Cashew Nutshell Liquid based Polyols for Tomorrow’sPolyurethane Foams

PSE Europe, Munich, 27-29 June 2017

Tom BerckmansCardolite Corporation

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Contents• Introduction to CNSL technology and

cardanol-based derivatives

• Cardanol-based Polyols:

• Typical QC properties

• Compatibility with oil-polyols

• Compatibility with blowing agents

• Aromaticity

• Thermal stability

• Cardanol-based polyols in PUR foams:

• Examples and properties

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Cardolite is the leading manufacturer of products derived from cashew nutshell liquid (CNSL), a

natural, renewable chemical raw material.

Cashew Liquid Technology

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• CNSL is a naturally occurring, non-food chain, renewable oil from the shell of the cashew nut, obtained as by-product of the cashew nut industry mainly in Brazil, India, and Vietnam.

• CNSL is approximately 25% of the cashew kernel by weight.

Average Structure and Benefits• Better adhesion to metal panels or other construction substrates• Surfactant effect (reduce cost in formulation)

• Water resistance• Humidity resistance• Low viscosity• Surface tension

• Thermal and fire resistance • Chemical resistance

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OH

CNSL PolyolsOverview

7 Typical QC properties7

Grade Polyol Type Appearance Avg. Viscosity(cPs@25 oC)

Avg. OH value(mg KOH/g) Avg. Func. Biocontent

(calc. %)NX-5285 CNSL Aromatic Dark brown liquid 2500 210 ~3.5 90%

NX-9004 CNSL Aromatic Dark brown liquid 5250 185 ~3.8 90%

NX-9001 CNSL Novolac Red-brown liquid 2100 175 ~4.4 88%NX-9001LV CNSL Novolac Red-brown liquid 1000 175 ~3.8 88%LITE 9001 CNSL Novolac Orange liquid 2000 170 ~4.3 88%

NX-9005 non-CNSL branchedpolyether-polyester Yellow liquid 3300 170 ~3.2 79%

GX-9006 CNSL Novolac Red-brown liquid 3000 205 ~4.4 95%NX-9007 CNSL Branched Yellow liquid 2900 180 ~3.3 80%NX-9008 CNSL Polyether triol Yellow liquid 3300 330 ~3 61%GX-9101 CNSL Mannich Red-brown liquid 2500 420 ~3 72%GX-9102 CNSL Mannich Red-brown liquid 7750 440 ~4 78%GX-9103 CNSL Mannich Red-brown liquid 10500 475 ~4 60%GX-9104 CNSL Mannich Red-brown liquid 5500 245 ~3 59%GX-9105 CNSL Mannich Red-brown liquid 2500 390 ~3 71%NX-9201 CNSL Polyester diol Brown liquid 1400 72 ~2 87%NX-9203 CNSL Polyester diol Brown liquid 3700 98 ~2 69%

GX-9301LV CNSL Aminoalcohol Yellow liquid 2750 318 ~3 72%GX-9301 CNSL Aminoalcohol Dark yellow liquid 3750 285 ~3 72%

GX-9302 CNSL Aminoalcohol Pale amber liquid 1500 382 ~3 71%

Cardanol-based polyols are designed to cover a wide range of physico-chemical properties and functionality, while maintaining a high bio-content

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Cardanol-based polyols show excellent compatibility with polyether polyols, but limited with

polyester polyols

Cardanol-polyolpetro-polyol GX-9101 GX-9102 GX-9104 NX-9001 GX-9006

Mannich (OH425) X X X X XAromatic Polyester (OH240) XXXXXX XXXXXX XXXXXX XXXXXX XXAliphatic Polyester (OH350) XXXXXX XXXXXX XXXXXX XXXXXX XX

Propoxylatedsorbitolpolyether(OH300) X X X X XAlkoxylatedsucrosebasedpolyether(OH360) X X XXX X X

Alkoxylatedsucrose/DEGbased polyether (OH440) X X XX XXX XEthoxylated/propoxylated glycerine basedpolyether(OH33) X X XXX X X

PPG1000(OH114) X X X X XPropoxylated glycerine polyetherpolyol(OH156) X X X X X

Propyleneoxide/ethyleneoxidebasedpolyetherpolyol(OH48) X X X X X

X clearblendatboth25/75and50/50CNSL/petroleumratio

XX clearblendat50/50,butphaseseparationat25/75CNSL/petroleumratio

XXX clearblendat50/50andcloudybutnon-separatingblendat25/75CNSL/petroleumratio

XXXX cloudyblendat50/50,butphaseseparationat25/75CNSL/petroleumratio

XXXXX cloudyblendat25/75,butphaseseparationat50/50CNSL/petroleumratio

XXXXXX phaseseparationatboth25/75and50/50CNSL/petroleumratio

Compatibility with petro-polyols

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Cardanol-based polyols show excellent miscibility with methyl-formate (ECOMATE), n-pentane and HFO (Solstice LBA), and

acceptable compatibility with HFC (Solkane 365/227)

Polyol/methyl-formate(60/40w/w)

Polyol/HFC(60/40w/w)

Polyol/n-pentane(60/40w/w)

Polyol/HFO(60/40w/w)

PolyolType Storageconditions Wt.Miscibility (%)

GX-9101

24h@RT

≥40 ~10 ≥40 ≥40

GX-9102 ≥40 ~12 ≥40 ≥40

GX-9104 ≥40 ~10 ≥40 ≥40

Petro-Mannich(OH425) ≥40 ~25 ~4 ≥40

Petro-Mannich(OH450) ≥40 ~26 ~2 ≥40

GX-9006 ≥40 ~6 ≥40 ≥40

NX-9001 ≥40 ~6 ≥40 ≥40

Aromatic-PApolyester(OH240) ≥40 ~6 ~2 ~9

Aromatic-PETpolyester(OH240) ≥40 ~12 ~2 ~25

Aliphaticpolyester(OH350) ≥40 ~14 ~1 ~23

Polyetherpolyol(OH360) ≥40 ≥40 ≥40 ≥40

Compatibility with blowing agents

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ü GX-9104 shows similar reactivity retention to the reference formula with a 16.7%versus 20% reduction in string time

ü CNSL-polyols can be designed to deliver optimum performance with new generationBA with minimum loss in reactivity over time without the need of specialty catalysts

Compatibility with blowing agents

Components Reference Formula1 Formula2Polyether polyol (OH360) 22.5 22.5 22.5

Aromaticpolyesterpolyol(OH250) 55 55

Petro-Mannichpolyol(OH470) 22.5 22.5

GX-9101 22.5

GX-9104 55

Polycat5 0.3

Polycat8 4.19

DabcoT120 0.3

TegostabB8461 1.47

TCPP 5.27

PHTblend 18.81

Water 2.91

Solstice LBA 17.27

NCOIndex 115

Timeelapsed T0 T1(10dd@50°C) T0 T1(10dd

@50°C) T0 T1(10dd@50°C)

MixTime(sec) 3 3 3 3 3 3

StringTime(sec) 10 12 9 13 12 14

TackFreeTime(sec) 14 23 12 21 16 28

Aromaticity11

Cardanol-based polyols’ aromaticity values are not too far from the typical ones of aromatic polyester polyols (20-22%) and petro-based

Mannich polyols (17.5-19%)

Cardanol-based polyol Aromaticity(%)NX-5285 21,5

NX-9004 21,5

NX-9001LV 20,2

NX-9001 20,2

LITE9001 20,2

GX-9006 23,1

GX-9007 3

GX-9101 17,3

GX-9102 18,6

GX-9103 16,1

GX-9104 12,4

GX-9105 15,9

GX-9201 5,2

GX-9203 17,5

GX-9301 17,8

GX-9301LV 17,8

GX-9302 16,1

Thermal stability

Polyol Type Temperature@20%weightloss(°C)*

JeffolSG-360 Sucrose-basedpolyether(OH360) 222.03

Isoexter4356 Aromatic-PETbasedpolyesterpolyol(OH240) 245.16

Isoexter4442 AromaticPA-polyesterpolyol(OH240) 217.01

Isoexter4537 Aliphatic polyester (OH350) 260.96

JeffolR425X nonylphenol-based Mannich (OH425) 234.95

RokopolRF151V nonylphenol-basedMannich(OH448) 241.03

GX-9006 CNSL-basednovolac polyol(OH200) 299.92

GX-9104 CNSL-Mannich (OH240) 295.95

GX-9102 CNSL-Mannich (OH450) 255.95

GX-9101 CNSL-Mannich (OH430) 248.08

Cardanol-based polyols show high thermal resistance, equal (polyester) or superior (polyether, Mannich) to petro

based polyols

*TGAanalysis conditions:airflow,scan from25°Cto400°C

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Cardanol-based rigid PU foams: Examples and Average Performances

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Cardanol-based Mannich polyols GX-9101 and GX-9102 provide faster reactivity, achieving at least comparable, when not improved,

compression strengths at similar densities.

Spray foams: GX-9101 and GX-9102

Components PU1 PU2 PU3 PU4Polyether polyol (OH490) 15

Aromatic-PApolyesterpolyol(OH240) 20 25

Glycerine 2

petro-Mannich (OH425) 35

GX-9101 35

Polyether polyol (OH360) 65

PHT4blend 8

petro-Mannich(OH448) 10

GX-9102 10

TCPP 11 20

LK-221E 0,5

DC-193 1 1,4

Water 2 1,5

Polycat 203 1 0,9 1,2

Dabco 33LV 0,5 0,3 1,2

SolsticeLBA 12,5 14

Index 110 120

MixTime(sec) 3 8

GelTime(sec) 14 13 51 40

Tack FreeTime(sec) 25 23 99 75

Density(Kg/m3) 27 26.9 42.6 42.5

Compressionstrength(kPa) 115 101 178 186

Thermalconductivity (W/mK)24°C n.a. 24,7 24,9

10°C n.a. 23,4 23,6

Fire performances: burning Rate15

CNSL-based Mannich polyols show lower combustion rate than petroleum-based Mannich polyols.

Foam Formulation 1Mannich Polyol

Sucrose/glycerine based polyetherPolyester polyolTCPPSilicone surfactantWaterAmine catalystsSolkane 365/227pMDI Index 115

Foam Formulation 2Mannich Polyol

Polyester & Sucrose based polyolsTCPPSilicone surfactantWaterAmine catalystsTin catalystSolkane 365/227pMDI Index 115

0 5 10 15 20 25 30 35

GX-9101

GX-9102

GX-9103

425OH Petro Mannich

cm/min

Burning rate cm/min (ASTM D1692)

0 5 10 15 20 25 30 35 40

GX-9102

GX-9103

470OH Petro Mannich

cm/min

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PU foams based on cardanol-Mannich polyols show Limiting Oxygen Index (LOI) valuescomparable to petro-based references

Fire performances: LOI

Components PU5 PU6Polyether polyol (OH490) 15

Aromatic-PApolyesterpolyol(OH240) 20

Glycerine 2

petro-Mannich(OH425) 35

GX-9101 35

Polyetherpolyol(OH360)

PHT4blend

petro-Mannich(OH448)

GX-9102

TCPP 11

LK-221E 0,5

DC-193 1

Water 2

Polycat203 1 0,9

Dabco33LV 0,5 0,3

SolsticeLBA 12,5

Index 110

Limiting Oxygen Index(LOI,%) 23,8 24,2

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GX-9102 based foam shows lower THR (Total Heat Released), faster char

formation and lower emissions of both dangerous carbon

dioxide and carbon monoxide during combustion

Fire performances: cone calorimeter

Components PU3 PU4Aromatic-PApolyesterpolyol(OH240) 25

Polyetherpolyol(OH360) 65

PHT4blend 8

petro-Mannich(OH448) 10

GX-9102 10

TCPP 20

LK-221E

DC-193 1,4

Water 1,5

Polycat203 1,2

Dabco33LV 1,2

SolsticeLBA 14

Index 120

Density(Kg/m3) 42.6 42.5

FormulationParameter PU3 PU4

Timetoignition(TTI,sec) 3 3

HeatReleaseRate(HRR,kW/m2) 58,17 81,31

PeakofHeatReleaseRate(pkHRR,kW/m2) 186,78 314,58

TotalHeatReleased(THR,MJ/m2) 18,3 14,1

TotalSmokeRelease(TSR,m2/m

2) 563,8 820,4

MassLost(ML,g) 11,02 8,68

COyield(kg/kg) 0,1558 0,1339

CO2 yield(kg/kg) 1,28 1,09

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A GX-9102-based foam (HFO blown), tested accordingly to E84

tunnel test, has been rated as Class B (35 flame spread), with a very low

smoke developed value (300).

Fire performances: tunnel test (E84)

GX-9104 and CNSL-novolac polyols can be used in spray foams formulations maintaining excellent reactivity, fire resistance and mechanical properties.

High CNSL-content PU: Spray Systems19

Components Polyoltype Ref.1 1 Ref.2 1 2Puranol RF8360(OH360) 360OH(Sucrosebasedpolyetherpolyol) 35 35 35 35

RokopolRF-151V(OH448) 448OH(petro-basedMannichpolyol) 40 60

JeffolR425X(OH425) 425OH(petro-basedMannichpolyol) 40 40 40

Isoexter4356(OH240) 240OH(Aromaticpolyesterpolyol) 25 25

GX-9104(OH257) 257OH(CNSLMannich polyol) 25

NX-5285(OH200) 200OH(CNSLbasedpolyol) 25

NX-9004(OH185) 185OH(CNSLbasedpolyol) 15 25

Glycerine(OH1828) 1880OH 0,5 0,5

TCPP Flameretardant 20 20 20 20 20

DABCOT12 Tin-basedcatalyst 0.5 0.5 0.25 0.25 0.25

DABCO33LV Tertiary aminecatalyst 1,2 1.5 1.6 1.7

DC193 Siliconesurfactant 1.4 1.4

TegostabB8461 Siliconesurfactant 1.4 1.4 1.4

Polycat5 Tertiary aminecatalyst 1

Water Blowingagent 1.9 1.92 1.9 1.9 1.9

Solkane365/227 Blowingagent 14 14

ECOMATE Blowingagent 8 8 8

pMDIIndex Isocyanate(Ongronat2100) 110 115 110 110 110

PerformanceMT(sec) 5 5 5 5 5

GT(sec) 10 11 11 16 17

TFT(sec) 22 15 20 20 23

Density (kg/m3) 37.8 34.6 33.5 34.8 35.9

Compression (kPa) 161 136 85 92 98

UL-94(vertical) HBF HBF HBF HBF HBF

UL-94(horizontal) V0 V0 V0 V0 V0

AfterflameUL-94vertical(seconds) 1.7 2.5 4.7 7.3 5

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GX-9104, a low OH-value cardanol-based Mannich polyol, can be used in PIR systems, providing good final foam

performances.

Components PU5 PU6 PU7 PU8Polyether polyol (OH360) 30

Aromatic-PApolyesterpolyol(OH240) 70

GX-9104 70 20

Aromatic-PETpolyesterpolyol(OH240) 50 40

Aliphaticpolyesterpolyol(OH350) 50 40

TCPP 15 20

SiliconeDC5598 1,4 2,5

DabcoEM400 3

Water 1,2 1,01 0,7

DabcoTMR2 1,2

DabcoK15 1,5

PMDETA 0,5 0,4

Cat.LB 1,2

DabcoK15 1,5

Solstice LBA 20

Pentane 15

Index 250 222

MT(sec) 8 15

GT(sec) 43 38 126 102

TFT(sec) 95 70 185 156

Density(Kg/m3) 37.4 37.7 31.7 32.2

Compression strength (kPa) 282 294 155 146

Thermalconductivity (W/mK)24°C 22,4 21,1 n.a.

10°C 23 21,7 n.a.

LOI(%) 27,0 24,5 24,7 24,8

High CNSL-content PU: PIR Systems

High CNSL-content PU: PIR Systems

Components Type Ref 1 2A 2B 2C 3A 3B 3C 4A 5A 5B

Isoexter 4356 240OH (aromatic polyester polyol) 44 44 44 44 44 44

Isoexter 3392 190OH (aliphatic polyester polyol) 15 15

Voranol RN482 482OH (polyether polyol) 13 13 13 13 13 13 13 13 13 13 13

Glycerol 1828 OH 0.4 0.4 0.3 0.47 0.3GX-9104 224OH (CNSL Mannich polyol) 43.6 43.6 43.7 44 44GX-9006 198OH (CNSL novolac polyol) 15 15 15NX-9001 194OH (CNSL novolac polyol) 15 15 15

NX-9005 170OH (branched polyether-polyester) 15

NX-9007 178OH (CNSL branched poyol) 15 15TCPP flame retardant 21 21 21 21 21 21 21 21 21 21 21RT0073 silicone surfactant 3 3 3 3 3 3 3 3 3 3 3DABCO TMR 2 tertiary amine catalyst 1.7 1.65 1.57 1.61 1.6 1.7 1.72 1.63 1.6 1.6 1.6

DABCO K15 catalyst is a solution of potassium-octoate in diethylene glycol 1 0.91 0.88 0.97 0.84 1 1.1 0.93 0.84 0.87 0.84

NIAX A-1 amine catalyst 0.58 0.4 0.4 0.52 0.4 0.58 0.62 0.51 0.4 0.4 0.4

Water blowing agent 0.77Part A total 100Pentane blowing agent 12.1pMDI Index isocyanate 280PerformanceMix Time (sec) 7 7 7 7 7 7 7 7 7 7 7String Time (sec) 55 55 57 46 56 53 45 54 59 57 59

Tack Free Time (sec) 92 88 100 86 86 86 84 94 98 93 95

Density (kg/m3) 34.0 34.5 35.1 34.8 35.7 35.8 34.6 35.2 35.2 34.8 34.5Compression (kPa) 151 157 174 160 180 174 187 167 155 161 179

UL-94 Vertical V0 V0 V0 V0 V0 V0 V0 V0 V0 V0 V0

Horizontal HBF HBF HBF HBF HBF HBF HBF HBF HBF HBF HBF

NX-9001, GX-9006, and NX-9007 can replace aliphatic polyester polyols to improve compression strength and maintain excellent fire properties and reactivity

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High CNSL-content PU: Pour in place Systems

CNSL-polyols can be used in low-medium reactive systems (e.g. pour in place) to improve final mechanical properties, with a reduction of catalyst package

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Components Ref.1 1 2 Ref.2 3 4 5GX-9203 40 40

GX-9101 10 10 10

Polyether polyol (OH360) 42,7 42,7 42,7 42,7 42,7 42,7 42,7

Trifunctional bio-polyol (OH119) 40 40 40 40

Petro-Mannich (OH425) 10

GX-9102 10 10

GX-5166 40

Petro-Mannich (OH470) 10

Glycerin 4

Water 2,4

Polycat 5 0,4 0,4 0,16 0,4 0,4 0,16 0,4

DabcoT12 0,04 0,04 0,02 0,05 0,044 0,02 0,04

Tegostab8461 1

pMDIIndex 110 110

MT(sec) 5 5

CT(sec) 16 15 11 14 13 12 10

ST(sec) 49 39 34 43 46 39 27

TFT(sec) 81 59 46 67 84 57 43

Density(kg/m3) 45,8 46,6 46,8 45,7 46,1 46,6 42,2

Compression (kPa) 201 212 227 194 216 203 234

Conclusions CNSL based polyols for Rigid Foam:

• Are a non-food chain, bio-renewable alternative to both petroleum and other renewable based polyols

• Are compatible with standard blowing agents

• Are compatible with polyether polyols and can be used with polyester polyols with minor modifications to the formulas

• Increase reactivity which reduces the use level of catalysts

• Can contribute to fire performances

• Can increase compression strength

• Can be designed to give a wide range of properties

• Can be used at high levels to maximize final bio-content

• Chemistry can be easily tuned to obtain different derivatives suitable for PU applications, including cardanol-based surfactants as alkoxylated-NP replacement with comparable HLB values

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Thank you!