cnsl diols:outstanding hydrophobicity, reactivity …...cnsl diols:outstanding hydrophobicity,...
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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