Patent GB-804989-A (GB)
Title: Titanate ester compositions and processes for imparting water-repellency
Filed: 1956-08-30
Abstract: A composition for imparting water-repellency to porous or fibrous materials comprises an aqueous emulsion of a silicone resin incorporating an ester of titanic acid with a polyhydric alcohol. Preferably the silicone resins used are sufficiently uncured to be soluble in organic solvents.  Particularly suitable are methyl and methylphenyl silicones having an R : Si ratio of between 1.2 and 1.9 and amyl silicones having an R : Si ratio of between 1.1 and 1.8. Suitable esters of titanic acid with polyhydric alcohols are those in which the polyhydric alcohol is glycerol or pentaerythritol. Preferably the esters are modified by treatment with an alkaline-reacting organic substance, e.g. an amine or an amino-alcohol such as diethylene triamine, monoisobutylamine, cyclohexylamine, morpholine, di- and tri-ethanolamines or di- and tri-isopropanolamines.  The emulsion can also contain silicone oils, for example, liquid silicones in which the organic groups are lower alkyl groups and the R : Si ratio is roughly 2.0.  In order to obtain stable emulsions the addition of emulsifying agents, e.g. the double titanate of triethanolamine and stearic acid, a condensation product of tall oil with ten molecular equivalents of ethylene oxide for each acid group present, a polyethylene glycol alkylphenyl ether in which the alkyl group has from 8 to 15 carbon atoms, triethanolamine oleate and octadecylamine acetate, is necessary. Other substances can be incorporated in the emulsion, for example, liquid paraffin, fatty acids, alcohols, urea-formaldehyde resins or melamine resins. Preferably in the final emulsion the silicone resin content is from 0.5 to 6 per cent by weight and the titanate catalyst content from 0.01 to 0.5 per cent by weight.  In the examples water-repellent compositions are made by mixing the following materials: (1) a solution of a methyl phenyl silicone in toluene, trichloroethylene, triethanolamine, oleic acid, water and glyceryl titanate modified with triethanolamine; (2) a mixture as in (1) except that part of the water is replaced by an emulsion containing liquid paraffin, a polyoxyethyl ether of a fatty alcohol and water; (3) a solution of a methylphenyl silicone in toluene, trichloroethylene, a polyethylene glycol alkylphenyl ether, water and glyceryl titanate modified with triethanolamine; (4) an amyl silicone resin, stearylamine acetate, water and glyceryl titanate modified with triethanolamine; (5) a solution of a methyl silicone in toluene, a methyl silicone oil, triethanolamine, oleic acid, water and glyceryl titanate modified with triethanolamine; (6) a solution of methyl phenyl silicone in toluene, trichloroethylene, a double titanate of triethanolamine and oleic acid, a polyethyleneglycol alkylphenyl ether, carboxymethyl cellulose, water, glyceryl titanate modified with triethanolamine and an emulsion consisting of liquid paraffin, a polyoxyethyl ether of a fatty alcohol and water; (7) a mixture as in (1) except that the glyceryl titanate is modified with diisopropanolamine; (9) a mixture as in (1) except that the glyceryl titanate is modified with cyclohexylamine; (8) a mixture as in (1) except that the glyceryl titanate is modified with diethylenetriamine; and (10) a mixture as in (1) except that the glyceryl titanate is modified with morpholine. Specifications 723,989 and 804,990 are referred to.ALSO:Titanate compounds for use in compositions imparting water-repellency to porous or fibrous materials are obtained by esterifying titanium tetrachloride with a polyhydric alcohol and treating the product with an alkaline-reacting organic substance to reduce its acidity. Suitable polyhydric alcohols are glycerol and pentaerythritol. Suitable alkaline-reacting organic substances are, for example, diethylenediamine, monoisobutylamine, cyclohexylamine, morpholine, di- and tri-ethanolamines and di- and triisopropanolamines.  The titanate compounds are incorporated in an aqueous emulsion of a silicone resin which may also contain silicone oils and the compositions are used for waterproofing (see Group IV (a)).  In the examples (a) titanium tetrachloride is heated with glycerol and the product is heated with triethanolamine; (b) titanium tetrachloride is heated with glycerol and the product is heated with diisopropanolamine; (c) titanium tetrachloride is heated with glycerol and the product is heated with cyclohexylamine; (d) titanium tetrachloride is heated with glycerol and the product heated with diethylenetriamine; (e) titanium tetrachloride is heated with glycerol and the product heated with morpholine; the products in all cases are incorporated in compositions for imparting water-repellency.  Specifications 723,989, [Group IV (a)), and 804,990 are referred to.