Patent GB-949126-A (GB)
Title: Improvements in or relating to organosilanes
IPC: C07F7/18
Filed: 1962-01-24
Abstract: Silicious materials, which may be incorporated as fillers in resins, are first treated by organo silanes of the general formula <FORM:0949126/C1/1> in which R is hydrogen or methyl, R1 is a divalent group composed of carbon, hydrogen and oxygen atoms, the oxygen atoms being present as ether linkages with or without hydroxyl groups, in R1 the ratio of C: O being not greater than 3: 1 and R1 being attached to both the COO and the R11 groups through CO linkages; a is ON1, R11 is an alkylene radical containing from 1 to 4 C atoms and X is an hydrolyzable atom or radical (see Division C3). They are also treated by aqueous solutions of the silanes.  Specified silicious materials are mica, clay, asbestos, quartz, diatomaceous earth, silica aerogel, and fume silica.ALSO:The invention comprises organosilanes of the general formula CH2=CR.COOR1aR11SiX3, wherein R is hydrogen or methyl, R1 is a divalent group composed of C, H and oxygen, the oxygen being present as ether linkages with or without hydroxyl groups, in R1 the ratio of C:O being not greater than 3:1, the R1 being attached to both the COO and the R11 groups through C-O linkages, a is Oor 1, R11 is an alkylene radical containing 1-4 C atoms, and X is a hydrolysable atom or radical, and also comprises the polysiloxanes of the general formula CH2= CROOOR1-R11-SiO1.5. Specified R11 radicals are methylene, propylene, ethylene, butylene and isobutylene. Specified R1 groups are-CH2CH2O-, -(CH2CH2O)50-, [(-CH2CH2O-) (-C4H8O-)10], <FORM:0949126/C3/1> <FORM:0949126/C3/2> Specified X groups are chlorine, bromine, iodine, fluorine, Me2N-, Et2N-, methoxy, ethoxy, butoxy, isopropoxy, -OCH2CH2OH, radicals of general formula -O(CH2CH2O)nY where Y is an aliphatic hydrocarbon radical containing 1-4 carbon atoms, phenoxy, cresyloxy, cetoxy, formyloxypropionoxy, Me2C=NO-, <FORM:0949126/C3/3> <FORM:0949126/C3/4> CF3.CF2O-, CF3.COO-, Me2N.CH2CH2O-, <FORM:0949126/C3/5> and CN.CH2CH2O-.  The compounds of the invention are prepared by (i) addition reaction of CH2=CR.COOR1aR111, where R111 is an unsaturated radical, e.g. vinyl, allyl, methallyl and butenyl, with a compound of the general formula H.SiX3, in the presence of a platinum catalyst; (ii) the addition reaction of <FORM:0949126/C3/6> which is prepared by reacting unsaturated epoxides <FORM:0949126/C3/7> with HSiX3, with a hydroxy ester of acrylic or methacrylic acid, in the presence of a catalyst; (iii) reaction of a tertiary amine salt of acrylic or methacrylic acid (the organic radicals attached directly to N- in the salt being alkyl containing 1-4 carbon atoms) with a chloroalkylsilane of the general formula Cl.CH2(CH2)xSi(OZ)3, where Z is alkyl or acyl, x is 0-3. The reaction is preferably carried out in the presence of an inert organic solvent, at a temperature of 100-150 DEG C., and in the presence of polymerization inhibitors, those specified being hydroquinone and N1N1-diphenylphenylene diamine. The examples describe the preparation of (1) <FORM:0949126/C3/8> (2)  CH2=CH. COO (CH2)3 Si (OMe)3; (3) <FORM:0949126/C3/90> CH2=CH-COO (M2)3SiA3, where A is -OEt, OiPr, -OAc, -OCH2OH2OBu, and -OCH2CH2-OMe; (4) <FORM:0949126/C3/101> (5) <FORM:0949126/C3/112>  The compounds of the invention are used to provide composite articles of improvised strength. This is achieved by treating a base member or filler with the above silanes or their hydrolysis product, curing the silane and thereafter applying a resin to the treated base member. Or the silane may be added to the resin, and then the mixture is applied to the base member or filler. The silane may be added as an aqueous solution or as a solution in an organic solvent.  Base members specified are metallic materials, silicious materials, textiles, shaped solids, sheets, films, fibres, metal oxides, organic plastics, organosiloxane resins and rubbers, natural and synthetic rubbers, and cellulosic products. Silicious materials are preferred (see Division C1). The treated materials are incorporated in organic resins and rubbers containing olefinic unsaturation. Specified rubber materials are hevea braziliensis, gutta balata, and gutta percha.  Specified resins are styrene, acrylic, methacrylic and polyester resins, and butadiene-styrene copolymers. The treated base members may be laminated (see Division B5).ALSO:Base members of many types are coated with a silane of the formula CH2=CRCOOR1aR11SiX3 where R is hydrogen or methyl, R1 is a divalent group composed of carbon, hydrogen and oxygen, the oxygen being present as ether linkages with or without hydroxyl groups, and R1 being attached to both the COO and the R11 groups through the C-O linkages, a is 0 or 1, R11 is an alkylene radical of 1 to 4 carbon atoms and X is a hydrolysable atom or radical (see Division C3), or they may be coated with the hydrolysates of these compounds.  Suitable base members are glass cloth, sheets and fibres, vitreous enamel, ceramic surfaces, metallic substances, metal oxides, and organic plastics including rubbers, polysiloxanes and cellulosic products.  They may be in the form of films, sheets, fibres and other shaped solids.  The silicon compounds may be applied by dipping in aqueous or organic solvent solution and the treated member allowed to dry.ALSO:Glass fibres are sized with aqueous solutions of silanes of the formula CH2 = CHRCOOR1a R11 Si X3 where R is hydrogen or methyl, R1 is a divalent group composed of carbon, hydrogen and oxygen, the oxygen being present as ether linkages with or without hydroxy groups, and R1 being attached to both the COO and the R11 groups through the C-O linkages, a is O or 1, R11 is an alkylene radical of 1 to 4 carbon atoms and X is a hydrolysable atom or radical (see Division C3).  The fibres may be contacted with a roller, moving belt or pad moistened with the solution to give a pick-up of 0.1 to 0.75% by weight of silicon compound, calculated as polysiloxane, based on the glass.