Patent GB-736397-A (GB)
Title: Improvements in or relating to esters of vinyloxyalkoxy-containing alcohols and monocarboxylic acids and a process of producing the same
IPC: C08F20/28
Filed: 1952-02-22
Abstract: Esters of formula CH2=CHO(A DEG )mCOR, where R is a cycloalkyl, aryl, aralkyl, alkyl group of not over 17 carbon atoms or cyanomethyl group, A is an alkylene group -CnH2n, where n is 2-14, or a vinyl or phenyl substituted ethylene group, and m is 1-6, preferably 1-3, may be polymerized or copolymerized particularly with unsaturated polymer-forming compounds which polymerize in the presence of an acidic catalyst and form heteropolymers with a ,b -unsaturated anhydrides such as maleic, chloromaleic and citraconic anhydrides. The polymers may be hydrolysed to yield polymers containing hydroxyl groups which on reaction with aldehydes and ketones yield acetals and ketals and with polycarboxylic acids and anhydrides yield resinous polyesters.  The esters are made by reacting alcohols of formula CH2=CHO(A DEG )m H with an ester of a lower monohydric saturated aliphatic alcohol and an acid of formula RCOOH (see Group IV (b)). Representative of ether alcohols specified are vinyloxyethanol, 2-(vinyloxyethoxy)-1-methyl ethanol, vinyloxyethoxy - vinyl - and - phenylethanol, 4-vinyloxy-butanol, 5-vinyloxypentanol, vinyloxyethoxy ethanol, vinyloxyethoxyethoxy ethanol and vinyloxy-1-methyl ethanol. Representative of esters specified for reaction with the alcohols are ethyl acetate, cyanoacetate, butyrate, stearate and benzoate, methyl laurate and 3,5,5-trimethylhexoate and butyl naphthenate. Polymerization catalysts specified are azodiisobutyronitrile, dimethylazodiisobutyrate, boron trifluoride and its coordination complexes, iodine, phosphoric or p-toluene-sulphonic acids and aluminium and stannic chlorides.  Organic peroxides cause polymerization but are less effective than azo or acidic catalysts. Temperatures for polymerization, which may be effected in a solvent, vary from - 80 to +100 DEG  C.  The polymers obtained are used for laminating, binding and coating and hydrolysed products may be used as sizing, binding and finishing agents.  Copolymers may be obtained from the esters and polymerizable vinylidene compounds, preferably monovinylidene compoundsadvantageously 5-99 per cent of the ester being present. Vinylidene compounds specified are styrene, p- and a -methylstyrene, isobutylene and vinyl methyl, butyl, octyl, dodecyl, stearyl and allyl ethers copolymerizable with acid catalysts and vinyl acrylate and methacrylate copolymerizable with azo type catalysts.  In examples (15) vinyloxyethyl acetate, (17) vinyloxybutylacetate, (18) 5-vinyloxypentyl acetate, and (19) vinyloxyethoxyethyl acetate are polymerized in the presence of boron trifluoride etherate and the products hydrolysed with sodium methylate, (16) polyvinyloxylethyl acetate is heated with potassium hydroxide and aqueous ethanol and the benzene insoluble product reacted with n-butyraldehyde or methylene bis-(4-phenylisocyanate), (20) vinyloxyethyl acetate is polymerized in the presence of azodiisobutyronitrile to yield a polymer which may be admixed with a polyvinyl acetal to form a tough flexible material, (21) vinyloxyethyl acetate is polymerized in the presence of benzoyl peroxide, (22) vinyloxyethyl benzoate is polymerized in the presence of boron trifluoride etherate; copolymers are formed using boron trifluoride etherate as catalyst from (23) vinyloxypentyl acetate and allyl and methallyl vinyl ethers, (24) vinyloxypentyl acetate and vinyl butyl ether, (25) 2-(b -vinyloxyethyloxy)-1-methylethyl acetate and allyl vinyl ether, (26) vinyloxyethyl acetate and allyl vinyl ether, (28) vinyloxyethyl laurate and stearate, (29) vinyl n-butyl ether and vinyloxyethyl stearate, (30) vinyl 2-ethylhexyl ether and vinyloxyethyl stearate, and (31) vinyl octadecyl ether and vinyloxyethyl laurate; using azodiisobutyronitrile as catalyst from (32) acrylonitrile and vinyloxyethyl acetate; and using dimethyl azodiisobutyrate as catalyst from (27) vinyloxyethyl acetate and allyl acetate, and (33) vinyl acetate and vinyloxyethyl acetate.  The product of (23) is soluble in organic solvents but becomes insoluble when heated with benzoyl peroxide, the product of (25) is hydrolysed with sodium methylate to yield a water-soluble product which becomes insoluble on heating or on further polymerization with peroxide catalysts, films laid down from a water-solution becoming insoluble when heated, air-drying of such films being accelerated by the presence of a cobalt drier, and the product of (26) is hydrolysed with sodium methalate the resultant water-soluble polymer giving insoluble films after baking when prepared from aqueous solutions additionally containing hydrogen peroxide or ammonium persulphate or a cobalt drier; in (34) a copolymer is made by treating a mixture of vinyl acetate and vinyloxyethyl acetate with sodium methylate and in (35) a heteropolymer is made by treating a mixture of vinyloxyethylacetate and maleic anhydride with benzoyl peroxide. Representative of solvents used in the preparations of the polymers or copolymers are propane, methyl chloride, ether, toluene and ethyl acetate.ALSO:Compounds of formula CH2=CHO(AO)mCOR are made by reacting ether alcohols of formula CH2=CHO(AO)mH at 30-160 DEG  C. with an ester of a lower monohydric saturated aliphatic alcohol and an acid of formula RCOOH in the presence of an anhydrous, strongly basic alkali metal alcoholate as catalyst, R being an alkyl, aryl, cycloalkyl, aralkyl group of not more than 17 carbon atoms or cyanomethyl group, A being an alkylene group of 2-14 carbon atoms, a vinyl-substituted ethylene group, or a phenyl-substituted ethylene group, and m is an integer of not more than 6, preferably 1-3. Alcoholates specified include sodium methylate, potassium butylate, tetramethyl ammonium methoxide and dimethyl di - (chlorobenzyl)-ammonium methoxide; 0.05-1 per cent of catalyst based on reactants is specified.  Esters specified include methyl, ethyl, propyl and butyl esters of acids such as acetic, caproic, myristic, benzoic, chlorobenzoic, naphthenic and hexahydrophenylacetic acids. Vinyloxy-containing alcohols specified include those made by reacting acetylene with glycols such as ethylene, octylene, tetradecylene, pentaethylene or tripropylene glycols in the presence of a strong alkali and may be further modified to give mixed products by reaction with an alkylene oxide such as butylene, and styrylene oxide or butadiene monoxide.  Alcohol displaced during the reaction is taken off by distillation.  Numerous examples are provided and esters obtained from alcohols such as vinyloxyethanol, 2 - (vinyloxyethoxy) - 1-methyl ethanol, vinyloxyethoxy - 1 - vinyl ethanol, vinyloxyethoxy - 1 - phenylethanol, 4-vinyloxybutanol, 5-vinyloxypentanol, vinyloxyethoxy ethanol, vinyloxy - ethoxyethoxyethanol and vinyloxy-1-methyl ethanol and esters such as ethyl acetate, ethyl cyanoacetate, ethyl butyrate, methyl laurate, ethyl stearate, butyl 2-ethylhexoate, methyl 3,5,5-trimethylhexoate, ethyl benzoate and butyl naphthenate in the presence of catalysts such as sodium methylate and ethylate. The preparation of the following starting alcohols is also described: vinyloxyethoxy-ethanol and -propanol by reacting b -vinyloxyethanol respectively with ethylene oxide and propylene oxide in the presence of sodium hydroxide, vinyloxyethoxyethoxyethanol by reacting vinyloxyethoxyethanol with ethylene oxide in the presence of potassium hydroxide or reacting acetylene with triethylene glycol, vinyloxyethoxy-1-vinyl- and -phenyl-ethanol by reacting vinyloxyethanol respectively with butadiene monoxide and styrene oxide in the presence of potassium hydroxide, vinyloxy-5-pentanol by reacting 1,5-pentanediol with acetylene in the presence of potassium or potassium hydroxide, the divinyl ether of the diol also being formed, vinyloxypentyloxyethanol by reacting vinyloxypentanol with etholene oxide in the presence of potassium hydroxide, vinyloxyethoxyethanol - methylvinylmethyl ether by reacting vinyloxyethanol with allyl glycidyl ether in the presence of potassium hydroxide and the mono-vinyl ethers of 2,2 - dimethyl - 1,3 - propanediol, 1,4 - butane diol, phenylethanediol and 2-ethyl-1,3-hexanediol-are also described together with a vinyloxyoctyloxypropanol made by reacting vinyloxy-2-ethyl-3-hexanediol with propylene oxide and vinyloxy - butoxy - and -butoxyethoxy - ethanol made by reacting vinyloxy-butanol with one or two mols. of ethylene oxide.ALSO:Esters of formula CH2 = CHO(AO)mCOR where R is a cycloalkyl, aryl, aralkyl, alkyl group of not over 17 carbon atoms or cyanomethyl group, A is an alkylene group, -Cn H2n-, where n is 2-14, or a vinyl or phenyl substituted ethylene group, and m is 1-6, preferably 1-3, may be polymerized or copolymerized particularly with unsaturated polymer forming compounds which polymerize in the presence of an acidic catalyst and form heteropolymers with a -, b -unsaturated anhydrides such as maleic, chloromaleic and citraconic anhydrides and when containing higher fatty acid residues the products thus obtained are stated to be oil additives.  For the preparation of the esters and polymers (see Groups IV (b) and IV (a)) respectively.  In examples copolymers are made in the presence of boron trifluoride etherate from (28) vinyloxyethyl laurate and vinyloxyethyl stearate, (29) vinyloxyethyl stearate and vinyl n-butyl ether, (30) vinyloxyethyl stearate and vinyl 2-ethylbenzyl ether and (31) vinyloxyethyl laurate and vinyl octadecyl ether and the products when dissolved, e.g. in amounts of 0.25 or 0.5 per cent in oils such as a Pennsylvanian lubricating oil are shown to have pour point depressing or viscosity index improving characteristics.