Patent GB-1282885-A (GB)
Title: Novel organofunctional silicon compounds and their preparation
IPC: C07F7/18
Filed: 1969-06-11
Abstract: 1282885 Organosilanes and siloxanes; polyethers; polyesters UNION CARBIDE CORP 11 June 1969 [11 June 1968] 29502/69 Headings C3R C3S and C3T [Also in Division C5] Novel organofunctional silanes and siloxanes of the formulµ wherein a is 1, 2 or 3 ; b is an integer of from 1 to 6; c is an integer of from 1 to 4; d is 0, 1, 2 or 3; the sum of c+d does not exceed 4; e is 1, 2 or 3; f is 0, 1 or 2; the sum of e+f does not exceed 3; R denotes a radical free of aliphatic unsaturation having a valence of from 1 to 6, said valence being equal to bc/a for the first formula and be/a for the second formula, and said R radical being selected from H, C 1-18  monovalent hydrocarbon groups optionally substituted by halogen, alkoxy, cyano, nitro, hydroxy or R<SP>3</SP>O(C n H 2n O) x - (wherein R<SP>3</SP> denotes a C 1-18  monovalent hydrocarbon group, n is 2, 3 or 4 and x is an integer of from 1 to 100), C 1-18  acyl groups optionally substituted by hydroxy, C 1-18  alkoxy or R<SP>3</SP>O(C n H 2n O) x -, C 2-18  divalent hydrocarbon groups, (wherein R<SP>4</SP> denotes a C 2-18  divalent hydrocarbon group), -R<SP>5</SP>O(CO-R<SP>4</SP>-COOR<SP>5</SP>-) x - (wherein R<SP>5</SP> denotes a C 2-18  divalent hydrocarbon group),  C 3-18  trivalent hydrocarbon groups, trivalent groups of the formula  R<SP>6</SP>(CO-) 3 - (wherein R<SP>6</SP> denotes a C 3-18  trivalent hydrocarbon group), C 3-18  tetravalent hydrocarbon groups, tetravalent groups of the formula C 4-18  pentavalent hydrocarbon groups, pentavalent groups of the formula C 4-18  hexavalent hydrocarbon groups and hexavalent groups of the formula Y denotes -O-, -S- or -N(R<SP>111</SP>)- (wherein R<SP>111</SP> denotes H or a C 1-18  monovalent hydrocarbon group); R<SP>1</SP> denotes a divalent halogen-substituted C 2-18  alkylene, cycloalkylene or alkylenearylene group, the halogen atom and the Y-group being bonded to adjacent non- aromatic carbon atoms in R<SP>1</SP>; and R<SP>11</SP> denotes a monovalent organic group bonded to silicon and selected from alkoxy, aryloxy, hydrocarbon, C 1-18  hydrocarbon substituted by R<SP>3</SP>(C n H 2n O) x C n H 2n - or C 1-18  substituted hydrocarbon in which the substituents are halogen, alkoxy, acyl, acyloxy, cyano, nitro or hydroxy; are prepared by reacting at temperatures ranging from -100‹ to +200‹ C. olefinically unsaturated silanes of the formula R<SP>0</SP> c SiR<SP>11</SP> d  and olefinically unsaturated siloxanes containing at least one unit of the formula (wherein R‹ denotes an alkenyl, cycloalkenyl or alkenylaryl group) with active hydrogencontaining compounds of the formulµ respectively, together with a positive halogen compound. Such positive halogen compounds include alkyl hypohalites, acyl hypohalites, N-haloamines, N-haloamides, N-haloimides, 1 - haloalkynes, alpha - halocarbonyl compounds, halonitromethanes, halocyanomethanes, halomethanes, haloacylmethanes, activated haloaromatic compounds, nitryl and sulphenyl halides, molecular halogens, interhalogen compounds and inorganic hypohalites. Examples describe the preparation of from 3 - vinylheptamethyltrisiloxane, trifluoroethanol and tert - butylhypochlorite; from vinyltrimethylsilane, trifluoroethanol and tert. - butylhypochlorite; from 3 - (3 - cyclohexenyl)heptamethyltrisiloxane, trifluoroethanol and tert. - butylhypochlorite; 2 - (2,2,2 - trifluoroethoxy) - 1- chloroethylmethyl cyclosiloxanes (mostly trimers and tetramers) of the unit formula from corresponding vinylmethylcyclosiloxanes, trifluoroethanol and tert.-butylhypochlorite ; from 3 - vinylheptamethyltrisiloxane, 1H,1H- perfluorooctanol and tert.-butyl hypochlorite; from vinylmethyldiethoxysilane, ethanol and tert. - butyl hypochlorite ; from 3 - vinylheptamethyltrisiloxane, ethanol and tert.-butyl hypochlorite; from vinyltriethoxysilane, ethanol and N- bromosuccinimide; 2 - (2 - hydroxyethoxy)- 1 - chloroethyltrimethylsilane from vinyltrimethylsilane, ethylene glycol and tert.- butylhypochlorite ; from vinylmethyldiethoxysilane, acetic acid and tert.-butylhypochlorite; (imparting flame retardant properties to silicone rubber) from decavinylhexadecamethyldodecasiloxane, 2,4,6 - tribromophenol and tert.- butyl hypochlorite; from vinyltriethylsilane, trifluoroethanol and tert.-butyl hypochlorite; from vinyltriethylsilane, ethanol and tert.- butyl hypochlorite; and from 3 - vinylheptamethyltrisiloxane, tert.- butyl hypochlorite and 2-methoxyethanol, methanol, ethanol, 2 - propanol and tert. - butanol respectively; 3(2 - acetoxy -1-chloroethyl)heptamethyltrisiloxane from 3 - vinylheptamethyltrisiloxane, acetic acid and tert.-butyl hypochlorite; 2 - acetoxy - 1 - chloroethyltriethylsilane from vinyltriethylsilane, acetic acid and tert.-butyl hypochlorite; and a jelled product from a vinyl-dimethylsiloxane having an average of 9 CH 2  : CHSiMeO units and an average of 11 Me 2 SiO units to the molecule, ethylene glycol and tert.-butyl hypochlorite. The preparation is also described of 3-[2-(2-cyanoethoxy)-, 2- meta - nitrophenoxy)-, 2 - (triphenylmethoxy)-, 2 - (octadecylthio)-, 2 - stearamido-, 2 - anilino-, 2 - stearoyl-, 2 - benzoyl-, 2 - acetylthio-, and 2 - (para - chlorophenoxy) - 1 - chloroethyl]- heptamethyltrisiloxanes, and by reaction between 3-vinylheptamethyltrisiloxane, tert. - butyl hypochlorite and, respectively, 2 - cyanoethanol, meta - nitrophenol, triphenylcarbinol, octadecane thiol, stearamide, aniline, stearic acid, benzoic acid, thioacetic acid para-chlorophenol and and of by reaction between vinylmethyldiethoxysilane, tert. - butyl hypochlorite and, respectively, ethylene glycol, glycerol, pentaerythritol, a pentaerythritol - ethylene oxide adduct of the formula C[CH 2 O(C 2 H 4 O) 14 H] 4 , sorbitol, glucose, a glycol-terminated ethylene glycol terephthalate polyester of the formula phthalic acid, trimellitic acid, an acid-terminated ethylene glycol terephthalate polyester of the formula ethylene diamine, succinamide, urea and 1,2- ethanedithiol. Uses.-As chemical intermediates (e.g. for silicone alkyl resins), as sizes for paper, glass fibres, cotton fabrics and other organic textiles to impart lubricity and/or water repellency thereto, as anticorrosive coatings, as encapsulating materials for electronic components, as flame retardant additives for silicone rubber, as elastomers and adhesives, is fillers for moulding compositions or paints, as surfactants or defoamers, as hydraulic fluids, lubricants or coolants, and as modifiers (e.g. thickeners) for greases and known silicone lubricating oils.