Patent GB-774420-A (GB)
Title: Improvements in or relating to the preparation of hydroxy-substituted unsaturated esters
IPC: C08G63/58
Filed: 1954-09-27
Abstract: An hydroxy-substituted unsaturated ester is obtained by reacting a polyepoxide having in the molecule an average number of epoxy groups greater than 1.0 with an acid ester of a polybasic acid and an ethylenically unsaturated alcohol.  The polyepoxides may be monomeric or polymeric and preferably have a molecular weight between 125 and 3000.  Suitable polyepoxides are: (a) monomeric compounds such as butadiene dioxide, epoxidized mono-, di-, and triglycerides containing more than one epoxy group, 1,4-bis-(2,3-epoxypropoxy) benzene, diglycidyl ether, diglycidylthioether, and 1,2,5,6-diepoxy hexane; (b) glycidylpolyethers of polyhydric phenols obtained by reacting a polyhydric phenol with an excess of epichlorhydrin or dichlorhydrin in an alkaline medium at 50 DEG  to 150 DEG C. Specified polyhydric phenols are resorcinol, methyl resorcinol, catechol and polynuclear phenols such as bisphenol [(2,2-bis-(4-hydroxyphenyl) propane], novolac resins and 2,2-bis-(4-hydroxyphenyl) butane. The novolac resins are preferably obtained by condensing an aldehyde such as formaldehyde with a polyhydric phenol such as bisphenol.  Other suitable polyepoxides are: (c) polyepoxy glycidyl polyethers obtained by reacting epichlorhydrin or dichlorhydrin with a polyhydric alcohol and then treating the product with an alkaline component; (d) polyepoxy polyesters obtained by esterifying a polycarboxylic acid with an epoxy-containing alcohol, e.g. the diglycidyl ester of adipic acid; (e) polymers and copolymers of epoxy-containing monomers having at least one polymerizable ethylenic linkage.  These monomers may be polymerized alone or with other ethylenically unsaturated monomers such as styrene or vinyl acetate.  Suitable polyepoxides of this type are polymers of the 2-alkenyl glycidyl ethers, e.g. poly-(allyl 2,3-epoxypropyl ether) and the copolymer of allyl 2,3-epoxypropyl ether and styrene.  Suitable polyhydric alcohols from which the polyepoxides of type (c) above may be derived, include glycerol, ethylene glycol, hexanetriol, sorbitol, mannitol, pentaerythritol, glycerol methyl ether, polyvinyl alcohol and polyallyl alcohol, and mixtures thereof.  Suitable glycidyl polyethers are obtained by reacting the polyhydric alcohol at 50-125 DEG  C. with epichlorhydrin preferably in the presence of 0.1 to 5 per cent by weight of an acid-acting compound such as boron trifluoride.  The resulting chlorhydrin ether may be fully or partially dehydrochlorinated by heating at about 50-125 DEG  C. with a small excess of a base such as sodium aluminate.  Specified polyepoxides of this type are glycerol triglycidyl ether, mannitol tetraglycidyl ether, pentaerythritol tetraglycidyl ether and sorbitol tetraglycidyl ether.  The unsaturated acid esters used as starting materials are obtained by esterifying at least one and at most all but one of the acid groups of a polybasic acid with an ethylenically unsaturated alcohol.  The polybasic acid may be inorganic or organic and may be saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic. Specified acids include malonic, succinic, phthalic, tetrachlorophthalic, maleic, fumaric, dichlormaleic, methylmaleic, and diethylmaleic acids, and phosphorus-containing acids, e.g. phosphoric and phosphonic acids such as benzenephosphonic acid and butanephosphonic acid.  Specified unsaturated alcohols include allyl, methallyl, crotyl, and cinnamyl alcohols, 3-buten-1-ol, 4-chloro-3-buten-1-ol, 4-hexen-1-ol, 2,4-hexadiene-1-ol, 5-cyclohexyl-3-hexen-1-ol, and 3-chloro-2-buten-1-ol.  The process for the production of the hydroxy-substituted unsaturated esters is preferably carried out at temperatures ranging from room temperature up to about 150 DEG  C. and the polyepoxides and acid esters are preferably combined in chemically equivalent ratios varying from 1 : 3 to 1 : 1.  A list of preferred acid esters is given and this includes allyl hydrogen chlorobutane phosphonate.  Derivatives of the products wherein the hydroxy groups formed by the opening of the epoxy ring are esterified with the acid ester may be obtained by using an excess of the acid ester.  The reaction may be conducted in the presence of a solvent or diluent, e.g. toluene, benzene, dioxane, ethyl alcohol and the methyl ether of ethylene glycol monoacetate. The hydroxy esters may be further reacted through the hydroxy group with polyfunctional agents, e.g. with diisocyanates, polycarboxylic acids or their anhydrides and various resinous products such as amine-aldehydes or amide-aldehyde type resins or those prepared from formaldehyde and amides or amines such as urea, thiourea and phenyl urea.  They may also be reacted through the ethylenic group with hydrogen sulphide and mercaptans. Suitable diisocyanates and polycarboxylic acids and their anhydrides are specified.  The hydroxy esters may also be further reacted with monocarboxylic acids such as acetic, butyric, and stearic acids to produce ester derivatives valuable as plasticizers and lubricants or with polyethylenically unsaturated monocarboxylic acids, e.g. rosin acids such as abietic acid and acids from linseed, soyabean, perilla and dehydrated castor oils. They may also be cured to form hard films and are valuable as hardening agents for laminating compositions containing polyesters, styrene modified polyesters, urea resins or phenolic resins and as curing agents for acrylic rubbers.  They are also stated to be compatible with vinyl polymers and cellulose ethers and esters.  The products may also be polymerized alone or with other ethylenically unsaturated monomers such as styrene, alpha-methylstyrene, dichlorostyrene, and vinyl naphthalene, the alkyl esters of the mono and polycarboxylic unsaturated acids such as methyl acrylate or methacrylate, butyl methacrylate, propyl acrylate, dibutyl fumarate and dimethyl and dihexyl maleates; the alkenyl esters of saturated monocarboxylic acids; vinylidene halides such as the chloride and fluoride; vinyl halides such as the chloride and bromide; vinyl esters of hydrocyanic acid; the vinyl ethers; and the vinyl ketones and examples of these types are given.  The polymerization may be effected in the presence of a free radical yielding catalyst, e.g. the peroxide catalysts and is preferably effected in the absence of air, e.g. in the presence of nitrogen.  The hydroxy esters and their derivatives, e.g. monocarboxylic acid derivatives, are valuable as polymerizable plasticizers for vinyl polymers, e.g. the vinyl chloride polymers and for this purpose they may be used alone or in combination with known plasticizers, e.g. dioctyl phthalate or tricresyl phosphate. Examples are given for the reaction of allyl hydrogen maleate with (1) poly-(allyl glycidyl ether) having an average number of about 2.5 epoxy groups per molecule, the product being polymerized alone or with styrene; (2) with a polyether of average molecular weight 350 and an average of 1.75 epoxy groups derived from bisphenol and epichlorhydrin, the product being polymerized in the presence of benzoyl peroxide; (3) with a polyether of average molecular weight 710 and an average number of 1.9 epoxy groups derived from bisphenol and epichlorhydrin; (4) with a polyester derived from a novolac resin and epichlorhydrin; (5) with epoxidized soyabean oil.  In other examples: (6) the products obtained in (4) and (5) are separately combined with vinyl acetate, acrylonitrile and methyl methacrylate respectively and each mixture polymerized in the presence of di-tert-butyl peroxide to yield resinous products; (7) allyl hydrogen phthalate is reacted with poly-(allyl glycidyl ether) and the product cured at 230 DEG  C for 1/2 hour to yield a hard tough film; (8) allyl hydrogen phthalate is reacted with the polyether used in (2) and the product cured as in (7); (9) allyl hydrogen maleate (2 moles) is reacted with a mixture of isomeric vinyl cyclohexene dioxides (1 mole) and the product cured as in (7); (10) allyl hydrogen benzene phosphonate (2 moles) is reacted with one mole of the polyether used in (2) and the product cured in an oven at 230 DEG  C.; methallyl hydrogen cyclohexane phosphonate, diallyl hydrogen phosphate and allyl hydrogen butane-phosphonate may be used similarly; (11) the reaction product obtained in (2) is reacted with two molecular proportions of acetic anhydride to form the diacetate and the product is then combined with polyvinyl chloride and the mixture polymerized.  The products obtained in (1), (2) and (3) when mixed with a drier containing cobalt naphthenate and lead naphthenate, spreading the mixture on glass plates or tin panels and heating yield hard flexible films, and the products of (4) and (5) when spread on glass plates and curing at 220 DEG  C. yield hard flexible films.  The acid ester used in (1), (2) and (3) may be replaced by allyl hydrogen fumarate, allyl hydrogen methylmaleate or allyl hydrogen dichloro-maleate.ALSO:A hydroxy-substituted unsaturated ester is obtained by reacting a polyepoxide having in the molecule an average number of epoxy groups greater than 1.0 with an acid ester of a polybasic acid and an ethylenically unsaturated alcohol.  The polyepoxides may be monomeric or polymeric and preferably have a molecular weight between 125 and 3000.  Suitable polyepoxides are: (a) compounds such as butadiene dioxide, epoxidized mono-, di-, and tri-glycerides containing more than one epoxy group, 1,4 - bis - (2,3 - epoxypropoxy) benzene, diglycidyl ether, diglycidylthioether, and 1,2,5,6-diepoxy hexane; (b) glycidylpolyethers of polyhydric phenols obtained by reacting a polyhydric phenol with an excess of epichlorhydrin or dichlorhydrin in an alkaline medium at 50 to 150 DEG  C.  Specified polyhydric phenols include resorcinol, methyl resorcinol, catechol and polynuclear phenols such as bisphenol [(2,2-bis-(4-hydroxyphenyl) propane], and 2,2 - bis - (4 - hydroxyphenyl) butane.  Other suitab