Patent GB-766810-A (GB)
Title: Titanated alkoxy silanes
Filed: 1954-01-18
Abstract: Silyl titanates, which are useful as stabilizers for vinyl resins and as water-repellents, are prepared by reacting (1) a silane of the formula HwRxSiOR1(4-(x+w)) <FORM:0766810/IV(a)/1> or a siloxane of the unit formula RSi(OR1)mO 3-m/2 where R is an organic group having 1 to 18 carbon atoms, R1 is an aliphatic hydrocarbon group of 1 to 18 carbon atoms, w is 0 or 1, x is 0 or an integer of 1 to 3, x+w being not greater than 3, z is 1 or 2, Z is a monovalent group of the same class as R or OR1, and m is 1/3 to 2, with (2) a titanium salt of hydrochloric or hydrobromic acid or of a saturated fatty acid having 1 to 4 carbon atoms in the molecule.  The products may have the unit formula TiO4+4n-(vx+y)SinRx(OR1)y where n is at least 1, v is the average valency of the groups R, vx is 0 to 2n, y is n to 3u, vx+y is not greater than 3n, R is connected to silicon through a carbon-silicn bond, and at least some of the OR1 groups are attached to silicon atoms.  They vary from oils to hard, insoluble, powdery products.  The group R may be alkyl, alkenyl, cycloalkyl, aryl or aralkyl, or alkylene or arylene. R1 may be the same as the monovalent aliphatic R. Specific examples of the silicon-containing starting materials are methyl, ethyl, propyl, butyl and lauryl triethyl orthosilicates, triethoxysilane, ethyltriethoxy silane, diethyldiethoxysilane, ethyldiethoxysilane, ethyltrimethoxysilane, ethyltri-n-propoxysilane, ethyltributoxysilanes, ethyltri-n-pentoxysilane, n - propyltriethoxysilane, isobutyltriethoxysilane, vinyltriethoxysilane, allyltriethoxysilane, n-hexyltriethoxysilane, phenyltriethoxysilane, phenyltri - n - propoxysilane, phenyltri - iso - pentoxysilane, cyclohexyltributoxysilane, cyclohexyltrioctyloxysilane, and siloxanes such as diphenyltetraethoxydisiloxane, butylbutoxysiloxanes, ethylbutoxysiloxanes, sec.-butylbutoxysiloxanes and butyl-2-pentoxysiloxanes.  The preparation of such siloxanes is described.  The titanium salt is preferably the tetrachloride but may be the tetrabromide, orthoformate, orthoacetate, orthopropionate and orthobutyrates.  Reaction is preferably effected by refluxing, and residual chloro or bromo groups are neutralized by sodium in excess ethanol, an alkali alkoxy silicate or an alkali metal or ammonium salt of a saturated lower fatty acid.  When the groups R1 have more than 4 carbon atoms, it is preferred to produce first a titanate having lower alkoxy or alkenoxy groups and then to exchange these by reaction with the higher alcohol.  The products impart water-repellency to paper and textiles and may be added to wax, asphalt, &c. to improve their adhesion to paper, shingles, road aggregates, &c. as an example of their stabilizing properties, ethyl ethoxysilyl titanates are added in amounts of 1, 3 and 5 per cent to a solution of vinyl chloride-vinyl acetate copolymer in methyl ethyl ketone from which films are cast.ALSO:An additive for materials such as asphalt and wax to improve their adhesion to road aggregates, paper and shingles &c. comprises a silyl titanate prepared by reacting a titanium salt of hydrochloric or hydrobromic acid or of a saturated fatty acid having 1 to 4 carbon atoms with a silane or siloxane containing silicon-bonded alkoxy or alkenoxy groups (see Group IV(a).  In an example, a mixture of asphalt and 1 per cent of an ethyl ethoxysilyl titanate is added to crushed stone.