Patent GB-763636-A (GB)
Title: Improvements in or relating to vinyl ethers
IPC: C08F28/00
Filed: 1954-03-29
Abstract: 763,636. Polymers of vinyloxyalkylcarbamates. ROHM & HAAS CO. March 29, 1954 [April 10, 1953], No. 9094/54. Class 2 (6). [Also in Groups III, IV (b), IV (c), VI and VIII] One or more vinyloxyalkylcarbamates of formula wherein Z is a methylene or polymethylene group optionally containing hydrocarbon substituents and containing not more than seven carbon atoms; R is hydrogen or an alkyl, alkenyl, cyclohexyl or benzyl group; R‹ is a monovalent or divalent residue of an esterforming hydroxy compound (e.g. a hydrocarbon group optionally containing one or more ether or thioether linkages and/or chlorine or nitro substituents); n is 1 or 2; and R<SP>1</SP> and R<SP>11</SP> are alkyl groups and either or both may also be hydrogen when both R is other than hydrogen and Z is such that O and N are separated by a chain of 4C or more, alone or admixed with one or more other monomers are polymerized in bulk, aqueous emulsion or organic solution. in the presence of a polymerization catalyst. The other monomers may be acrylates (e.g. methyl and butyl acrylates), methacrylates (e.g. methyl, ethyl and butyl methacrylates), acrylonitrile, methacrylonitrile, acrylamides, methacrylamides, styrene, ureidoethyl vinyl ether, ureidopropyl vinyl ether, vinyl hydroxyethyl ether, vinyl esters (e.g. vinyl acetate, vinyl butyrate and vinyl laurate) or mixtures thereof. In aqueous emulsion the emulsifier may be an octylphenoxypolyethoxyethanol. Specified solvents are dimethylformamide and xylene. Exemplified vinyloxyalkyl carbamates are methyl and ethyl N - (vinyloxy - tert. - butyl) carbamates; ethylene, propylene, diethylene glycol and thiodiethylene bis - [N - (vinyloxy - tert. - butyl) carbamates]; methyl, allyl, benzyl, cyclohexyl, dodecyl and octadecyl N-vinyloxyethyl-N- methylcarbamates; methyl N-vinyloxyethyl- N-cyclohexylcarbamate; ethyl N-vinyloxyethyl - N - 2 - ethylhexylcarbamate; methyl N - vinyloxyethyl - N - α - methylbenzylcarbamate; methallyl N-vinyloxyethyl-N- ethylcarbamate; butyl N-vinyloxyethyl-N- butylcarbamate; ethyl 5-N-vinyloxypentylcarbamate; ethyl N-2-vinyloxyisobutylcarbamate; allyl N-vinyloxyethyl-N-butylcarbamate; methyl N-vinyloxyethylcarbamate and diethylene glycol bis - (N - vinyloxyethyl N- methylcarbamate). The catalyst may be azodiisobutyronitrile; azodiisobutyramide; dimethyl, diethyl or dibutyl azodiisobutyrate; azobis - (α : γ - dimethylvaleronitrile); azobis- (α - methylbutyronitrile); azobis - (α - methylvaleronitrile); dimethyl or diethyl azobismethylvalerate; a mercaptan; acetyl, caproyl, lauroyl or benzoyl peroxide; tert.-butyl hydroperoxide ; butyl perbenzoate; or ammonium, potassium or sodium persulfate (e.g. in conjunction with diethylenetriamine). Homopolymers containing an allyl group may be converted to cross-linked products by heating or by air drying in presence of cobalt compounds. The polymers may be deposited from solvents as hard films, if desired, after previous treatment with diethylenetriamine. Vinyloxyalkylcarbamate monomers having large substituents (e.g. ethyl N-vinyloxyethyl-N-2-ethylhexylcarbamate) may be employed as plasticizers for vinyl chloride polymers (e.g. vinyl chloride/vinyl acetate copolymer). Vinyloxyalkylcarbamate monomers and in particular diethylene glycol bis-(N-methyl-N-vinyloxyethylcarbamate) may be mixed with an adipic acid/maleic anhydride/propylene glycol condensate and benzoyl peroxide and the mixture used to impregnate fibre-glass sheets which are subsequently heated to 140‹ C.