polyurethanes: the case for renewable succinic acid...
TRANSCRIPT
Polyurethanes: The Case for Renewable Succinic Acid Based Polyester Polyols
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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
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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
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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
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May
-06
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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
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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
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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