F F
CF2
CF2F2C
CFFCO O
F F
F2C CF2
CF2CF2
CFFCO O
F F
A B DC
Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives
Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA
1919
292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)
F 2C CXY +
FC CFO
CO
F2CCF2
CF2
CF2TBPPi 75oC
C4F5H5
FC CF
OC
O
F2CCF2
CF2
F2C
CXY
F 2C
n
n
m
m
zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)
Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578
20
Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)
Run Monomer M2 Monomers in the feed(mol )
F-Ox M2
Copolym compsby microanal
(mol)F-Ox M2
Copolym compsby NMR(mol )
F-Ox M2
Conv(wt)
Tg(degC)
Td10(degC)
1 F2C=CFCl 20 80 35 65 374 626 63 105 322
2 F2C=CFCl 40 60 62 38 615 385 70 148 354
3 F2C=CFOC3F7
64 36 874 126 852 148 82 144 342
4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359
5 F2C=CH2 14 86 382 618 378 622 65 108 370
6 F2C=CH2 35 65 584 416 579 421 67 138 356
nR lt 135
21
210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP
CTFEVCAHVE) oligomers in good yield and high Tg were synthesized
2 Successful acrylation of hydroxy functionalized cooligomers
3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties
4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties
dArr
Suitable for waveguides applications
22
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
2323
31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to
hydrogenated analogues
Lower interfacial tension and CMC
Excellent chemical and thermal stability
Oleophobicity oil and fat repellants
Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc
Traditional commercial fluorosurfactants
Long fluorocarbon chain C6ltRFltC12
Perfluorooctane sulphonate (PFOS)
Perfluooctanoic acid ( PFOA)
their derivatives
2424
32 DRAWBACKS OF FLUORINATED SURFACTANTS
Bioaccumulable
Toxic and persistent
Wide-spread in the environment
3M company suggested perfluorinated chain le C4
bull Low bioconcentration factor
bull Low toxicity
bull Still high product performance
2525
General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4
Hydrophobic
G G GF- blockRF
Hydrophobic Hydrophilic
a ) for RF (CF3)2CF
b) for fluorinated monomer CH2=CH (TFP)
CF3
nCH2=CH + (CF3)2CFI RF - hydrophobic - I
CF3 CF3CF3
G
CF3
CF3CF-CH2-CH-CH2-CH Hydrophilic
CF3 CF3
Degradation
33 Synthesis of different end products as fluorinated surfactants
26
CF I + n nCFI
CF3
CF3
O
O
nCFCF3 I
O
O
Rad
nCFCF3
Zn
HSOH
O
nCFCF3
SOH
O
HOO
p
nCFCF3
SO
OO p
H2C CH2
nCFCF3
I
NNEt3
nCFCF3
NEt3nCF
CF3
N
I I
Surfactant C Surfactant B
Surfactant A
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants
Anionic surfactant
27
Surfactant Appearance Fluoroalkyl
10 decomp temperature a
(oC)
Tg and melting point b (oC)
(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC
(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145
(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175
Table 1 Properties of synthesized fluorinated surfactants
a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin
b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin
G Kostov et al USP 0027349 (2007)
28
Conditions Weight losses ()
Surfactant A Surfactant B Surfactant C
(1) Base-acid resistance
98 H2SO4 25 oC 7 days 00 lt12 00
60 HNO3 25 oC 7 days - gt400 lt20
37 HCl 25 oC 7 days 00 gt150 00
40 NaOH 25 oC 7 days 00 00 00
(2) Solubility in selected solvents Solubility (g100mL)
Water 25oC 72 hrs gt10 gt10 gt10
Methanol 25oC 72 hrs gt10 gt10 gt10
Diethyl ether 25oC 72 hrs lt1 lt1 lt1
Benzene 25oC 72 hrs lt2 lt2 lt2
Acetone 25oC 72 hrs lt10 lt10 lt10
Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-
Conclusions
The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6
29
Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA
30
Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis
34 Phosphorous containing TFP surfactants
31
3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate
Hydrolysis
Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)
32
Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to
those of PFOA (white)
33
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated Surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
34
Main characteristics of themembrane
To separate oxygen from hydrogen
To insure a good protonic conductivity
To be chemically physically andmechanically stable in acid media andat high temperatures
Rеasonable cost applications
No electronic conductivity
41 FUEL CELL MEMBRANES
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
13
Main characteristics of CTFEVCA copolymers
Table 1 Selected monomercopolymer compositions of CTFEVCA copolymers and their main characteristics
CTFE inmonommixture(mol )
CTFEa
incopolym
(mol )
Yield
(wt )
Mnd
(gmol-1)
PDIb Tg
(degC)
Td10
(degC)
NC-Hcm3
(10-3)
nD
(23degC)
8070605040
603518459398346
640641658706722
28002500225020001800
2220252520
7090
100110120
274295289246254
5484115148162
14379143581435714459
-
Polar organic solvents acetone THF EtOAc DMF DMSO
Reactive diluents HDDA NVP and the couple HDDAATRIFESolubility
14
262 STUDY OF CTFEVCAHFP TERPOLYMERIZATION
Objective to improve the solubility in reactivediluents and fluorine content in copolymers
Reaction conditions
CTFEVCA = 067 = const
HFP in monomer mixture ndash from 5 to 20 mol (21to 10 mol in copolymer composition ndash 19F NMR
Characterization of CTFEVCAHFP terpolymers
- solubility in reactive diluents
- Tg ~ 120degCTd ~ 250degC
- NC-Hcm3 (nD resp)
15
n(C C lF C F 2 )x (C H 2 C H )y (C H C H )z
O
(C H 2 )n
O H
OOCO
O(C H 2 )n
O H
4 0 0 0 g m o l-1M n lt o ligo m e riza tio n
n = 2 o r 4+C = CF
C l
F
F
C HH C
OC
O
O
+
Scheme 3 CTFE VCA hydroxy VE terpolymerization
263 SYNTHESIS OF CTFEVCAHYDROXY VINYL ETHER TERPOLYMERS
16
OCH2 =CH C
O(CH2)n
O
R]nCH)z(CHCH)y(CH2CF2)x(CClFH[
acrylation
O H
(CH2)n
O
R]nCH)z(CHCH)y(CH2CF2)x(CClFH[
OC
OO
OC
OO
Function polymerizableunder UV
Scheme 6 Acrylation of ndashOH functionalized CTFEVCA co-polymers
27ACRYLATION OF HYDROXY FUNCTIONALIZED CO-POLYMERS
CH2=CHCOCl
CH2=C(CH3)COCl
17
28 Characterization of UV-cured materialsDMA analysis
Tg of acrylated CTFEVCAHBVE compositions ~90degC
E ndash modulus 1 GPa at 20degC 50 MPa at 120degC
Taird10 ~ 200ndash220degC
DSC analysis
Tg of acrylated CTFEVCA-CH2OH compositions ~ 100ndash105degC
Taird10 ~ 230ndash240degC
1
2
2
3
18
29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber
291 Monomer synthesis
F3CCF2FC
O O
F F
CF3F3CCFFC
O O
F F
CF2
CF2F2C
CFFCO O
F F
F2C CF2
CF2CF2
CFFCO O
F F
A B DC
Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives
Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA
1919
292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)
F 2C CXY +
FC CFO
CO
F2CCF2
CF2
CF2TBPPi 75oC
C4F5H5
FC CF
OC
O
F2CCF2
CF2
F2C
CXY
F 2C
n
n
m
m
zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)
Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578
20
Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)
Run Monomer M2 Monomers in the feed(mol )
F-Ox M2
Copolym compsby microanal
(mol)F-Ox M2
Copolym compsby NMR(mol )
F-Ox M2
Conv(wt)
Tg(degC)
Td10(degC)
1 F2C=CFCl 20 80 35 65 374 626 63 105 322
2 F2C=CFCl 40 60 62 38 615 385 70 148 354
3 F2C=CFOC3F7
64 36 874 126 852 148 82 144 342
4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359
5 F2C=CH2 14 86 382 618 378 622 65 108 370
6 F2C=CH2 35 65 584 416 579 421 67 138 356
nR lt 135
21
210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP
CTFEVCAHVE) oligomers in good yield and high Tg were synthesized
2 Successful acrylation of hydroxy functionalized cooligomers
3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties
4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties
dArr
Suitable for waveguides applications
22
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
2323
31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to
hydrogenated analogues
Lower interfacial tension and CMC
Excellent chemical and thermal stability
Oleophobicity oil and fat repellants
Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc
Traditional commercial fluorosurfactants
Long fluorocarbon chain C6ltRFltC12
Perfluorooctane sulphonate (PFOS)
Perfluooctanoic acid ( PFOA)
their derivatives
2424
32 DRAWBACKS OF FLUORINATED SURFACTANTS
Bioaccumulable
Toxic and persistent
Wide-spread in the environment
3M company suggested perfluorinated chain le C4
bull Low bioconcentration factor
bull Low toxicity
bull Still high product performance
2525
General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4
Hydrophobic
G G GF- blockRF
Hydrophobic Hydrophilic
a ) for RF (CF3)2CF
b) for fluorinated monomer CH2=CH (TFP)
CF3
nCH2=CH + (CF3)2CFI RF - hydrophobic - I
CF3 CF3CF3
G
CF3
CF3CF-CH2-CH-CH2-CH Hydrophilic
CF3 CF3
Degradation
33 Synthesis of different end products as fluorinated surfactants
26
CF I + n nCFI
CF3
CF3
O
O
nCFCF3 I
O
O
Rad
nCFCF3
Zn
HSOH
O
nCFCF3
SOH
O
HOO
p
nCFCF3
SO
OO p
H2C CH2
nCFCF3
I
NNEt3
nCFCF3
NEt3nCF
CF3
N
I I
Surfactant C Surfactant B
Surfactant A
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants
Anionic surfactant
27
Surfactant Appearance Fluoroalkyl
10 decomp temperature a
(oC)
Tg and melting point b (oC)
(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC
(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145
(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175
Table 1 Properties of synthesized fluorinated surfactants
a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin
b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin
G Kostov et al USP 0027349 (2007)
28
Conditions Weight losses ()
Surfactant A Surfactant B Surfactant C
(1) Base-acid resistance
98 H2SO4 25 oC 7 days 00 lt12 00
60 HNO3 25 oC 7 days - gt400 lt20
37 HCl 25 oC 7 days 00 gt150 00
40 NaOH 25 oC 7 days 00 00 00
(2) Solubility in selected solvents Solubility (g100mL)
Water 25oC 72 hrs gt10 gt10 gt10
Methanol 25oC 72 hrs gt10 gt10 gt10
Diethyl ether 25oC 72 hrs lt1 lt1 lt1
Benzene 25oC 72 hrs lt2 lt2 lt2
Acetone 25oC 72 hrs lt10 lt10 lt10
Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-
Conclusions
The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6
29
Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA
30
Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis
34 Phosphorous containing TFP surfactants
31
3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate
Hydrolysis
Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)
32
Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to
those of PFOA (white)
33
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated Surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
34
Main characteristics of themembrane
To separate oxygen from hydrogen
To insure a good protonic conductivity
To be chemically physically andmechanically stable in acid media andat high temperatures
Rеasonable cost applications
No electronic conductivity
41 FUEL CELL MEMBRANES
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
14
262 STUDY OF CTFEVCAHFP TERPOLYMERIZATION
Objective to improve the solubility in reactivediluents and fluorine content in copolymers
Reaction conditions
CTFEVCA = 067 = const
HFP in monomer mixture ndash from 5 to 20 mol (21to 10 mol in copolymer composition ndash 19F NMR
Characterization of CTFEVCAHFP terpolymers
- solubility in reactive diluents
- Tg ~ 120degCTd ~ 250degC
- NC-Hcm3 (nD resp)
15
n(C C lF C F 2 )x (C H 2 C H )y (C H C H )z
O
(C H 2 )n
O H
OOCO
O(C H 2 )n
O H
4 0 0 0 g m o l-1M n lt o ligo m e riza tio n
n = 2 o r 4+C = CF
C l
F
F
C HH C
OC
O
O
+
Scheme 3 CTFE VCA hydroxy VE terpolymerization
263 SYNTHESIS OF CTFEVCAHYDROXY VINYL ETHER TERPOLYMERS
16
OCH2 =CH C
O(CH2)n
O
R]nCH)z(CHCH)y(CH2CF2)x(CClFH[
acrylation
O H
(CH2)n
O
R]nCH)z(CHCH)y(CH2CF2)x(CClFH[
OC
OO
OC
OO
Function polymerizableunder UV
Scheme 6 Acrylation of ndashOH functionalized CTFEVCA co-polymers
27ACRYLATION OF HYDROXY FUNCTIONALIZED CO-POLYMERS
CH2=CHCOCl
CH2=C(CH3)COCl
17
28 Characterization of UV-cured materialsDMA analysis
Tg of acrylated CTFEVCAHBVE compositions ~90degC
E ndash modulus 1 GPa at 20degC 50 MPa at 120degC
Taird10 ~ 200ndash220degC
DSC analysis
Tg of acrylated CTFEVCA-CH2OH compositions ~ 100ndash105degC
Taird10 ~ 230ndash240degC
1
2
2
3
18
29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber
291 Monomer synthesis
F3CCF2FC
O O
F F
CF3F3CCFFC
O O
F F
CF2
CF2F2C
CFFCO O
F F
F2C CF2
CF2CF2
CFFCO O
F F
A B DC
Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives
Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA
1919
292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)
F 2C CXY +
FC CFO
CO
F2CCF2
CF2
CF2TBPPi 75oC
C4F5H5
FC CF
OC
O
F2CCF2
CF2
F2C
CXY
F 2C
n
n
m
m
zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)
Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578
20
Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)
Run Monomer M2 Monomers in the feed(mol )
F-Ox M2
Copolym compsby microanal
(mol)F-Ox M2
Copolym compsby NMR(mol )
F-Ox M2
Conv(wt)
Tg(degC)
Td10(degC)
1 F2C=CFCl 20 80 35 65 374 626 63 105 322
2 F2C=CFCl 40 60 62 38 615 385 70 148 354
3 F2C=CFOC3F7
64 36 874 126 852 148 82 144 342
4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359
5 F2C=CH2 14 86 382 618 378 622 65 108 370
6 F2C=CH2 35 65 584 416 579 421 67 138 356
nR lt 135
21
210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP
CTFEVCAHVE) oligomers in good yield and high Tg were synthesized
2 Successful acrylation of hydroxy functionalized cooligomers
3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties
4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties
dArr
Suitable for waveguides applications
22
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
2323
31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to
hydrogenated analogues
Lower interfacial tension and CMC
Excellent chemical and thermal stability
Oleophobicity oil and fat repellants
Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc
Traditional commercial fluorosurfactants
Long fluorocarbon chain C6ltRFltC12
Perfluorooctane sulphonate (PFOS)
Perfluooctanoic acid ( PFOA)
their derivatives
2424
32 DRAWBACKS OF FLUORINATED SURFACTANTS
Bioaccumulable
Toxic and persistent
Wide-spread in the environment
3M company suggested perfluorinated chain le C4
bull Low bioconcentration factor
bull Low toxicity
bull Still high product performance
2525
General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4
Hydrophobic
G G GF- blockRF
Hydrophobic Hydrophilic
a ) for RF (CF3)2CF
b) for fluorinated monomer CH2=CH (TFP)
CF3
nCH2=CH + (CF3)2CFI RF - hydrophobic - I
CF3 CF3CF3
G
CF3
CF3CF-CH2-CH-CH2-CH Hydrophilic
CF3 CF3
Degradation
33 Synthesis of different end products as fluorinated surfactants
26
CF I + n nCFI
CF3
CF3
O
O
nCFCF3 I
O
O
Rad
nCFCF3
Zn
HSOH
O
nCFCF3
SOH
O
HOO
p
nCFCF3
SO
OO p
H2C CH2
nCFCF3
I
NNEt3
nCFCF3
NEt3nCF
CF3
N
I I
Surfactant C Surfactant B
Surfactant A
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants
Anionic surfactant
27
Surfactant Appearance Fluoroalkyl
10 decomp temperature a
(oC)
Tg and melting point b (oC)
(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC
(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145
(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175
Table 1 Properties of synthesized fluorinated surfactants
a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin
b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin
G Kostov et al USP 0027349 (2007)
28
Conditions Weight losses ()
Surfactant A Surfactant B Surfactant C
(1) Base-acid resistance
98 H2SO4 25 oC 7 days 00 lt12 00
60 HNO3 25 oC 7 days - gt400 lt20
37 HCl 25 oC 7 days 00 gt150 00
40 NaOH 25 oC 7 days 00 00 00
(2) Solubility in selected solvents Solubility (g100mL)
Water 25oC 72 hrs gt10 gt10 gt10
Methanol 25oC 72 hrs gt10 gt10 gt10
Diethyl ether 25oC 72 hrs lt1 lt1 lt1
Benzene 25oC 72 hrs lt2 lt2 lt2
Acetone 25oC 72 hrs lt10 lt10 lt10
Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-
Conclusions
The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6
29
Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA
30
Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis
34 Phosphorous containing TFP surfactants
31
3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate
Hydrolysis
Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)
32
Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to
those of PFOA (white)
33
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated Surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
34
Main characteristics of themembrane
To separate oxygen from hydrogen
To insure a good protonic conductivity
To be chemically physically andmechanically stable in acid media andat high temperatures
Rеasonable cost applications
No electronic conductivity
41 FUEL CELL MEMBRANES
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
15
n(C C lF C F 2 )x (C H 2 C H )y (C H C H )z
O
(C H 2 )n
O H
OOCO
O(C H 2 )n
O H
4 0 0 0 g m o l-1M n lt o ligo m e riza tio n
n = 2 o r 4+C = CF
C l
F
F
C HH C
OC
O
O
+
Scheme 3 CTFE VCA hydroxy VE terpolymerization
263 SYNTHESIS OF CTFEVCAHYDROXY VINYL ETHER TERPOLYMERS
16
OCH2 =CH C
O(CH2)n
O
R]nCH)z(CHCH)y(CH2CF2)x(CClFH[
acrylation
O H
(CH2)n
O
R]nCH)z(CHCH)y(CH2CF2)x(CClFH[
OC
OO
OC
OO
Function polymerizableunder UV
Scheme 6 Acrylation of ndashOH functionalized CTFEVCA co-polymers
27ACRYLATION OF HYDROXY FUNCTIONALIZED CO-POLYMERS
CH2=CHCOCl
CH2=C(CH3)COCl
17
28 Characterization of UV-cured materialsDMA analysis
Tg of acrylated CTFEVCAHBVE compositions ~90degC
E ndash modulus 1 GPa at 20degC 50 MPa at 120degC
Taird10 ~ 200ndash220degC
DSC analysis
Tg of acrylated CTFEVCA-CH2OH compositions ~ 100ndash105degC
Taird10 ~ 230ndash240degC
1
2
2
3
18
29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber
291 Monomer synthesis
F3CCF2FC
O O
F F
CF3F3CCFFC
O O
F F
CF2
CF2F2C
CFFCO O
F F
F2C CF2
CF2CF2
CFFCO O
F F
A B DC
Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives
Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA
1919
292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)
F 2C CXY +
FC CFO
CO
F2CCF2
CF2
CF2TBPPi 75oC
C4F5H5
FC CF
OC
O
F2CCF2
CF2
F2C
CXY
F 2C
n
n
m
m
zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)
Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578
20
Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)
Run Monomer M2 Monomers in the feed(mol )
F-Ox M2
Copolym compsby microanal
(mol)F-Ox M2
Copolym compsby NMR(mol )
F-Ox M2
Conv(wt)
Tg(degC)
Td10(degC)
1 F2C=CFCl 20 80 35 65 374 626 63 105 322
2 F2C=CFCl 40 60 62 38 615 385 70 148 354
3 F2C=CFOC3F7
64 36 874 126 852 148 82 144 342
4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359
5 F2C=CH2 14 86 382 618 378 622 65 108 370
6 F2C=CH2 35 65 584 416 579 421 67 138 356
nR lt 135
21
210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP
CTFEVCAHVE) oligomers in good yield and high Tg were synthesized
2 Successful acrylation of hydroxy functionalized cooligomers
3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties
4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties
dArr
Suitable for waveguides applications
22
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
2323
31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to
hydrogenated analogues
Lower interfacial tension and CMC
Excellent chemical and thermal stability
Oleophobicity oil and fat repellants
Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc
Traditional commercial fluorosurfactants
Long fluorocarbon chain C6ltRFltC12
Perfluorooctane sulphonate (PFOS)
Perfluooctanoic acid ( PFOA)
their derivatives
2424
32 DRAWBACKS OF FLUORINATED SURFACTANTS
Bioaccumulable
Toxic and persistent
Wide-spread in the environment
3M company suggested perfluorinated chain le C4
bull Low bioconcentration factor
bull Low toxicity
bull Still high product performance
2525
General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4
Hydrophobic
G G GF- blockRF
Hydrophobic Hydrophilic
a ) for RF (CF3)2CF
b) for fluorinated monomer CH2=CH (TFP)
CF3
nCH2=CH + (CF3)2CFI RF - hydrophobic - I
CF3 CF3CF3
G
CF3
CF3CF-CH2-CH-CH2-CH Hydrophilic
CF3 CF3
Degradation
33 Synthesis of different end products as fluorinated surfactants
26
CF I + n nCFI
CF3
CF3
O
O
nCFCF3 I
O
O
Rad
nCFCF3
Zn
HSOH
O
nCFCF3
SOH
O
HOO
p
nCFCF3
SO
OO p
H2C CH2
nCFCF3
I
NNEt3
nCFCF3
NEt3nCF
CF3
N
I I
Surfactant C Surfactant B
Surfactant A
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants
Anionic surfactant
27
Surfactant Appearance Fluoroalkyl
10 decomp temperature a
(oC)
Tg and melting point b (oC)
(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC
(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145
(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175
Table 1 Properties of synthesized fluorinated surfactants
a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin
b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin
G Kostov et al USP 0027349 (2007)
28
Conditions Weight losses ()
Surfactant A Surfactant B Surfactant C
(1) Base-acid resistance
98 H2SO4 25 oC 7 days 00 lt12 00
60 HNO3 25 oC 7 days - gt400 lt20
37 HCl 25 oC 7 days 00 gt150 00
40 NaOH 25 oC 7 days 00 00 00
(2) Solubility in selected solvents Solubility (g100mL)
Water 25oC 72 hrs gt10 gt10 gt10
Methanol 25oC 72 hrs gt10 gt10 gt10
Diethyl ether 25oC 72 hrs lt1 lt1 lt1
Benzene 25oC 72 hrs lt2 lt2 lt2
Acetone 25oC 72 hrs lt10 lt10 lt10
Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-
Conclusions
The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6
29
Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA
30
Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis
34 Phosphorous containing TFP surfactants
31
3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate
Hydrolysis
Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)
32
Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to
those of PFOA (white)
33
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated Surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
34
Main characteristics of themembrane
To separate oxygen from hydrogen
To insure a good protonic conductivity
To be chemically physically andmechanically stable in acid media andat high temperatures
Rеasonable cost applications
No electronic conductivity
41 FUEL CELL MEMBRANES
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
16
OCH2 =CH C
O(CH2)n
O
R]nCH)z(CHCH)y(CH2CF2)x(CClFH[
acrylation
O H
(CH2)n
O
R]nCH)z(CHCH)y(CH2CF2)x(CClFH[
OC
OO
OC
OO
Function polymerizableunder UV
Scheme 6 Acrylation of ndashOH functionalized CTFEVCA co-polymers
27ACRYLATION OF HYDROXY FUNCTIONALIZED CO-POLYMERS
CH2=CHCOCl
CH2=C(CH3)COCl
17
28 Characterization of UV-cured materialsDMA analysis
Tg of acrylated CTFEVCAHBVE compositions ~90degC
E ndash modulus 1 GPa at 20degC 50 MPa at 120degC
Taird10 ~ 200ndash220degC
DSC analysis
Tg of acrylated CTFEVCA-CH2OH compositions ~ 100ndash105degC
Taird10 ~ 230ndash240degC
1
2
2
3
18
29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber
291 Monomer synthesis
F3CCF2FC
O O
F F
CF3F3CCFFC
O O
F F
CF2
CF2F2C
CFFCO O
F F
F2C CF2
CF2CF2
CFFCO O
F F
A B DC
Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives
Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA
1919
292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)
F 2C CXY +
FC CFO
CO
F2CCF2
CF2
CF2TBPPi 75oC
C4F5H5
FC CF
OC
O
F2CCF2
CF2
F2C
CXY
F 2C
n
n
m
m
zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)
Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578
20
Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)
Run Monomer M2 Monomers in the feed(mol )
F-Ox M2
Copolym compsby microanal
(mol)F-Ox M2
Copolym compsby NMR(mol )
F-Ox M2
Conv(wt)
Tg(degC)
Td10(degC)
1 F2C=CFCl 20 80 35 65 374 626 63 105 322
2 F2C=CFCl 40 60 62 38 615 385 70 148 354
3 F2C=CFOC3F7
64 36 874 126 852 148 82 144 342
4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359
5 F2C=CH2 14 86 382 618 378 622 65 108 370
6 F2C=CH2 35 65 584 416 579 421 67 138 356
nR lt 135
21
210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP
CTFEVCAHVE) oligomers in good yield and high Tg were synthesized
2 Successful acrylation of hydroxy functionalized cooligomers
3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties
4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties
dArr
Suitable for waveguides applications
22
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
2323
31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to
hydrogenated analogues
Lower interfacial tension and CMC
Excellent chemical and thermal stability
Oleophobicity oil and fat repellants
Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc
Traditional commercial fluorosurfactants
Long fluorocarbon chain C6ltRFltC12
Perfluorooctane sulphonate (PFOS)
Perfluooctanoic acid ( PFOA)
their derivatives
2424
32 DRAWBACKS OF FLUORINATED SURFACTANTS
Bioaccumulable
Toxic and persistent
Wide-spread in the environment
3M company suggested perfluorinated chain le C4
bull Low bioconcentration factor
bull Low toxicity
bull Still high product performance
2525
General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4
Hydrophobic
G G GF- blockRF
Hydrophobic Hydrophilic
a ) for RF (CF3)2CF
b) for fluorinated monomer CH2=CH (TFP)
CF3
nCH2=CH + (CF3)2CFI RF - hydrophobic - I
CF3 CF3CF3
G
CF3
CF3CF-CH2-CH-CH2-CH Hydrophilic
CF3 CF3
Degradation
33 Synthesis of different end products as fluorinated surfactants
26
CF I + n nCFI
CF3
CF3
O
O
nCFCF3 I
O
O
Rad
nCFCF3
Zn
HSOH
O
nCFCF3
SOH
O
HOO
p
nCFCF3
SO
OO p
H2C CH2
nCFCF3
I
NNEt3
nCFCF3
NEt3nCF
CF3
N
I I
Surfactant C Surfactant B
Surfactant A
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants
Anionic surfactant
27
Surfactant Appearance Fluoroalkyl
10 decomp temperature a
(oC)
Tg and melting point b (oC)
(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC
(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145
(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175
Table 1 Properties of synthesized fluorinated surfactants
a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin
b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin
G Kostov et al USP 0027349 (2007)
28
Conditions Weight losses ()
Surfactant A Surfactant B Surfactant C
(1) Base-acid resistance
98 H2SO4 25 oC 7 days 00 lt12 00
60 HNO3 25 oC 7 days - gt400 lt20
37 HCl 25 oC 7 days 00 gt150 00
40 NaOH 25 oC 7 days 00 00 00
(2) Solubility in selected solvents Solubility (g100mL)
Water 25oC 72 hrs gt10 gt10 gt10
Methanol 25oC 72 hrs gt10 gt10 gt10
Diethyl ether 25oC 72 hrs lt1 lt1 lt1
Benzene 25oC 72 hrs lt2 lt2 lt2
Acetone 25oC 72 hrs lt10 lt10 lt10
Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-
Conclusions
The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6
29
Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA
30
Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis
34 Phosphorous containing TFP surfactants
31
3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate
Hydrolysis
Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)
32
Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to
those of PFOA (white)
33
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated Surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
34
Main characteristics of themembrane
To separate oxygen from hydrogen
To insure a good protonic conductivity
To be chemically physically andmechanically stable in acid media andat high temperatures
Rеasonable cost applications
No electronic conductivity
41 FUEL CELL MEMBRANES
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
17
28 Characterization of UV-cured materialsDMA analysis
Tg of acrylated CTFEVCAHBVE compositions ~90degC
E ndash modulus 1 GPa at 20degC 50 MPa at 120degC
Taird10 ~ 200ndash220degC
DSC analysis
Tg of acrylated CTFEVCA-CH2OH compositions ~ 100ndash105degC
Taird10 ~ 230ndash240degC
1
2
2
3
18
29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber
291 Monomer synthesis
F3CCF2FC
O O
F F
CF3F3CCFFC
O O
F F
CF2
CF2F2C
CFFCO O
F F
F2C CF2
CF2CF2
CFFCO O
F F
A B DC
Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives
Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA
1919
292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)
F 2C CXY +
FC CFO
CO
F2CCF2
CF2
CF2TBPPi 75oC
C4F5H5
FC CF
OC
O
F2CCF2
CF2
F2C
CXY
F 2C
n
n
m
m
zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)
Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578
20
Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)
Run Monomer M2 Monomers in the feed(mol )
F-Ox M2
Copolym compsby microanal
(mol)F-Ox M2
Copolym compsby NMR(mol )
F-Ox M2
Conv(wt)
Tg(degC)
Td10(degC)
1 F2C=CFCl 20 80 35 65 374 626 63 105 322
2 F2C=CFCl 40 60 62 38 615 385 70 148 354
3 F2C=CFOC3F7
64 36 874 126 852 148 82 144 342
4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359
5 F2C=CH2 14 86 382 618 378 622 65 108 370
6 F2C=CH2 35 65 584 416 579 421 67 138 356
nR lt 135
21
210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP
CTFEVCAHVE) oligomers in good yield and high Tg were synthesized
2 Successful acrylation of hydroxy functionalized cooligomers
3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties
4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties
dArr
Suitable for waveguides applications
22
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
2323
31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to
hydrogenated analogues
Lower interfacial tension and CMC
Excellent chemical and thermal stability
Oleophobicity oil and fat repellants
Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc
Traditional commercial fluorosurfactants
Long fluorocarbon chain C6ltRFltC12
Perfluorooctane sulphonate (PFOS)
Perfluooctanoic acid ( PFOA)
their derivatives
2424
32 DRAWBACKS OF FLUORINATED SURFACTANTS
Bioaccumulable
Toxic and persistent
Wide-spread in the environment
3M company suggested perfluorinated chain le C4
bull Low bioconcentration factor
bull Low toxicity
bull Still high product performance
2525
General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4
Hydrophobic
G G GF- blockRF
Hydrophobic Hydrophilic
a ) for RF (CF3)2CF
b) for fluorinated monomer CH2=CH (TFP)
CF3
nCH2=CH + (CF3)2CFI RF - hydrophobic - I
CF3 CF3CF3
G
CF3
CF3CF-CH2-CH-CH2-CH Hydrophilic
CF3 CF3
Degradation
33 Synthesis of different end products as fluorinated surfactants
26
CF I + n nCFI
CF3
CF3
O
O
nCFCF3 I
O
O
Rad
nCFCF3
Zn
HSOH
O
nCFCF3
SOH
O
HOO
p
nCFCF3
SO
OO p
H2C CH2
nCFCF3
I
NNEt3
nCFCF3
NEt3nCF
CF3
N
I I
Surfactant C Surfactant B
Surfactant A
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants
Anionic surfactant
27
Surfactant Appearance Fluoroalkyl
10 decomp temperature a
(oC)
Tg and melting point b (oC)
(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC
(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145
(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175
Table 1 Properties of synthesized fluorinated surfactants
a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin
b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin
G Kostov et al USP 0027349 (2007)
28
Conditions Weight losses ()
Surfactant A Surfactant B Surfactant C
(1) Base-acid resistance
98 H2SO4 25 oC 7 days 00 lt12 00
60 HNO3 25 oC 7 days - gt400 lt20
37 HCl 25 oC 7 days 00 gt150 00
40 NaOH 25 oC 7 days 00 00 00
(2) Solubility in selected solvents Solubility (g100mL)
Water 25oC 72 hrs gt10 gt10 gt10
Methanol 25oC 72 hrs gt10 gt10 gt10
Diethyl ether 25oC 72 hrs lt1 lt1 lt1
Benzene 25oC 72 hrs lt2 lt2 lt2
Acetone 25oC 72 hrs lt10 lt10 lt10
Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-
Conclusions
The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6
29
Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA
30
Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis
34 Phosphorous containing TFP surfactants
31
3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate
Hydrolysis
Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)
32
Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to
those of PFOA (white)
33
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated Surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
34
Main characteristics of themembrane
To separate oxygen from hydrogen
To insure a good protonic conductivity
To be chemically physically andmechanically stable in acid media andat high temperatures
Rеasonable cost applications
No electronic conductivity
41 FUEL CELL MEMBRANES
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
18
29 CTFEPerfluorovinyl dioxolane co-polymers for optical fiber
291 Monomer synthesis
F3CCF2FC
O O
F F
CF3F3CCFFC
O O
F F
CF2
CF2F2C
CFFCO O
F F
F2C CF2
CF2CF2
CFFCO O
F F
A B DC
Figure 7 Chemical structures of substituted perfluoro-2-methylenendash13-dioxolane derivatives
Collaboration with Prof Y Okamoto and Dr F Mikes Brooklyn Polytechnic USA
1919
292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)
F 2C CXY +
FC CFO
CO
F2CCF2
CF2
CF2TBPPi 75oC
C4F5H5
FC CF
OC
O
F2CCF2
CF2
F2C
CXY
F 2C
n
n
m
m
zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)
Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578
20
Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)
Run Monomer M2 Monomers in the feed(mol )
F-Ox M2
Copolym compsby microanal
(mol)F-Ox M2
Copolym compsby NMR(mol )
F-Ox M2
Conv(wt)
Tg(degC)
Td10(degC)
1 F2C=CFCl 20 80 35 65 374 626 63 105 322
2 F2C=CFCl 40 60 62 38 615 385 70 148 354
3 F2C=CFOC3F7
64 36 874 126 852 148 82 144 342
4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359
5 F2C=CH2 14 86 382 618 378 622 65 108 370
6 F2C=CH2 35 65 584 416 579 421 67 138 356
nR lt 135
21
210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP
CTFEVCAHVE) oligomers in good yield and high Tg were synthesized
2 Successful acrylation of hydroxy functionalized cooligomers
3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties
4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties
dArr
Suitable for waveguides applications
22
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
2323
31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to
hydrogenated analogues
Lower interfacial tension and CMC
Excellent chemical and thermal stability
Oleophobicity oil and fat repellants
Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc
Traditional commercial fluorosurfactants
Long fluorocarbon chain C6ltRFltC12
Perfluorooctane sulphonate (PFOS)
Perfluooctanoic acid ( PFOA)
their derivatives
2424
32 DRAWBACKS OF FLUORINATED SURFACTANTS
Bioaccumulable
Toxic and persistent
Wide-spread in the environment
3M company suggested perfluorinated chain le C4
bull Low bioconcentration factor
bull Low toxicity
bull Still high product performance
2525
General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4
Hydrophobic
G G GF- blockRF
Hydrophobic Hydrophilic
a ) for RF (CF3)2CF
b) for fluorinated monomer CH2=CH (TFP)
CF3
nCH2=CH + (CF3)2CFI RF - hydrophobic - I
CF3 CF3CF3
G
CF3
CF3CF-CH2-CH-CH2-CH Hydrophilic
CF3 CF3
Degradation
33 Synthesis of different end products as fluorinated surfactants
26
CF I + n nCFI
CF3
CF3
O
O
nCFCF3 I
O
O
Rad
nCFCF3
Zn
HSOH
O
nCFCF3
SOH
O
HOO
p
nCFCF3
SO
OO p
H2C CH2
nCFCF3
I
NNEt3
nCFCF3
NEt3nCF
CF3
N
I I
Surfactant C Surfactant B
Surfactant A
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants
Anionic surfactant
27
Surfactant Appearance Fluoroalkyl
10 decomp temperature a
(oC)
Tg and melting point b (oC)
(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC
(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145
(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175
Table 1 Properties of synthesized fluorinated surfactants
a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin
b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin
G Kostov et al USP 0027349 (2007)
28
Conditions Weight losses ()
Surfactant A Surfactant B Surfactant C
(1) Base-acid resistance
98 H2SO4 25 oC 7 days 00 lt12 00
60 HNO3 25 oC 7 days - gt400 lt20
37 HCl 25 oC 7 days 00 gt150 00
40 NaOH 25 oC 7 days 00 00 00
(2) Solubility in selected solvents Solubility (g100mL)
Water 25oC 72 hrs gt10 gt10 gt10
Methanol 25oC 72 hrs gt10 gt10 gt10
Diethyl ether 25oC 72 hrs lt1 lt1 lt1
Benzene 25oC 72 hrs lt2 lt2 lt2
Acetone 25oC 72 hrs lt10 lt10 lt10
Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-
Conclusions
The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6
29
Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA
30
Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis
34 Phosphorous containing TFP surfactants
31
3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate
Hydrolysis
Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)
32
Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to
those of PFOA (white)
33
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated Surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
34
Main characteristics of themembrane
To separate oxygen from hydrogen
To insure a good protonic conductivity
To be chemically physically andmechanically stable in acid media andat high temperatures
Rеasonable cost applications
No electronic conductivity
41 FUEL CELL MEMBRANES
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
1919
292 Co-polymerization of perfluorovinyl dioxolane (F-Ox) with different fluorinated comonomers M2 ( CTFE PPVE PMVE and VDF)
F 2C CXY +
FC CFO
CO
F2CCF2
CF2
CF2TBPPi 75oC
C4F5H5
FC CF
OC
O
F2CCF2
CF2
F2C
CXY
F 2C
n
n
m
m
zX=Y=H (VDF)X=F Y=Cl (CTFE)X=F Y=OCF3 (PMVE)
Mikes F Teng H Kostov G Ameduri B Koike Y Okamoto Y Journal of Polym Sci Part A Polymer Chemistry 2009 47 (23) 6571-6578
20
Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)
Run Monomer M2 Monomers in the feed(mol )
F-Ox M2
Copolym compsby microanal
(mol)F-Ox M2
Copolym compsby NMR(mol )
F-Ox M2
Conv(wt)
Tg(degC)
Td10(degC)
1 F2C=CFCl 20 80 35 65 374 626 63 105 322
2 F2C=CFCl 40 60 62 38 615 385 70 148 354
3 F2C=CFOC3F7
64 36 874 126 852 148 82 144 342
4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359
5 F2C=CH2 14 86 382 618 378 622 65 108 370
6 F2C=CH2 35 65 584 416 579 421 67 138 356
nR lt 135
21
210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP
CTFEVCAHVE) oligomers in good yield and high Tg were synthesized
2 Successful acrylation of hydroxy functionalized cooligomers
3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties
4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties
dArr
Suitable for waveguides applications
22
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
2323
31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to
hydrogenated analogues
Lower interfacial tension and CMC
Excellent chemical and thermal stability
Oleophobicity oil and fat repellants
Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc
Traditional commercial fluorosurfactants
Long fluorocarbon chain C6ltRFltC12
Perfluorooctane sulphonate (PFOS)
Perfluooctanoic acid ( PFOA)
their derivatives
2424
32 DRAWBACKS OF FLUORINATED SURFACTANTS
Bioaccumulable
Toxic and persistent
Wide-spread in the environment
3M company suggested perfluorinated chain le C4
bull Low bioconcentration factor
bull Low toxicity
bull Still high product performance
2525
General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4
Hydrophobic
G G GF- blockRF
Hydrophobic Hydrophilic
a ) for RF (CF3)2CF
b) for fluorinated monomer CH2=CH (TFP)
CF3
nCH2=CH + (CF3)2CFI RF - hydrophobic - I
CF3 CF3CF3
G
CF3
CF3CF-CH2-CH-CH2-CH Hydrophilic
CF3 CF3
Degradation
33 Synthesis of different end products as fluorinated surfactants
26
CF I + n nCFI
CF3
CF3
O
O
nCFCF3 I
O
O
Rad
nCFCF3
Zn
HSOH
O
nCFCF3
SOH
O
HOO
p
nCFCF3
SO
OO p
H2C CH2
nCFCF3
I
NNEt3
nCFCF3
NEt3nCF
CF3
N
I I
Surfactant C Surfactant B
Surfactant A
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants
Anionic surfactant
27
Surfactant Appearance Fluoroalkyl
10 decomp temperature a
(oC)
Tg and melting point b (oC)
(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC
(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145
(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175
Table 1 Properties of synthesized fluorinated surfactants
a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin
b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin
G Kostov et al USP 0027349 (2007)
28
Conditions Weight losses ()
Surfactant A Surfactant B Surfactant C
(1) Base-acid resistance
98 H2SO4 25 oC 7 days 00 lt12 00
60 HNO3 25 oC 7 days - gt400 lt20
37 HCl 25 oC 7 days 00 gt150 00
40 NaOH 25 oC 7 days 00 00 00
(2) Solubility in selected solvents Solubility (g100mL)
Water 25oC 72 hrs gt10 gt10 gt10
Methanol 25oC 72 hrs gt10 gt10 gt10
Diethyl ether 25oC 72 hrs lt1 lt1 lt1
Benzene 25oC 72 hrs lt2 lt2 lt2
Acetone 25oC 72 hrs lt10 lt10 lt10
Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-
Conclusions
The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6
29
Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA
30
Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis
34 Phosphorous containing TFP surfactants
31
3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate
Hydrolysis
Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)
32
Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to
those of PFOA (white)
33
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated Surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
34
Main characteristics of themembrane
To separate oxygen from hydrogen
To insure a good protonic conductivity
To be chemically physically andmechanically stable in acid media andat high temperatures
Rеasonable cost applications
No electronic conductivity
41 FUEL CELL MEMBRANES
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
20
Co-polymerization of perfluorovinyl dioxolane(F-Ox) with different fluorinated co-monomers M2 ( CTFE PPVE PMVE and VDF)
Run Monomer M2 Monomers in the feed(mol )
F-Ox M2
Copolym compsby microanal
(mol)F-Ox M2
Copolym compsby NMR(mol )
F-Ox M2
Conv(wt)
Tg(degC)
Td10(degC)
1 F2C=CFCl 20 80 35 65 374 626 63 105 322
2 F2C=CFCl 40 60 62 38 615 385 70 148 354
3 F2C=CFOC3F7
64 36 874 126 852 148 82 144 342
4 F2C=CFOCF3 21 79 507 493 528 472 74 154 359
5 F2C=CH2 14 86 382 618 378 622 65 108 370
6 F2C=CH2 35 65 584 416 579 421 67 138 356
nR lt 135
21
210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP
CTFEVCAHVE) oligomers in good yield and high Tg were synthesized
2 Successful acrylation of hydroxy functionalized cooligomers
3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties
4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties
dArr
Suitable for waveguides applications
22
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
2323
31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to
hydrogenated analogues
Lower interfacial tension and CMC
Excellent chemical and thermal stability
Oleophobicity oil and fat repellants
Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc
Traditional commercial fluorosurfactants
Long fluorocarbon chain C6ltRFltC12
Perfluorooctane sulphonate (PFOS)
Perfluooctanoic acid ( PFOA)
their derivatives
2424
32 DRAWBACKS OF FLUORINATED SURFACTANTS
Bioaccumulable
Toxic and persistent
Wide-spread in the environment
3M company suggested perfluorinated chain le C4
bull Low bioconcentration factor
bull Low toxicity
bull Still high product performance
2525
General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4
Hydrophobic
G G GF- blockRF
Hydrophobic Hydrophilic
a ) for RF (CF3)2CF
b) for fluorinated monomer CH2=CH (TFP)
CF3
nCH2=CH + (CF3)2CFI RF - hydrophobic - I
CF3 CF3CF3
G
CF3
CF3CF-CH2-CH-CH2-CH Hydrophilic
CF3 CF3
Degradation
33 Synthesis of different end products as fluorinated surfactants
26
CF I + n nCFI
CF3
CF3
O
O
nCFCF3 I
O
O
Rad
nCFCF3
Zn
HSOH
O
nCFCF3
SOH
O
HOO
p
nCFCF3
SO
OO p
H2C CH2
nCFCF3
I
NNEt3
nCFCF3
NEt3nCF
CF3
N
I I
Surfactant C Surfactant B
Surfactant A
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants
Anionic surfactant
27
Surfactant Appearance Fluoroalkyl
10 decomp temperature a
(oC)
Tg and melting point b (oC)
(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC
(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145
(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175
Table 1 Properties of synthesized fluorinated surfactants
a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin
b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin
G Kostov et al USP 0027349 (2007)
28
Conditions Weight losses ()
Surfactant A Surfactant B Surfactant C
(1) Base-acid resistance
98 H2SO4 25 oC 7 days 00 lt12 00
60 HNO3 25 oC 7 days - gt400 lt20
37 HCl 25 oC 7 days 00 gt150 00
40 NaOH 25 oC 7 days 00 00 00
(2) Solubility in selected solvents Solubility (g100mL)
Water 25oC 72 hrs gt10 gt10 gt10
Methanol 25oC 72 hrs gt10 gt10 gt10
Diethyl ether 25oC 72 hrs lt1 lt1 lt1
Benzene 25oC 72 hrs lt2 lt2 lt2
Acetone 25oC 72 hrs lt10 lt10 lt10
Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-
Conclusions
The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6
29
Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA
30
Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis
34 Phosphorous containing TFP surfactants
31
3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate
Hydrolysis
Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)
32
Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to
those of PFOA (white)
33
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated Surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
34
Main characteristics of themembrane
To separate oxygen from hydrogen
To insure a good protonic conductivity
To be chemically physically andmechanically stable in acid media andat high temperatures
Rеasonable cost applications
No electronic conductivity
41 FUEL CELL MEMBRANES
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
21
210 CONCLUSIONS AND PERSPECTIVES1 Binary (CTFEVCA) and ternary (CTFEVCAHFP
CTFEVCAHVE) oligomers in good yield and high Tg were synthesized
2 Successful acrylation of hydroxy functionalized cooligomers
3 Photocrosslinking rarr original cured fluoroacrylated materials of low nD high Tg ampTd and good mechanical properties
4 Novel functionalized copolymers of CTFE with perfluorinateddioxolanes with excellent optical properties
dArr
Suitable for waveguides applications
22
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
2323
31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to
hydrogenated analogues
Lower interfacial tension and CMC
Excellent chemical and thermal stability
Oleophobicity oil and fat repellants
Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc
Traditional commercial fluorosurfactants
Long fluorocarbon chain C6ltRFltC12
Perfluorooctane sulphonate (PFOS)
Perfluooctanoic acid ( PFOA)
their derivatives
2424
32 DRAWBACKS OF FLUORINATED SURFACTANTS
Bioaccumulable
Toxic and persistent
Wide-spread in the environment
3M company suggested perfluorinated chain le C4
bull Low bioconcentration factor
bull Low toxicity
bull Still high product performance
2525
General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4
Hydrophobic
G G GF- blockRF
Hydrophobic Hydrophilic
a ) for RF (CF3)2CF
b) for fluorinated monomer CH2=CH (TFP)
CF3
nCH2=CH + (CF3)2CFI RF - hydrophobic - I
CF3 CF3CF3
G
CF3
CF3CF-CH2-CH-CH2-CH Hydrophilic
CF3 CF3
Degradation
33 Synthesis of different end products as fluorinated surfactants
26
CF I + n nCFI
CF3
CF3
O
O
nCFCF3 I
O
O
Rad
nCFCF3
Zn
HSOH
O
nCFCF3
SOH
O
HOO
p
nCFCF3
SO
OO p
H2C CH2
nCFCF3
I
NNEt3
nCFCF3
NEt3nCF
CF3
N
I I
Surfactant C Surfactant B
Surfactant A
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants
Anionic surfactant
27
Surfactant Appearance Fluoroalkyl
10 decomp temperature a
(oC)
Tg and melting point b (oC)
(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC
(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145
(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175
Table 1 Properties of synthesized fluorinated surfactants
a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin
b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin
G Kostov et al USP 0027349 (2007)
28
Conditions Weight losses ()
Surfactant A Surfactant B Surfactant C
(1) Base-acid resistance
98 H2SO4 25 oC 7 days 00 lt12 00
60 HNO3 25 oC 7 days - gt400 lt20
37 HCl 25 oC 7 days 00 gt150 00
40 NaOH 25 oC 7 days 00 00 00
(2) Solubility in selected solvents Solubility (g100mL)
Water 25oC 72 hrs gt10 gt10 gt10
Methanol 25oC 72 hrs gt10 gt10 gt10
Diethyl ether 25oC 72 hrs lt1 lt1 lt1
Benzene 25oC 72 hrs lt2 lt2 lt2
Acetone 25oC 72 hrs lt10 lt10 lt10
Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-
Conclusions
The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6
29
Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA
30
Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis
34 Phosphorous containing TFP surfactants
31
3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate
Hydrolysis
Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)
32
Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to
those of PFOA (white)
33
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated Surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
34
Main characteristics of themembrane
To separate oxygen from hydrogen
To insure a good protonic conductivity
To be chemically physically andmechanically stable in acid media andat high temperatures
Rеasonable cost applications
No electronic conductivity
41 FUEL CELL MEMBRANES
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
22
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
2323
31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to
hydrogenated analogues
Lower interfacial tension and CMC
Excellent chemical and thermal stability
Oleophobicity oil and fat repellants
Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc
Traditional commercial fluorosurfactants
Long fluorocarbon chain C6ltRFltC12
Perfluorooctane sulphonate (PFOS)
Perfluooctanoic acid ( PFOA)
their derivatives
2424
32 DRAWBACKS OF FLUORINATED SURFACTANTS
Bioaccumulable
Toxic and persistent
Wide-spread in the environment
3M company suggested perfluorinated chain le C4
bull Low bioconcentration factor
bull Low toxicity
bull Still high product performance
2525
General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4
Hydrophobic
G G GF- blockRF
Hydrophobic Hydrophilic
a ) for RF (CF3)2CF
b) for fluorinated monomer CH2=CH (TFP)
CF3
nCH2=CH + (CF3)2CFI RF - hydrophobic - I
CF3 CF3CF3
G
CF3
CF3CF-CH2-CH-CH2-CH Hydrophilic
CF3 CF3
Degradation
33 Synthesis of different end products as fluorinated surfactants
26
CF I + n nCFI
CF3
CF3
O
O
nCFCF3 I
O
O
Rad
nCFCF3
Zn
HSOH
O
nCFCF3
SOH
O
HOO
p
nCFCF3
SO
OO p
H2C CH2
nCFCF3
I
NNEt3
nCFCF3
NEt3nCF
CF3
N
I I
Surfactant C Surfactant B
Surfactant A
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants
Anionic surfactant
27
Surfactant Appearance Fluoroalkyl
10 decomp temperature a
(oC)
Tg and melting point b (oC)
(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC
(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145
(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175
Table 1 Properties of synthesized fluorinated surfactants
a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin
b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin
G Kostov et al USP 0027349 (2007)
28
Conditions Weight losses ()
Surfactant A Surfactant B Surfactant C
(1) Base-acid resistance
98 H2SO4 25 oC 7 days 00 lt12 00
60 HNO3 25 oC 7 days - gt400 lt20
37 HCl 25 oC 7 days 00 gt150 00
40 NaOH 25 oC 7 days 00 00 00
(2) Solubility in selected solvents Solubility (g100mL)
Water 25oC 72 hrs gt10 gt10 gt10
Methanol 25oC 72 hrs gt10 gt10 gt10
Diethyl ether 25oC 72 hrs lt1 lt1 lt1
Benzene 25oC 72 hrs lt2 lt2 lt2
Acetone 25oC 72 hrs lt10 lt10 lt10
Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-
Conclusions
The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6
29
Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA
30
Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis
34 Phosphorous containing TFP surfactants
31
3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate
Hydrolysis
Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)
32
Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to
those of PFOA (white)
33
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated Surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
34
Main characteristics of themembrane
To separate oxygen from hydrogen
To insure a good protonic conductivity
To be chemically physically andmechanically stable in acid media andat high temperatures
Rеasonable cost applications
No electronic conductivity
41 FUEL CELL MEMBRANES
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
2323
31 Advantages of fluorinated surfactantsBetter surface active and better hydrophobic compared to
hydrogenated analogues
Lower interfacial tension and CMC
Excellent chemical and thermal stability
Oleophobicity oil and fat repellants
Useful in many industrial fields paints coatings detergents fire-fighting foams pharmaceuticals etc
Traditional commercial fluorosurfactants
Long fluorocarbon chain C6ltRFltC12
Perfluorooctane sulphonate (PFOS)
Perfluooctanoic acid ( PFOA)
their derivatives
2424
32 DRAWBACKS OF FLUORINATED SURFACTANTS
Bioaccumulable
Toxic and persistent
Wide-spread in the environment
3M company suggested perfluorinated chain le C4
bull Low bioconcentration factor
bull Low toxicity
bull Still high product performance
2525
General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4
Hydrophobic
G G GF- blockRF
Hydrophobic Hydrophilic
a ) for RF (CF3)2CF
b) for fluorinated monomer CH2=CH (TFP)
CF3
nCH2=CH + (CF3)2CFI RF - hydrophobic - I
CF3 CF3CF3
G
CF3
CF3CF-CH2-CH-CH2-CH Hydrophilic
CF3 CF3
Degradation
33 Synthesis of different end products as fluorinated surfactants
26
CF I + n nCFI
CF3
CF3
O
O
nCFCF3 I
O
O
Rad
nCFCF3
Zn
HSOH
O
nCFCF3
SOH
O
HOO
p
nCFCF3
SO
OO p
H2C CH2
nCFCF3
I
NNEt3
nCFCF3
NEt3nCF
CF3
N
I I
Surfactant C Surfactant B
Surfactant A
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants
Anionic surfactant
27
Surfactant Appearance Fluoroalkyl
10 decomp temperature a
(oC)
Tg and melting point b (oC)
(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC
(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145
(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175
Table 1 Properties of synthesized fluorinated surfactants
a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin
b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin
G Kostov et al USP 0027349 (2007)
28
Conditions Weight losses ()
Surfactant A Surfactant B Surfactant C
(1) Base-acid resistance
98 H2SO4 25 oC 7 days 00 lt12 00
60 HNO3 25 oC 7 days - gt400 lt20
37 HCl 25 oC 7 days 00 gt150 00
40 NaOH 25 oC 7 days 00 00 00
(2) Solubility in selected solvents Solubility (g100mL)
Water 25oC 72 hrs gt10 gt10 gt10
Methanol 25oC 72 hrs gt10 gt10 gt10
Diethyl ether 25oC 72 hrs lt1 lt1 lt1
Benzene 25oC 72 hrs lt2 lt2 lt2
Acetone 25oC 72 hrs lt10 lt10 lt10
Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-
Conclusions
The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6
29
Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA
30
Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis
34 Phosphorous containing TFP surfactants
31
3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate
Hydrolysis
Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)
32
Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to
those of PFOA (white)
33
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated Surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
34
Main characteristics of themembrane
To separate oxygen from hydrogen
To insure a good protonic conductivity
To be chemically physically andmechanically stable in acid media andat high temperatures
Rеasonable cost applications
No electronic conductivity
41 FUEL CELL MEMBRANES
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
2424
32 DRAWBACKS OF FLUORINATED SURFACTANTS
Bioaccumulable
Toxic and persistent
Wide-spread in the environment
3M company suggested perfluorinated chain le C4
bull Low bioconcentration factor
bull Low toxicity
bull Still high product performance
2525
General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4
Hydrophobic
G G GF- blockRF
Hydrophobic Hydrophilic
a ) for RF (CF3)2CF
b) for fluorinated monomer CH2=CH (TFP)
CF3
nCH2=CH + (CF3)2CFI RF - hydrophobic - I
CF3 CF3CF3
G
CF3
CF3CF-CH2-CH-CH2-CH Hydrophilic
CF3 CF3
Degradation
33 Synthesis of different end products as fluorinated surfactants
26
CF I + n nCFI
CF3
CF3
O
O
nCFCF3 I
O
O
Rad
nCFCF3
Zn
HSOH
O
nCFCF3
SOH
O
HOO
p
nCFCF3
SO
OO p
H2C CH2
nCFCF3
I
NNEt3
nCFCF3
NEt3nCF
CF3
N
I I
Surfactant C Surfactant B
Surfactant A
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants
Anionic surfactant
27
Surfactant Appearance Fluoroalkyl
10 decomp temperature a
(oC)
Tg and melting point b (oC)
(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC
(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145
(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175
Table 1 Properties of synthesized fluorinated surfactants
a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin
b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin
G Kostov et al USP 0027349 (2007)
28
Conditions Weight losses ()
Surfactant A Surfactant B Surfactant C
(1) Base-acid resistance
98 H2SO4 25 oC 7 days 00 lt12 00
60 HNO3 25 oC 7 days - gt400 lt20
37 HCl 25 oC 7 days 00 gt150 00
40 NaOH 25 oC 7 days 00 00 00
(2) Solubility in selected solvents Solubility (g100mL)
Water 25oC 72 hrs gt10 gt10 gt10
Methanol 25oC 72 hrs gt10 gt10 gt10
Diethyl ether 25oC 72 hrs lt1 lt1 lt1
Benzene 25oC 72 hrs lt2 lt2 lt2
Acetone 25oC 72 hrs lt10 lt10 lt10
Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-
Conclusions
The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6
29
Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA
30
Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis
34 Phosphorous containing TFP surfactants
31
3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate
Hydrolysis
Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)
32
Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to
those of PFOA (white)
33
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated Surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
34
Main characteristics of themembrane
To separate oxygen from hydrogen
To insure a good protonic conductivity
To be chemically physically andmechanically stable in acid media andat high temperatures
Rеasonable cost applications
No electronic conductivity
41 FUEL CELL MEMBRANES
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
2525
General strategy synthesis of fluorinated surfactants with fluorinated linear block Ci le 4
Hydrophobic
G G GF- blockRF
Hydrophobic Hydrophilic
a ) for RF (CF3)2CF
b) for fluorinated monomer CH2=CH (TFP)
CF3
nCH2=CH + (CF3)2CFI RF - hydrophobic - I
CF3 CF3CF3
G
CF3
CF3CF-CH2-CH-CH2-CH Hydrophilic
CF3 CF3
Degradation
33 Synthesis of different end products as fluorinated surfactants
26
CF I + n nCFI
CF3
CF3
O
O
nCFCF3 I
O
O
Rad
nCFCF3
Zn
HSOH
O
nCFCF3
SOH
O
HOO
p
nCFCF3
SO
OO p
H2C CH2
nCFCF3
I
NNEt3
nCFCF3
NEt3nCF
CF3
N
I I
Surfactant C Surfactant B
Surfactant A
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants
Anionic surfactant
27
Surfactant Appearance Fluoroalkyl
10 decomp temperature a
(oC)
Tg and melting point b (oC)
(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC
(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145
(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175
Table 1 Properties of synthesized fluorinated surfactants
a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin
b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin
G Kostov et al USP 0027349 (2007)
28
Conditions Weight losses ()
Surfactant A Surfactant B Surfactant C
(1) Base-acid resistance
98 H2SO4 25 oC 7 days 00 lt12 00
60 HNO3 25 oC 7 days - gt400 lt20
37 HCl 25 oC 7 days 00 gt150 00
40 NaOH 25 oC 7 days 00 00 00
(2) Solubility in selected solvents Solubility (g100mL)
Water 25oC 72 hrs gt10 gt10 gt10
Methanol 25oC 72 hrs gt10 gt10 gt10
Diethyl ether 25oC 72 hrs lt1 lt1 lt1
Benzene 25oC 72 hrs lt2 lt2 lt2
Acetone 25oC 72 hrs lt10 lt10 lt10
Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-
Conclusions
The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6
29
Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA
30
Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis
34 Phosphorous containing TFP surfactants
31
3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate
Hydrolysis
Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)
32
Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to
those of PFOA (white)
33
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated Surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
34
Main characteristics of themembrane
To separate oxygen from hydrogen
To insure a good protonic conductivity
To be chemically physically andmechanically stable in acid media andat high temperatures
Rеasonable cost applications
No electronic conductivity
41 FUEL CELL MEMBRANES
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
26
CF I + n nCFI
CF3
CF3
O
O
nCFCF3 I
O
O
Rad
nCFCF3
Zn
HSOH
O
nCFCF3
SOH
O
HOO
p
nCFCF3
SO
OO p
H2C CH2
nCFCF3
I
NNEt3
nCFCF3
NEt3nCF
CF3
N
I I
Surfactant C Surfactant B
Surfactant A
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
CF3
Scheme 1 Straightforward strategies for the preparation of 333-trifluoropropene-based surfactants
Anionic surfactant
27
Surfactant Appearance Fluoroalkyl
10 decomp temperature a
(oC)
Tg and melting point b (oC)
(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC
(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145
(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175
Table 1 Properties of synthesized fluorinated surfactants
a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin
b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin
G Kostov et al USP 0027349 (2007)
28
Conditions Weight losses ()
Surfactant A Surfactant B Surfactant C
(1) Base-acid resistance
98 H2SO4 25 oC 7 days 00 lt12 00
60 HNO3 25 oC 7 days - gt400 lt20
37 HCl 25 oC 7 days 00 gt150 00
40 NaOH 25 oC 7 days 00 00 00
(2) Solubility in selected solvents Solubility (g100mL)
Water 25oC 72 hrs gt10 gt10 gt10
Methanol 25oC 72 hrs gt10 gt10 gt10
Diethyl ether 25oC 72 hrs lt1 lt1 lt1
Benzene 25oC 72 hrs lt2 lt2 lt2
Acetone 25oC 72 hrs lt10 lt10 lt10
Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-
Conclusions
The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6
29
Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA
30
Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis
34 Phosphorous containing TFP surfactants
31
3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate
Hydrolysis
Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)
32
Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to
those of PFOA (white)
33
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated Surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
34
Main characteristics of themembrane
To separate oxygen from hydrogen
To insure a good protonic conductivity
To be chemically physically andmechanically stable in acid media andat high temperatures
Rеasonable cost applications
No electronic conductivity
41 FUEL CELL MEMBRANES
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
27
Surfactant Appearance Fluoroalkyl
10 decomp temperature a
(oC)
Tg and melting point b (oC)
(CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 yellow viscliq 24 200 Tglt 0 oC
(CF3)2CF(TFP)CH2CH2N+C5H5I- yellow solid 45 250 145
(CF3)2CF(TFP)CH2CH2N+(CH3)3I- yellow solid 47 230 175
Table 1 Properties of synthesized fluorinated surfactants
a) TGA Thermal Analyst Instrument 51 heating rate 10oCmin temperature range of 30-580oC air flow of 60 mLmin
b) DSC Perkin-Elmer Pyris 1 heating rate 20oCmin
G Kostov et al USP 0027349 (2007)
28
Conditions Weight losses ()
Surfactant A Surfactant B Surfactant C
(1) Base-acid resistance
98 H2SO4 25 oC 7 days 00 lt12 00
60 HNO3 25 oC 7 days - gt400 lt20
37 HCl 25 oC 7 days 00 gt150 00
40 NaOH 25 oC 7 days 00 00 00
(2) Solubility in selected solvents Solubility (g100mL)
Water 25oC 72 hrs gt10 gt10 gt10
Methanol 25oC 72 hrs gt10 gt10 gt10
Diethyl ether 25oC 72 hrs lt1 lt1 lt1
Benzene 25oC 72 hrs lt2 lt2 lt2
Acetone 25oC 72 hrs lt10 lt10 lt10
Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-
Conclusions
The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6
29
Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA
30
Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis
34 Phosphorous containing TFP surfactants
31
3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate
Hydrolysis
Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)
32
Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to
those of PFOA (white)
33
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated Surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
34
Main characteristics of themembrane
To separate oxygen from hydrogen
To insure a good protonic conductivity
To be chemically physically andmechanically stable in acid media andat high temperatures
Rеasonable cost applications
No electronic conductivity
41 FUEL CELL MEMBRANES
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
28
Conditions Weight losses ()
Surfactant A Surfactant B Surfactant C
(1) Base-acid resistance
98 H2SO4 25 oC 7 days 00 lt12 00
60 HNO3 25 oC 7 days - gt400 lt20
37 HCl 25 oC 7 days 00 gt150 00
40 NaOH 25 oC 7 days 00 00 00
(2) Solubility in selected solvents Solubility (g100mL)
Water 25oC 72 hrs gt10 gt10 gt10
Methanol 25oC 72 hrs gt10 gt10 gt10
Diethyl ether 25oC 72 hrs lt1 lt1 lt1
Benzene 25oC 72 hrs lt2 lt2 lt2
Acetone 25oC 72 hrs lt10 lt10 lt10
Table 2 Chemical resistance and solubility of synthesized fluorinated surfactantsSurfactant A ndash (CF3)2CF(TFP)(CH2)3SCH2CO2(PEO)CH3 Surfactant B -(CF3)2CF(TFP)CH2CH2N+C5H5I- Surfactant C - (CF3)2CF(TFP)CH2CH2N+(CH3)3I-
Conclusions
The samples remained almost unaffected in 98 H2SO4 and 40 NaOHbut not stable in 60 HNO3 at RTSoluble in H2O CH3OH but not in (C2H5)2O and C6H6
29
Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA
30
Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis
34 Phosphorous containing TFP surfactants
31
3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate
Hydrolysis
Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)
32
Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to
those of PFOA (white)
33
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated Surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
34
Main characteristics of themembrane
To separate oxygen from hydrogen
To insure a good protonic conductivity
To be chemically physically andmechanically stable in acid media andat high temperatures
Rеasonable cost applications
No electronic conductivity
41 FUEL CELL MEMBRANES
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
29
Figure 2 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA
30
Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis
34 Phosphorous containing TFP surfactants
31
3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate
Hydrolysis
Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)
32
Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to
those of PFOA (white)
33
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated Surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
34
Main characteristics of themembrane
To separate oxygen from hydrogen
To insure a good protonic conductivity
To be chemically physically andmechanically stable in acid media andat high temperatures
Rеasonable cost applications
No electronic conductivity
41 FUEL CELL MEMBRANES
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
30
Scheme 2 Radical telomerization of 333-trifluoropropene (TFP) with diethyl hydrogenophosphonate followed by hydrolysis
34 Phosphorous containing TFP surfactants
31
3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate
Hydrolysis
Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)
32
Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to
those of PFOA (white)
33
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated Surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
34
Main characteristics of themembrane
To separate oxygen from hydrogen
To insure a good protonic conductivity
To be chemically physically andmechanically stable in acid media andat high temperatures
Rеasonable cost applications
No electronic conductivity
41 FUEL CELL MEMBRANES
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
31
3 5 Controlled radical copolymerization of VDF and TFP in the presence of xanthate
Hydrolysis
Scheme 4 Oligo(VDF-co-TFP)-b-oligo(VAc) block cooligomers obtained by MADIX technology and their hydrolysis into fluorinated surfactants (where Xa = SC(S)OEt)
32
Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to
those of PFOA (white)
33
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated Surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
34
Main characteristics of themembrane
To separate oxygen from hydrogen
To insure a good protonic conductivity
To be chemically physically andmechanically stable in acid media andat high temperatures
Rеasonable cost applications
No electronic conductivity
41 FUEL CELL MEMBRANES
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
32
Figure 3 Surface tensions and conductimetries vs concentration of poly(VDF-co-TFP)-b-oligo(VA) surfactant ( black) compared to
those of PFOA (white)
33
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated Surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
34
Main characteristics of themembrane
To separate oxygen from hydrogen
To insure a good protonic conductivity
To be chemically physically andmechanically stable in acid media andat high temperatures
Rеasonable cost applications
No electronic conductivity
41 FUEL CELL MEMBRANES
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
33
CONTENTS
1-Introduction Objectives
2-Functionalized fluoropolymers for plastic optical fibres
3-Original fluorinated Surfactants potentially non-bioaccumulable
4-Functional fluoropolymers for fuel cell membranes
5-Conclusions and perspectives
34
Main characteristics of themembrane
To separate oxygen from hydrogen
To insure a good protonic conductivity
To be chemically physically andmechanically stable in acid media andat high temperatures
Rеasonable cost applications
No electronic conductivity
41 FUEL CELL MEMBRANES
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
34
Main characteristics of themembrane
To separate oxygen from hydrogen
To insure a good protonic conductivity
To be chemically physically andmechanically stable in acid media andat high temperatures
Rеasonable cost applications
No electronic conductivity
41 FUEL CELL MEMBRANES
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
35
Poor thermostability
Low hydrolytic stability
Instability to Radiations
Non-negligible solubility in usedfuels
Good thermalstability
Stability to hydrolysis and to acids
Good durability
Properties of super acide (-CF2-SO3H)
Good resistance to oxidation
Hydrogenated membranes versus fluorinated membranes
Hydrogenated membranes Fluorinated membranes
4 2Fluorinated ionomers for IE membranes
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
36
Perfluorinated ionomers
bull Clemson-produced sulphonyl imide ionomer
bull Commercially available Nafion ionomer (DuPont)
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO3 H
CF3
acidic proton
(CF2CF2)n (CF2CF)
OCF2CFOCF2CF2 SO2NSO2CF3
CF3
H
acidic proton
EW=1100 n = 66
EW = 1075 n = 50EW = 1200 n = 63EW = 1470 n = 90 D DesMarteau
421 SULFONYLFLUORIDE COPOLYMERS
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
37
PEM fuel cells mdash Nafionreg
A - fluorocarbonbackbone
B - interfacial zoneC - ionic clusters
Yeo and Yeager Modern Aspects of Electrochemistry Vol 16 Plenum Press New York 1985 p437
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
38
bullSynthesis of sulphonylfluorine co-monomer(CF2=CFCF2OCF2CF2SO2F) ndash
bull Du Pont technology
bullCo-polymerization
nCF2=CF2 + xCF2=CFCF2OCF2CF2SO2F
R(CF2CF2)n-(CF2CF)-x
CF2O(CF2)2SO2F
rTFE=1002 plusmn 063
r2=03 plusmn 09
R˙
G Kostov et al J Appl Polym Sci 1993 47 735
422 OUR SULFOFLUORINATED MEMBRANES
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
39
28732823ndashMelting temperature (ordmC)
30803140ndashThermal stability (ordmC)
313343408Copolymer yield (wt)
936863428
077072039
(-SO2F) content in the copolymer
IEC (meqg)
m2 (mol)
050077295TFEPPOTESF mol ration in the feed
Samples1 2 3
Parameters
Table 423 Copolymerization of TFE with PPOTESF in bulk
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
40
x F 2C =C FC l + y H2C =CC H2 F
[(C F 2C F)n (C H2 C )m
C H2F]p
C l
R
CTFE FMS
1-(fluoromethyl)styrene
Synthesis of poly(CTFE-co-FMS) copolymers
SULPHONATION
PEMFC
Collaboration with Prof Gouverneur Oxford Univ
43 CTFE-based copolymers for electrolytemembranes
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
41
44 CARBOXYL CONTAINING MEMBRANES
bullSynthesis of carboxyl comonomer CF2=CF-CO2CH3 (MTFP) ndash
bullAsahi glass technology
bull Co-polymerization
CF2=CF2 + CF2=CF-CO2CH3 + CH2=CH2 CH2=CH(CH3) copolymer
40 10 30 20 mol
AR meqg ndash 12-29
R ohmcm2 ndash 12-158
αhydr - 73-99
Tg lt 250C
TdOCO ordmC gt 360
TfOCO ordmC ndash 180ndash190
σ MPa ndash 35ndash40
ε - 150ndash200
Application chloro ndash alkaline electrolysis PEMFC
J Membrane Sci 1992 68 133
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
42
Fuel cell challenges high temp operationFuel cell challenges high temp operation
bull DOE fuel cell cost target of $30kW ndash Incremental advances are
not adequatendash High riskhigh payoff basic
research coupled with applied programs
ldquohellipa sophisticated set of guiding principles that are based on carefully designed and executed experimental and theoretical studiesrdquo
Li et al Chem Mater 2003 15 4896-4915 DOE Basic Energy Sciences Workshop on Hydrogen Storage Production and Use httpwwwscdoegovbesreportsfilesNHE_rptpdf
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
4343
MeOH crossover
Cost ($ 400-500 m2)
Drying from 80degC including poor performances
Search for intermediate and high temperaturemembranes
To replace H2O by immobilized amphotericsolvents
Our choice nitrogenous heterocycles C Weiser Fuel Cells 2004 4 245
Drawbacks of sulphonated membranes
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
4444
N
N
O
O
Ph
+
F
F
Cl
F
N
NH
O
O
F F
F Cl
n
Rad H2Pd(OH)2
(A)
(A) + PEEK-S
100 degCIEC 08 to 04Conductivity ~ 10 mScm-1
(at 100 degC 30 RH)
45 Functional fluorinated co-polymers for quasi-anhydrous fuel cell membranes
Industrial Partner PSA Peugeot-Citroeumln 2006ndash2009
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
45
CH2 CF2 CH2 C
CF3
CO2H
CF2 CF
CF3
x y z
1) A lL iH 4
E aton C ataly stNH2
NH22)
OH S O 3N a
S O 3N aN aO 3S
CH2 CF2 CH2 C
CF3
CH2
CF2 CF
CF3
x y z
O S O 3 N a
S O 3N aN aO 3S
H +
CH2 CF2 CH2 C
CF3
CF2 CF
CF3
x y z
NHN
PROTON EXCHANGE MEMBRANES QUASI-ANHYDROUS MEMBRANES
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
46
Remaining challenges
bull Find a useful balance between mechanical properties and glass transition temperature
bull Design membranes whose final structure enables proton conductivity suitable for fuel cell start up at 25ordmC as well as continuous operation at 120-150ordmC
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
47
Membranes combining 2 conduction mechanisms
bull Use both water (Tlt100ordmC) and heterocyclic network (high Tgt100ordmC) as the proton conducting media
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
48
Conclusions and perspectives
bull The new functionalized fluoropolymers are thermally stable up to 300ordmC with good dual conductivity
bull Efficient methods to mechanically stabilize the conductive films have to be developed
bull Exploratory experiments combining hydrated and anhydrous conducting domains are promising and will further be developed
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION
49
COMPANIES
Solvay (B)Atofina (F)MEFI (F)Chemtura (USA)PSA Peugeot Citroeumln (F)
ACKNOWLEDGEMENTS
ACADEMICS
Prof B Boutevin (IAM ENSCM F)Dr Al Rousseau ( INSA de Lyon F)Prof Y Okamoto (Brooklyn Polytechnic US)Dr B Ameduri (IAM ENSCM F)Prof V Gouverneur (Oxford Univ GB)
50
THANK YOU FOR YOUR KIND ATTENTION
THANK YOU FOR YOUR KIND ATTENTION