c18 polyester polyols - elevance · 1/14/2019 · lessons from nature – suberin, a c18-based...
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C18PolyesterPolyolsAHighPerformance,Bio-basedSpecialtyPolyesterPolyol
July2018
RustyPittman,[email protected]
CONFIDENTIAL
Copyright2019,ElevanceRenewableSciences,Inc.Allrightsreserved.
Elevance’sproprietarymetathesistechnologyenablesnovelcommercialbuildingblocks
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UnsaturatedC10MethylEster
UnsaturatedC12MethylEster
C10-C18Olefins
Elevance Proprietary Olefin Metathesis (Gresik Biorefinery) and Traditional Oleo Chemical Processes
Palm Oil Feedstock
Primary Bio-refinery Products
Copyright2019,ElevanceRenewableSciences,Inc.Allrightsreserved.
Elevance’sC18PolyolsaresynthesizedfromthesecondarycrossmetathesisofourC10andC12unsaturatedesters
3
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
Copyright2019,ElevanceRenewableSciences,Inc.Allrightsreserved.
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
11
Typicalpolyolcategory/performanceattributes
12
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
Copyright2019,ElevanceRenewableSciences,Inc.Allrightsreserved.
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
Copyright2019,ElevanceRenewableSciences,Inc.Allrightsreserved.
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