Patent GB-674841-A (GB)
Title: Esters derived from unsaturated ethers of polyhydric alcohols and compositions containing the said esters
IPC: C07C69/83
Filed: 1948-04-21
Abstract: Resinous polymeric esters are formed by heating unsaturated mono-ethers of polyhydric alcohols, wherein the hydrogen atom of one hydroxyl group has been replaced by an olefinic hydrocarbon, or halogenated hydrocarbon, radical, or polymers or copolymers of such ethers with monocarboxylic acids.  Examples of ethers include allyl, methallyl, 2-chlorallyl, 3-chlorallyl, methyl and ethyl vinyl carbinyl, ethallyl, cinnamyl, 2-pentenyl, 2 - isohexenyl, 2 - dodecenyl, crotyl, 2-chlorocrotyl, linoleyl and linonenyl monoethers of glycerol, allyl mono-ethers of erythritol and pentaerythritol, 2-chloroallyl mono-ether of xylitol, methallyl mono-ether of sorbitol, allyl mono-ether of methyl glycerol, and cinnamyl mono-ether of beta-phenyl glycerol.  To polymerize, the ethers are heated in the presence of a peroxide catalyst or oxygen-containing gas, e.g. air.  Copolymerizable compounds include styrene, vinyl chloride, vinyl acetate, vinylidene chloride, acrylonitrile, diallyl phthalate, methyl methacrylate and ethyl acrylate.  The esterifying acids are preferably drying oil acids obtained, for example, from soya bean, linseed, tung, perilla, menhaden and sardine oils. Esterification is effected in an inert atmosphere at 100-250 DEG  C., preferably while passing a stream of carbon dioxide or nitrogen through the mixture. Catalysts are not generally needed but such substances as p-toluene sulphonic acid, zinc chloride, stannic chloride, calcium, barium and zinc acetates, hydrochloric acid and litharge, may be used in amounts of from 0.1-2 per cent.  Other acids than the above which may be used are abietic acid, hydrogenated rosin acid, isomerized abietic acid, congo resin, benzoic, toluic, naphthenic, acetic, propionic, octoic, pelargonic, lauric, myristic, palmitic, stearic, crotonic, sorbic, acrylic and methacrylic acids. With acids such as the last two, temperatures of 50-100 DEG  C. are used with an inhibitor, e.g. sulphur, tannic acid, b -naphthylamine, and hydroquinone, to prevent premature polymerization.  Modified products are obtained by reacting the ethers with polycarboxylic acids or anhydrides before or during the esterification with the monocarboxylic acid. Suitable acids are phthalic, chlorinated and hydrogenated phthalic, maleic, chlorinated maleic, fumaric, itaconic, succinic, tartaric, citric, alkyl succinic, alkylene succinic and mellitic acids; polybasic acids derived from the thermal polymerization of drying oil or other unsaturated monobasic fatty acids or their p  esters; acids derived from the reaction of maleic, fumaric, or itaconic acids with terpenes, rosin, cyclopentadiene, butadiene, methyl pentadiene and drying oil acids or their esters. The products are useful as film-forming agents, gasket and brake lining binders, and cements, and for the preparation of casting, moulding and laminated plastics.  They are also useful as modifying agents for other resins or film-forming agents, e.g. nitrocellulose, ethyl cellulose, cellulose acetate and acetobutyrate, chlorinated rubber, hydrochlorinated and cyclized rubber, polyvinyl formal and butyral, polyvinyl chloride, copolymers of vinyl chloride and vinyl esters, e.g. vinyl acetate and butyrate, copolymers of vinylidene chloride and ethyl acrylate or methyl methacrylate, polyamide resins, urea - formaldehyde, urea - melamine, phenol-formaldehyde and alkyd resins and heat polymerized or blown drying oils.  The esters alone or mixed with other resins are suitable for wood and metal finishes. Products particularly suitable for plasticizing the above resins are obtained by hydrogenating the polymeric ether and then esterifying with a saturated fatty acid, e.g. acetic or lauric, or with abietic or hydrogenated abietic acid.  Hydrogenation is effected in solution in a lower alcohol in the presence of a catalyst, e.g. Raney nickel, while stirring at 50-200 DEG  C. under a pressure of 2-100 atmospheres of hydrogen.  Alternatively the polymeric ether may first be esterified and the ester hydrogenated.  Samples have been furnished under Sect 2 (5) of the Acts of (1) glycerol-a -allyl ether stearate, a straw-coloured, waxy solid; (2) poly-(glycerol-a -allyl ether) stearate, a waxy solid; (3) glycerol-a -allyl ether crotonate, a yellow liquid; (4) linseed fatty acids ester of glycerol-a -allyl ether, an amber liquid; poly-(glycerol-a -allyl ether) abietate, a solid; (6) glycerol-a -allyl ether phthalate sorbate, a solid; (7) phthalic-linseed fatty acids ester of glycerol-a -allyl ether, a turbid liquid; (8) linseed fatty acids ester of pentaerythritol mono-allyl ether; and (9) phthalic-linseed fatty acids ester of pentaerythritol mono-allyl ether.  The Specification as open to inspection under Sect. 91, comprises also esters of di- and tri-ethers of polyhydric alcohols, e.g. diallyl diether and dimethallyl diether of glycerol, diallyl diether of pentaerythritol, dimethylallyl diether of erythritol, triallyl tri-ether of adonitol, tricinnamyl ether of pentaerythritol, di- and tri-allyl ethers of sorbitol and mannitol, pentaallyl ether of perseitol and partially alkylated starch, sucrose and cellulose.  This subject-matter does not appear in the Specification as accepted.ALSO:Esters are formed by heating unsaturated mono-ethers of polyhydric alcohols, wherein the hydrogen atom of one hydroxyl group has been replaced by an olefinic hydrocarbon or halogenated hydrocarbon radical, with mono-carboxylic acids.  Examples of ethers are allyl, methallyl, 2-chlorallyl, 3-chlorallyl, methyl and ethyl vinyl carbinyl, ethallyl, cinnamyl, 2-pentenyl, 2-isohexenyl, 2-dodecenyl, crotyl, 2-chlorocrotyl, linoleyl and linonenyl mono ethers of glycerol, allyl mono-ethers of erythritol and pentaerythritol, 2 - chlorallyl mono-ether of xylitol, methallyl mono-ether of sorbitol, allyl mono-ether of methyl glycerol and cinnamyl mono-ether of beta-phenyl glycerol.  The acids are preferably drying oil acids obtained, for example, from soya bean, linseed, tung, perilla, menhaden and sardine oils. Esterification is effected in an inert atmosphere at 100-250 DEG  C., preferably while passing a stream of carbon dioxide or nitrogen through the mixture. Catalysts are not generally needed but such substances as p-toluene sulphonic acid, zinc chloride, stannic chloride, calcium, barium and zinc acetates, hydrochloric acid and litharge, may be used in amounts of from 0.1-2 per cent.  Other acids than the above which may be used are abietic, hydrogenated rosin acid, isomerized abietic acid, Congo resin, benzoic, toluic, naphthenic, acetic, propionic, octoic, pelargonic, lauric, myristic, palmitic, stearic, crotonic, sorbic, acrylic, and methacrylic acids.  With acids such as the last two, temperatures 50-100 DEG  C. are used with an inhibitor, e.g. sulphur, tannic acid, b  - naphthylamine and hydroquinone, to prevent polymerization. Modified products are obtained by reacting the ethers with polycarboxylic acids or anhydrides before or during the esterification with the monocarboxylic acid.  Suitable acids are phthalic, chlorinated and hydrogenated phthalic, maleic, chlorinated maleic, fumaric, itaconic, succinic, tartaric, citric, alkyl succinic, alkylene succinic and mellitic acids; polybasic acids derived from the thermal polymerization of drying oil or other unsaturated monobasic fatty acids or their esters; acids derived from the reaction of maleic, fumaric or itaconic acids with terpene, rosin, cyclopentadiene, butadiene, methyl pentadiene and drying oil acids or their esters.  The products are useful as film-forming agents, wood and metal finishes, binders and casting, moulding and laminated plastics.  Samples have been furnished under Sect. 2(5) of the Acts including (1) glycerol-a -allyl ether stearate; (2) glycerol-a -allyl ether crotonate; (3) linseed fatty acids ester of glycerol-a -allyl ether; (4) glycerol-a -allyl ether phthalate sorbate; (5) phthalic linseed fatty acids ester of glycerol-a -allyl ether; (6) linseed fatty acids ester of pentaerythritol monoallyl ether; (7) phthalic-linseed fatty acids ester of pentaerythritol mono-allyl ether.  The Specification as open to inspection under Sect. 91 comprises also esters of di- and tri-ethers of polyhydric alcohols, e.g. diallyl and dimethallyl diethers of glycerol, diallyl diether of pentaerythritol, dimethallyl diether of erythritol, triallyl tri-ether of adonitol, tricinnamyl ether of pentaerythritol, di- and triallyl ethers of sorbitol and mannitol, penta-allyl ether of perseitol and partially alkylated starch, sucrose and cellulose. This subject-matter does not appear in the Specification as accepted.