Unsaturated esters of epoxy-substituted polycarboxylic acids and polymers thereof

  • Inventors:
  • Assignees: Bataafsche Petroleum
  • Publication Date: September 18, 1957
  • Publication Number: GB-783132-A

Abstract

Esters of a polycarboxylic acid containing at least one 1,2-epoxy group in the molecule and a monohydric alcohol having in the molecule at least one aliphatic carbon-carbon unsaturated linkage (see Group IV (b)), may be used as plasticisers for vinyl polymers, e.g. homopolymers and copolymers of styrene, a -methylstyrene, vinyl naphthalene, vinyl phenol, acrylic acid esters, esters of substituted acrylic acids, vinylidene chloride, vinyl chloride, acrylonitrile, methacrylonitrile, vinyl esters, diallyl phthalate, diallyl succinate, vinyl ethers, vinyl ketones and vinyl pyridine, either alone or in combination with other plasticisers, e.g. dioctyl phthalate, dibutyl phthalate, tricresyl phosphate and dibutyl sebacate. The amount of plasticiser is generally 20 to 150 parts, preferably 40 to 75 parts, by weight per 100 parts by weight of resin. The novel esters may also be used as stabilizers for halogen-containing polymers in amounts of 0.1 to 20 per cent by weight, or when used in combination with urea and thiourea derivatives, metal salts or organic and inorganic acids, in smaller amounts of 0.01 to 10 per cent by weight of the polymer. They may also be used as combined stabilizer-plasticisers. The novel unsaturated epoxyesters may be polymerized through the unsaturated groups by heating in the presence of a peroxide, e.g. benzoyl, acetyl, benzoyl acetyl, lauryl, dibutyryl, or succinyl peroxides, t.-butyl perbenzoate, t.-alkyl hydroperoxides, peracetic acid and perphthalic acid, the catalyst being employed in amounts of 0.01 to 5 per cent by weight of the monomer. Low molecular weight polymers are obtained at 150-300 DEG C. and higher molecular weight polymers at 50-125 DEG C. The novel esters may also be copolymerized with vinyl-type monomers such as those described above, the dissimilar monomers being present in amounts of 2 to 90 per cent of the ester monomers. The polymers so formed may be used as plasticisers, lubricants, stabilizers and as ion exchange resins. The novel unsaturated epoxy esters may be polymerized through the epoxy groups by adding epoxy polymerization catalysts. Where the esters contain a single epoxy group, suitable catalysts are the Friedel-Crafts catalysts, such as aluminium chloride or bromide, zinc chloride, boron trifluoride, silicon tetrachloride, stannic chloride or bromide, titanium tetrachloride and bismuth trichloride, the catalysts being used in amounts of 1 to 10 per cent by weight of the monomers. Where the esters possess a plurality of epoxy groups, suitable catalysts are ethylene diamine, 2,3,6-tri-(dimethylamino ethyl) phenol, amine-aldehyde resins, amide-aldehyde resins, dialdehydes, polybasic acids, such as organic and mineral acids, and their anhydrides, and polymercaptans, the catalysts being used in amounts of 0.1 to 5 per cent by weight of the monomers. In some cases, it may be necessary to heat at 30 DEG to 80 DEG C., to effect polymerization. The esters may also be copolymerized with other epoxy-substituted monomers such as epichlorohydrin, glycidol, butadiene monoxide or dioxide, diglydidyl ether, allyl glydidyl ether, and glycidyl ethers of polyhydric phenols or polyhydric alcohols, the dissimilar monomers being employed in amounts from 2 to 90 per cent by weight of the epoxy esters. Copolymers of this type are useful as lubricants and emulsifiers. The polymers and copolymers formed from the novel esters are useful in the formation of coatings, pottings and castings. In the formation of baked coatings, the esters may be first polymerized through the epoxy group and the polymer so formed is added to the coating composition containing solvents, pigments and driers, peroxide catalysts are added and the coating is baked on the desired surface at 100 DEG to 200 DEG C. In the formation of pottings or castings, the esters are polymerized through the epoxy group or unsaturated group to form a soluble linear polymer, the catalyst to be used with the remaining functional group is then added and the mixture is poured or forced into the mould or casting and heated to the desired temperature. The esters may also be polymerized by addition and epoxy polymerization simultaneously by mixing the peroxide catalyst with the ester and then adding the epoxy catalyst. In examples, (1) the diallyl ester of epoxidized 8,12-eicosadiene-dioic acid is polymerized to a soft solid by adding stannic chloride in chloroform; the monomeric ester is also polymerized by heating with benzoyl peroxide; a hard casting is formed by adding both 2,4,6-(dimethylaminoethyl) phenol and benzoyl peroxide to the epoxy-ester and heating to 70 DEG C.; (2) the diallyl ester of epoxidized 4-cyclohexene-1,2-dicarboxylic acid is polymerized in the presence of stannic chloride, the viscous liquid polymer is dissolved in a ketone and applied to metal strips which are then baked at 200 DEG C. for 30 minutes to form a clear hard film; benzoyl peroxide is added to a portion of the above viscous liquid polymer and the mixture heated to a solid casting; (3) the di-(allyloxyethyl) ester of epoxidized 4-cyclohexene-1,2-dicarboxylic acid is used as a plasticiser-stabilizer for polyvinyl chloride); the ester is also polymerized in the presence of benzoyl peroxide; (4) the diallyl ester of epoxidized dimerized linoleic acid is treated as in (2); (5) the divinyl ester of epoxidized 8,12-eicosadienedioic acid is treated as in (2); (6) the divinyl ester of epoxidized 1,4-cyclohexadiene-1,2-dicarboxylic acid is heated with benzoyl peroxide. Specifications 14246/13, [Class 2 (ii), 762,340 and 770,481 are referred to.ALSO:The invention comprises an ester of a polycarboxylic acid containing at least one 1,2-epoxy group in the molecule and a monohydric alcohol having in the molecule at least one aliphatic carbon to carbon unsaturated linkage. The epoxy-substituted acids may possess 2, 3, 4 or more carboxyl groups and are obtained from aliphatic, aromatic or heterocyclic acids which may contain further substituents, such as chlorine atoms or ether radicals. Preferred epoxy-substituted polycarboxylic acids are obtained by epoxidizing mono- or polyethylenically unsaturated polycarboxylic acids such as maleic acid, aconitic acid, itaconic acid, allylmalonic acid, and 2-butenedioic acid; monoethylenically unsaturated cyclic polycarboxylic acids obtained by condensing maleic acid (or anhydride followed by hydrolysis) with a compound having a conjugated system of double bonds; polyethylenically unsaturated cyclic carboxylic acids obtained either by condensing a chloromaleic acid with a compound having a conjugated system of double bonds and dehydrohalogenating the resulting product, or by reacting maleic acid with a halogenated olefinic compound and dehydrohalogenating the resulting product; dimerized polyethylenically unsaturated fatty acids, such as are obtained by heating polyethylenically unsaturated monocarboxylic acids, such as linoleic acid, with a Friedel-Crafts catalyst such as boron trifluoride, polyethylenically unsaturated polycarboxylic acids obtained by reacting a cyclic peroxide with a compound having a conjugated system of double bonds in the presence of a heavy metal capable of existing in several valency forms, such as iron or cobalt, as described in Specification 762,340; 3,5-cyclohexadiene-1,2-dicarboxylic acids and alkenyl-substituted succinic acids. The unsaturated alcohols used to form the novel esters are monohydric alcohols having in the molecule at least one aliphatic carbon-to-carbon linkage, e.g. an ethylenic or acetylenic linkage, preferably not more than four carbon atoms removed from the terminal hydroxyl group, and may be substituted with aliphatic, alicyclic, aromatic or heterocyclic radicals, or with further substituents such as halogen atoms or alkoxy radicals. Suitable alcohols are the a ,b -ethylenically unsaturated aliphatic monohydric alcohols containing from 2 to 15 carbon atoms, and the b ,g -ethylenically unsaturated aliphatic monohydric alcohols containing from 3 to 18 carbon atoms. Examples of these alcohols are vinyl alcohol, allyl alcohol, 2-hexenol, 2-chloro-2-hexenol, 1-pentenol, 3-chloro-2-octenol, 3,5-dibutyl - 2 - decenol and 3 - butyl - 1 - octenol. b ,g -acetylenic alcohols such as propargyl alcohol, 2-pentyrol, and 4-chloro-2-hexynol, may also be used. The novel esters may be prepared by esterification of the epoxy-substituted carboxylic acids and unsaturated alcohols, or by esterification of an appropriate unsaturated polycarboxylic acid with an unsaturated alcohol, followed by selective epoxidation of the ethylenic group or groups in the acid radical. The esterification may be effected by heating the components together and removing the water of esterification, preferably as fast as it is formed in the reaction mixture. For the esterification of the epoxy-substituted acids mild catalysts, such as formic acid, monosodium sulphate and aluminium sulphate, may be used in amounts varying from 0.1 to 5 per cent by weight, so as not to affect the epoxy groups. Inert organic solvents or diluents, such as benzene, toluene, cyclohexanone and xylene, may be present if desired. Temperatures between 40 DEG and 100 DEG C. are suitable, 50 DEG to 80 DEG C. being preferred. It may be desirable to conduct the reaction in an inert atmosphere, such as nitrogen, in some cases, and atmospheric superatmospheric or subatmospheric pressures may be used. Esters of vinylic alcohols may be prepared by reacting the desired acid with acetylene in the presence of a mercuric salt, e.g. mercuric sulphate, as described in Specification 14246/13, [Class 2 (iii)], or by reacting the desired acid with a preformed vinyl ester, e.g. vinyl acetate, in the presence of an ester-exchange catalyst and successively distilling off an acid corresponding to the acid radical of the vinyl ester and then the desired vinyl ester, as de

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