Oxymer Diols for PUD
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Oxymer™ diols for PUD
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OutlineHigh performance diols for polyurethane dispersions– Oxymer™ Polycarbonate polyols
Experimental– Polyurethane dispersions
Results– Coating performance
Conclusion
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Oxymer™ – polycarbonate diolsPolycarbonates offer
High chemical resistanceVery good hydrolysis and UV resistanceExcellent outdoor durabilityOverall high performance
Perstorp’s range of polycarbonate polyols includes Oxymer™ M112 and C112
Oxymer™ polycarbonate diol are based on rigid carbonate-linkage and branched aliphatic 1,3-diolsOxymer™ no crystallinity, high hydrophobicity and low surface energy
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0 500 1000 1500 2000
Tensile properties – flexibilityThe polycaprolactones are very suitable for applications with high demands on flexibility
1,000 g/mol based 2,000 g/mol based
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HD polycarbonate
PTMEG
Capa 220 1A
HDO-adipate
Strain in %
Forc
e in
N
Forc
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Strain in %
HDO – polycarbonate
Capa 210 1A
PTMEG
HDO-adipate
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The characteristics of Oxymer™
M112Oxymer™ M is a rigid hydrophobic diol
Low surface energy due to hydrophobic side-branchesExcellent acid and alkali resistanceHigh hardnessVery good outdoor durability and hydrolytical stabilityRecommended for rigid substrates, e.g. metal
Waterdrop contact angle (θ) on polyurethane coating with
Oxymer™ M112 and 1,6-Hexanediol polycarbonate as macrodiol
74 °C 54 °C
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The characteristics of Oxymer™
C112Oxymer™ C is the more flexible diol in the range
Very good outdoor durabilityExcellent hydrolytic stabilityImproved flexibility and abrasion resistance compared to Oxymer™ MImproved wetting and adhesive properties (substrate dependant)Very good alkali and acid resistanceSuitable for plastic and wood substrate
A winning formula for performance
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Materials and PUD preparation
Oligomer Physical state(RT)
Tm/Tg (°C) Viscosity (Pas)75°, 60-1s
Oxymer™ M112 Clear viscous liquid -23 1.1 (75 °C)
Oxymer™ C112 Clear viscous liquid -33 1.5 (75 °C)
HDO-PCD Solid -61 0.4 (75 °C)
PTMEG Solid ND 0.1 (75 °C)
NPG-Adipate Solid -55 0.4 (75 °C)
Oxymer™ – liquid polycarbonate diols based on substituted aliphatic diols
Oxymer™ M112 and C112 were evaluated in physically drying PUDs prepared using the pre-polymer mixing process
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Oxymer™ increases coating hardnessIncluding Oxymer™ in your formulation will increase the coatings hardness.
Flexibility of physically dried polyurethane dispersion measuredas Erichsen flexibility on force dried films (25 μm ± 5 μm or 24 h at 80 °C) on aluminum panels.
Oxymer™ M112 is the more rigid diol
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Oxymer M112 Oxymer C112 HDO polycarbonate NPG-adipate PTMEG
Kön
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Pendulum hardnessDFT: ~30 µm
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Oxymer™ C maintains flexibilityOxymer™ C112 manages to combine coating hardness with flexibility
Evaluated on Aluminum plates using Erichsen cupping testForced dried samples 24 h at 80 °C. Dry film thickness 25 μm ± 5 μm on Al.
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Oxymer M112 Oxymer C112 HDO polycarbonate NPG-adipate PTMEG
mm
Erichsen cupping testFlexibility on Al
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Polyurethanes with Oxymer™ have improved resistance to acid and baseOxymer™ display excellent resistance towards both alkali and acidic media
Evaluated by chemical spot tests. 5-1, where 5 = no visible change; 1 = distinct mark with altered surface Forced dried samples 24 h at 80 °C. Dry film thickness 30 μm ± 5 μm on glass panels.
Excellent
Poor
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Oxymer M112 Oxymer C112 HDO-PCD NPG-adipate PTMEG
HCI (aq. 5% 1 h) NaOH (aq. 5% 15 min.) Water (16 h)
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Excellent
Poor0
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Oxymer M112 Oxymer C112 HDO-PCD NPG-adipate PTMEG
Oxymer™ offers improved wetting and adhesion to plasticsOxymer™ has low surface tension → Improved wetting and adhesionOxymer™ display improved adhesion to both plastic and metal substrates
XXX
ABS Polyamide PVC Aluminum
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Oxymer™ C improves abrasion resistance
Abrasion resistance evaluated using Scotch Brite gloss retention test –1,000 g/mol macrodiols Forced dried samples 24 h at 80 °C. Dry film thickness 25 μm ± 5 μm on black glass panels.
The combination of hardness and flexibility of Oxymer™ C112 results in good abrasion resistance
Number of double rubs
Glo
ssre
tent
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at 8
5 °C
Oxymer M112
Oxymer C112
HHDO Polycarbonate
NPG-adipate
PTMEG
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UV-PUD with Oxymer™
Macrodiol 50.09
Bis-MPA 6.71
Di-propylene glycol di-methyl ether 40.00
DBTL 100% 2 drops
IPDI 33.34
Di-TMP tetra acrylate (Ebecryl 140) 25.00
4-metoxyphenol 0.025
TEA 4.30
Water 245.06
Ethylene diamine 2.70
Summa 407.70
NCO/OH 1.5Extender NH/NCO 0.9Neutralization, % 85Solid content, % 30
The UV-PUDs were mixed with Irgacure500 (1.5% w/w).
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Sample Thickness Pendulum hardness Pencil hardness
Fomrez 66-112 22 110 H/2H
Oxymer M 112 20 201 6H/7H
Oxymer C 112 25 180 6H/7H
Hexanediol polycarbonate 25 154 3H/4H
UV-PUD, hardnessThin coatings
Thicker coatings
Applied on glass panels, force dried at 80 °C for 30 minutes.Evaluated 1 week after curing.
Sample Thickness Pendulum hardness Pencil hardness
Fomrez 66-112 44 87 2H/3H
Oxymer M 112 42 153 6H/7H
Oxymer C 112 42 138 5H/6H
Hexanediol polycarbonate 42 118 6H/7H
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UV-PUD, chemical resistance
Applied on glass panels, force dried at 80 °C for 30 minutes.Chemical spot test 1 week after curing, evaluation 24 hours after testing.
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Fomrex 66-112, 16 µm Oxymer M 112, 17 µm Oxymer C 112, 17 µm Hexanediol PC, 25 µm
Water (24 h) Ethanol 48% (6 h) NaOH 5% (30 min) HCL 5% (1 h)
Note: Varying thickness of coatings
Excellent
Poor
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UV-PUD, MEK and flexibility
Thickness ~20 µm.Applied on Aluminium panels, force dried at 80 °C for 30 minutes.Evaluated 1 week after curing.
Sample MEK Erichsen flexibility
Fomrez 66-112 40 > 6.0
Oxymer M112 160 > 6.0
Oxymer C112 130 > 6.0
Hexanediol polycarbonate 30 > 6.0
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UV-PUD, cross cut adhesion
Thickness ~20 µm.Applied on Aluminium panels, force dried at 80 °C for 30 minutes.Evaluated 1 week after curing.
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Fomrex 66-112 Oxymer M 112 Oxymer C 112 Hexanediol PC
Excellent
Poor
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ConclusionThe Oxymer™ products are excellent starting diols for PUDs
Oxymer™ polycarbonate diols improves the resistance against hydrolysis, has very good outdoor resistance, high hardnessand good adhesionOxymer™ C112 has good flexibility and increases the abrasionresistanceOxymer™ M112 , the most hydrophobic carbonate diol, gives the highest resistance towards chemicals and solvents (polar) and offers advantages when applying to plastic coatings
Putting the care into chemicals
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PUD formulationPUDs prepared according to prepolymer mixing
Macrodiols (1,000 g/mol)
Oxymer™ M112
Oxymer™ C112
HD polycarbonate (hexane diol polycarbonate)
Polyester (neopentyl glycol-adipic acid)
Polyether (poly(tetramethylene ether)
General PUD formation 1,000 g/mol
Macrodiol 16.7
Bis-MPA 2.2
IPDI 10.4
NMP 10.0
DBTL 0.005
Triethyl amine (TEA) 1.4
Water 58.6
Ethylene diamine 0.6
Total 100.0
Theoretical data 1,000 g/mol
Bis-MPA/macrodiol molar ratio 1.0
NCO/OH ratio 1.4
NH/NCO ratio 0.8
TEA/COOH ratio 0.85
Non volatile content, % m/m 30