Susterra presentation - CPI 2009.pdf - DuPont Tate & Lyle

Polyurethanes 2009Technical Conference

Susterra® Propanediol – From the Leading Edge of Biotechnology,a Renewable and Sustainable Building Block for the Urethane Industry

A Collaboration Between:

National Harbor, MDOctober 5 - 7, 2009

DuPont Tate & Lyle BioProducts Confidential

2Acknowledgement

Sergio Franyutti

Tom Clark

Andy Schuster

Bryan Healy

Anna Hilpipre

Dawn Hamilton

Linda Tish

Alan Riby

Joe DeSalvo

Ed Miller Jr.

Bob Miller

Judith van Gorp

Gyorgyi Fenyvesi

Steve Hurff

Matt Page

Ron Rawlins


3A Successful Collaboration…

Founded in 1988 in central Iowa, ITWC Urethane Solutions initially produced prepolymers for the production of urethane tires. Since that time, ITWC constructed a state-of-the-art polyester polyol plant and has developed into a major prepolymer and urethane system supplier in North America.

DuPont Tate & Lyle Bio Products, a joint venture formed in Loudon, TN 2004, provides renewably sourced Susterra®1,3-propanediol (Bio-PDO™) from corn sugar, a sustainable & renewable resource. Susterra® delivers superior functionality and enables our customers to offer renewable, natural and sustainable products.


4Agenda

• Backround• Susterra® propanediol: from a renewable source via a small footprint

• PolyUrethanes: diol chemistry for cast elastomers

• Experimental/Results• Susterra® propanediol as curative in MDI / Polyester Polyol Prepolymers

– Comparison of Susterra® and 1,4-butanediol

• Susterra® propanediol as monomer in MDI / Polyester Polyol Prepolymers

– Comparison of Susterra®, ethylene glycol, and 1,4-butanediol

• Susterra® propanediol as monomer in Aromatic Polyurethanes

– Comparison of Susterra® and ethylene glycol

• Conclusion & Path Forward• Susterra®: performance beyond “green”

HO OHHO OH


5

1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 20052004 2006 2007

History of Bio-PDO™ Development– A Highly Collaborative Endeavor

Broad Biocatalyst Patent Allowed

Genencor-DuPont collaboration started

Gen II biocatalystmilestone

Commercial biocatalyst delivered

Gen I biocatalystmilestone

PDO Genes Isolated

Tate & Lyle-DuPontJoint Venture started

Process development team formed

Polymer-grade Bio-PDO

Ground breakingLoudon, TN

100MM ppy Loudon plant start up

Detailed engineering design started


6

(Bio-derived 1,3-Propanediol)GlucoseCorn

Fermentation process using patented biocatalyst

Refinementto 99.7% purity

Process to Susterra® Propanediol

Susterra®

CO2

bioprocessbioprocess

Susterra® propanediol is a renewably sourced offering from DuPont Tate & Lyle Bio Products and manufactured via a proprietary corn sugar fermentation process.


7100% Bio-Based Content

• "Biobased Content" is the percentage of the total organic carbon that is modern (present day) in origin.

• Analyses were performed by conventional radiocarbon analytical methods using ASTM method D6866.

• Analyses are believed to be accurate to within 2-3% (absolute).


8

LCA is the only standardized method to evaluate the environmental footprint of a whole supply chain. Energy consumption and Green House Gas (CO2) emissions are key factors in determining environmental footprint.

Life Cycle Analysis Approach

Cradle-to-gate

Cradle-to-graveCO2

Biodegradation of product results in no net CO2 increase

ManufacturingTransportation Transportation

Use/Reuse/Maintenance

Recycle

Waste Management

AirEmissions

WaterborneWastes

Solid WastesCo-products

EnergyRaw Materials

Raw MaterialAcquistion


9Susterra® Life Cycle Assessment* “Cradle to Gate”

2.18

5.0

3.75

63.9

111.0103.6

0

1

2

3

4

5

6

Susterra® Propanediol(PO route)

PropyleneGlycol

Susterra® Propanediol(PO route)

PropyleneGlycol

GH

G E

mis

sion

s (k

g CO

2 eq

uiv

/ kg)

0

20

40

60

80

100

120

Non Renewable Energy (M

J/kg)

GHG Emission Non Renewable Energy

Green House Gas Emissions- 56% less than Propanediol,- 42% less than Propylene Glycol

Non Renewable Energy Use- 42% less than Propanediol, - 38% less than Propylene Glycol

*Susterra® LCA data based on Loudon process design data; peer reviewed by Five Winds International.

The corn-based process for Susterra® propanediol has a small footprint compared to the petroleum-based processes for 1,3-propanediol and 1,2-propanediol.


10Polyurethanes – Clear Differentiation

Miscible in Polyols

Handling Issues (viscosity/heating

issues)Controlled Substance

Renewably Sourced

Susterra™ Yes No No YesBDO Yes Yes Yes NoDEG Yes No No NoEG No No No No

• Susterra® propanediol offers polyurethane formulators and manufacturers arenewably sourced, non-controlled substance.

• Susterra® is an alternative short chain diol that provides similar performance to 1,4-butanediol and, in addition, offers improved handling at lower temperatures.

• The molecule has higher reactivity per pound and is comparable in cost to BDO.


11Susterra® as a Polyurethanes Raw MaterialShort chain diols are used in polyurethanes as:

Monomers in polyester polyols

Curatives or Chain extenders

Polyester PolyolHO OH

DiisocyanateOCN NCO+

UrethaneGroup

UrethaneGroup

C

O

C

O

Polyester PolyolO O N NCO

H

OCN N

H

Step 2:Prepolymer

C R

O

C

O

OH(n)HO R' OH(n + 1)HO+ Polyester PolyolHO OHStep 1:Polyester Polyol

Dicarboxylic Acid Glycol

N N

H

C

O

O

PolyesterPolyol

O C N N

O H

R' OO C

PrepolymerR' OHHO

+

O H

Hard Segment Hard SegmentSoft Segment

C

OH

O N N

H

C

O

R' O C

O H

Chain ExtenderStep 3:Crosslinking

Susterra®


12Typical Bio Content in Susterra® based Polyurethanes

Susterra® can yield a final product containing up to 33% renewably sourced material.

----

23 – 100 wt%

up to 40 wt%

Bio-Content of Material

up to 33 wt%Polyurethane

3 - 10 wt%Chain Extender

23 - 30 wt%Polyester Polyol

Contribution to Final PUSusterra® Based Material

• Some renewably sourced content can be obtained using Susterra® as a curative.

• More Susterra® is incorporated when used as monomer in the polyester prepolymer.

• Renewably sourced content is confirmed by using the conventional radiocarbon analytical method ASTM D6866.


13Polyurethane Applications

Susterra® has been found an excellent short-chain diol for manufacturing prepolymers and cast elastomer products.

Foam CASE• Coatings• Adhesives• Sealants• Elastomers

• Cast Elastomers

forklift wheels and tires

Transportation Mechanical Sports & Recreation

casters

pipeline cleaning pigspipeline cleaning pigs

motor couplers

sealsgaskets

engine mounts

heavy duty suspension bushings

hydro cyclones

skate wheels

footwear

Industrial


14Overview of Experiments

Comparison of Susterra® - and ethylene adipates in aromatic polyurethanes

PU’s over a range of hardness based on Susterra® adipate and Susterra®curatives and their comparison to standard high performance elastomers

Comparison of curatives Susterra® and BDO

3

2

1

No.

25-30 wt%• DMTDAdimethylthiotoluenediamineEthacure® 300

• TDI 80/20

• TDI 100

• Susterra® adipate

• Ethylene adipate

30-55 wt%• Susterra®

• Susterra® adipate

• MDI• Susterra® adipate

30-55 wt%• Susterra®

• BDO

• MDI• Ethylene adipate

• EG/BDO adipate

• Butylene adipate

Renewable Content (ASTM D6866)

CurativePrepolymerIsocyanate

Polyester Polyol

Source: ITWC, inc. Urethane Solutions


15Susterra® Propanediol as Curative

• Three polyester polyols:

• Xthane IT22, ethylene adipate

• Xthane IT33, ethylene butylene adipate

• Xthane IT25, butylene adipate

• Converted into prepolymers with one di isocyante:

• MDI

• To compare two curatives:

• EXT-1034, Susterra® propanediol

• EXT-1006, 1,4-butanediol

The above design allows for the observation of trends: differences between Susterra® and 1,4-BDO that appear in a range of

polyester polyol/polyurethane compositions.



16Susterra® Propanediol as Curative

90

80

70

60

50

8000

6000

4000

2000

0

MDI Pol. Prepol.

Chain Ext.

BG A

A

EG/B

G AA

EG A

A

BDO

Suster

ra(R

)BDO

Suste

rra(R

)BD

O

Suste

rra(R

)

3000

2000

1000

0

BG AA

EG/B

G AA

EG AA

BDO

Suste

rra(R

)BD

O

Suster

ra(R

)BDO

Suste

rra(R

)

30

20

10

0

Hardness (A) Tensile Strength [MPa]

300% Modulus [MPa] Compression Set [%]

• Elastomers based on Susterra® PDO are comparable to those based on BDO.• PDO can replace BDO as a curative in PU elastomers.

NegligableDifference

PDO: DecreasedTensile

Unclear TrendPDO Positive

BDOSusterra®



17

48

36

24

12

0

600

450

300

150

0

MDI Pol. Prepol.

Chain Ext.

BG A

A

EG/BG A

A

EG A

A

BDO

Suster

ra(R

)BDO

Suste

rra(R

)BD

O

Suster

ra(R

)

20

15

10

5

0

BG AA

EG/B

G AA

EG AA

BDO

Suste

rra(R

)BD

O

Suster

ra(R

)BD

O

Suste

rra(R

)

10.0

7.5

5.0

2.5

0.0

Resilience [%] Die C Tear [KN/m]

Taber Abr. [mm3] Pot Life [min.]

Susterra® Propanediol as Curative

The bio based elastomers show improved Taber abrasion and improved pot life.

Unclear Trend PDO Positive with IT22

PDO PositiveCatalyst Maximization

PDO Positive

BDOSusterra®



18Susterra® Propanediol as Co-Reactant with Adipic Acid

Susterra® was reacted with adipic acid to yield three different polyesters:

Polyester Polyol: Poly S2000PAR Poly S1000PAR Poly S500PARSusterra® Adipate Susterra® Adipate Susterra® Adipate

2000 Mw 1000 Mw 500 Mw

Bio Content, wt.% (ASTM D6866) 37 40 45Funtionality 2 2 2Appearance @ 25°C Solid Solid LiquidHydroxyl Number, range 52-58 mg KOH/g 105-115 mg KOH/g 215-235 mg KOH/gAcid Number, maximum 0.7 mg KOH/g 0.7 mg KOH/g 0.7 mg KOH/gWater Content, maximum 0.05% 0.05% 0.05%Color, APHA maximum 100 100 100Viscosity @ 60°C 1200-1400 mPa.s 330-380 mpa.s 90-100 mPa.sSpeciifc Gravity @ 25°C 1.14 1.14 1.15Bulk Density @ 25°C 9.50 lb/gal 9.50 lb/gal 9.58 lb/gal



19Susterra® Propanediol as co-reactant with Adipic Acid

• The three adipates were converted into prepolymers Xthane IR95 using:

• MDI

• Prepolymers were cured with:

• EXT-1034, Susterra® propanediol

• Poly S2000PAR, Susterra® based polyester polyols

• Three different hardnesses were prepared:

• 75 Shore A, EXT-1034/S2000PAR = 8/92 wt%

• 85 Shore A, EXT-1034/S2000PAR = 20/80 wt%

• 95 Shore A, EXT-1034/S2000PAR = 100/0wt%



20Properties of IR95 cured with Susterra® and S2000PAR

958575

170

160

150

140

130

120

110

100

90

80

Hardness (A)

Perc

enta

ge o

f PU

: "H

ardn

ess=

75"

Resilience

Tensile Strength

Compression SetDie C Tear Strength

Taber Abrasion

100% Modulus

Physical and mechanical properties show expected trends upon increased hardness:• Improved Modulus, Tear Strength, and Tensile Strength • Deteriorated Abrasion, Compression Set, and Resislience (Bayshore Rebound)



21Comparison of Susterra® and Standard PU’s

Pot L

ife [m

in.]

Tabe

r Abr

. [mm3]

Compr

essio

n Se

t [%

]

300%

Mod

ulus [

MPa]

Ult. E

longa

tion [

%]

Tens

ile St

reng

th [M

Pa]

Die C

Tea

r [KN

/m]

Split

Tear

[KN/

m]

Resili

ence

[%]

PPPPPPPPP

Shore A = 75

Shore A = 85

Shore A = 95

PropertiesValues expressed as

percentage within the group.

BDO adipate / BDO

Susterra® adipate / PDO-S2000PAR

EG/BDO adipate / BDO

EG adipate / BDO

Susterra® based PU’s show:

• Improved Resilience• Improved Compression Set• Improved Abrasion Resist.• Improved Potlife

Careful formulation & (DMA)analysis is needed for:

• Tear Strength• Tensile Properties



22Susterra® PDO in Aromatic Polyurethanes

• Two Polyester polyols:

• Susterra® Adipate

• Ethylene Adipate

• Were converted into prepolymers using:

• TDI 80/20

• TDI 100

• Propolymers were cured using:

• aromatic diamine Ethacure® 300 (Albemarle Corporation) DMTDA: dimethylthiotoluenediamine



23Susterra® PDO in Aromatic Polyurethanes

The bio based elastomers exhibit better resilience, compression set, abrasion resistance, and potlife. They show lower tear and tensile strength.

48

36

24

12

0

240

180

120

60

0

8000

6000

4000

2000

0

Hardness (A )

TDI Prepol.

hardso

ft

E G AA

PDO

AA

EG A

A

PDO

AA

30

20

10

0

hardso

f t

E G A A

PDO

AA

E G AA

PDO

AA

40

30

20

10

0

hardso

ft

EG A

A

P DO A

A

EG A

A

PDO A

A

8

6

4

2

0

Resilience [%] Split Tear [KN/m] Tensile Strength [MPa]

C ompression Set [%] Taber A br. [mm3] Pot Life [min.]

PDO Strength PDOArea of Attention

PDO Strength PDO Strength PDO Strength

PDOArea of Attention



24Identified Susterra® Strengths and Envisioned Applications

25-30 wt%

30-55 wt%

30-55 wt%

RenewableContent

• Resilience

• Abrasion resist.

• Compression set

• Potlife

• Resilience• Abrasion resist.

• Compr. set• Potlife

• Abrasion resist.• Pot life

Observed Strengths

3

2

1

No.

High wear appl.

Maximize cat. load.

•DMTDA•TDI 80/20

•TDI 100

•Susterra® AA

•EG AA

High wear appl.

Maximize cat. load.

•Susterra®

•Susterra® AA

•MDI•Susterra® AA

High wear appl.Increased catalyst loading for improved performance

•Susterra®

•BDO

•MDI•EG AA

•EG/BG AA

•BG AA

Envisioned Applications

CurativePrepolymerIsocyanate

Polyester Polyol

• Susterra® PDO can be used in PU’s as curative and building block giving renewably sourced products without extensive re-formulation.

• Susterra® strengths (e.g., improved abrasion resistance and pot life / catalyst loading) are general trends observed in a range of elastomeric materials.



25Conclusions

• Susterra® propanediol can be used as curative in traditional MDI-ester prepolymers below 10% NCO content, giving elastomers with properties comparable to incumbent products based on ethyleneglycol and/or 1,4-butanediol.

• In the case of the Xthane IR95 prepolymer, based on Poly S2000PAR Susterra®adipate ester and cured with more Susterra®, it is clearly demonstrated how this bio based monomer can successfully be used to maximize the renewable content of a polyurethane cast elastomer system without compromising performancecompared to currently used systems.

• Susterra® PDO extends pot-life thus allowing catalyst maximization, which usually leads to enhanced overall properties.

• Interesting to note was the improved abrasion resistance and compression set when the Susterra® based polyesters were reacted with TDI and cured with Ethacure 300®. Of special interest, warranting further investigation is the 70 Shore A elastomer in high wear applications.



26Path Forward

• Further work has already begun using Susterra® based polyesters to formulate:

• Quasi prepolymers

• One Shot systems

• Specialty Foams.

• Now is the time!

• The demand for green products in the Polyurethane industry has just started!

• Susterra® Propanediol monomer is well positioned as key building block!

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Susterra presentation - CPI 2009.pdf - DuPont Tate & Lyle

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