Process for preparing a curable silylated polyurethane resin
View Patent ↗The present invention relates to a process for the production of silylated polyurethane resins free of unreacted residual isocyanate possessing consistent viscosity and stability and products therefrom.
1. A process for preparing a curable silylated polyurethane resin which comprises:
a) silylating hydroxyl-terminated polyurethane polymer obtained from the reaction of polyol with di-isocyanate and/or polyisocyanate and optionally containing residual di-isocyanate and/or polyisocyanate with isocyanatosilane under anhydrous conditions to provide silylated polyurethane possessing residual hydroxyl groups and containing residual isocyanate selected from the group consisting of di-isocyanate, polyisocyanate and isocyanatosilane: and,
b) scavenging residual isocyanate present in the silylated polyurethane with at least one isocyanate-reactive scavenging agent to provide silylated polyurethane resin of reduced isocyanate content,
the silylated polyurethane resin of reduced isocyanate content resulting from step (b) possessing a viscosity following aging which is less than that of the isocyanate-containing silylated polyurethane resin resulting from step (a) following the same conditions of aging.
2. The process of claim 1 wherein the silylated polyurethane resin of reduced isocyanate content resulting from step (b) following aging possesses a viscosity which is about 10 percent less than that of the isocyanate-containing silylated polyurethane resin resulting from step (a) following the same conditions of aging.
3. The curable silylated polyurethane resin of reduced isocyanate content resulting front the process of claim 2 .
4. The process of claim 1 wherein the silylated polyurethane resin of reduced isocyanate content resulting from step (b) following aging possesses a viscosity which is about 60 percent less than that of the isocyanate-containing silylated polyurethane resin resulting from step (a) following the same conditions of aging.
5. The curable silylated polyurethane resin of reduced isocyanate content resulting from the process of claim 4 .
6. The process of claim 1 wherein the hydroxyl-terminated polyurethane polymer is obtained from at least one polyol selected from the group consisting of polyether polyols, polyester polyols polyetherester polyols, polyesterether polyols, and polybutadiene polyols.
7. The process of claim 1 wherein the polyol possesses a number average molecular weights from about 500 to about 25,000 grams per mole.
8. The process of claim 7 wherein the polyol possesses a number average molecular weights from about 1,000 to about 20,000 grams per mole.
9. The process of claim 1 wherein the silylated polyurethane contains from about 0.01 to about 0.30 weight percent isocyanate.
10. The process of claim 1 wherein the silylated polyurethane contains from about 0.01 to about 0.15 weight percent isocyanate.
11. The process of claim 10 wherein R 1 is selected from the group consisting of methylene, ethylene, propylene, butylenes, isobutylene, 3-oxa-hexylene, dodecylene, phenylene, 1,4-bis-(methylene)benzene, 1,4-bis-(ethylene)benzene.
12. The process of claim 1 wherein the isocyanatosilane possesses the general formula:
OCN—R 1 —Si(R 2 ) y (OR 3 ) 3-y
wherein R 1 is a divalent hydrocarbon radical containing from about 1 to about 12 carbon atoms, optionally containing one or more heteroatoms, each R 2 is the same or different monovalent hydrocarbon radical of from about 1 to about 8 carbon atoms, each R 3 is the same or different monovalent hydrocarbon radical alkyl group of up to 6 carbon atoms and y is 0, 1 or 2.
13. The process of claim 10 wherein R 2 and R 3 are selected from the group consisting of methyl, ethyl, propyl, isopropyl, tert-butyl, hexyl, octyl, phenyl, 4-ethylphenyl, benzyl, and 2-phenylethyl.
14. The process of claim 1 wherein the isocyanatosilane is selected from the group consisting of 3-isocyanatopropyltrimethoxysilane, 2-isocyanatoisopropyltrimethoxysilane, 4-isocyanato-n-butyltrimethoxysilane, 2-isocyanato-1,1-dimethylethyltrimethoxysilane, 1-isocyanatomethyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 2-isocyanato-2-methylethyltriethoxysilane, 4-isocyanatobutyltriethoxysilane, 2-isocyanato-1,1-dimethylethyltriethoxysilane, 1-isocyanatomethyltriethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropyldimethylmethoxysilane, 3-isocyanatopropylphenylmethylmethoxysilane, 1-isocyanatomethylmethyldimethoxysilane, 3-isocyanatopropylethyldiethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 1-isocyanatomethylmethyldiethoxysilane, and mixtures thereof.
15. The process of claim 14 wherein the mono-alcohol possesses the general formula:
R 4 —OH
wherein R4 is a monovalent hydrocarbon radical containing from about 1 to about 30 carbon atoms, and optionally, contains a heteroatom.
16. The process of claim 15 wherein the alkyl hydrocarbon radical is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, pentyl, dodecyl, cyclohexyl, cyclopentyl, and 3-methylhexyl, and the alkenyl hydrocarbon radical is selected from the group consisting of vinyl, allyl, and methallyl, and the aryl hydrocarbon radical is phenyl, and the arenyl hydrocarbon radical is selected from the group consisting of 4-methylphenyl, 2,4-dimethylphenyl and 2,4,6-trimethylphenyl, and the aralkyl hydrocarbon radical is selected from the group consisting of benzyl and 2-phenylethyl.
17. The process of claim 1 wherein the isocyanate-reactive scavenging agent is a mono-alcohol or a mixture of mono-alcohols.
18. The process of claim 17 wherein the hydrocarbon radical is selected from the group consisting of linear alkyl, branched alkyl, cyclic alkyl, alkenyl, aryl, arenyl, aralkyl and mixtures thereof.
19. The process of claim 18 wherein the monoalkanol is at least one member selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and tert-butanol.
20. The process of claim 1 wherein the isocyanate-reactive scavenging agent is methanol when the polyurethane prepolymer is silylated with methoxysilane.
21. The process of claim 1 wherein the isocyanate-reactive scavenging agent is ethanol when the polyurethane prepolymer is silylated with ethoxysilane.
22. The process of claim 1 wherein the silylated polyurethane resin of reduced isocyanate content contains less than about 0.1 weight percent isocyanate.
23. The process of claim 1 wherein the silylated polyurethane resin of reduced isocyanate content contains less than about 0.02 weight percent isocyanate.
24. The curable silylated polyurethane resin of reduced isocyanate content resulting from the process of claim 1 .