Patent GB-1066346-A (GB)
Title: Silanes, their quaternary salts and polymers
IPC: C07F7/18
Filed: 1964-09-30
Abstract: Chloromethylallyl ether is prepared by passing anhydrous hydrogen chloride into an equimolar mixture of allyl alcohol and paraformaldehyde; the water layer is then removed and excess acid blown off with nitrogen (see Example 1).ALSO:The invention comprises (1) haloether silanes of formula XC(H)(R1)-OR-SiQQ1Q11; (2) haloether-siloxanes containing units of formula <FORM:1066346/C3/1> with or without units of formula <FORM:1066346/C3/2> ; and (3) the quaternary ammonium salts thereof; wherein Q, Q1 and Q11 are each a hydrogen or halogen atom, a hydroxy monovalent hydrocarbon or halohydrocarbon radical which is free from aliphatic unsaturation, or a radical of formula <\>bRO-, <\>bR-COO-, <\>bR2C=N-O-, <\>bR=C=N-O- or R11O(CH2CH2O)m-, where <\>bR is a hydrocarbon or a halohydrocarbon radical, R11 is an alkyl radical containing 1 to 4 carbon atoms, m is 1 or 2, R is a divalent aliphatic or cycloaliphatic hydrocarbon radical containing more than one carbon atom, R1 is a hydrocarbon radical containing 1 to 6 carbon atoms or a hydrogen atom, X is a halogen atom, n is 0-2, a is 0-3, Y is an H, hydrocarbon, halohydrocarbon, alkoxy, acyloxy, phenoxy, isocyanoxy, or hydroxy radical.  The quaternary ammonium salts are derived from tertiary amines containing not more than one aromatic group.  The haloether silanes may be prepared by the addition of HSiQQ1Q11 to XCH(R1)-O-W, where W is a monovalent unsaturated aliphatic or cycloaliphatic hydrocarbon carbon radical.  These may be hydrolysed or cohydrolysed to the corresponding haloether siloxanes.  The quaternary ammonium silanes and siloxanes may be prepared by mixing the corresponding haloether silane or siloxane with the appropriate tertiary amine; quaternary ammonium siloxanes may also be prepared by the hydrolysis of the corresponding quaternary ammonium silanes.  Many examples are given: typical examples describe the preparation of (1) ClCH2O(CH2)3Si(CH3)Cl2; (2) the siloxane therefrom of unit formula ClCH2O(CH2)3Si(CH3)O-; (6) the pyridine salt thereof of formula <FORM:1066346/C3/3> and (9) a quaternary ammonium siloxane copolymer comprising units of formulae (CH3)2SiO, (CH3)SiO3/2 and <FORM:1066346/C3/4>  Uses.-Waterproofing fabrics.ALSO:Fabrics are treated with a siloxane copolymer comprising (1) 0.5 to 50 mole per cent of (a) halo-ether siloxane units of formula XCH(R')-OR-Si(Q)n <FORM:1066346/D1-D2/1> , and/or the quaternary ammonium salts thereof (2) 99.5 to 50 mole per cent of units of formula <FORM:1066346/D1-D2/2> ; wherein, X is a halogen atom, R is a divalent aliphatic or cycloaliphatic hydrocarbon radical containing more than one carbon atom, R' is hydrogen or a monovalent hydrocarbon radical containing 1 to 6 carbon atoms, Q is a hydrogen or halogen atom or a hydroxy or monovalent hydrocarbon or halohydrocarbon radical free from aliphatic unsaturation, or a radical of formula <FORM:1066346/D1-D2/3> or R"O(CH2CH2O)m-, wherein R is a hydrocarbon or halohydrocabon radical, n is 0-2, m is 1 or 2, a is 0-3 and Y is an H, hydrocarbon, halohydrocarbon, alkoxy, acyloxy, phenoxy, hydrocarbyl-substituted isocyanoxy or hydroxy radical.  These siloxanes may be used per se or in admixture with conventional siloxane water-repellents.  Cellulose fabrics are prefered.  The siloxanes are preferably applied in the form of emulsion or in solution, preferably with a curing agent e.g. metal carboxylates or alkanol amine titanates.  Examples 11, 12 and 18 describe the treatment of cotton fabrics with various siloxanes.