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

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