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CNSL Diols:Outstanding hydrophobicity, reactivity and compatibility in polyurethane adhesive applications 1 January 2016, Cardolite

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CNSL Diols:Outstanding

hydrophobicity, reactivity and

compatibility in polyurethane

adhesive applications

1

January 2016, Cardolite

CNSL Diols: QC Data

Items GX-9201 GX-9203

Polyol type CNSL Diol CNSL Diol

Viscosity, cps @25 °C 950-1850 2200-5200

Hydroxyl value,

mg KOH/g 65-80 80-115

Acid value,

mg KOH/g <2 <2

Water content, % Trace Trace

Diols: Reactivity 3

Diol Isocyanate Gel time @ 25 °C

PPG1000 HMDI > 18 h

PPG2000 HMDI > 18 h

GX-9201 HMDI 58'33"

GX-9203 HMDI 16'31"

PPG1000 IPDI > 18 h

PPG2000 IPDI > 18 h

GX-9201 IPDI 4 h 45'

GX-9203 IPDI 3 h 43'

PPG1000 MDI 10 h 33'

PPG2000 MDI 11 h 56'

GX-9201 MDI 3 h 36'

GX-9203 MDI 2 h 21'

• 2K systems, Index 100

•No catalyst has been used • Desmodur XP2840: HMDI •Desmodur I : IPDI

• Isonate OP50 : monomeric MDI

CNSL based diols show greater reactivity to aliphatic and aromatic

isocyanates compared to PPG diols

Diols: Compatibility

4

Polyol type GX-9201 GX-9203 Poly BD

PPG 1000 100% Compatible 100% Compatible -

PPG 2000 100% Compatible 100% Compatible *Max

solubility: 55%

Poly BD Compatible at

<30% 100% Compatible -

CNSL based diols exhibit good compatibility to polyether and Poly

BD While Poly BD has limited compatibility to polyether

* Based on external literature

Moisture Sensitivity:CO2 Evolution

Graduated

cylinder

Flexible Tubing

Polyol/NCO/Water

CO2 evolution

Box

Formula

100g of polyol/NCO(Index 100)

+100g of water)

OH value

(mg KOH/g)

CO2 (ml) after 24hr

Monomeric MDI

(Isonate OP50)

Polymeric MDI

(Ongronat 2100)

PPG2000 57 >75* >75*

PPG1000 114 >75* >75*

PolyBD(Mw 4000) 48 18 14

GX-9201 72 19 23

GX-9203 92 34 37

•75 ml is the maximum volume of the syringe used in the test

CNSL Diols show reduced moisture sensitivity compared to PPG diols

Suspecting that CO2 evolution results are also affected by OH value

and density of diol and isocynate blend.

Diols: Mechanical Properties in 2K PU

2K PU system: Cured with polymeric MDI at 100 index, lap shear(cured 4hr/60 °C), Tg and Tensile strength (cured

4hr/70 °C +1hr/120 °C)

Single diols and blends systems were evaluated for mechanical

properties and Tg

Use of CNSL diols in PPG and PolyBD diols provides good mechanical

properties and Tg

Diols Tensile strength

(MPa) Elongation (%) Tg (°C), DSC

Lap shear

(MPa)*

GX-9201 0.20 29.03 -54.50 0.21

GX-9203 0.57 62.15 -17.50 0.72

PolyBD (MW 2800) 0.59 46.14 -74.30 0.44

GX-9201/PPG1000 (70/30) 0.33 29.55 -46.90 0.18

GX-9203/PPG1000 (70/30) 0.56 60.66 -24.50 0.33

PolyBD (MW 2800)/GX-9201 (70/30) 0.53 42.65 -72.20 0.46

PolyBD (MW 2800 Da)/GX-9203 (50/50) 0.70 93.21 -8.00 0.48

*sanded Al substrate

Diols in 2K PU: Hydrolytic Stability 7

0

2

4

6

8

10

12

14

16

18

Ha

rdn

es

s r

ed

uc

tio

n(%

)

Diols

Hardness variation(%) after 7day in 50% H2SO4

CNSL diols showed good hydrolytic stability in 50% H2SO4

CNSL diols and PolyBD blends showed significantly improved

hydrolytic stability in 50% H2SO4.

cured 4hr/70 °C +1hr/120 °C

Diols: Prepolymers I (15% NCO)

8

Diols Diol viscosity @25 °C

(cps)

Prepolymer viscosity

@25 °C (cps) NCO content (%)

PPG (MW 1000) 146 1912 15.5

PPG (MW 2000) 316 869 15.4

PolyMEG (MW 1000) 2248

(162 @40oC) 1461 14.9

PolyMEG (MW 2000) Solid @RT

(1348 @40oC) 2888 15.1

PolyBD (MW 4000) 4784 3036 15.3

Copolycarbonate diol 10300 16188 15.0

Aliphatic polycarbonate diol Solid @RT

(410 @75oC) 14529 15.3

GX-9201 958 1545 15.1

GX-9203 2178 2780 15.9

CNSL based prepolymers(NCO content 15%)

exhibited similar viscosity to references

Reference

commercial

products

Prepolymers I: Hydrophobicity

9

CNSL based prepolymers exhibited excellent hydrophobicity :

Poly BD>CNSL diols=Polycarbonate>PolyMEG>PPG

Diols Water uptake (%),

30day immersion @60 oC*

PPG1000 2.80

PPG2000 4.71

POLYMEG1000 2.37

POLYMEG2000 2.20

PolyBD (MW 4000) 0.64

Copolycarbonate diol 1.03

Aliphatic polycarbonate diol 1.39

GX-9201 1.41

GX-9203 1.50

*1,4-BDO extended prepolymers cured at RT for 18 h (T12 and Dabco 8154 have been used as

catalysts and BYK 054 as air release additive)

Prepolymers I : Chemical Resistance

10

CNSL based prepolymers showed outstanding chemical resistance:

Poly BD>CNSL diols=Polycarbonate>PolyMEG>PPG

Diols

Weight Variation %,

10% NaOH

(@ 25 °C), 30 day*

Weight Variation %, 20%

Acetic acid

(@ 25 oC), 30 day*

Weight Variatio%,

50% H2SO4

(@25 oC), 30 day*

PPG1000 1.58 4.92 6.11

PPG2000 1.75 7.05 32.72

POLYMEG1000 1.09 4.17 1.85

POLYMEG2000 0.96 5.96 15.55

PolyBD (MW 4000) 0.24 1.18 0.00

Copolycarbonate diol 0.56 1.08 0.14

Aliphatic polycarbonate diol 0.71 1.02 0.30

GX-9201 0.47 2.05 0.13

GX-9203 0.13 0.45 0.05

*1,4-BDO extended prepolymers cured at RT for 18 h (T12 and Dabco 8154 have been used as

catalysts and BYK 054 as air release additive)

Prepolymers I : Hydrolytic Stability 11

CNSL based prepolymers(NCO 15%) maintained good hardness after long time

exposure in different aqueous media

0%

10%

20%

30%

40%

50%

60%

PPG1000 PPG2000 POLYMEG1000 POLYMEG2000 PolyBD Copolycarbonatediol

Aliphaticpolycarbonate

diol

GX-9201 GX-9203

Red

ucti

on

in

Hard

ness(%

)

30dd @60C in water

30dd @25C in NaOH 10%

30dd @25C in Acetic Acid 20%

30dd @25C in H2SO4 50%

*1,4-BDO extended prepolymers cured at RT for 18 h (T12 and Dabco 8154 have been used as catalysts and BYK 054 as air

release additive)

Prepolymers II (NCO 7%)

12

Diols: 7% NCO

Prepolymer

Viscosity of

prepolymer(cps)

Tensile

strength

(MPa)

Elongation(%) Modulus(MPa) Hardness

Shore A

PPG 1000 29617 9.29 245.88 20.43 81.4

PPG 2000 26617 8.37 249.42 17.98 79

PTMEG 1000 21583 11.47 341.96 29.94 81.5

PTMEG 2000 25694 3.63 114.58 22.35 83

Aliphatic

polycarbonate diol 28631 26.97 202.23 55.76 91.2

PolyBD(mw 4000) 20365 5.41 101.41 24.86 88.4

GX-9201 19868 2.23 30.6 19.27 75.4

GX-9203 21056 5.1 82.83 32.61 82

*1,4-BDO extended prepolymers cured at RT for 18 h (T12 and Dabco 8154 have been used as catalysts and BYK 054 as air

release additive)

Prepolymers II: Hydrolytic Stability

13

0

5

10

15

20

PPG1000 PPG2000 Aliphaticpolycarbonate diol

PolyBD (MW 4000Da)

GX-9201 GX-9203

Re

du

cti

on

in

ha

rdn

es

s (

%)

Cured prepolymers (7% NCO) hardness variation

Hardness change %, H2O (@ 25 °C), 21 day

Hardness change %, NaOH 10% (@ 25 °C), 21 day

Hardness change %, H2SO4 30% (@25 °C), 21 day

CNSL based prepolymers(NCO 7%) maintained good hardness after long

time exposure in different aqueous media, indicating excellent hydrolytic

stability

CNSL Diols • Outstanding Hydrophobicity

• Excellent chemical resistance in

acid and alkaline

• Excellent hydrolytic stability

• Good compatibility to Poly BD

and Polyether diols

• Greater reactivity than Polyether

diols

• Excellent hydrolytic stability when

CNSL diols are blended with Poly

BD and polyether diols

• Low viscosity

• High biocontent