Patent GB-812505-A (GB)
Title: Titanate ester compositions and processes for imparting water-repellency
IPC: C07F7/00
Filed: 1957-03-19
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 dihydric alcohol. Suitable silicone resins are methyl, methylphenyl, amyl and methylamyl silicones having an R : Si ratio of between 1.2 and 1.9. Mixtures of silicone resins may be used.  Suitable esters of titanic acid are those of ethylene glycol, diethylene glycol, polyethylene glycols, propylene glycol, 1 : 3 and 2 : 3-butanediol.  A preferred titanate ester is obtained by esterifying titanium tetrachloride with a dihydric alcohol and treating the product with an alkaline-reacting organic substance such as an amine or amino-alcohol (see Group IV (b)).  The emulsion may also contain silicone oils, for example liquid silicones in which the organic groups are lower alkyl groups and the R : Si ratio is about 2.0.  To obtain stable emulsions it is preferable to add emulsifying agents such as the double titanate of triethanolamine and stearic acid, a condensation product of tall oil with ten mols. of ethylene oxide per acid group, a polyethylene glycol alkylphenyl ether in which the alkyl group has from 8 to 15 carbon atoms, triethanolamine oleate and octadecylamine stearate. Stabilizers such as carboxymethylcellulose can also be added.  Liquid paraffin, fatty acids or alcohols, urea-formaldehyde resins and melamine resins, insecticides or fungicides may also be added.  The titanate catalyst lowers the temperature required for final polymerization and curing of the silicones on the material being treated, but a certain amount of heating is still desirable and should take place at a temperature not exceeding 160 DEG  C. Preferably the silicone resin content of the emulsion is from 0.5 to 6 per cent by weight and the titanate ester content corresponds to 0.01 to 0.5 per cent by weight of titanium.  The composition is suitable for the treatment of textiles, leather, paper, cardboard, masonry, wood and concrete (see Group VIII).  Examples describe the preparation of silicone emulsions comprising (5) an amyl silicone resin (R : Si = 1.6), stearylamine acetate, a titanate ester of 1 : 3-butanediol treated with triethanolamine, and water; (6) a methylphenyl silicone (R : Si = 1.6, Me : Ph = 2) in toluene, tall oil condensed with 10 mols. of ethylene oxide, trichloroethylene, carboxymethylcellulose, a titanate ester of propylene glycol treated with triethanolamine, and water; (7) an emulsion as described in (5) except that the catalyst is a titanate ester of diethylene glycol treated with triethanolamine; (8) a silicone emulsion as described in (6) except that the catalyst is a titanate ester of ethylene glycol treated with triethanolamine.  Specification 723,989 is referred to.ALSO:An ester of titanic acid with a dihydric alcohol is obtained by esterifying titanium tetrachloride with a dihydric alcohol and treating the product with an alkaline-reacting organic substance. The esterification may be effected at about 115 DEG  C. and the crude titanate mixed with 1 to 6 mols. of an amine or aminoalcohol per atom of titanium and heated carefully until a liquid is formed which gives no precipitate on dilution with water (170 DEG  C.). Suitable dihydric alcohols for the ester-formation are ethylene glycol, diethylene glycol, polyethylene glycols, propylene glycol, 1 : 3 or 2 : 3-butanediol.  Suitable alkaline-reacting substances are diethylenetriamine, monoisobutylamine, octylamine, cyclohexylamine, morpholine, di- and tri-ethanolamines, di- and tri-isopropanolamines, aminobutanol, aminoethylpropanediol and tri-(hydroxymethyl) aminoethane.  Mixtures of such substances may be used.  In examples: (1) titanium tetrachloride and 1,3-butanediol are heated together at 116 DEG C to form a water-soluble product, triethanolamine is added and the mixture is heated up to 170 DEG  C.; (2) titanium tetrachloride and propylene glycol are heated at 110 DEG  for 1 hour, triethanolamine is added and the mixture heated to 170 DEG C; (3) TiCl4 and diethylene glycol are similarly reacted and the product treated with triethanolamine; (4) a titanate catalyst is produced as in (3) using ethylene glycol.  The titanate esters may be used as catalysts in silicone emulsions (Group IV (a)) for imparting water repellancy to porous and fibrous materials (see Group VIII). Specification 723,989, [Group VIII], is referred to.