Patent GB-765792-A (GB)
Title: Improvements in or relating to vinyl ethers
IPC: C08F16/28
Filed: 1954-03-29
Abstract: Melamine vinyl ethers of the formula <FORM:0765792/IV(a)/1> wherein Z is a methylene or polymethylene group optionally carrying hydrocarbon substituents and optionally containing oxygen or sulphur atoms in the chain thereof; R is hydrogen or a hydrocarbon group of up to 18 carbon atoms and having hydrogen on the carbon atom attached to N; R1 and R11 are hydrogen, phenyl or alkyl groups, with the proviso that, when R is hydrogen, R1 and R11 are alkyl groups and, when R1 or R11 is hydrogen, R is hydrocarbon, alone or admixed with one or more other monomers, are polymerized in bulk, aqueous emulsion, or aqueous or organic solution or suspension in the presence of a polymerization catalyst.  The other monomers may be acrylic acid esters (e.g. methyl, ethyl, butyl, 2-ethylhexyl, 3 : 5 : 5-trimethylhexyl, dodecyl, ethoxyethyl, butoxyethyl, phenoxyethyl, cyclohexyl and benzyl acrylates), methacrylic acid esters (e.g. methyl, ethyl, propyl, butyl, hexyl, octyl, dodecyl, cetyl, ethoxyethyl, butoxyethyl, cyclohexyl, benzyl and dimethylaminoethyl methacrylates), acrylamides, acrylonitrile, methacrylonitrile, vinyl esters (e.g. vinyl acetate), ureidoethyl vinyl ether, bisvinyloxyethylurea, vinylpyridine or mixtures thereof.  In aqueous emulsion the emulsifier may be an octylphenoxypolyethoxyethanol. Specified organic solvents are dimethylformamide and ethoxyethyl acetate. Exemplified melamine vinyl ethers are N - methyl - N - vinyloxyethyl -, N - a  : a  - dimethyl - b  - vinyloxyethyl -, N - methyl - N - 2-vinyloxypropyl -, N - 3 : 5 : 5 - trimethylhexyl-N - 21 - vinyloxyethyl -, N - cyclohexyl - N - 2-vinyloxyethyl -, N - 2 - ethylhexyl - N - 21-vinyloxyethyl -, N - nonyl - N - vinyloxyethyl- and N - butyl - N - 2 - vinyloxypropylmelamines.  The catalyst may be dimethyl or diethyl azodi - isobutyrate, azodi - isobutyronitrile, azobis (a  : g  : dimethylvaleronitrile), azobis (a  - methylbutyronitrile), dimethyl or diethyl azobismethylvalerate and ammonium persulphate in conjunction with diethylenetriamine.  The above polymers and copolymers may be reacted with formaldehyde to form the corresponding methylol derivatives.  The latter compounds may be converted to corresponding alkoxymethyl derivatives by treating solutions thereof in an appropriate alcohol (e.g. methanol, isopropanol, butanol) with phosphoric or formic acid.  The polymers and copolymers may be used for coating and casting compositions, as anion-exchange resins, as cross-linking agents for cellulose and wool, in textile finishing and paper manufacture and as sizing agents.  The methylol and alkoxymethyl derivatives may be used as antistatic agents, stiffeners and stabilizers, for incorporation in alkyd resins and for imparting wet strength to paper; they form hard films on curing.  The alkoxymethyl derivatives may also be mixed with urea-formaldehyde or melamine-formaldehyde condensates and the mixture incorporated in alkyd resins or cured to give hard films and coatings.  Melamine vinyl ether monomers of the above formula may be mixed with urea or melamine and the mixture reacted with formaldehyde to form resins for use in textile finishing, as adhesives and in coatings.ALSO:The invention comprises compounds of formula <FORM:0765792/IV(b)/1> wherein Z is a methylene or polymethylene group optionally carrying hydrocarbon substituents and optionally containing oxygen or sulphur atoms in the chain thereof; R is hydrogen or a hydrocarbon group of up to 18C and having hydrogen on the carbon attached to N; R1 and R11 are hydrogen, phenyl or alkyl groups, with the proviso that when R is hydrogen, R1 and R11 are alkyl groups and when R1 or R11 is hydrogen, R is hydrocarbon.  The compounds are prepared by reacting dicyandiamide with cyanamides of formula <FORM:0765792/IV(b)/2> in presence of a basic catalyst such as an alkali metal hydroxide or alkoxide, or a quaternary ammonium hydroxide.  The reaction is preferably conducted at 50-125 DEG  C. in presence of an inert organic solvent.  A list of starting materials is given.  The examples describe the preparation of N - methyl - N - vinyloxyethyl -, N - a  : a -dimethyl - b  - vinyloxyethyl -, N - methyl - N-2 - vinyloxypropyl -, N - 3 : 5 : 5 - trimethylhexyl - N - 21 - vinyloxyethyl -, N - cyclohexy.-N - 2 - vinyloxyethyl -, N - 2 - ethylhexyl - N-21 - vinyloxyethyl -, N - nonyl - N - vinyloxyethyl - and N - butyl - N - 2 - vinyloxypropylmelamines.  Specification 761,902 is referred to.ALSO:Melamine vinyl ether monomers of the formula <FORM:0765792/IV(b)/1> wherein Z is a methylene or polymethylene group optionally carrying hydrocarbon substituents and optionally containing oxygen or sulphur atoms in the chain thereof; R is hydrogen or a hydrocarbon group of up to 18 carbon atoms and having hydrogen on the carbon atom attached to N; R1 and R11 are hydrogen, phenyl or alkyl groups, with the proviso that, when R is hydrogen, R1 and R11 are alkyl groups and, when R1 or R11 is hydrogen, R is hydrocarbon, are polymerized alone or in admixture with one or more other vinyl or vinylidene compounds to give cross-linking agents for wool, sizing agents and textile finishing agents.  These polymers and copolymers may be converted to methylol and alkoxymethyl derivatives (e.g. methoxymethyl, isopropoxymethyl and butyloxymethyl derivatives) which are used as antistatic agents, stiffeners and stabilizers.  Melamine vinyl ethers of the above formula may also be mixed with urea or melamine and the mixture reacted with formuldehyde to form resins for use as textile finishing agents.  Exemplified melamine vinyl ethers are N-methyl-N-vinyloxyethyl-N - a :a  - dimethyl - b  - vinyloxyethyl-, N-methyl-N-2-vinyloxypropyl-, N - 3:5:5 - trimethyl-hexyl-N-21-vinyloxyethyl-, N-cyclohexyl-N-2-vinyloxyethyl-, N-2-ethylhexyl-N-21-vinyloxyethyl-, N-nonyl-N-vinyloxyethyl- and N-butyl-N-2-vinyloxypropyl-melamines.  Specified co-monomers are acrylic acid esters (e.g. methyl, ethyl, butyl, 2-ethylhexyl, 3:5:5-trimethylhexyl, dodecyl, ethoxyethyl, butoxyethyl, phenoxyethyl, cyclohexyl and benzyl acrylates), methacrylic acid esters (e.g. methyl, ethyl, propyl, butyl, hexyl, octyl, dodecyl, cetyl, ethoxyethyl, butoxyethyl, cyclohexyl, benzyl and dimethylaminoethyl methacryates), acrylamides, acrylonitrile, methacrylonitrile, vinyl esters (e.g. vinyl acetate), ureidoethyl vinyl ether, bisvinyloxyethylurea, vinylpyridine or mixtures thereof. Polymers and copolymers inteded for textile finishing agents are employed as aqueous dispersions.ALSO:A fungicidal composition comprises N-methyl - N - vinyloxyethylmelamine dissolved in water.