Patent GB-759812-A (GB)
Title: Improvements in method of making composite resin-glass structures
IPC: C08L67/06
Filed: 1954-09-14
Abstract: Prior to bonding with an unsaturated polyester resin or a mixture of the resin, a monomer and a polymerization catalyst by curing the resins, glass is pre-treated with a material selected from liquid reaction products of vinylchlorosilanes with saturated aliphatic dihydric alcohols, vinyl-2-chloroalkoxysilanes in which the alkoxy group contains from 2 to 6 carbon atoms, and vinylacyloxysilanes in which each acyloxy group is aliphatic and contains from 2 to 6 carbon atoms.  The material may be applied to the glass as an admixture with water and a water-miscible organic solvent selected from ethanol, isopropanol, or acetone and the water and solvent removed subsequently.  The polyester resin is preferably one containing unesterified carboxyl groups and having an acid number of from 5 to 100.  The monomer is preferably immiscible with water, e.g. styrene, diallyl phthalate, or triallyl cyanurate.  The reaction products of vinylchlorosilanes with saturated, aliphatic, dihydric alcohols may be prepared according to the process of Specification 710,051, preferred silanes are vinyltrichlorosilane, divinyldichlorosilane and trivinylchlorosilane, and preferred alcohols ethylene glycol, propylene glycol, trimethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, pentanediol-2,4 and 2-ethyl hexanediol-1,3.  Examples of vinyl-2-chloroalkoxysilanes are vinyltris-(2-chloroethoxy) silane, vinyltris-(2 - chloropropoxy) silane and divinylbis - (2-chloroethoxy) silane. The preferred vinylacyloxysilane is vinyltriacetoxysilane. Unsaturated polyester resins mentioned are the reaction product of maleic anhydride, ethylene glycol and dicyclopentadiene, the reaction product of maleic anhydride, phthalic anhydride and propylene glycol, and the reaction product of maleic anhydride, phthalic anhydride, and tetrachlorophthalic anhydride.  The glass may be in the form of chopped fibres, fibres, woven fabrics or sheets.  Specified catalysts are t-butyl-, cumene-, and para-methane hydroperoxides, di-t-butyl diperoxyphthalate, t-butyl peroxyacetate, di-t-butyl, dibenzyl, methylethyl ketone, cyclohexanone, benzoyl, parachlorobenzoyl, 2,4-dichlorobenzoyl and lauroyl peroxides.  The reaction of (1) diethylene glycol and vinyl-trichlorosilane; (2) propylene glycol and vinyltrichlorosilane; (3) pentanediol-2,4 and vinyltrichlorosilane; (4) ethylene glycol and vinyltrichlorosilane; (5) 2-ethylhexanediol-1,3 and vinyltrichlorosilane; (6) diethylene glycol and cyclohexenyltrichlorosilane; (7) diethylene glycol and amyltrichlorosilane; (8) ethylene glycol and diethyldichlorosilane; and (9) diethylene glycol and diphenyldichlorosilane are described. The resins may be cured by infra-red heating.  Specifications 540,168, 540,169 and 735,405 also are referred to.ALSO:Glass fibres e.g. in the form of chopped fibres, fibres or woven fabrics, prior to bonding to unsaturated alkyd resins are pretreated with a material selected from liquid reaction products of vinylchlorosilanes with saturated aliphatic dihydric alcohols, vinyl-2-chloroalkoxysilanes in which the alkoxy group contains from 2 to 6 carbon atoms, and vinylacyloxy-silanes in which each acyloxy group is aliphatic and contains from 2 to 6 carbon atoms. The material may be applied to the fibres dissolved in a mixture of water and a water miscible organic solvent selected from ethanol, isopropanol, or acetone.  The reaction product of the vinylchlorosilane with the saturated, aliphatic, dihydric alcohol may be prepared according to the process set out in Specification 710,051 [Group IV(a)], preferred silanes are vinyltrichlorosilane, divinyldichlorosilane, and trivinylchlorosilane, and preferred alcohols ethylene glycol, propylene glycol, triethylene glycol, dipropylene glycol, pentanediol-2, 4 and 2-ethyl hexanediol-1, 3.  Examples of vinyl-2-chloroalkoxy silanes are vinyltris-(2-chloro-ethoxy) silane, vinyltris-(2-chloropropoxy) silane and divinylbis-(2-chloroethoxy) silane.  The preferred vinylacyloxysilane is vinyltriacetoxysilane. Specifications 540,168, 450,169 and 735,405 [Group IV(a)] also are referred to.