Patent GB-970598-A (GB)
Title: Vinyl sulphide-containing silicon compounds
IPC: C07F7/18
Filed: 1963-02-04
Abstract: Siliceous materials in the form of fibres, flakes, or granules, of glass, silica, quartz, asbestos, silicates, mica &c. are sized with vinyl-sulphide-containing silicon compounds. These may be applied in any conventional manner, in solution or alone, as siloxane compounds, or as silanes which hydrolyse to siloxanes in situ.  The silanes have the general formula <FORM:0970598/C1/1> and the siloxanes <FORM:0970598/C1/2> where R is a group containing C and H atoms, with or without O atoms, only.  The oxygen may be present as -OH, -COO-, or -O-. A is methyl or hydrogen, Y is a monovalent hydrocarbon or halohydrocarbon radical, X is halogen, or R1O(CH2CH2O)n or R1COO (CH2CH2O)n where R1 is an alkyl group of fewer than 5 C atoms, and n is 0, 1 or 2, and a  or b are each 1, 2, or 3, and total 2, 3, or 4 (see Division C3).ALSO:The invention comprises compounds of the formula (I) [Yy(X3-y)Si-CH2CHA]a-R-[S-CH=CH2]b wherein X is a halogen or is of formula R1(OCH2CH2)nO-, where n is 0, 1 or 2, and R1 is an aliphatic radical of less than five carbon atoms, or is R11CO-, where R11 is an aliphatic radical of less than five carbon atoms; R is attached to sulphur by a carbon-sulphur bond, and contains carbon and hydrogen or oxygen atoms only, the latter being in hydroxyl, ether or carboxyl groups only, and no carbon having more than one ether group attached; A is a hydrogen atom or methyl group; Y is a monovalent hydrocarbon or halohydrocarbon radical, lacking aliphatic unsaturation; y is 0, 1 or 2; and a and b are each 1, 2 or 3, and total 2, 3, or 4. The invention also comprises siloxanes containing units of the general formula (II) [O 3-y/2 (Yy)Si-CH2CHA]a-R-[S-CH=CH2]b the remaining units being of formula ZcSiO 4-c,/2 where Z is a monovalent hydrocarbon or halohydrocarbon radical, and c is 0, 1, 2, or 3. Preferred forms of compounds (I) are (R111O)3Si-CH2CHA-R1111-S-CH=CH2 where R111 is an alkyl group of less than three carbon atoms, and R1111 contains less than eight atoms of carbon and oxygen together, and preferred forms of (II) are the corresponding hydrolysates O3/2Si-CH2CHA-R1111-S-CH= CH2.  The compounds (I) may be prepared in three ways: (a) by reaction of a silane Yy(X3-y)SiH with a compound CH2=CHC .... S-CH=CH2 in the presence of a catalyst, e.g. chlorplatinic acid or platinum/charcoal, the silane adding preferentially to the vinyl group not attached directly to sulphur; (b) by reaction of an epoxy silane <FORM:0970598/C3/1> with alcohols or acids terminated -S-CH=CH2. Amine catalysts are suitable.  X should not be sensitive to hydroxyl groups; or (c) by reaction of an epoxy silane as in (b) and an epoxy vinyl sulphide with a di-, tri-, or tetra-hydroxy alcohol. The siloxanes (II) are prepared (d) from the compounds (I) by hydrolysis, or by co-hydrolyzing them with other silanes ZcSiX4-c or (e) from siloxanes containing Si-H bonds or epoxy groups, in the manner of (a), (b) and (c) above. The compounds may be copolymerized with vinylic and acrylic resins e.g. styrene, methyl methacrylate, butyl acrylate, vinyl chloride, vinylidene dichloride, acrylonitrile and allyl cyanurate, or with unsaturated polyester resins e.g. copolymers of maleic acid with ethylene glycol, butadiene, mixtures of butadiene and styrene, and chloroprene. The Examples 1-11 describe the preparation, according to method (a) of (CH3O)3SiCH2CH2CH2O-CH2 CH2SCH =CH2, and compounds having (CH3O)3Siattached to -(CH2)3SCH=CH2, -(CH2)4SCH =CH2, -(CH2)3OOC.CH2SCH=CH2 and -(CH2)2O(CH2)2SCH=CH2, and hydrolysates of these, and of CH3SiCl2(CH2)2C6 H4SCH= CH2, C18H37(CH3)SiF(CH2)2 C6H10SCH= CH2, ClC6H4Si(OC4H9)2C18 H37SCH=CH2, (CH3OCH2CH2O)2Si(C2H4CF3 (CH3)2O CH2C­CCH2SCH=CH2, (CH3-COO)3Si(CH2)3SCH=CH2, [(CH3)2CHO](C6H5)Si(C6H11) (CH2)2CH(CH3) SCH=CH2, (C2H5COO)(C2H5)(pC6H4CF3 Si(CH2)3 OOC-CH2SCH=CH2, [CH3-COO-(CH2)2O(CH2)2O]2Si(2, 4-C6H3Br2) (CH2)4SCH=CH2, and [(CH2)3O (CH2)2O]2 [Cl(CH2)3]Si(CH2)3SCH=CH2, and of materials derived from various Si-H containing siloxanes and CH2=CHCH2SCH=CH2.  By method (b) is prepared (CH3O)3Si(CH2)3OCH2CHOH CH2O(CH2)2SCH=CH2, and by method (c) [(CH3O)3Si(CH2)3OCH2CHOHCH2 OCH2]1 or 2 C(CH3)[CH2OCH2CHOHCH2O(CH2)2 SCH = CH2]2 or 1, (CH3O)3Si(CH2) 3OCH2CHOHCH2 OOC CH2COO CH2CHOH CH2SCH=CH2 and [(CH3O)3Si(CH2)3OCH2CHOH CH2 OCH2]1, 2 or 3, C[CH2OCH2CHOH CH2O(CH2)2SCH= CH2]3, 2 or 1. Also prepared are co-hydrolysates of CH3SiCl2(CH2)3O(CH2)2SCH= CH2 with CH2=CH(CH3)SiCl2, C6H5(CH3)Si Cl2, CF2=CF(CH3)SiCl2, CH2=CH CH=CH (C6H5)SiCl2 and ClCH=CHCH2CH2 (CH3) SiCl2, and compounds (CH3COO)2(CH3) SiCH2CH(CH3)COOCH2CHOH CH2O(CH2) 2 SCH=CH2 and (CH3O)2[C6H5(CH3) CHCH2] Si(CH2)3OCH2CHOH CH2O(CH2)2SCH =CH2, Example 12 describes the preparation of a glass cloth laminate from a polyester resin (70 parts of phthalic acid/maleic acid/propylene glycol linear polyester in 30 parts of styrene, plus 0.5 part of benzoyl peroxide in 7 parts styrene). The compounds may also be used for sizing siliceous materials, for which purpose those of formula (R1 1 1O)3Si-CH2CHA-R1 1 1-SCH= CH2 and their hydrolyzates are preferred, and as coating compositions, alone or copolymerized with vinylic, acrylic or unsaturated polyester resins.ALSO:Glass cloth is coated with vinyl sulphide-containing silicon compounds, which may be applied in any conventional manner, in solution or alone, as siloxane compounds or as silanes which hydrolyse to siloxanes in situ.  The siloxanes have the general formula <FORM:0970598/B1-B2/1> and the silanes <FORM:0970598/B1-B2/2> where R is a group containing CH and O atoms only, the latter as -OH, -COO- or -O-groups, A is H or CH3, Y is a hydrocarbon or halohydrocarbon monovalent radical, X is halogen, or a group R1(O CH2CH2)nO or R1CO(OCH2CH2)nO, where R1 is an alkyl group of less than 5 carbon atoms and n is 0, 1, or 2, and a and b are each 1, 2, or 3, and total 2, 3, or 4 (see Division C3). In Example 12 glass cloth is dipped in solutions of 0,5% of (CH3O)3Si(CH2)3OCH2CHOHCH2O (CH2)2SCH=CH2 in methanol, 0,5% of <FORM:0970598/B1-B2/3> in 0,1% acetic acid in water, and 0,5% of <FORM:0970598/B1-B2/4> in a 3 : 1 water/propanol mixture.  The treated cloths are treated with an unsaturated polyester resin.