Low VOC epoxy silane oligomer and compositions containing same
View Patent ↗A process for producing a low VOC epoxy silane oligomer which includes hydrolyzing an epoxy silane, the epoxy silane upon hydrolysis of its hydrolyzable sites producing a reduced amount of volatile organic compound compared to that produced by the hydrolysis of a silane possessing an equivalent number of hydrolyzable sites all of which are hydrolyzable alkoxy groups, the hydrolyzing of the epoxy silane being carried out with less than 1.5 equivalents of water, said water being continuously fed during the hydrolysis reaction.
1. An epoxy silane oligomer composition which is produced by the process comprising reacting an epoxy silane with water in a molar ratio of water to epoxy silane of from 0.1 to 1.5, wherein the epoxy silane is produced by reacting at least one epoxy alkoxy-substituted silane monomer and, optionally, a copolymerizable alkoxy-substituted silane other than glycidoxy and cycloaliphatic epoxy silane having two or three alkoxy groups, with a diol or dicarboxylic acid.
2. The epoxy silane oligomer composition of claim 1 wherein the epoxy silane monomer is a glycidoxy and/or cycloaliphatic epoxy silane having two or three alkoxy groups.
3. The epoxy silane oligomer composition of claim 2 wherein the glycidoxy silane is at least one member selected from the group consisting of gamma-glycidoxypropyl trimethoxysilane, gamma-glycidoxypropyl triethoxysilane and gamma-glycidoxypropyl methyldiethoxysilane; the cycloaliphatic epoxy silane is at least one member selected from the group consisting of beta-(3,4-expoxycyclohexyl)-ethyl trimethoxysilane and beta-(3,4-epoxycyclohexyl)-ethyl triethoxysilane; and, optional copolymerizable silane other than glycidoxy and cycloaliphatic epoxy silane is at least one member selected from the group consisting of vinyl trimethoxysilane, vinyl triethoxysilane, vinyl methyl dimethoxysilane, vinyl triisopropoxysilane, octyl triethoxy silane, propyl triethoxy silane, propyl trimethoxy silane, methyl trimethoxysilane, methyl triethoxysilane, polyalkyleneoxidetrimethoxy silane, methacryl trimethoxy silane, methacryl triethoxy silane and methacryl triisopropoxy silane.
4. The epoxy silane oligomer composition of claim 1 wherein the production of the epoxy silane is carried out in the presence of a catalyst and, optionally, a solvent.
5. The epoxy silane oligomer composition of claim 4 wherein the catalyst is selected from the group consisting of p-toluenesulfonic acid, sulfuric acid, hydrochloric acid, chlorosilanes, chloroacetic acids, phosphoric acid, sodium methoxide, sodium ethoxide, titanium alkoxides, titanium-containing chelates, zirconium alkoxides, zirconium-containing chelates and any combination thereof.
6. The epoxy silane oligomer composition of claim 4 wherein the solvent is an alcohol-free solvent, wherein the alcohol-free solvent is at least one member selected from the group consisting of acetone, toluene, aliphatic hydrocarbon, paraffin, aromatic hydrocarbon, ketone and ester.
7. The epoxy silane oligomer composition of claim 1 , which further comprises continuously removing by-product alcohol produced during the reaction.
8. The epoxy silane oligomer composition of claim 1 wherein the epoxy silane monomer is combined with a monomeric silane with the proviso that the monomeric silane is non-reactive with the epoxy functionality of the epoxy silane monomer.
9. The epoxy silane oligomer composition of claim 8 wherein the monomeric silane is at least one member selected from the group consisting of gamma-glycidoxypropyl trimethoxysilane, gamma-glycidoxypropyl triethoxysilane, gamma-glycidoxypropyl methyldimethoxysilane, gamma-glycidoxypropyl methyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinylmethyldimethoxysilane, gamma-methacryloxypropyl trimethoxysilane, gamma-methacryloxypropyl triethoxysilane, gamma-methacryloxypropyl triisopropoxysilane, octyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, polyalkyleneoxidetrimethoxysilane, 3-methacryloxypropyltrimethoxy silane, 3-methacryloxypropyltriethoxy silane and 3-methacryloxypropyltriisopropoxy silane.
10. The epoxy silane oligomer composition of claim 1 wherein the dicarboxylic acid is selected from the group consisting of adipic acid and malonic acid.
11. The epoxysilane oligomer composition of claim 1 wherein the diol has the Formula (2):
HO(R 10 CR 11 ) f OH (2)
wherein:
each occurrence of R 10 is independently chosen from the set of groups consisting of a hydrogen; straight alkyl, cyclic alkyl, branched alkyl, alkenyl, aryl, and aralkyl group containing from 1 to 20 carbon atoms; an ether group containing from 1 to 20 carbon atoms; a polyether group containing from 1 to 20 carbon atoms; and a heterocarbon group containing from 1 to 20 carbon atoms;
each occurrence of R 11 is independently chosen from the set of groups consisting of a hydrogen; straight alkyl, cyclic alkyl, branched alkyl, alkenyl, aryl, and aralkyl group containing from 1 to 20 carbon atoms; an ether group containing from 1 to 20 carbon atoms; a polyether group containing from 1 to 20 carbon atoms; and a heterocarbon group containing from 1 to 20 carbon atoms; and
each occurrence of the subscript f is an integer from 1 to 15 carbon atoms.
12. The epoxysilane oligomer composition of claim 11 wherein the diol is selected from the group consisting of ethylene glycol, propylene glycol, neopentyl glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,3-butanediol, 2-methyl-2,4-pentanediol, 1,4-butanediol, cyclohexane dimethanol, pinacol, polysiloxane diol and polyether siloxane diol.