Patent GB-772666-A (GB)
Title: Improvements in or relating to vinyl ethers
IPC: D21H17/45
Filed: 1954-03-29
Abstract: Vinyl ethers of the formula <FORM:0772666/IV(a)/1> wherein X is oxygen or sulphur, A is an alkylene group of two or three carbon atoms, at least two of which occur between nitrogen atoms, and Z is a cycloalkylene group or an alkylene group having at least two carbon atoms between oxygen and nitrogen atoms and optionally bearing a phenyl, vinyl or alicyclic hydrocarbon substituent, and derivatives thereof in which the hydrogen atom attached to the nitrogen atom is replaced by an alkyl group of 1 to 5 carbon atoms, alone or admixed with one or more other monomers, are polymerized in bulk or in aqueous or organic solution, emulsion or suspension, in the presence of a polymerization catalyst.  The comonomers may be acrylic or methacrylic acid; acrylonitrile; acrylamide; methacrylamide; an N-substituted acrylamide or methacrylamide, e.g. N-methyl or N-benzyl acrylamide or methacrylamide; an ester of acrylic or methacrylic acid, e.g. ethylene diacrylate or dimethacrylate or methyl, ethyl, allyl, butyl, amyl, octyl, dodecyl, octadecyl, vinyloxyethyl, methoxyethyl, phenoxyethyl, ethoxyethyl, cyclohexyl, benzyl, tetrahydrofurfuryl, oleyl or nitroethyl acrylate or methacrylate; an alkyl itaconate; a vinyl ester, e.g. vinyl acetate, propionate, butyrate or laurate; a vinyl ether, e.g. hydroxyethyl vinyl ether; an allyl ester, e.g. allyl acetate or butyrate; styrene; a methylstyrene; a vinylpyridine; divinylbenzene; diallyl phthalate or mixtures thereof.  In aqueous emulsion the emulsifier may be an octylphenoxypolyethoxyethanol. Specified solvents are methanol, dimethylformamide, ethyl acetate and ethoxyethyl acetate. Exemplified vinyl ether monomers are 2 - (2 - ketoimidazolidyl) ethyl vinyl ether, 1 - (2 - vinyloxyethyl) - 2 - hexahydropyrimidone, 1 - (3 - vinyloxypropyl) - 2 - hexahydropyrimidone, 1 - (2 - vinyloxypropyl) - 2 - imidazolidone, 1 - (2 - phenyl - 2 - vinyloxyethyl) - 2 - imidazolidone, 1 - (2 - cyclohexyl - 2 - vinyloxyethyl) - 2 - imidazolidone, 1 - (2 - cyclohexyl - 2 - vinyloxyethyl) - 2 - thioimidazolidone, 1 - (2 - vinyl - 2 - vinyloxyethyl) - 2 - imidazolidone, 1 - (4 - vinyloxycyclohexyl) - 2 - imidazolidone and 1-(2-vinyloxyethyl)-2-thioimidazolidone.  The catalyst may be azodiisobutyronitrile; azodiisobutyramide; dimethyl, diethyl or dibutyl azodiisobutyrate; azobis-(a : g -dimethylvaleronitrile); azobis - (a  - methylbutyronitrile); azobis-(a -methylvaleronitrile); dimethyl, diethyl or dibutyl azobismethylvalerate; benzoyl, lauroyl, caproyl, acetyl, methyl ethyl ketone or cumene peroxide; tert.-butyl hydroperoxide; ammonium, sodium or potassium persulphate; butyl perbenzoate or hydrogen peroxide.  The peroxide catalysts are preferably used in a redox system in conjunction with hydrazine, ferrous sulphate or sodium sulphite, bisulphite, metabisulphite or hydrosulphite. The catalysts may also be used in conjunction with metal activators and regulators such as mercaptoethanol.  The above polymers and copolymers are converted into methylol derivatives by reaction with formaldehyde in alkaline solution.  The methylol derivatives are further converted to alkoxymethyl derivatives by reaction with the corresponding alcohol in acid solution. Butoxymethyl derivatives are exemplified.  The polymers, copolymers and their methylol and alkoxymethyl derivatives may be used as sizes for nylon and polyester fibres, as textile finishing agents, for imparting wet strength to paper, for shrinkproofing wool or rayon, to impart fullness, stiffness and water-resistance to leather, for forming into films and fibres, as additives to viscose and cellulose acetate dopes from which films and fibres are made, as ingredients of enamels and lacquers, as adhesives and for imparting protective coatings to wood and asbestos shingles. In an example a solution of a 2 - (2 - ketoimidazolidyl) ethyl vinyl ether/methyl methacrylate copolymer in ethoxyethyl acetate is treated with a 20 per cent solution of formaldehyde in butanol and 1 per cent of para-toluenesulphonic acid; the solution is pigmented with titanium dioxide and the resulting enamel is sprayed on to steel plates and baked to form a film having resistance to soap and hot water.  Vinyl ether monomers of the above general formula may be used as modifiers of urea-formaldehyde or melamineformaldehyde condensates, for which purpose they may replace 1-30 per cent by weight of the urea or melamine.  In an example 2-(2-ketoimidazolidyl) ethyl vinyl ether replaces 20 per cent by weight of the urea in a condensate of 1.0 mol. of urea with 1.3 mols. of formaldehyde.  The product may be applied to textiles.ALSO:The invention comprises compounds of the formula <FORM:0772666/IV(b)/1> and derivatives thereof in which the hydrogen atom attached to the nitrogen atom is replaced by an alkyl group of 1 to 5 carbon atoms, wherein X is oxygen or sulphur, A is an alkylene group of two or three carbon atoms at least two of which occur between nitrogen atoms, and Z is a cycloalkylene group or an alkylene group having at least two carbon atoms between oxygen and nitrogen atoms and optionally bearing a phenyl, vinyl, or alicyclic hydrocarbon substituent.  The compounds are prepared (1) by reacting a compound HOZNHANHR (wherein R is hydrogen or a C1-5 alkyl group) with acetylene to form a compound CH2 = CHOZNHANHR which is either heated with urea, thiourea or a lower alkyl carbonate or reacted with a tert.-alkylisothiocyanate and the resulting thiourea derivative decomposed by subsequent heating; (2) by heating a compound HOZNHANHR with urea or a lower alkyl carbonate to form an N-hydroxyalkylene-imidazolidone or -hexahydropyrimidone which is then reacted with acetylene.  The examples describe the preparation of 2-(2-ketoimidazolidyl) ethyl vinyl ether, 1-(2-vinyloxyethyl)-2-hexahydropyrimidone, 1-(3-vinyloxypropyl)-2-hexahydropyrimidone, 1-(2-vinyloxypropyl)-2-imidazolidone, 1-(2-phenyl-2-vinyloxyethyl)-2-imidazolidone, 1 - (2 - cyclohexyl - 2 - vinyloxy-ethyl)-2-imidazolidone, 1-(2-cyclohexyl-2-vinyl-oxyethyl) - 2 - thioimidazolidone, 1 - (2 - vinyl - 2 - vinyloxyethyl)-2-imidazolidone, 1 - (4-vinyloxy-cyclohexyl)-2-imidazolidone and 1 - (2-vinyloxy-ethyl)-2-thioimidazolidone.  Starting materials of the general formula HOZNHANH2 are prepared (1) by reacting a 1 : 2- or 1 : 3-cyclic ether with ethylene, propylene or trimethylene diamine; (2) by reacting an aminoalcohol HOZNH2 with acrylonitrile, glycolonitrile or formaldehyde and hydrogen cyanide to form a cyano derivative which is subsequently reduced.ALSO:Polymers and copolymers of vinyloxy ethers of the formula <FORM:0772666/IV(b)/1> wherein X is oxygen or sulphur, A is an alkylene group of two or three carbon atoms, at least two of which occur between nitrogen atoms, Z is a cycloalkylene group or an alkylene group having at least two carbon atoms between oxygen and nitrogen atoms and optionally bearing a phenyl, vinyl or alicyclic hydrocarbon substituent, and the hydrogen atom attached to the nitrogen atom may be replaced by an alkyl group of 1 to 5 carbon atoms, and methylol derivatives thereof, are employed in the form of aqueous solutions or dispersions as warp sizes and finishing agents for nylon and polyester fibres, and as stabilizing agents for wool and rayon fabrics, the wool being shrink-proofed either by application and subsequent curing in presence of ammonium choride or oxalic acid as catalyst, or by impregnation, subsequent treatment with formaldehyde solution and curing.  Exemplified vinyl ether monomers are 2 - (2 - ketoimidazolidyl) ethyl vinyl ether, 1 - (2 - vinyloxyethyl) - 2 - hexahydropyrimidone, 1 - (3 - vinyloxypropyl) - 2 - hexahydropyrimidone, 1 - (2 - vinyloxypropyl) - 2 - imidazolidone, 1 - (2 - phenyl - 2 - vinyloxyethyl) - 2 - imidazolidone, 1 - (2 - cyclohexyl - 2 - vinyloxyethyl) - 2 - imidazolidone, 1 - (2 - cyclohexyl - 2 - vinyloxyethyl) - 2 - thioimidazolidone, 1 - (2 - vinyl - 2 - vinyloxyethyl) - 2 - imidazolidone, 1 - (4 - vinyloxycyclohexyl) - 2 - imidabolidone and 1 - (2 - vinyloxyethyl) - 2 - thiomidazolidone.  The comonomer may be acrylic or methacrylic acid; acrylonitrile, acrylamide, methacrylamide; an N- - substituted acryamide or methacrylamide, e.g. N-methyl or N - benzyl acrylamide or methacrylamide; an ester of acrylic or methacrylic acid, e.g. ethylene diacrylate or dimethacrylate or methyl, ethyl, allyl, butyl, amyl, octyl, dodecyl, octadecyl, vinyloxyethyl, methoxyethyl, phenoxyethyl, ethoxyethyl, cyclohexyl, benzyl, tetrahydrofufuryl, oleyl and nitroethyl acrylate or methacrylate, an alkyl itaconate; a vinyl ester, e.g. vinyl acetate, propionate, butyrate or laurate; a vinyl ether ,e.g. hydroxyethyl vinyl ether; an allyl ester, e.g. allyl acetate or butyrate; styrene; a methylstyrene; a vinylpyridine; divinylbenzene; diallyl phthalate or a mixture thereof.