Patent GB-770080-A (GB)
Title: Alkenylaryl glycidyl ethers and polymers thereof
IPC: C08G65/28
Filed: 1955-04-12
Abstract: Monomeric ethers of the formula: (R)mAr(O-E)n, where R is a hydrocarbon radical containing an olefinic linkage, m and n are 1, 2 or 3, Ar is an aromatic nucleus of valency m + n, O is an ether oxygen atom, and E is a hydrocarbon radical containing an epoxide group in which the carbon atoms linked to the epoxy oxygen do not include the carbon atom attached to the ether oxygen, are homoor co-polymerized via the olefinic linkage to yield epoxy resins, which may be further reacted with amines, polycarboxylic acids or fatty acids.  The ethers may also be polymerized via the epoxy groups to give drying resins or reacted through the epoxy group with carboxylic acids or anhydrides to give alkyd resins.  A large number of monomeric ethers are specified including 2-allylphenyl glycidyl ether, 1:2-bis(glycidyloxy) - 4 - vinylbenzene, 2 - allyl - 1 - naphthyl glycidyl ether, 2-(2-cyclohexenyl)phenyl glycidyl ether and 2-allylphenyl 1:2-epoxy - 1 - phenylbut - 3 - yl ether. Polymerization via the olefinic linkage is effected by heating the monomeric ether at 50 DEG  to 300 DEG  C. in the presence of molecular oxygen or 0.1 to 10 per cent by weight of a tertiary alkyl hydroperoxide such as tertiary butyl hydroperoxide or a di(tertiary alkyl)-peroxide such as di (tertiary buty) peroxide. Other catalysts mentioned are hydrogen peroxide, benzoyl, acetyl, benzoyl acetyl, lauroyl, dibutyryl, and succinyl peroxides, tertiary butyl perbenzoate, perbenzoic acid and cumene hydroperoxide.  In a similar manner the monoethers may be copolymerized with 1-99 per cent by weight of one or more compounds containing a vinylidene group such as styrene, acrylonitrile, vinyl chloride, vinyl acetate, methyl methacrylate and diallyl phthalate.  The polymerizations via the olefinic linkage are arrested by cooling after more than 10 per cent of the monomer is converted to polymer and a non-solvent such as hexane is added and the precipitated polymer filtered off.  The addition-polymers may be blended with polyvinyl or polyvinylidene chloride as plasticizers and stabilizers, they may be mixed with amines or polycarboxylic acids and heat-cured for use in adhesives, laminating, surface coating and moulding, or reacted with unsaturated drying or semi-drying oil fatty acids for use as protective coating vehicles.  The monoethers of the invention may also be polymerized via the epoxy group in the presence of a Friedel-Crafts metal halide or other catalyst as described in Specifications 650,117 and 660,377 to give drying resins, e.g. polymerization of a glycidyl ether gives an olefin-containing aryl polyether of polyglycerol.  In examples of addition-polymerization, a homopolymer of 2-allylphenyl glycidyl ether prepared by heating with ditertiary-butyl peroxide to 150 DEG C. and precipitating with hexane is, (3), mixed with diethylene triamine, butyl alcohol and toluene and heat-cured, or, (4), mixed with sec.-butyl alcohol, toluene and diethylene triamine and heat-cured, to give films; (5) a copolymer of 2-allylphenyl glycidyl ether and methyl methacrylate prepared by heating to 125 DEG  C. with ditertiary-butyl peroxide and precipitating with hexane, is similarly heat-cured in the presence of ethylene diamine, toluene and butyl alcohol; (b) vinyl acetate is copolymerized with 2-allylphenyl glycidyl ether in the presence of ditertiary-butyl peroxide at 125 DEG  C.; (7) 2:6-diallylphenyl glycidyl ether and methyl methacrylate are copolymerized in the presence of di-tertiary-butyl peroxide at 125 DEG  C. and heatcured with ethylene diamine; (8) vinyl acetate and 2:6-diallylphenyl glycidyl ether are copolymerized in the presence of benzoyl peroxide at 65 DEG  C.  In an example of epoxypolymerization, o-allyl-phenyl glycidyl ether is polymerized by heating in the presence of triethylamine at 50 DEG  C.ALSO:The invention comprises ethers of the formula (R)mAr(O-E)n, where R is a hydrocarbon radical containing an olefinic linkage, m and n each have a value of 1, 2 or 3, Ar is an aromatic nucleus of valency m + n, O is an ether oxygen atom, and E is a hydrocarbon radical containing an epoxide group, the arrangement being such that the carbon atoms linked to the epoxy oxygen atom do not include the carbon atom to which said ether oxygen atom is directly attached.  The ethers are prepared by adding an equivalent amount of sodium hydroxide in aqueous solution to a mixture of a phenol containing an olefinically unsaturated hydrocarbon substituent and about 4 to 10 equivalents of a haloepoxide, the addition being conducted while distilling off water from the reaction mixture as an azeotrope with the haloepoxide. The equivalency refers to the phenolic hydroxyl groups of the phenol. The reaction temperature is from 60 DEG  to 150 DEG  C. or the refluxing or distilling temperature of the reaction mixture.  The by-product salt may be removed by filtration, unreacted haloepoxide distilled off and the ether isolated by distillation.  The phenols contain from 1 to 3 phenolic hydroxyl groups and from 1 to 3 olefinic hydrocarbon substituents and may be either mono- or polynuclear with or without fused ring systems.  Phenols specified are 2-, 3- and 4-vinylphenol, 3 : 5 - dibromo - 4 - vinyl phenol, 2 : 3 : 5 - tribromo - 4 - vinylphenol, 2 -, 3 - and 4 - propenylphenol, 2 - and 4 - isopropenylphenol, 2-butenylphenol, 2 - (1 - ethylpropenyl) phenol, 2 - (2 - methylpropenyl) phenol, 2 - heptenylphenol, 2 - hydroxy - 4 - vinyl phenol, 2-methoxy - 4 - vinylphenol, 2 - hydroxy - 3 - and 2 - hydroxy - 4 - propenylphenol, 2 -, 3 - and 4 - allylphenol, 2 - allyl - 3 -, 2 - allyl - 4 - and 2 - allyl - 6 - methyl phenol, 2 : 6 - diallyl-phenol, 2 - allyl - 4 : 6 - dimethylphenol, 2 : 6-diallyl - 3 - methylphenol, 2 - allyl - 4 - methyl-6 - propylphenol, 2 - allyl - 3 : 5 : 6 - trimethylphenol, 2 - allyl - 6 - chlorophenol, 2 - allyl - 4-bromophenol, 2 - allyl - 6 - hydroxyphenol, 4-allyl - 2 - hydroxyphenol, 2 - allyl - 5 - hydroxyphenol, 2 - allyl - 6 - and 2 - allyl - 4 - methoxyphenol, 2 : 5 - diallyl - 6 - and 2 : 6 - diallyl - 5-hydroxyphenol, 2 : 4 : 6 - triallylphenol, 2-allyl - 4 - acetoxyphenol, 2 : 4 : 6 - triallyl - 3-allyloxyphenol, 4 - acetyl - 2 - allyl - 6 - methoxyphenol, 2 - allyl - 6 - carboethoxyphenol, 2-allyl - 1 - and 1 - allyl - 2 - napthol, 2 - allyl-4 - phenylphenol, 2 - allyl - 5 - hydroxy - 4-nitrophenol, 2 - methallylphenol, 4 - chloro - 2-methallylphenol, 2 : 6 - dimethallylphenol, 2-crotylphenol, 4 - crotyl - 2 : 6 - dichlorophenol, 2 - allyl - 4 - phenylazophenol, 1 - (a  - phenylallyl) - 3 - carbomethoxy - 2 - napthol, 2-carbomethoxy - 6 - methyl - 4 - (g  - phenylallyl)-phenol and 2-(2-cyclohexenyl) phenol. Haloepoxides specified are epichlorhydrin, epibromohydrin, 1 - chloro - 2 : 3 - epoxybutane, 1-chloro - 3 : 4 - epoxybutane, 2 - chloro - 3 : 4-epoxybutane, 1 - chloro - 2 - methyl - 2 : 3-epoxypropane, 1 - bromo - 2 : 3 - epoxypropane, 2 - chloromethyl - 1 : 2 - epoxybutane, 1-bromo - 4 - methyl - 3 : 4 - epoxypentane, 1-bromo - 4 - ethyl - 2 : 3 - epoxypentane, 4-chloro - 2 - methyl - 2 : 3 - epoxypentane, 1-chloro - 2 - methyl - 2 : 3 - epoxyoctane and 1-chloro - 2 : 3 - epoxyoctane.  Alkenylaryl glycidyl ethers specified are 2-allylphenyl glycidyl ether, 2 : 6-diallylphenyl glycidyl ether, 2 - vinylphenyl glycidyl ether, 3 : 5 - dibromo-4 - vinylphenyl 3 : 4 - epoxybutyl ether, 2-(1 - ethylpropenyl) phenyl 2 : 3 - epoxyoctyl ether, 1 : 2 - bis - (glycidyloxy) 4 - vinylbenzene, 2 - methoxy - 4 - vinylphenyl glycidyl ether, 2 - allyl - 3 : 5 : 6 - trimethylphenyl 2-methyl - 2 : 3 - epoxypentan - 4 - yl ether, 2 : 4 : 6 - triallyl - 3 - allyloxyphenyl glycidyl ether, 2 - allyl - 1 - naphthyl glycidyl ether, 2-crotylphenyl 2 - methyl - 2 : 3 - epoxypropyl ether, 2 - (2 - cyclohexenyl) phenyl glycidyl ether, 2 : 4 : 6-triallylphenyl glycidyl ether, 2-allyl - 4 - acetoxyphenyl glycidyl ether, 2-allylphenyl 1 : 2 - epoxy - 1 - phenylbut - 3 - yl ether, 1 : 3 : 5 - tris(glycidyloxy) - 2 - allylbenzene, 2 - allyl - 6 - carboethoxyphenyl glycidyl ether and 2 - allyl - 4 - phenyl - azophenyl glycidyl ether.  In examples: (1) 2-allylphenol and epichlorhydrin are refluxed while aqueous sodium hydroxide is added, vapour from the reaction mixture being condensed and separated, the aqueous layer being removed and the epichlorhydrin returned to the reaction, the reaction mixture is then cooled, salt removed by filtration and washed with toluene, the washings and filtrate combined and distilled to yield finally 2-allylphenyl glycidyl ether; (2) a similar reaction using 2 : 6-diallylphenol, epichlorhydrin and aqueous sodium hydroxide yields 2 : 6-diallylphenyl glycidyl ether. The alkenylaryl epoxy ethers are intermediates in the production of epoxy resins, drying resins and alkyd resins (see Group IV (a)). Specifications 650,117 and 660,377 are referred to.