sustainable materials based on aliphatic polyesters,iasc...
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DR. S. SIVARAMA 201, Polymers & Advanced MaterialsLaboratory, National Chemical Laboratory,Pune-411 008, INDIATel : 0091 20 2589 2614Fax : 0091 20 2589 2615Email : s.sivaram@ncl.res.in
SUSTAINABLE MATERIALS BASED ON ALIPHATIC POLYESTERS : TEACHING OLD
CHEMISTRY SOME NEW TRICKS
Indian Academy of Science, Bangalore
Mid-Year Meeting
July 5, 2013
-
SUSTAINABLE DEVELOPMENT (CHEMISTRY)
“ Development (chemistry or chemical industry) that meet the needs of the
present without compromising the ability of future generations to meet their
own needs”
In other words, each generation must bequeath to its successor at least as
large a productive base it inherited from its predecessor
Brundtland Report
UN World Commission on Environment and
Development, 1987
www.un.org/documents/ga/res/42/ares 42-187.htm
We do not inherit the earth from our ancestors; we borrow it from our children.
Native American Proverb
-
ORGANIC CHEMICALS AND MATERIALS
• Exclusive dependence on fossil fuelbased resources
• Generation of wastes that need disposal
Can the chemical and materials needsof humankind be based on the concept
of sustainability of both
resources and environment?
RIL, Mumbai 281205
REDUCE
REUSERECYCLESustainability is the key concern of science, technology,
industry and society today
-
Over 30 billion
liters of bottled water is
consumed annually
Every second we throw away about
1500 bottles
What is the
solution ?
Poly( ethylene terephthalate)
-
FROM HYDROCARBONS TO CARBOHYDRATES : FROM NON
RENEWABLES TO RENEWABLES
Can a part of the chemicals / materials manufacturing progressively shift
to renewable carbohydrate resources (biomass) ?
RIL, Mumbai 281205
Biomass
Chemicals
Materials
Carbon dioxide
Water
Is such a virtuous cycle just a dream ?
-
Objectives
Expand the chemistry toolbox with new methods and techniques for next generation products
SUSTAINABLE POLYMERS FROM BIO-DERIVED AND
BIO-RENEWABLE RESOURCES
Materials Platform
Aliphatic Polyesters
-
Aliphatic polyesters
C
O
(CH2)m C
O
O (CH2)n O
x
C
O
C
CH3
H
O
n
C
O
(CH2)5 O
n
C
O
C
O
O CH2 CH2 O
n
C
O
C
O
O (CH2)n O
m
C
O
C
O
O CH2 CH2 O
m
C
O
C
O
O (CH2)n O
m
C
O
C O
O
O
n
Aliphatic-Aromatic polyesters
Fully Aromatic polyesters
GENERAL CLASSES OF POLYESTERS
n : 2 PETn: 2 PBT
60 million tons per annum; One third goes for making bottles !
< 200,000 tons per annum !
-
POLY (LACTIC ACID )S : AN ALIPHATIC
POLYESTER FROM THE MOST SIMPLE AB MONOMER
Insoluble in water, moisture and grease
resistant
Biodegradable and compostable
Clarity and glossiness similar to PET
Requires 20 to 50% less fossil fuels to
produce than PET
Physical properties similar to PET
-
� Patents
� Publications
� Patents
� Publications
POLY(LACTIC ACID)
51
6
53
2
65
1
91
1
93
1
11
73
13
77
16
33
19
07
19
30 2
00
6
20
14
23
02
11
90
33
1
41
7
63
7
71
2
82
0
10
44
12
02 1
28
4
14
93
16
15
18
24
19
99
19
99
49
8
0
500
1000
1500
2000
2500
2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013
Publication Year
No
. o
f P
ate
nts
/Pu
bli
cati
on
s
-
ALIPHATIC POLYESTERS
� Patents
� Publications
� Patents
� Publications
Publication Year
No
. o
f P
ate
nts
/Pu
bli
cati
on
s
40
4
39
5
39
9
48
0
53
2
52
9
44
8 46
3
49
8
53
5
51
1
45
3
56
0
27
3
10
6
14
2
11
9
14
1
15
9
16
2
18
0
16
8 17
7
17
8
18
2
18
3
17
9
89
0
100
200
300
400
500
600
2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013
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ALIPHATIC POLYESTERS : PIONEERING CHEMISTRY OF
WALLACE HUME CAROTHERS
1896-1937
STUDIES ON POLYMERIZATION AND RING FORMATION
Twenty eight papers from 1929 to 1935
Carothers addressed one important question:
(a) If two bifunctional molecules, e. g., one dibasic acid and one glycol or diamide, react, two possibilities occur. The reaction can result (1) in a chain polymer of lower or higher molecular weight, which still bears either hydroxyl or carboxyl terminal groups or (2) in a smaller or larger ring, which does not contain the reactive group.
Under what conditions does either of these two possibilities take place and what is the molecular weight of the resulting compound?
Published 1940
54 papers400 pages
Enough forone lifetime !
-
CAROTHER’S DELINEATION OF POLYMERIZATION OF
HYDROXY CARBOXYLIC ACIDS
1 α-hydroxy acetic acid
(Glycolic acid)
2 β-Hydroxy Propionic acid
3 γ-Hydroxy butyric acid
4 δ-Hydroxy pentanoic acid
5 ε-Hydroxy Caproic acid
+ Oligomers
+ Oligomers
+ Oligomers
+ Oligomers
Ref. : Carothers, Chem Rev; 8 353 (1931)
-
IX. Polymerization*
TABLE OF CONTENTS
I. Definitions1. Current definitions2. Proposed definitions3. Linear and non-linear polymers 4. Types of compounds capable of
polymerizing 5. Types of polymerization 6. Condensation polymerizations and
bi functional reactions II. Condensation polymerization
1. Polyesters a. The self- esterification of hydroxy
acids 86b. Polyesters from dibasic acids
and glycols 90
* Wallace H. Carothers; Chemical Reviews
8, 353-426 (1931); Communication No. 55 from the Experimental Station of the E. I. du Pont de Nemours and Company.Received March 21, 1931. Published June 1931.
Key questions
� On what factors do the relative
rates k1 and k2 depend ?
� What is the importance of general
acid catalysis in these reactions?
� Can larger oligomers undergo
thermolysis to large rings?
� If ring formation limits chain growth
reaction, is there an alternative
method to make high molecular weight linear aliphatic polyesters ?
-
DIRECT CATALYTIC POLYCONDENSATION OF L(+)- LACTIC
ACID
CH O
O CH
H3C
CH3
O OLewis acid
heat-----(2)
nC O CH C OH
CH3
OO
CH
CH3
HO__
-----(1)HO CH C OH
CH3
O
H O CH C OH
CH3
OnH2O
Lewis acid
Issues
� Water tolerant Lewis acid catalyst
� Water removal is rate limiting
� Reversible ester hydrolysis of polymer
� Competing lactide and macrocycle
formation : Loss of reactive end groups
CH O
O CH
H3C
CH3
O OLewis acid
heat-----(2)
nC O CH C OH
CH3
OO
CH
CH3
HO__
-----(1)HO CH C OH
CH3
O
H O CH C OH
CH3
OnH2O
Lewis acid
CH O
O CH
H3C
CH3
O OLewis acid
heat-----(2)
nC O CH C OH
CH3
OO
CH
CH3
HO__
-----(1)HO CH C OH
CH3
O
H O CH C OH
CH3
OnH2O
Lewis acid
Water Tolerant Lewis Acid
CH O
O CH
H3C
CH3
O OLewis acid
heat-----(2)
nC O CH C OH
CH3
OO
CH
CH3
HO__
-----(1)HO CH C OH
CH3
O
H O CH C OH
CH3
OnH2O
Lewis acid
-
O CHH
CH3
C
O
OH
n
n = 5 - 24< 150 oC
150 - 190 oC O CHH
CH3
C
O
OH
n
n = 14 - 30
O CH
CH3
C
O
n
+
> 190 oC O CH
CH3
C
O
n
n = 13 - 40
solvent Temp. C Conv.,% Lactide,% Mn,VPO Mw/Mn
Xylene 143 96 Nil 800 2.0
Mesitylene 165 76 27 1800 4.0
Decalin 190 82 15 5500 4.7
Mixtures of linear and cyclics
Exclusively cyclics !
Oligomer structures
established by 13 C NMR and
MALDI TOF MS
DIRECT CATALYTIC POLYCONDENSATION OF L(+)- LACTIC ACID
Shyamroy, Garnaik and Sivaram, J. Polymer Science: Part A: Polymer Chemistry, 43,2164 (2005)
-
SYNTHESIS OF PBA BY POLYCONDENSATION OF DIMETHYL ADIPATE (DMA) AND 1,4-BUTANEDIOL (BD)
Transesterification reaction
Polycondensation reaction
Stage 2
Stage 1
+ (CH2)4 OHHO(CH2)4 CCCH3O OCH3
O O
+(CH2)4 CCO O
O O
(CH2)4 (CH2)4HO OH CH3OH2
(CH2)4 CCO O
O O
(CH2)4 (CH2)4HO OHn
+(CH2)4 CCO O
O O
CH3 (CH2)4 O Hn(n-1) (CH2)4 OHHO
Back-biting reaction
Ring-closure reaction
THF formation
C
O
(CH2)4 C O
O
CH2CH2
CH2
CH2HO
O
C
O
(CH2)4 C
O
OH+
O (CH2)4 O C
O
(CH2)4 C
O
HO OCH3n nO (CH2)4 O C (CH2)4 C
O O
O C
O
+
OH
C
O
(CH2)4 C
O
O (CH2)4 O OHn
O (CH2)4 O C (CH2)4 C
O O
O C
O
n
All these reactions result in loss of end groups needed for
chain growth reaction
-
17
EFFECT OF REACTION TEMPERATURE ON POLYCONDENSATION REACTION
No. Temp. (0C)
Conv.a
(%mol)Conv.b
(%)Yield c
(% wt.)THF d
(%mol) Mn
e
(VPO) Mw/Mn
e Tme
(0C) Tc
e
(0C)
1 125 88 95 27 3.0 3980 1.6 58 22
2 150 92 97 75 3.7 7060 1.5 60 25
3 180 94 98 85 3.7 9010 1.5 61 20
4 200 95 97 86 4.4 7720 1.6 60 21
5 220 93 98 86 3.8 8120 1.6 61 21
a : conversions based on moles of methanol formed as determined by GC
b : % conversion calculated using the Carothers equation Xn = 1/1-p
c: yield of methanol insoluble fraction calculated based on the total weight of polymer obtained
d :THF calculated based on moles of BD from GC; e- Mn , Mw/Mn , Tm & Tc of methanol insoluble fraction
Neeta Kulkarni, PhD Thesis, 2007
-
18
Peak End group Structure
a hydroxy-ester
b hydroxy-hydroxy
c ester-ester
d No end group
e carboxy –hydroxy
H BA OCH3n
H BA O (CH2)4 OHn
C
O
(CH2)4CCH3O
O
BA OCH3n
(CH2)4
[BA]n O
O (CH2)4
O
O
H BA OHn
• MALDI-ToF MS analysis shows formation of varying amounts of cyclic oligomers and carboxylic end groups which result in loss of end groups and thereby limiting further step growth polymerization
• Cyclics of DP : 2 were detected even at 1250C whereas cyclics of DP 2 to 12 were detected at 180-2200C
• Structure of the oligomers changes from linear oligomers with hydroxy-ester end groups to cyclics with no end groups
MALDI-TOF MS of PBA, 1250C
MeOH Insoluble MeOH soluble
-
RING OPENING POLYMERIZATION OF CYCLIC ESTERS
Only practical way to polymerize glycolic or lactic acid is via their corresponding cyclic esters
-
GENERAL ACID CATALYZED SELF POLYMERIZATION OF LACTIC ACID
� Commercial 90 % lactic acid in water contains : HL = 60 % HL2+ oligomers = 27 % and LL = 13 %� Purification by crystallization possible only via Lactide� Lactide has a mp 96 0C and sublimes� Difficult to copolymerize Lactide by any other mechanism except ROP� Methyl Lactate is a volatile liquid with a bp of 144 0C
General Acid Catalysis
Need An AB monomer, which has a bp above 250 0C, high vapor pressure, easily
purified, hydrophobic , preferably a methyl ester
-
SYNTHESIS OF A LINEAR DIMER FROM L(+)-LACTIC ACID
AND METHYL-L-LACTATE
60 %
4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600.0
7.5
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200.1
cm-1
%T
-C=O
-OH
-C-H stretching
-C-O stretching
3441.77
2991.79 1456.04
1376.66
1227.07
1205.88 1130.85
1098.51
1047.71
977.73
919.60
823.32
681.09
Tue5av2#047.001.001.1r.esp
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 0.5 0Chemical Shift (ppm)
0.220.042.204.690.780.222.483.000.041.121.050.16
0.0
0
1.4
51
.49
1.5
21
.55
1.5
81
.66
1.7
61.7
9
2.1
4
3.2
4
3.7
63
.83
4.2
94.3
24
.35
4.3
94
.42
5.1
45
.18
5.2
15
.25
7.2
8
• bp : 107 0C at 5 mm• Can be purified by distillation
-
TRANS-ESTERIFICATION OF LINEAR DIMER
Titanium IsopropoxideTwo stage polymerization150-190 0C
Negligible Cyclization !
Neware and sivaram, research in progress
-
SYNTHESIS OF HIGH MOLECULAR WEIGHT LINEAR
ALIPHATIC POLYESTERS
� Coupling of preformed oligomer chains with suitably disposed end groups� Converting a reversible chain growth reaction into an irreversible reaction� Use of conformationally constrained cyclo-aliphatic diacid or diol monomers
-
HOMO COUPLING OF POLY(ACTIC ACID)S OLIGOMERSACTIVATED POLYCONDENSATION
O
O
H3C
O
H
H
15DP = 15
O
O
H3C
O
H
H
500
DIPC
DPTS (0.1 eq.)
CH2Cl2, 300C, 12 h
Mn increases from 15,000 to 50,000 !
RCOOH R' N C N R'+
R' NH C N R'
O C
O
R
R"OH
R' NH C
O
NH R' RCOOR"+esterurea
Shyamroy, Garnaik and Sivaram, Polymer Chemistry , 2013
-
CHAIN TERMINATION VIA N-ACYL UREA FORMATION
M = (CH3)2CH-NH-CO-N(CH(CH3)2)-(CO-CH(CH3)-O)n-H-----Na+
= 72n + 143 + 23Also 72n + 143 + 39 found (K+ )
M = (CH3)2N-C5H10NH+ -O-(CO-
CH-(CH3)-O)n-H-----Na+
= 72n + 51 + 23Also 72n + 51 + 39 found (K+ )
R N H C N R O C
O
R'
6.9 (O - acylurea) 6.9'(N - acylurea)
R N H C N R
C R'
O O
-
SYNTHESIS AND CHARACTERIZATION OF HYDROXYL
TERMINATED POLY(BUTYLENE ADIPATE)
1,4 Butanediol/Titanium isopropoxide
1500C /30 min
OO
O
O
n
OHPBAHO
HOO
O
O
OO
H
n
HOOH + CH3O
O
O
OCH3Titanium isopropoxide
1500C
(5)
ηinh in chloroformat 250C (dL/g)
Mn(VPO)
Mn(31P NMR)
Mn (GPC) Mw(GPC)
Mw/Mn Tm(0C)
0.211 2700 2430 7600 11,900 1.57 55
•Concentration of hydroxyl end groups as determined by 31P NMR was found to be 8.232 x 10-4 mol / g, corresponding to 1.9 hydroxyl groups per molecule
• The telechelic oligomer was found to be thermally stable up to 2000C by TGA.
-
27
Repeat unit structure
Sum of end groups (observed)
Structure of end groups
Series
89-91 1114,1314,1513,…Na+ adduct
89-91 1130,1329,1530,…K+ adduct
33-34 1056,1456,1656,…Na+ adduct
O (CH2)4 O C
O
(CH2)4 C
O
n
H BA OCH3n
H BA O (CH2)4 OHn
H BA O (CH2)4 OHn
Poly(butylene adipate) oligomers contain mainly chains with hydroxyl end groups along with small amounts of hydroxy ester end groups
END GROUP ANALYSIS OF PBA TELECHELIC BY MALDI-TOF MS
-
CHAIN EXTENSION WITH DIVINYL ADIPATE : FIRST
EXAMPLE OF IRREVERSIBLE POLYCONDENSATION
The reaction by product cannot reactwith the growing polymer chain !
GPC of telechelic and the polyester chain extended with divinyl adipate (DVA)
+OOH
O
O
O
OH
n
OO
O
O
n
OO
O
O
O
OO
O
O m
OO
O
O+
OHCH3 CHO
Mn : 2700
Mn : 36,500, Tm: 59°°°° C
Neeta Kulkarni and Sivaram, Macromol. Chem, 2013
-
HO (CH2)n OH n = 3, 3, 4
CH2OH
CH2OH
CH2OH
CH2OH
CH2OHHO2HC
CH2OH
HOH2C OHHO
OHHO
CH2OH
CH2OH
CH2OH
CH2OH
CH2OH
CH2OH
CH2OHHOH2C CH2OHHOH2C
ALIPHATIC POLYESTERS BASED ON CONFORMATIONALLY
CONSTRAINED MONOMERS
CC
O O
OHHOCC
O O
OCH3H3CO
C
O
OH
C
O
HO
C
C
O
O
OCH3
OCH3
C
O
OCH3
C
O
OCH3
C
C
O
OCH3
O
OCH3
DIOLS
DIACIDS
-
Sandhya, Ramesh and Sivaram, Macromolecules, 40, 6906 (2007)
ALIPHATIC POLYESTERS: SYNTHESIS
(i) Transesterification 180-230°C/6-10h(ii) Polycondensation 210-260°C/10-12 h/0.02 mbar
(i), (ii)
COOCH3
COOCH3
COOCH3H3COOC
OC COO (CH2)4 O( )n+
COOCH3
H3COOC
(CH2)4 OHHO
(
)n
COO
OC
(CH2)4 O
n)( OC COO (CH2)4 O
Catalyst : Titanium Isopropoxide
-
STRUCTURE –PROPERTY RELATIONSHIPS IN ALIPHATIC
POLYESTERS
ee: ae Mn Tm, ºC Tg, ºC IDT, ºC
100 20,000 163 31 403
70:30 16,500 56 -10 400
cis: trans Mn Tm, ºC Tg, ºC IDT, ºC
100 57,000 - -44 400
50:50 36,000 - -15 408
cis: trans Mn Tm, ºC Tg, ºC IDT, ºC
100 36,000 - -24 500
Mn Tm, ºC Tg, ºC IDT, ºC
exo-endo
37,000 - -56 480
-
� Slow rate of crystallizationAnnealing and cold crystallization
Nucleation
� Very brittle material ; Elongation : 3-4 %, Plasticization
Copolymerization
� Poor heat stabilityStereo-complexation
Copolymerization
� Poor chain entanglement in melt state leading to poor melt viscosities
CSIR Proprietary
PLLA : MAJOR PROPERTY DEFICITS AND METHODS FOR
IMPROVEMENT
CrosslinkingBranching
-
ISOSORBIDE: A BIO DERIVED RENEWABLE MONOMER
Hydrogenation
Acid catalyzed dehydration
-
L(+) LA- ISOSORBIDE COPOLYMER : SYNTHESIS
B. B. Idage, S.B. Idage and Sivaram, WO 151843, 2012 ( covered in US, Europe, China and Japan)
Mn : 80,000Melt or Solution70 to 150 o C
ROP
Solid State Polymerization (SSP)
150 o C, 2- 4 h
Mn : 39,000
Mn : 69,000
-
5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0
0.670.20 0.030.020.01
1.6
0
1.6
4
5.1
55.1
8
5.2
25.2
5
3.8
0
3.8
33
.853
.883.9
03.9
23
.94
3.9
7
3.9
94.0
1
4.0
7
4.3
4
4.3
8
4.4
1
4.4
4
4.4
6
4.4
9
4.8
3
4.8
6
4.8
8
1
2
7,43,8
6,5
δ ppm
1H NMR SPECTRA OF PLA-ISOSORBIDE COPOLYMER IN CDCL3
Isosorbide Content : 9 %
Mn Tm,˚C Tg, ˚C
Before SSP 39,000 140 40
After SSP 69,000 185 60
-
SYNTHESIS OF STAR BRANCHED POLY( LACTIC ACID)S IONOMER
Sn(Oct)2
1800C, 1 h+
+ DCM , 12h, 25˚C
NaH, THF, 25 ˚C
Mn : 18,000Mw / Mn; 1.13
mol ratio : 170 : 1
-
Acid
Ionomer
32 31 30 29 28 27 26
28.4
928.6
1
178 177 176 175 174 173 172 171 170 169 168 167 166
169.6
2
171.6
2
175.1
5
175.8
2
178 177 176 175 174 173 172 171 170 169 168 167 166
169.6
2
172.3
9
175.1
7
176.5
9
32 31 30 29 28 27
29.1
6
29.4
8
c
c
k
j.j’
k
f
f j.j’
-
15 20 25 30
0
10
20
30
40
50
60
RI (m
V)
Retension volume (mL)
sPLLA7
sPLLA7acid2
sPLLA7ionomer2
0.1 1 10 100
102
103
104
105
G',
G''
(Pa
s)
S train (%)
Amruta, Sivaram and Lele, research in progress
- -
-
- -
-
-CO2- Na
-CO2H
-OH
MOLECULAR WEIGHT DISTRIBUTION, STORAGE MODULUS AND
COMPLEX VISCOSITY OF STAR BRANCHED PLLA IONOMERS
-
Financial Support
� J.C.Bose Fellowship (DST)� S.S.Bhatnagar Fellowship (CSIR)� CSIR’s TAPSUN Programme
Acknowledgments
Students
Dr. Sandhya ShankarDr S. ShyamroyDr Neeta KulkarniMr Yogesh NevareMs Amruta KulkarniMegha DeorkarMaithili DumbreMs Dipti Lai
Acknowledgments
Colleagues
Dr B.B.IdageDr Ms. B. GarnaikDr.Ashish Lele
-
THANK YOU
-
0.1 1 10 100
10
100
1000
10000
Mo
du
lus
G'
&
G"
(Pa
)
Strain (%)
IonDCM+Py(10)12hr
IonDCM+Py(10)12hrrep
IonTHF(1.5)12hr
IonTHF(1.5)24hr
IonTHF(5)12hr
IonTHF(5)12hrrep
Strain Sweep
-
0.01 0.1 1 10 100
10
100
1000
10000
IonDCM+Py(10)4days
IonDCM+Py(10)4daysrep
IonTHF(1.5)24hr
IonTHF(5)12hr
IonTHF(5)12hrrep
Frequency (rad/s)
Frequency Sweep
-
Click reaction on D(+)Click reaction on D(+)--Glucose Glucose propargylpropargyl ether ether using using azidoazido--terminated PLGA terminated PLGA
Click reaction on D(+)Click reaction on D(+)--Glucose Glucose propargylpropargyl ether ether using using azidoazido--terminated PLGA terminated PLGA
� Reaction control : Excellent
� Homogeneous, low temp.
reaction
� Well defined structure
� Reaction control : Excellent
� Homogeneous, low temp.
reaction
� Well defined structure
nm
n
m
-
Poly(DLPoly(DL--LactideLactide--coco--glycolideglycolide))--glucose glucose
1H-NMR (500 MHz) Spectrum of Poly(D,L)Lactic-glycolicAcid - Star glucose (Mw ~30kDa) polymer in CDCl3 (55% Lactide/ 45% Glycolide mole ratio)
FTIR : cast-film on KBR salt-plate in transmission mode.
Polymer Mn (GPC) Mw (GPC) PDI
PLGA-Glucose 13635 19942 1.46
GPC analysis Poly(D,L)Lactic - Glycolic Acid - Star glucose copolymer in DCM using Polystyrene standards)
-
5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5
467.51144.40 10.976.00 3.22
1.5
5
3.3
34.1
4
4.3
4
5.1
5
Star PLA-1H
c
b
e
f
a+d
-
5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5
467.51144.40 10.976.00 3.22
1.5
5
3.3
34.1
4
4.3
4
5.1
5
Star PLA-1H
c
b
e
f
a+d
-
sPLLA3 1H
c
5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5
1227.66391.70 8.606.00 2.43
1.5
8
3.3
4
4.1
54.3
7
5.1
8
b e
f
a+d
-
5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5
1219.41395.00 24.9511.03 3.962.51
1.5
9
2.7
2
3.3
5
4.1
5
4.3
8
5.1
9
sPLLA3acid 1H
c
b
f
g+g’
a+d
e
-
Ionomer 1H
5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5
1257.99395.00 16.98 16.4810.44 1.92
1.5
6
2.6
4
3.3
44.1
4
4.3
5
5.1
7
c
b
e fg+g’
a+d
-
sPLLA3 13C
c
hg
a
e
d
b
f
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10
16.6
2
20.5
0
43.3
4
62.7
5
66.6
9
69.0
0
77.0
4
169.5
9
175.1
1
-
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20
16
.63
20
.50
28
.61
66
.69
69
.01
sPLLA3acid 13C
77
.05
16
9.6
2
17
1.6
2
17
5.1
5
17
5.8
2 a
e
j,j’
gh
b
df
c
k
CDCl3
-
75 70 65 60
395.00 7.80
66
.69
69
.00
75 70 65 60
395.00 2.97
66.6
9
69.0
1
d
d
b
b
sPLLA3 13C
sPLLA3acid 13C
-
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20
16.5
8
20.3
9
29.3
9
66.6
0
68.9
5
77.0
5
169.5
4
172.3
1
175.0
9176.1
0
sPLLA3ionomer 13C
ck
f
d
b
g
j,j’
h
a
e
-
ppm
2.53.03.54.04.55.05.5 ppm
168
170
172
174
176
178
sPLLA3ionomer 2D expt
c
f
k
-
Objectives
Perform curiosity-driven and use-inspired research to expand the sustainable
chemistry toolbox with new methods and new techniques for next generation
products
SUSTAINABLE POLYMERS FROM BIO-DERIVED AND
BIO-RENEWABLE RESOURCES
Materials Platform
Aliphatic Polyesters
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