GB786142A - A process for the production of organosilicon compounds - Google Patents

A process for the production of organosilicon compounds

Info

Publication number
GB786142A
GB786142A GB8518/56A GB851856A GB786142A GB 786142 A GB786142 A GB 786142A GB 8518/56 A GB8518/56 A GB 8518/56A GB 851856 A GB851856 A GB 851856A GB 786142 A GB786142 A GB 786142A
Authority
GB
United Kingdom
Prior art keywords
peroxide
radicals
allyl
methyl
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
GB8518/56A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Midland Silicones Ltd
Original Assignee
Midland Silicones Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US505561A external-priority patent/US2958707A/en
Application filed by Midland Silicones Ltd filed Critical Midland Silicones Ltd
Publication of GB786142A publication Critical patent/GB786142A/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0801—General processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C07F7/0872—Preparation and treatment thereof
    • C07F7/0889—Reactions not involving the Si atom of the Si-O-Si sequence
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/46—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes silicones

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)

Abstract

Organosilicon compounds are modified by grafting olefinic compounds on to silicon-bonded alkyl radicals, and this is effected by heating a mixture of (1) an organosilicon compound free from silicon-bonded hydrogen and aliphatic unsaturation but having at least one silicon-bonded radial containing less than 5 carbon atoms; (2) a substituted olefinic compound containing at least one aromatic hydrocarbon or at least one atom other than carbon and hydrogen, any remaining valencies being satisfied by hydrogen or carbon atoms; and (3) a free radical generator which is an organic peroxide (other than an aromatic acyl peroxide as claimed in the parent Specification) or an azo compound in which both nitrogen atoms of the azo linkage are attached to tertiary carbon atoms and the remaining valencies of these carbon atoms are satisfied by nitrile, carboxyalkyl, cycloalkylene, alkyl or YOOC-radicals, in which Y is an alkyl radical, at a temperature above that at which free radical generator forms free radicals. Reactant (2) is preferably used in amount of from 0.1 to 10 per cent by weight of (1) and may be, for example, styrene, vinyltoluene, divinylbenzene, p-phenylstyrene, tetrafluoroethylene, vinyl chloride, allyl chloride, trifluorochloroethylene, hexafluorobutadiene, vinylidene chloride, dichloroethylene, chlorocyclohexene, crotonaldehyde, acrylic aldehyde, cinnamic aldehyde, allyl alcohol, cyclohexenol, 4 - methylpenten - 3 - ol - 1, cinnamic alcohol and penten - 4 - ol - 2; acrylic, methacrylic, crotonic, vinylacetic, cinnamic, maleic, dimethylmaleic, lauroleic, oleic, linoleic and linolenic acids; diallyl and allylethyl ethers; methyl acrylate, methylmethacrylate, vinyl and allyl acetates; crotonamide, acrylamide and cinnamamide; acrylo -, methacrylo - and cinnamo - nitriles; allyl mercaptan; allyl -, allyl - ethyl - and vinyldimethyl - amines; allyl and vinyl sulphides; methylvinylketone, allylacetone and benzalacetophenone; allyl and cinnamyl isocyanates; and polymeric olefins containing residual c = c unsaturation such as polymers of perfluorobutadiene, chloroprene and copolymers of butadiene and acrylonitrile or styrene (polytetrafluoroethylene, polytrifluorochloroethylene and polyvinylchloride are inoperable). The organosilicon compound (1) may be a hydrolysable, non-hydrolysable or partially hydrolysed silane, a silazane, a silcarbane, a polysilane, a silanol or salt thereof, an organosilicon sulphide or a completely or partially condensed polysiloxane, and may have as silicon-bonded radicals free from aliphatic unsaturation in addition to the above defined alkyl radicals, higher alkyl, cycloalkyl, aryl and halogenated alkyl and aryl radicals; organo functional radicals, e.g. carboxy phenyl, gammahydroxypropyl, gamma-aminopropyl, pentachlorophenoxymethyl and other hydrocarbon radicals having aldehyde, ketone, nitrile, nitro, carboxyl, amide and hydrosulphide substituents; methylene, ethylene, propylene, phenylene, xenylene and cyclohexylene radicals. Compounds (3) specified are methyl, tertiary butyl, trans-decalin, 1-methyl cyclopentyl, 2-cyclohexene-1-yl, cumene, tetralin, triphenylmethyl, benzyl and p-nitrophenyldiphenylmethyl hydroperoxides; 3-methyl-3-hydroperoxy - 1 - butyne, a - hydroperoxy tetrahydrofuran and a -hydroperoxyethyl ethyl ether; peroxy - acetic, isovaleric, crotonic, trichloroacetic, lactic, benzoic and cinnamic acids; mono- and di-peroxyphthalic, p-methoxyperoxybenzoic, m - nitroperoxybenzoic and 2 : 4-dichloroperoxybenzoic acids; di - tertiarybutyl, diethyl, tertiarybutylmethyl and ditriphenylmethyl peroxides; ascaridole, 1 : 4-epydioxy - p - menthane, 1 : 4 : 2 : 3 - diepoxy-p-menthane, diacetylperoxide, dialkyl and diaryl peroxy dicarbonates of the formula ROOCOOCOOR (R = methyl, ethyl, phenyl or tolyl), ethyl peroxyacetate, tertiary butyl peroxybenzoate, di-tertiary butyl diperoxyphthalate, bis(1 - hydroxycyclohexyl) - peroxide, 1 - hydroxy - 11 - hydroperoxycyclohexyl peroxide, bis(hydroperoxycyclohexyl)peroxide, trimeric cyclohexanone peroxide, bis(hydroxyethyl)peroxide, bis(phenylhydroxymethyl) - peroxide, trimeric acetone peroxide, methylhydroxymethylperoxide and (Me3COO2C.Me2; and the azo compounds Me2(NC)CN = NC (CN)Me2, MeEt(NC)CN = NC(CN)Me.Et, Et2 (NC)CN = NC(CN)Et2 Pr2(NC)CN = NC(CN) Pr2, AmMe(NC)CN = NC(CN)MeAm, (HOOC CH2.CH2)Me(NC)CN = NC(CN)Me(CH2.CH2. COOH), (MeOOC)Me2CN = NCMe2(COOMe), (EtOOC)Me2CN = NCMe2(COOEt) and: <FORM:0786142/IV (a)/1> wherein Me, Et, Pr and Am are methyl, ethyl, propyl and amyl respectively. The reaction may be effected at normal, sub or super atmospheric pressure, at temperatures from 50 DEG to 150 DEG C. and in the presence or absence of inert hydrocarbon solvents. The products are useful as lubricants, surface-active agents, hydraulic fluids and electrical insulating materials. In Examples, trifluorochloroethylene was reacted with a trimethyl-end-blocked dimethylpolysiloxane in the presence of different free radical generators.
GB8518/56A 1954-04-13 1956-03-19 A process for the production of organosilicon compounds Expired GB786142A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US1131119XA 1954-04-13 1954-04-13
US505561A US2958707A (en) 1955-05-02 1955-05-02 Diorganopolysiloxane-halogenated olefin graft copolymers

Publications (1)

Publication Number Publication Date
GB786142A true GB786142A (en) 1957-11-13

Family

ID=90124762

Family Applications (2)

Application Number Title Priority Date Filing Date
GB9286/55A Expired GB766528A (en) 1954-04-13 1955-03-30 A process for the production of organosilicon compounds
GB8518/56A Expired GB786142A (en) 1954-04-13 1956-03-19 A process for the production of organosilicon compounds

Family Applications Before (1)

Application Number Title Priority Date Filing Date
GB9286/55A Expired GB766528A (en) 1954-04-13 1955-03-30 A process for the production of organosilicon compounds

Country Status (2)

Country Link
FR (1) FR1131119A (en)
GB (2) GB766528A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3139352A (en) * 1962-08-08 1964-06-30 Du Pont Process of using a masking coating of a telomer of tetrafluoroethylene
GB2145423A (en) * 1983-08-26 1985-03-27 Gen Electric Modified organopolysiloxane composition

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2909548A (en) * 1956-03-27 1959-10-20 Union Carbide Corp Copolymers of mono-vinyl methyl siloxanes and chlorotrifluoroethylene
US3013915A (en) * 1958-04-23 1961-12-19 Owens Corning Fiberglass Corp Reinforced polyolefins and process for making same
US3088964A (en) * 1958-09-29 1963-05-07 Dow Corning 2-phenylpropyl organosiloxanes
FR1526934A (en) * 1966-12-01 1968-05-31 Commissariat Energie Atomique Process for preparing hydrophilic silicones by radiochemical grafting
DE3030195A1 (en) 1980-08-09 1982-04-08 Bayer Ag, 5090 Leverkusen CROSSLINKABLE GRAFT POLYMERISAT DISPERSIONS AT ROOM TEMPERATURE
JPH0684495B2 (en) * 1986-06-03 1994-10-26 旭硝子株式会社 Surface modifier

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3139352A (en) * 1962-08-08 1964-06-30 Du Pont Process of using a masking coating of a telomer of tetrafluoroethylene
GB2145423A (en) * 1983-08-26 1985-03-27 Gen Electric Modified organopolysiloxane composition

Also Published As

Publication number Publication date
GB766528A (en) 1957-01-23
FR1131119A (en) 1957-02-18

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