C18PolyesterPolyolsAHighPerformance,Bio-basedSpecialtyPolyesterPolyol

July2018

RustyPittman,Rusty.pittman@elevance.com

CONFIDENTIAL

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Elevance’sproprietarymetathesistechnologyenablesnovelcommercialbuildingblocks

2

UnsaturatedC10MethylEster

UnsaturatedC12MethylEster

C10-C18Olefins

Elevance Proprietary Olefin Metathesis (Gresik Biorefinery) and Traditional Oleo Chemical Processes

Palm Oil Feedstock

Primary Bio-refinery Products

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Elevance’sC18PolyolsaresynthesizedfromthesecondarycrossmetathesisofourC10andC12unsaturatedesters

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C18DiesterCross-Metathesis&hydrogentation

DiolsC18Diester C18Polyols

C18Diesterandvariousdiolsarecombinedtocreateourfamilyofpolyols

C18diacidis~106-foldlesssolubleinwaterthanC6diacid,and103-foldlesssolubleinwaterthanC12diacid

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1.  “DicarboxylicAcids,”Kirk-OthmerEncyclopediaofChemicalTechnology2010,1-18.2.  WatersolubilityofC18diacidandC36dimeracidsisUSEPApredictedvalueusingEPISuite™

10-7 10-6 10-5 10-2 10-1 100 101 102 103 104 105 106-25

0

2575

100

125

150

175

200

C6

C4

C9

C10

C36 (dimer acid)

C18

Mel

ting

Poin

t (°C

)

Water Solubility (mg/L)

C12

OurLinearC18diacid/diesteroffersauniquebalanceofhydrophobicityandhighmeltingpointasapolyolbuildingblock

AliphaticDiacidProperties

Lessonsfromnature–suberin,aC18-basedpolyesterisaprotectivebiopolymer

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Suberin,thenaturalprotectivebiopolyesterincork,containsasignificantfractionoflongchainα,ω-difunctionalC18monomers.

Suberindisplaysabalanceoffavorablepropertiesimportanttospecialtypolymerdevelopment:

•  Flexibilityandhydrophobicity•  Lowmoisturevaporandgaspermeability•  Excellentchemicalresistance

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AfamilyofC18Polyolsareenabledwithvariousdiolco-monomers

aModifiedD4274.bAnalyticalmethodsavailableonrequest.cDSCbyElevanceanalyticalmethodERS-155-1.dASTMD664.eASTMD5386.fASTME1064.

C18Polyol

Hydroxylvaluea

mgKOH/g

Averagemolecularweightg/mol

Visco-SitybcPs

MeltingTemperaturec

°C

AcidValued

mgKOH/g

ColoreAPHA

WaterContentf

%

Appearance@25°C

CommercialPolyols101 119 1000 4450(25°C) 11 <1 60 <0.02 semi-liquid

201 56 2000 8600(35°C) 19 <1 70 <0.02 semi-solid

102 121 1000 965(25°C) 7 <1 90 <0.02 clearliquid

202 55 2000 4700(25°C) 11-15 <1 90 <0.02 clearliquid

DevelopmentalPolyols

205 56 2000 1788(45°C) 34 <1 125 <0.02 solid

206 53.4 2000 755(70°C) 60 <1 100 <0.02 solid

208 54 2000 383(100°C) 64-79 <1 125 <0.02 solid

209 56 2000 434(100°C) 67-82 <1 100 <0.02 solid

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C18Polyolswithdiversethermalpropertiesareavailable

7

-40 0 40 80 120

Hea

t Flo

w (W

/g) (

endo

up)

Temperature (°C)

201 202 203 204 205 206 208 209

1 W/g

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8

C18polyolsofferhighbiobasedcarboncontentdependingonthechoiceofdiol

0 10 20 30 40 50 60 70 80 9050

60

70

80

90

100

204

209

208

205

206

202

Bio

base

d Ca

rbon

Con

tent

(%)

Melting Point (°C)

201

203

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9

LowerviscositiesofC18polyolscansignificantlyimproveprocessabilitycomparedtospecialtypolycarbonate(PC)polyols

ThelowmeltviscositiesofC18polyolsenablehighsolids,loworzeroVOCPUapplications,e.g.,coatings.

20 30 40 50 60 70 80 90 100102

103

104

105

106

Visc

osity

(cP)

Temperature (°C)

PC-Ref 201 202 204

>50-fold

C18Polyol-TPUBenchmarkingStudy

Polyol Pros Cons

Polyetherpolyol

§  Excellenthydrolyticresistance

§  Goodflexibilityatlowtemperature

§  Lowpre-polymerviscosity

§  Lowsolvent/oilresistance

§  Lowheatresistance

§  Lowoxidative/UVresistance

Polyesterpolyol

§  Superiortensileandtearstrength

§  Abrasionresistance

§  Goodsolvent/oilresistance

§  Lowpre-polymerviscosity

§  Lowhydrolyticstability

Polycarbonate

polyol

§  Excellentsolventandheat

resistance

§  Highoxidative/UVresistance

§  Overallgoodmechanical

properties

§  Highviscosity

§  Lowflexibility

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Typicalpolyolcategory/performanceattributes

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WebenchmarkedC18polyolsagainstcommercialincumbentsinTPUsatconstanthardsegmentratios

TPU recipe: Polyol:1,4-BD:MDI (mol ratio) = 1:1:2.04 (HS = 23-24% w/w)

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Characterization&MechanicalPropertiesofC18TPUsandreferenceTPUs

aMeasured using a Perkin Elmer DSC-7 at a heating rate of 5°C/min from -60°C to 200°C (second heating cycle).bMeasuredusing Instron5500RModel1122accordingtoASTMD412. cMeasuredusing Instron5500RModel1122according to ASTMD624. dShore A hardnessmeasured using Gardco A56 according to ASTMD-2240. eMeasuredusingBashoreResiliometeraccordingtoASTMD2632.

MechanicalpropertiesofC18TPUswerecomparedtoreferenceTPUs(r.t.)

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§  CrystallineC18TPUsexhibitedyieldatlowstrain

§  Non-crystallineC18TPUswereelastomeric

C18TPUmechanicalpropertiescanbetunedthroughpolyolcomonomer(s)

§  C18TPUsexhibitedcomparableultimatetensilestrengthtoreferenceTPUs§  MostC18TPUsshowedsignificantlyhighertearstrengththanreferenceTPUs,

especiallythesemi-crystallinesamples

10 15 20 25 30 350

500

1000

1500

2000

2500

C6-BD

205

PCL

Tear

Str

engt

h (N

/cm

)

Tensile Strength (MPa)

201

209

206

PC-HD/1,5PD

PTMG

15

C18TPUsdisplayimprovedhydrolyticstabilityapproachingthatofpolycarbonatebasedpolyols

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§  Evaluationconditionsofhydrolyticresistance:7daysat70℃and95%RH

§  C18TPUsshowedthelowestwateruptake.

§  C18TPUsshowedmuchhigherretentionoftensilestrengthcomparedtoreferencepolyester-basedTPUs,comparabletoPC-basedTPU.

0 2 4 6 8 10 12 14 160

20

40

60

80

100

PCL C6-BD

Ret

entio

n of

Ten

sile

Str

engt

h (%

)

Water Uptake (wt %)

205

209

206

PC-HD/1,5PD201

PTMG

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17

Goodoilresistance

SomeC18polyolscanofferbetteroilresistance(measuredbyoiluptake)comparedtopolyetherpolyols

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18

CrystallineC18TPUsofferexcellentsolventresistance

C18Polyolswithlineardiolsofferexceptionalsolventresistance(measuredbyMEKuptake)comparedtoallotherTPUbenchmarks

Copyright2019,ElevanceRenewableSciences,Inc.Allrightsreserved.

C18Polyols–anewclassofspecialtypolyols

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LOWERMELTVISCOSITY

HigherSolids

Improvedprocessability,fasterthroughput

Enableslow/zeroVOCcoatings&adhesives

INCREASEDWATERRESISTANCE&

HYDROLYTICSTABILITY

Hydrolyticresistanceapproachingpolycarbonate

polyols

Expandsapplicationsforpolyesterbasedpolyurethanes

STRONG&SOLVENTRESISTANCE

Hightear/tensilestrengthtypicalofpolyesters

HighestSolventResistance

Highoverallperformanceandbio-based

Appendix

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21

SolubilityofC18polyolsinorganicsolvents

Solvent(solvent:polyol=2:1)

201 202 205 206 209

40C 20C 40,20C 40,20C 50C 40C 20C 80C 60C <50C

Xylene 3 3 3 3 3 3 0 3 3 0Toluene 3 3 3 3 3 3 0 3 3 0BuOAc 3 2 3 3 3 0 0 3 1 0EtOAc 3 2 3 3 3 0 0 - - 0NMP 3 2 3 3 2 0 0 3 1 0Acetone 3 2 3 3 3 0 0 - - 0DMF 1 0 3 3 2 0 0 - - 0DMAc 3 1 3 3 2 0 0 3 1 0THF 3 2 3 3 3 3 0 - - 0MEK 3 3 3 3 3 0 0 3 1 0

3: soluble 2: partially soluble, no obvious phase separation, mostly dissolved 1: partially soluble, obvious phase separation or suspension 0: practically insoluble -: not determined

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MiscibilityofC18polyolswithotherpolyols

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2: miscible 1: partially miscible, no obvious phase separation 0: practically immiscible

Other Polyol (polyol:C18 polyol = 1:1, r.t.)

C18 201 C18 202

Oxymer M56 2 0Eternacoll PH200D 0 0PTMG 1 (40 °C) 2PO3G 0 1

2 (40 °C)Fomrez 56-44 0 0 Capa 2203 0 0