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Summary of my research work ( industrial projects are not presented on these slides)TRANSCRIPT
Synthesis of Branched, Cyclic & Functional Polymers
Vijay Chavan, Dr. Roderic P. QuirkDepartment of Polymer Science,
The University of Akron,Akron, Ohio- 44325
Department of Polymer Science at AkronProgram Since 1967 First College of Polymer Science & Engineering in the world New Building constructed in 1991
Akron & Polymer History
• Goodrich (1869)
• Goodyear (1898)
• Firestone (1900)
• Gojo (1949) Purell Hand Sanitizer
• Akron Polymer Systems (2002) by Dr. Frank Harris – condensation polymerization products
Unique aspects of star polymers
• Different Architecture
• Lower solution viscosity
• Lower melt viscosity ,easier to process
• Preferential migration to surface
Grest, G. S.; Fetters, L. J.; Huang, J. S.; Richter, D. Advances in Chemical Physics 1996, 94, 67-163
Foster, M. D.; Greenberg, C. C.; Teale, D. M.; Turner, C. M.; Corona-Galvan, S.; Cloutet, E.; Butler, P. D.; Hammouda, B.; Quirk, R. P. Macromol. Symp. 2000, 149, 263-268.
Applications of star / branched polymers (500 patents)
• Synthetic Elastomers
• Coatings (improved hardness and drying)1
• Biolubricants2
• Emulsifiers 3
• Photolithographic materials 4
• Dental Cements 5, Adhesives & coatings 6
Prevents Cold Flow
Advantages of Anionic Polymerization
• Controlled Molecular weight , Narrow Molecular Weight Distribution, PDI < 1.1
Li
n
+ -C6H6
30 0C
--+
Li
Li Li
Initiation
Propagation
Ri>Rp most of the times
No termination and no transfer
Mn = grams of monomer
Moles of initiator
One initiator generates onePolymer chain
1) Star PS using DVB
Degree of Branching from 5 to 39
f = Mn branch/Mn linear = 5-39
[DVB]/[PSLi] = 2 to 30
Hseih, H.L.; Quirk, R.P. Anionic Polymerization: Principles and Practical Appplications; Marcel Dekker, Inc.: New York, 1996
P Li +
P Li
P
Possibility of gelling
2) Star polymers by condensing living P-Li+ with chlorosilanes
Cl Si Cl
Cl
ClSi
P Li +
Morton, M.; Helminiak, T. E.; Gadkary, S. D.; Bueche, F. J. Polym. Sci. 1962, 57, 471-482
Mn star / Mn arm = 4.09After fractionation
PDI= 1.09
Combination of vinyl and chlorine group
Si
Cl
Nucleophilic substitution
PS- Li+
VDMCS
VInyldimethylchlorosilane
PS+
SiSiCl PSPS- Li +
Chaumont, P.; Herz, J.; Rempp, P. Eur. Polym. J. 1979, 15, 537-540.
THF, -70 0C
Excess
Mn = 20kPDI = 1.1
Addition of living PSLi to VDMCS
Reaction done in THF at -70 0C
Wilczek, L., US Patent 6,740,723 , Feb 11, 2003
Reaction of PSLi with VDMCS
Branches upon branches
Si
Cl
PSLi +
f max = Mn branched / Mn linear = 5
THF , -780C
Approx 1:1 ratio
Dupont
Aim of the research
• Understand the chemistry and efficiency of VDMCS addition to PSLi
• Find evidence of architecture
ExperimentStyrene
MethanolVDMCS
Methanol
Ampoule for base sample
Vacuum
Methanol
Solution
Ampoule for base sample after 12 hrs
Inlet for initiator
GPC Analysis
PS-VDMCS 30 C-1.5 eq
0
0.2
0.4
0.6
0.8
1
1.2
18 20 22 24 26 28
Retention volume
RI s
ign
al
PS-VDMCSbase at 30 C PS-VDMCS-12hrsPS-VDMCS-3days-30C
Mnbase= 2,500 g/mol
PDI = 1.02
Mn: 23,000 g/mol
PDI: 1.3
1H NMR PS-VDMCS-2.ESP
12 10 8 6 4 2 0 -2 -4Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
No
rma
lize
d In
ten
sity
CHLOROFORM-d
7.2
7
No Vinyl peaks
TMS Si reference.esp
32 24 16 8 0 -8 -16 -24 -32 -40 -48 -56Chemical Shift (ppm)
-0.1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
No
rma
lize
d In
ten
sity
-37.30
0
TMS
PS-VDMCS-1.5-30C-3day
Reported peaks for –Si-Cl (17.65 ppm) and –Si-OCH3 (6.66 ppm) are absent indicating complete substitution of Cl
29Si NMR
VDMCS-1.5-50C-3DAY-SI.ESP
32 24 16 8 0 -8 -16 -24 -32 -40 -48 -56Chemical Shift (ppm)
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Nor
mal
ized
Inte
nsity
-37.
30
VDMCS-2.5-50C-3DAY-SI.ESP
32 24 16 8 0 -8 -16 -24 -32 -40 -48 -56Chemical Shift (ppm)
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Nor
mal
ized
Inte
nsity
-37.
30
VDMCS-2.5-30C-3DAY-SI.ESP
32 24 16 8 0 -8 -16 -24 -32 -40 -48 -56Chemical Shift (ppm)
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Nor
mal
ized
Inte
nsity
-37
.30
VDMCS-5EQ-30C-3DAY-SI.ESP
32 24 16 8 0 -8 -16 -24 -32 -40 -48 -56Chemical Shift (ppm)
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Nor
mal
ized
Inte
nsity
-37.
30
VDMCS-5EQ-50C-3DAY-SI.ESP
32 24 16 8 0 -8 -16 -24 -32 -40 -48 -56Chemical Shift (ppm)
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Nor
mal
ized
Inte
nsity
-37
.30
PS-VDMCS-1.5-50C-3day PS-VDMCS-2.5-30C-3day
PS-VDMCS-2.5-50C-3day PS-VDMCS-5-30C-3day
PS-VDMCS-5-50C-3day
Effect of concentration of VDMCS
No of arms Vs Concentration of VDMCS
123456789
10
0 1 2 3 4 5 6
Eq of VDMCS
f (n
o o
f ar
ms)
Behavior unlike DVB
n
Si
Cl
n
n
n
Si
n
n
Si
n
Si Si
Si
Si
Si
Si
Si
Si
Si
Si
Si
-
-
Li +
Li+
-
-
-
-
Vinyl 1
Anion 2
Vinyl 1
Viscosity of Star and Linear
[n] Intrinsic viscosity Vs Mn
0
0.02
0.04
0.06
0.08
0.1
0.12
0.14
0.16
0.18
0.2
10000 12000 14000 16000 18000 20000 22000 24000
Mn (g/mol)
[n]
Intr
ins
ic v
isc
os
ity
[n] linear
[n] branched
gη
[η] star
[η] linear=
Contraction parameter
Contraction factor gη = [η]branched/ [η]linear
Deffieux, A.; Schappacher, M. Macromolecules, 1999, 32, 1797-1802*Roovers, J. Branched Polymers II, Springer, 1999, 169
(f = Mn star/ Mn linear )
Experimental contraction factor (gη) Vs No of arms (f)
0
0.1
0.2
0.3
0.4
0.5
0.6
7 7.5 8 8.5 9 9.5 10
f
gη g1 observed
Roover's Equation
gη literatureFor f=8.9 is 0.44*Observed is 0.46
Contraction parameter observed vs theoretical
fObserved
[n]/[n]linCalculated
gn
8.90 0.46 0.44
8.09 0.48 0.47
9.36 0.40 0.42
7.50 0.49 0.49
7.94 0.53 0.47
8.33 0.47 0.46
Melt Viscosity Data
Melt Viscosity of Stars and Linear
0
20
40
60
80
100
120
140
150 160 170 180 190 200 210
Temp (0C)
Mel
t V
isco
sity
(P
a.s)
Linear 18K
Star 17K-6
Star 22k-1
Linear Mn = 18k, PDI= 1.02Star 17k, PDI = 1.21, Star 22k , PDI = 1.30
Constant strain Cone and plate rheometerNewtonian region
VDMCS star , Mn = 23k , PDI = 1.47 DVB Star , Mn = 26k , PDI = 1.58
TGA curve
0
20
40
60
80
100
120
200 300 400 500 600Temperature
We
igh
t L
os
s (
%)
VDMCS 23k StarDVB 26k Star
Thermal Stability
Conclusion
• Efficient synthesis of star polymers was achieved
• Viscosities lower than linear analogues
• Just 1.5 eq of VDMCS are enough to generate 8 arms Behavior is different than DVB
• No residual double bonds or chlorine groups
Vijay Chavan*, Roderic P. Quirk, Shih Fan Wang, Mark D. Foster, Rebecca Agapov, Rahul Kulkarni, Xinfei Yu, Wumin Yu
Topographical Evidence of Cyclic Polymers
Two main methods of making cyclic polymers
1) End to end chain coupling
-Very low quantities obtained
-Needs very high dilution ( mg product per liter of solvent)
- Good for low mol weight polymers
2) Ring opening metathesis
• -Very efficient, vol of solvent can be as little as that of the monomer or even bulk
• -High quantity of polymer obtained
• -Potential to make continuous process ?
A)Cyclization by anionic polymerization
Na, Napthalene-
Na Na
Cl
Cl
+
+
mg of product in liters of solventMixtures of products
Geiser, D.; Hocker, H. Macromolecules 1980,13, 653.
Slow addition
Tetrahydropyran
Mn = 4k-24 k,
Smart way of separationReacted the linear polymers with High MW PSLi and fractionated
B)Cyclization by click chemistry
Br Br
1) NaN3 2) Click reaction, CuBr, BiPy, 120oC, 1 hr
N
N
N
DMF, 25oC
Laurent, B.A.; Grayson, S.M. J. Am. Chem. Soc., 2006, 128 (13), 4238
75o C, CuBr,PMDETA, ATRP
Mn = 2k, PDI = 1.08200 mg product for 1 liter solvent
2) Ring opening metathesis by Dr. Robert Grubbs
Nobel Prize Winner in Chemistry 2005
http://en.wikipedia.org/wiki/File:Robert_Grubbs.jpg
Can cyclic catalyst make cyclic polymer ?
Fürstner, A.; Ackermann, L.; Babor, B.; Goddard, R.; Lehmann, C. W.; Mynott, R.; Stelzer, F.; Thiel, O. R. Chem. Eur. J. 2001, 7, 3236.
Ru Complex A
t-BuOK/ Toluene, rt, 1.5hr
Ru CH
PCy3
PCy3Cl
Cl
Ph
N
CH3
H3C
CH3
HC CH
N
C
Ru CH
PCy3Cl
Cl
Ph
N
CH3
H3C
CH3
HC CH
N
C
Br -
H
1)
2)
Fürstner, A.; Ackermann, L.; Babor, B.; Goddard, R.; Lehmann, C. W.; Mynott, R.; Stelzer, F.; Thiel, O. R. Chem. Eur. J. 2001, 7, 3236.Bielawski, C. W.; Benitez, D.; Grubbs, R. H. Science 2002, 297, 2041-2044.Bielawski, C. W.; Benitez, D.; Grubbs, R. H. J. Am. Chem. Soc. 2003,125, 8424-8425.
Complex A
Cyclic catalyst
N
CH3
H3C
CH3
HC CH
N
CH
Ru
PCy3Cl
Cl
n-Hexane
reflux 1hr
N
CH3
H3C
CH3
HC CH
N
CH
Ru CH
PCy3Cl
Cl
Ph
3
Fürstner, A.; Ackermann, L.; Babor, B.; Goddard, R.; Lehmann, C. W.; Mynott, R.; Stelzer, F.; Thiel, O. R. Chem. Eur. J. 2001, 7, 3236.
Bielawski, C. W.; Benitez, D.; Grubbs, R. H. Science 2002, 297, 2041-2044.Bielawski, C. W.; Benitez, D.; Grubbs, R. H. J. Am. Chem. Soc. 2003,125, 8424-8425.
Red
Yellow
Complex 12c
Fürstner, A.; Ackermann, L.; Babor, B.; Goddard, R.; Lehmann, C. W.; Mynott, R.; Stelzer, F.; Thiel, O. R. Chem. Eur. J. 2001, 7, 3236.
Pentane/Ether : 4:1 volume ratio
Argon
Argon
31P NMR linear catalyst
12CP31.ESP
45 40 35 30 25 20 15 10 5 0 -5 -10 -15 -20 -25 -30 -35 -40Chemical Shift (ppm)
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
No
rma
lize
d In
ten
sity
34
.31
N
CH3
H3C
CH3
HC CH
N
C
Ru CH
PCy3Cl
Cl
Ph
31P NMR Cyclic catalystCYCLICCATAPUREP31.ESP
40 35 30 25 20 15 10 5 0 -5 -10 -15 -20 -25 -30Chemical Shift (ppm)
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
No
rma
lize
d In
ten
sity
28
.94
N
CH3
H3C
CH3
HC CH
N
CH
Ru
PCy3Cl
Cl
3
N N
Ru
PCy33
CH2Cl2, Vacuum, 40oC, 14 hrsCl
Cl
n
Synthesis of Cyclic Polybutadiene
Mn = 88 k, PDI = 2.06
CDT conc. 2.92 mol/L
5 g cyclic polymer in 10 mL solution
80% yield
SEC chromatogram of cyclic polybutadiene and linear polybutadiene (narrow PDI prepared by anionic polymerization)
H Si Cl
Si
Cl
Example of grafting on 1,4-polybutadiene
Hydrosilation on backbone
Iraqi, A.; Seth, S.; Vincent, C. A.; Cole-Hamilton, D.; Watkinson, M. D.; Graham, I. M.; Jeffrey, D. Journal of Materials Chemistry 1992, 2, 1057-1064.
n
SiH
Karstedt's catalyst,800C, 24 hrs
Sim
Si
m
Si
m
Si
m
Si m
Si
m
Si
m
Si
m
Si
m
Si
m
Sim
Si
m
Si
m
Si
m
Si
m
Si m
Si
m
Si
m
Si
m
Si
m
Grafting of CyPBD with PS-SiH
0.24 mmols
SEC curves
10 15 20 25 30
Elution Volume (mL)
Lig
ht
Sc
att
eri
ng
Inte
ns
ity
RALS of CyPBD
RALS of PSSiH
RALS of Grafted Ring
SEC chromatograms of cylic polybutadiene, starting PS-SiH and grafted polymer.
Table 1 Molecular weight data of starting and grafted polymers
Sr.NoSample ID Mn (g/mol) Mw (g/mol) Mw/Mn
1 PS-SiH 8,300 8,300 1.01
2 CyPBD 88,400 182,600 2.06
3 Grafted Ring
2,004,000 12,410,000 6.19
Conclusion
• Cyclic polybutadiene was grafted with PS
• The cyclic nature was proven with the help of AFM
Preference for reduction over electrophilic addition by polyisobutylene cations
Vijay Chavan, Prof Roderic P.Quirk, Prof. Judit E. Puskas
Cationic Stability
Si
H
H
CF3COOH, CH2Cl2
OH
3-ethyl-3-pentanol
H
Carey, F. A.; Tremper, H. S. J. Org. Chem. 1971, 36, 758-761.
Reaction scheme
Hexanes: MeCl60 : 40
Si
H
Cl
TiCl4
TMPCl IB
VPDS Si
H
[DtBP]= 0.007 mol/L; [TMPCl] = 0.035 mol/L; [IB] = 0.577 mol/L; [VPDS]= 0.047 mol/L; [TiCl4]= 0.227 mol/L; [DMA]= 0.019 mol/L
GPC data
0
100
200
300
400
500
600
700
10 15 20 25 30 35
Retention Vol (mL)
RI d
etec
tor
resp
on
se
PIB-Cl
Part 2
Figure 1: GPC trace of PIB-Cl and Part 2 a) Refractive Index (RI) detector response b) Light scattering data.
GPC Light scattering
730
740
750
760
770
780
790
10 15 20 25 30 35
Retention Vol (mL)
RA
LS
PIB-Cl lightscattering
Part 2 lightscattering
Table 1: Molecular weight data
Mn
Base(GPC)(g/mol)
Mw base
(GPC)(g/mol)
PDIBase
Mn
Base(NMR)(g/mol)
Mn part 2
(GPC)(g/mol)
Mw
Part 2(GPC)(g/mol)
PDIPart 2
1,550 1,950 1.25 1,900 1,700 2,150 1.27
[DtBP]= 0.007 mol/L; [TMPCl] = 0.035 mol/L; [IB] = 0.577 mol/L; [VPDS]= 0.047 mol/L; [TiCl4]= 0.227 mol/L; [DMA]= 0.019 mol/L
B4P33 proton on 500 MHz newest 64 scans 5 s relax delay.esp
8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5Chemical Shift (ppm)
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
No
rma
lize
d In
ten
sity
312.505.802.00
CHLOROFORM-d
7.2
7
1.9
8
1.7
0
1.4
3
1.1
2
Figure 2: Proton NMR of PIB-Cl starting polymer
Cl
1.12
1.43
1.98
1.70
1.12
1.43
cdcl3_01
8 7 6 5 4 3 2 1Chemical Shift (ppm)
0.05
0.10
0.15
0.20
0.25
0.30
Nor
mal
ized
Inte
nsity
CHLOROFORM-d
7.27
1.70
1.43
1.13
1.01
Figure 3: Proton NMR of part 2.
H
1.12
1.431.70
1.12
1.43
B4P33 PIBCL C13 SPECTRA.ESP
104 96 88 80 72 64 56 48 40 32 24Chemical Shift (ppm)
0.05
0.10
0.15
0.20
0.25
0.30
No
rma
lize
d In
ten
sity
CHLOROFORM-d
77
.00
71
.71
59
.58
58
.89
58
.26
38
.19
37
.82
36
.02
35
.19
32
.61
31
.23
Figure 4: 13C NMR of PIB-Cl
Cl
31.2359.58
58.89
36.02
32.61
58.26
71.71
32.61
32.61 32.61 38.19
cdcl3_01
96 88 80 72 64 56 48 40 32 24 16Chemical Shift (ppm)
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
No
rma
lize
d In
ten
sity
CHLOROFORM-d
77
.00
59
.59
58
.90
58
.27
56
.64
55
.23
38
.21
36
.09
32
.52
31
.31
29
.61
25
.88
24
.23
Figure 5: 13C NMR of part 2
H
32.52
32.52
55.2358.2736.0931.31
38.21
59.59
36.09
24.23
32.52
32.52 31.31
Si
H
Cl
TiCl4Rate determining step
H
Si
+
TiCl5
Rapid
Si
Cl
+TiCl4
TMPCl IB
VPDS
Figure 6 : Mechanism
Conclusion of cationic polymerization
• Hydride transfer dominates over vinyl group addition
• No vinyl group addition
Acknowledgements• Prof. Roderic Quirk• Prof. Mark Foster• Prof. Judit Puskas• Prof. Scott Collins• Prof. Chrys Wesdemiotis, David Dabney, Aleer (MALDI)• Marcia Weidknecht, Prof. Isayev• Bob Ponton (Glass apparatus), Jack Gillespie• Ania Supady, Sachin Chavan, Family back in India• John Page (GPC), Venkat Dudipala (Si-NMR)• Mike Olechnowicz• Shih-Fan Wang• Camila, Jon, Elizabeth, Wenbin, Xinfei, Manuela,Sumana,• Lucas, Sham, Kurt• Friends in Akron
FundingRepsol YPF, SpainDynasol ElastomersFMC, Lithium DivisionChemetall Foote Corporation
• 1-Simms, J. A. Prog. Org. Coat. 1993, 22, 367-377
• 2- Grinstaff, M. W.; Wathier, M.; Joshi, N.; Stoddart, S., WO 2010033137, March 25, 2010
• 3- Findlay, P. H.; Rannard, S. P.l; Royles, B. J.; Weaver, J.V., WO 2009144471 , Dec 3, 2009
• 4- Taketsuji, K.; Yokoyama, S.; Otomo, A., JP 2009249500 , Oct 29, 2009
• 5- Xie, D., WO 2009129221, Oct 22, 2009
• 6-Du Fresne V.H.; Schoenfelder, D.; Bruchmann, B.; Schroeder, M.; Schumacher, K.; Terrenoire,
• A., WO 2009109622 , Sept 11, 2009
• 7-Nakayama, Y.; Nemoto, Y. , JP 2008086558, Apr 17, 2008
• 8- Wang, Y.; Gale, D.C.; Huang, B.; Trollsas, M. O.; Glauser, T.; Ludwig, F. , US 20070282435 , Dec 6, 2007
Applications of branched polymers references
References
• (1) Quirk, R. P.; Chen, W. C. Makromol. Chem. 1982, 183, 2071-2076• (2) Quirk, R. P.; Kim, H.; Polce, M. J.; Wesdemiotis, C. Macromolecules• 2005, 38, 7895.• (3) Roovers, J. Polym. Prepr.(Am. Chem. Soc. Div. Polym. Chem.)1989, 30• (1), 77-78.• (4) Um, J.; Park, J.; Lee, M. Annual Technical Conference - Society of• Plastics Engineers 2006, 64th, 436-440.• (5) Gilman, H.; Cartledge, F. K. J. Organomet. Chem. 1964, 2, 447.• (6) Bielawski, C. W.; Benitez, D.; Grubbs, R. H. Science 2002, 297, 2041-• 2044.• (7) Bielawski, C. W.; Benitez, D.; Grubbs, R. H. J. Am. Chem. Soc. 2003,• 125, 8424-8425.• (8) Schappacher, M.; Deffieux, A. Science 2008, 319, 1512-1515.• (9) Iraqi, A.; Seth, S.; Vincent, C. A.; Cole-Hamilton, D. J.; Watkinson, M.• D.; Graham, I. M.; Jeffrey, D. J. Mater. Chem. 1992, 2, 1057-1064• (10) Furstner, A.; Ackermann, L.; Gabor, B.; Goddard, R.; Lehmann, C. W.;• Mynott, R.; Stelzer,F.; Thiel, O. R. Chemistry--A European Journal 2001• 7, 3236-3253.