Polyurethanes: The Case for Renewable Succinic Acid Based Polyester Polyols

2

Succinic Acid Polyols

• Renewable content up to 100% based on choice of diol

• Comparable performance to adipic polyols

• Price competitive with adipic polyols

• Long term stability of raw material pricing

• Smaller carbon footprint

3

Application Areas for Polyester Polyol Testing

Cast Elastomers

251 kMT SAC

Coatings and Adhesives

115 kMT resin

TPU

95 kMT SAC

Specialty Flexible Foams

27 kMT SAC

Shoe soles, belts, hoses

Industrial and Consumer Paints and adhesives,

Polyurethane dispersions, 2K coatings

Belts, hoses, wheels, medical, shoes,

electronics

Reticulated foam, laminated foams

Adipic/EG, Adipic/DEG, Adipic/BDO, Adipic/HDO f~ 2.0

OH # 110

Adipic/DEG f ~2.4-2.7 OH # 56

SAC/EG, SAC/DEG, SAC/BDO, SAC/HDO f ~ 2.0

OH # 110

SAC/DEG f ~ 2.4-2.7 OH # 56

Typi

cal

End

Use

A

pplic

atio

n A

rea

Incu

mbe

nt

Com

posi

tion

Myr

iant

Te

sted

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Myriant Development Partnerships

Google Maps Image

Contract research laboratory • Polyurethanes, coatings, polymers • Formulation development • Polymer and product design • Performance characterization

Polymer manufacturing • Lab scale • Pilot scale • Commercial scale • Polyester polyols • Specialty additives

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Polyurethane Synthesis

• Basic laboratory formulation to highlight performance differences between succinic and adipic based polyester polyols

• Desmodur N3200 • Liquid aliphatic isocyanate

• 23.0 % NCO, Viscosity 2500 cPs, f ~3.2

• Components (polyol + catalyst and isocyanate) preheated to 70 °C

• 1 minute mixing time, overnight cure at 85 °C

OCNNH N NH

NCO

O O

NCO

6

Foams Coatings, Adhesives, Elastomers, TPU’s

Acid Succinic Adipic Succinic Adipic Succinic Adipic Succinic Adipic Succinic Adipic

Code Number DGTA-56 AGTA

Control DGTB-56

AGTB Control

EG-110 AEG

Control DG-110

ADEG Control

HD-110 AHD

Control

Diol DEG (90)/ PEG (10)/

TMP DEG/TMP

DEG (90)/ PEG 10)/

TMP DEG/TMP EG EG DEG DEG HDO HDO

Functionality Branched (f ~ 2.4) Branched (f ~ 2.7) Linear Linear Linear

OH Number 61 76 64 60 107 90 113 116 108 95

Viscosity, (60 °C, cPs) 3150 440 4000 1340 400

(80°C) 415 440 250 450 450

Bio-based Carbon Content 47% 0% 47% 0% 66% 0% 50% 0% 40% 0%

Properties of Polyester Polyols

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Properties of Polyester Polyols

Higher Tg for succinic acid based polyurethanes

Diol Succinic Adipic

EG -6 °C -30 °C

DEG -12 °C -29 °C

BDO -16 °C -38 °C

HDO -33 °C -44 °C

Tg for test polyurethanes made from polyester polyol indicated. Second scan at 10 °C/min.

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Properties of Polyester Polyols

Comparable Tensile Properties across all compositions

0

50

100

150

200

250

300

AA/DEG SA/DEG AA/HDO SA/HDO

Brea

k St

ress

(psi

)

Break Stress (psi)

0

200

400

600

800

1000

1200

1400

1600

1800

2000

AA/DEG SA/DEG AA/HDO SA/HDO

Tens

ile M

odul

us (p

si)

Modulus (psi)

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Properties of Polyester Polyols

Comparable Shore D hardness for polyurethanes

Diol Succinic Adipic

DEG/TMP 16 17

BDO 28 21

DEG 20 20

HDO 16 25

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Physical Property Comparison - Conclusions

• Succinic polyurethanes have higher Tg’s than adipic polyurethanes, but will still perform well at a broad range of temperatures

• Mechanical properties are comparable • Shore A and D hardness, Tensile properties, Tabor abrasion

• Succinic polyester polyols have slightly higher viscosities, but still processable

• Succinic acid polyurethanes are better than Adipic acid for: • Chemical resistance

• Abrasion resistance

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Bio Succinic versus Adipic Acid Market Price

Adipic acid market price:

Highly volatile, with generally increasing trend since 2006

Succinic acid formula price:

Lower volatility than adipic market price and roughly equal average price over the period.

Green line: Historical adipic acid prices from PCI Nylon report

Blue line: Example of corn-based succinic acid

Corn-based formula pricing offers comparable average price and more stability than historic adipic acid market pricing

0

20

40

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80

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120

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160

180

May

-06

Nov

-06

May

-07

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-07

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-08

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-08

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-09

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-11

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-12

Pric

e, U

S$/lb

, Nor

mal

ized

to M

ay 2

006,

Adi

pic

Aci

d =1

00

Adipic Acid

Succinic Acid

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Life Cycle Analysis: Myriant Bio Succinic Acid Production

Greenhouse gas reduction: • 94% compared to Petro-based Succinic Acid • 93% compared to Petro-based Adipic Acid

Reduced Carbon Footprint

2.98 2.6

0.18

-0.41 -1.00 -0.50 0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50

Petro-Succinic Acid

Petro-Adipic Acid

Bio-Succinic Acid

Bio-Succinic Acid with

Integrated Heat and

Energy Balance

kg C

O2-

eq/k

g Su

ccin

ic A

cid

* Life Cycle Analysis of Bio-Succinic Acid production using the IPCC 2007 (GWP) method

14

Succinic Acid Polyols

• Renewable content up to 100% based on choice of diol

• Comparable performance to adipic polyols

• Price competitive with adipic polyols

• Long term stability of raw material pricing

• Smaller carbon footprint

15

Not All Chemicals Are Created Equal™

• Bio-Succinic Acid Process Has Low Greenhouse Gas Emissions

94% Less Than Petrochemical Succinic Acid* 93% Less Than Petrochemical Adipic Acid*

• Renewable Feedstocks Are Less Expensive And Less Volatile Than Petroleum

• Efficient Fermentation And Downstream Processes Optimize Production Costs

• Feedstock Can Be Sorghum (Non-Food) Based Or Corn Based

• Drop-In Replacement Anywhere Succinic Acid Is Currently Being Used

• Replaces Petroleum Based Chemicals In Urethane, Plasticizer, Coatings And Polymer Applications

* Life Cycle Analysis of Bio-Succinic Acid production using the IPCC 2007 (GWP) method