GB895091A

GB895091A - Improvements in or relating to organosilicon compounds

Info

Publication number: GB895091A
Application number: GB24120/60A
Authority: GB
Original assignee: Dow Corning Corp
Current assignee: Dow Silicones Corp
Priority date: 1959-07-13
Filing date: 1960-07-11
Publication date: 1962-05-02

Abstract

Silicon-bonded hydroxyl groups in organosilicon compounds are condensed without the rupture of any siloxane groups by contacting (A) an organosilicon compound containing at least one silicon-bonded hydroxyl group per molecule, the remaining silicon valencies in the organosilicon compound being satisfied by radicals selected from silicon-bonded oxygen atoms, hydrocarbon radicals and hydrocarbon radicals containing functions selected from ether linkages, aromatic halogen atoms, nitrile groups, hydroxyl groups and aliphatic fluorine atoms, the last mentioned being separated from any silicon atom by at least three carbon atoms, with (B) a compound compatible with (A) and selected from (1) a salt of (a) a phosphoric acid, the only active hydrogen atoms in the acid being attached to the phosphorous through an oxygen atom, and (c) a basic amino compound, any active hydrogen in the amino compound being attached to nitrogen and any remaining nitrogen valencies being satisfied by carbon atoms, the total number of carbon atoms per molecule in (1) being at least 18, and (2) a salt of (b) formic acid or a carboxylic acid wherein the only active hydrogen is a part of a carboxyl group attached to a carbon atom, and a basic amino compound (c) the total number of carbon atoms per molecule in (2) being at least 6. Siloxane bonds are produced with the elimination of water. An active hydrogen atom is defined as one which reacts with methyl magnesium iodide at room temperature to give methane. Heat curable compositions consist essentially of a mixture of an organopolysilocane (A) containing an average of from 1,0 to 1,7 monovalent hydrocarbon radicals per silicon atom and an average of more than two silicon-bonded hydroxyl groups per molecule, and a salt of a carboxylic acid (2). The organosilicon compound (A) can be any silane, silcarbane or siloxane or any mixture thereof in which the only functional groups attached directly to any silicon atom are hydroxyl groups. Any other groups present in the molecule must not interfere with the condensation. The remaining silicon valencies may be satisfied by any radical such as the methyl, ethyl, isopropyl, tertiary butyl, 2-ethylhexyl, dodecyl, octadecyl, myricyl, vinyl, allyl, hexadienyl, cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl, phenyl, naphthyl, xenyl, benzyl, phenylethyl, xylyl, tolyl, dimethylphenyl, 2,4,6-trichlorobenzyl, perchlorophenyl, 2-bromonaphthyl, p-iodophenylethyl, 4-fluorophenyl, 3,3,3-trifluoropropyl, a ,a ,a -trifluorotolyl-3,3,4,4,-5,5,5-heptafluoropentyl, 5,5,5-trifluoro-2-trifluoromethylamyl, 4-ethyl-4-hydroxyhexyl, 3-hydroxyallyl, cresyl, p-hydroxyphenyl, 2-(4-hydroxycyclohexyl) - ethyl, g - cyanopropyl, b -cyanoethyl, 2-ethoxyethyl, 4-tetrahydropyranyl, CH3O(CH2CH2O)2CH2-, CH2 = CHCH2OCH2 -, furyl, 5-hydroxy-6-methoxyhexyl, C6H5CH5 -CH2CHOHCH2O(CH2)3-, pentafluoroethoxyethyl, 2-fluoro-4-tetrahydropyranyl, p-ClC6H4 -CH2CHOHCH2O(CH2)3-, methylene, vinylene, vinylidene, cyclohexylidene, phenylene, tolylene, toluenyl, toluylene, -CH2(OCH2CH2)6 OCH2-CH2CH2- -(CH2) 4CHOHCH2OCH2-, -CH2-CH2CHFCH2CH2-, iodophenylene and-C H2- <FORM:0895091/IV (a)/1> -CH2- radicals, tertiary carbon atoms and quaternary carbon atoms. If R is any of the monovalent radicals and R1 is any of the polyvalent radicals above the organosilicon compound may be a monomeric compound such as R3SiOH, R2Si(OH)2, RSi(OH)3, R3SiR1Si(OH)3, R3SiR1-Si(R2)OH, HO(R2)SiR1Si(R)(OH)2, HO(R2)Si-R1[Si(R2)OH]2, HO(R2)SiOSi(OH)(R)OSi(R2)-OH or HO[Si(R2)O]5Si(OH)2O[Si(R2)O]5H: specific compounds mentioned are CF3CH2CH2Si-(OH)2Me, (HO)3SiO[Si(C6H5)(Me)O]2, Si(C6H5)-(Me)OH, C6H5(Me)(CH2 = CH)SiOH, HOSi- <FORM:0895091/IV (a)/2> (Me)Si(C6H5)CH2CH2CH2CH2 CH2CH2OCH2-OCH2Si(Me2)OH and p-MeC6H4Si(OH)(Me)O-[Si(Me2)CH = CH-Si(Me2)O]2Si(Me2)OH, or can be a polymeric material made up of one or more units such as R3SiO0,5, R2SiO, RSiO1,5, R2Si(OH)O0,5, RSi(OH)O, SiO4/2 and O0,5(R2)-SiR1Si(R2)O0,5. The phosphoric acids (a) may be phosphoric, phenylphosphoric, monooctadecylphosphoric and diethylphosphonic acids. The carboxylic acids (b) may be n-octanoic, succinic, abietic, acetic, cyanoacetic, phenoxyacetic, acrylic, b -benzoylacrylic, angelic, anisic, N-acetylanthranilic, arachidic, atropic, benzoic, o-bromobenzoic, p-cyanobenzoic, 2,6-dichlorobenzoic, 2,5-dinitrobenzoic, m-fluorobenzoic, brassidic, dl-camphalic, capric, cinnamic, palmitic, butyric, cyclohexanecarboxylic, cyclopropanecarboxylic, 3-furancarboxylic, 5-nitro-2-furoic, 10-hendecenoic, isobutyric, lauric, levulinic, lignoceric, linoleic, oleic, stearic, tetrahydropyromucic, decanoic, 3-ethylpentanoic, 2,4-xylic, adipic, azelaic, o-carboxymethoxybenzoic, 1-camphoric, myristic, 1,2-cyclobutanedicarboxylic, pimelic, sebacic, 1,2,3,4,5,6-cyclohexanehexacarboxylic, traumatic, 1,3-cyclopentanedicarboxylic, diphenic, caprylic, ethylmalonic, 2-ethylhexoic, tridecanoic, suberic, o-chlorophenoxyacetic, hexanoic, 3-ethoxypropionic, trimethyl-n-hexanoic and 2,2-dimethylpropanoic acids, Me3SiCH2CO2H and [HO2-CCH2CH2Si(Me2)]2O. The amino compounds (c) may be ammonia, o-aminoacetanilide, iminodiacetonitrile, m-aminoacetophenone, allylamine, diallylamine, N-methylallylamine, amylamine, decylamine, di-m-tolylamine, N,N-dimethylallylamine, aniline, p-bromoaniline, 2,6-dinitroaniline, m-fluoroaniline, o-iodoaniline, o-nitroaniline, 2,3,4,5-tetrachloroaniline, o-anisidine, 9-anthrylamine, 4,41-diaminoazobenzene, histamine, anthranilonitrile, benzylamine, p-methoxybenzylamine, dicyclohexylamine, diethylenetriamine, difurfurylamine, b -ethoxyethylamine, tetrahydrofurfurylamine, benzylhydrazine, p-bromophenylhydrazine, 1-methyl-1-phenylhydrazine, 4,41-diaminohydrazo-benzene, p-3-leucaniline, methylamine, morpholine, 5-nitronaphthylamine, piperazine, 1,2-dimethyl-4-pentenylamine, N,N-diethyl-p-phenylenediamine, piperidine, 2-aminopyridine, 6-nitro-o-toluidine, 2-amino-p-tolunitrile, 9-phenanthrylamine, tribenzylamine, triethylamine, eicosylamine, dodecylamine, tetradecylamine, N-methylhexylamine, di-2-ethylhexylamine, 4,41-diaminobenzophenone, 4,41-diaminodiphenyl ether, tri-n-butylamine, 3,4-dichloroaniline, didodecylamine, ethylamine, diisopropylamine, trimethylamine, 2,5-dimethylpiperazine, octadecylamine, ethylenediamine, tetraethylene-pentamine, 1,2-diaminopropane, n-hexylamine, isobutylamine, tertiary butylamine, cyclohexylamine, tertiary octylamine, tertiary monylamine, tridecylamine, menthanediamine, tridecyldodecenylamine, tridecyldodecylamine, dibenzylamine, di-n-hexylamine, N,N-dimethyldodecylamine, triisoamylamine, tri-n-hexylamine, tetramethylethylenediamine, tetramethylguanidine, tetramethylene diamine, di-eicosylamine, tri-eicosylamine [NH2CH2-CH2CH2(Me2)Si]2O, and NH2CH2CH2-NHCH2CH2CH2Si (C6H5)2Me. In a typical example a phenylmethylpolysiloxane with hydroxyl end-groups was heated with n-hexylamine 2-ethylhexoate and then phenylmethylvinylsilanol was added. The mixture was further heated. Sym-diphenyldimethyl-divinyldisiloxane was removed by distillation leaving a phenylmethylvinylsiloxy-endblocked phenylmethylpolysiloxane. The process may be used for the polymerisation of linear polymers in the preparation of rubber-grade gums and for the curing of resins.ALSO:Amine salts of carboxylic acids or of phosphoric, alkylphosphoric or arylphosphoric acids are prepared by mixing together the appropriate amines and acids in the proportions corresponding to their mol ratios in the final salt. The amines mentioned are: o-aminoacetanilide, iminodiacetonitrile, m-aminoacetophenone, allylamine, diallylamine, N-methylallylamine, amylamine, decylamine, N,N-dimethylamylamine, aniline, p-bromoaniline, 2,6-dinitroaniline, m-fluoroaniline, o-iodoaniline, o-nitroaniline, 2,3,4,5-tetrachloroaniline, o-anisidine, 9-anthrylamine, 4,41-diamino - azobenzene, anthranilonitrile, benzylamine, p - methoxybenzylamine, dicyclohexylamine, diethylenetriamine, difurfuralamine, di - m - tolylamine, b - ethoxyethylamine, tetrahydrofurfurzlamine, listamine, benzylhydrazine, p - bromophenylhydrazine, 1 - methyl - 1 - phenylhydrazine, 4,41 - diaminohydrazobenzene, p - 3 - leucaniline, methyl amine, morpholine, 5 - nitronaphthylamine, 1,2 - dimethyl - 4 - pentenylamine, N,N - diethyl-p - phenylenediamine, piperazine, piperidine, 2 - aminopyridine, 6 - nitro - o - toluidine, 2 - amino - p - tolunitrile, 9 - phenanthrylamine, tribenzylamine, triethylamine, eicosylamine, dodecylamine, tetradecylamine, N - methylhexylamine, di - 2 - ethylhexylamine, 4,41 - diaminobenzophenone, 4,41 - diaminodiphenyl ether, tri - n - butylamine, 3,4 - dichloroaniline, didodecylamine, ethylamine, diisopropylamine, trimethylamine, 2,5 - dimethylpiperazine, octadecylamine, ethylenediamine, tetraethylenepentamine, 1,2 - diaminopropane, n - hexylamine, isobutylamine, tertiary butylamine, cyclohexylamine, tertiary octylamine, tertiary nonzlamine, tridecylamine, menthanediamine, tribecyldodecenylamine, tridecyldodecylamine, dihenzylamine, di - n - hexylamine, N,N - dimethyldodecylamine, triisoamylamine, tri - n - hexylamine, tetramethylethylenediamine, tetramethylguanidine, tetramethyleneguanidine, tetramethylene diamine, di - eicosylamine and tri-eicosylamine. The carboxylic acids mentioned are: n-octanoic, succinic, abietic, acetic, cyanoacetic, phenoxyacetic, acrylic, b -benzoylacrylic, angelic, anisic, N-acetylanthranilic, arachidic, atropic, benzoic, o-bromobenzoic, p-cyanobenzoic, 2,6-dichlorobenzoic, 2,5-dinitrobenzoic, m-fluorobenzoic, brassidic, dl-campholic, capric, cinnamic, cyclohexanecarboxylic, cyclopropanecarboxylic, formic, 3-furancarboxylic, 5-nitro-2-furoic, 10-hendecenoic, isobutynic, lauric, levulinic, lignoceric, linoleic, oleic, stearic, tetrahydropyromucic, 3-ethylpentanoic, 2,4-xylic, adipic, azelaic, o-carboxymethoxybenzoic, 1-camphoric, 1,2 - cyclobutanedicarboxylic, 1,2 3,4,5,6 - cyclohexanehexacarboxylic, 1,3 - cyclopentanedicarboxylic,