Patent GB-715913-A (GB)
Title: Improvements in or relating to esters of vinyloxyalkoxy compounds and unsaturated carboxylic acids
IPC: C07C69/54
Filed: 1952-02-25
Abstract: The invention comprises polymers and copolymers of compounds of formula CH2=CHO(AO)mCOR where R is an acyclically unsaturated hydrocarbon group of at least 2 carbon atoms, A is an alkylene group of not more than 14 carbon atoms, a vinyl substituted alkylene group, or a phenyl substituted alkylene group, and m is an integer of not over six, preferably 1-3.  The polymers and copolymers are made by conventional means, e.g. in the presence of acidic or free radicle liberating catalysts. Specified acidic catalysts are boron trifluoride and its complexes with oxygenated compounds, iodine, phosphoric acid, p-toluene sulphonic acid, aluminium chloride and stannic chloride. Temperatures of -80 DEG -+50 DEG  C. are indicated for reaction and organic solvents, e.g. propane or methyl chloride are preferably present.  Polymers obtained by acid catalysts are thermoplastic resins which are soluble in organic solvents and which are rendered insoluble on treatment with free radicle catalysts or on oxidation.  Free radicle catalysts mentioned are organic peroxides, azo-diisobutyronitrile and dimethyl azodiisobutyrate. Free radicle catalysts yield insoluble polymers and copolymers. Representative of many compounds specified for copolymerization with the vinyloxy esters are citraconic and chloromaleic anhydride, p-methylstyrene, isobutylene, vinyl methyl ether, octyl allyl ether, vinyl butyrate, ethyl acrylate, diallyl phthalate, vinyl acrylate, allyl vinyl ether and allyl succinyl allyl glycolate.  In examples, polymers are formed in (19) from vinyloxyethyl acrylate, (20) b -vinyloxyethyl methacrylate, crotonate and oleate, (21) vinyloxyethyl linoleate, (22) vinyloxyethyl sorbate, (24) vinyloxybutyl methacrylate and (25) 5-vinyloxypentyl methacrylate in the presence of boron trifluoride etherate and in (23) from vinyloxyethyl methacrylate in the presence of azodiisobutyronitrile, and copolymers are formed from (26) vinyloxyethyl methacrylate, allyl vinyl ether and n-butyl vinyl ether in the presence of boron trifluoride etherate, (27) vinyloxyethyl methacrylate and styrene in the presence of aluminium chloride, (28) polyvinyloxyethyl acrylate and vinyl acetate, styrene or methyl methacrylate in the presence of benzoyl peroxide, (29) vinyloxyethyl crotonate and styrene in the presence of boron trifluoride, (30) vinyloxyethyl methacrylate and isobutylene in the presence of boron trifluoride, (31) vinyloxyethyl methacrylate and styrene in the presence of boron trifluoride and the product dried and moulded in the presence of tert.-butyl hydroperoxide, (32) vinyloxyamyl methacrylate and maleic anhydride in the presence of benzoyl peroxide, (33) vinyloxyethyl crotonate and maleic anhydride in the presence of benzoyl peroxide, (34) polyvinyloxypentyl methacrylate and maleic anhydride in the presence of benzoyl peroxide and in (35) polyvinyloxyethyl acrylate is reacted with dodecyl mercaptan in the presence of sodium methoxide.  In many examples films formed from soluble polymers are hardened by air-drying optionally with a cobalt drier or by means of benzoyl peroxide.  The primary first stage soluble polymers may be reacted with alcohols, mercaptans, primary and secondary amines and cyanoacetates.  The polymers may be used for coatings, laminations and binding.ALSO:The invention comprises compounds of formula CH2 = CHO(AO)mCOR where R is an acyclically unsaturated hydrocarbon group of at least 2 carbon atoms, A is an alkylene group of not more than 14 carbon atoms, a vinyl substituted alkylene group or a phenyl substituted alkylene group, and m is an integer of not over six, preferably 1-3.  They may be made by alcoholysis of the appropriate ester of an olefinically unsaturated carboxylic acid and a lower monohydric saturated aliphatic alcohol in the presence of an alkaline transesterification or alcoholysis catalyst, e.g. sodium and potassium and other alkali metal alcoholates including alcoholates of the vinyloxy-containing alcohols and quaternary ammonium alcoholates.  Representative of specified catalysts are potassium butylate, sodium methylate tetramethyl ammonium tert.-butoxide and dimethyl di(chlorobenzyl) ammonium methoxide. Quantities of catalyst of 0.05-1 per cent are specified and small amounts of catalyst are desirably added during the course of the reaction.  The lower alcohol liberated is desirably distilled off.  Alcoholysis temperatures mentioned are 50-180 DEG  C. and polymerization inhibitors, e.g. b -naphthol, may be present.  Many esters are specified for alcoholysis representative of the acid groupings present being a -methacrylic, crotonic, cinnamic, allyloacetic, hydrosorbic, myristolenic, oleic, 2,4-pentadienoic, geranic and propiolic.  Preferred acid groups contain 2-17 carbon atoms.  The vinyloxy-containing alcohols used in the alcoholysis may be made by reacting acetylene and glycols in the presence of strong alkaline catalysts, the vinyl ether thus obtained being used directly for alcoholysis or further reacted with alkylene oxides or similar oxides to give longer or mixed ether chains and subsequently reacted with the ester.  The esters are used to prepare resinous polymers, c.f. Group IV (a).  In examples the following esters are prepared: vinyloxyethyl methacrylate, crotonate, oleate, linoleate, acrylate, and sorbate, vinyloxyethoxyethyl 2-ethyl-2-hexenoate and methacrylate, vinyloxybutyl methacrylate, vinyloxyethoxy - 1 - methylethyl methacrylate, vinyloxyethoxy - 1 - vinylethyl methacrylate, vinyloxyethoxy - 1 - phenylethyl methacrylate, vinyloxy - 5 - pentyl methacrylate, 3 - vinyloxy - 2 - ethylhexyl methacrylate, 3 - vinyloxy - 2,2 - dimethylpropyl methacrylate and vinyloxyethoxyethoxyethyl methacrylate.  The following alcohols are made vinyloxyethoxyethanol from b -vinyloxyethanol and ethylene oxide, vinyloxyethoxy - 2 - propanol from vinyloxyethanol and propylene oxide, vinyloxyethoxyethoxyethanol from vinyloxyethoxyethanol and ethylene oxide or acetylene and triethylene glycol, vinyloxyethoxy - 1 - vinyl ethanol from vinyloxyethanol and butadiene monoxide, vinyloxyethoxy (phenyl) ethanol from vinyloxyethanol and styrene oxide, vinyloxy - 5 - pentanol from 1,5 - pentanediol and acetylene, vinyloxypentyloxyethanol from vinyloxypentanol and ethylene oxide, vinyloxyethoxy - 1 - crotoxymethyl ethanol from vinyloxyethanol and allyl glycidyl ether. The above reactions are effected with bases such as sodium hydroxide. Reaction of glycols with acetylene is effected at about 130-150 DEG C. and 300-500 p.s.i. The alcohols may be treated with an alkylene oxide to yield polyether alcohols thus vinyloxyoctyloxypropanol is made from 1-vinyloxy-2-ethyl-3-hexanol and propylene oxide.