Patent GB-574606-A (GB)
Title: Complex esters and polymers thereof
IPC: C08G63/50
Filed: 1941-12-01
Abstract: Polyesters are made by esterifying a polybasic acid or its acid chloride with a monohydroxy carboxylic acid ester of an unsaturated alcohol.  Suitable polybasic acids are diglycollic, dilactic, cyanuric, oxalic, maleic, dimethyl maleic, phenyl malonic, fumaric, tartaric, succinic, malonic, phthalic, glutaric, adipic, pimelic, sebacic, itaconic, mesaconic, citraconic, citric, malic, terephthalic, acetone dicarboxylic, carbonic, sulphuric, sulphurous, phosphoric, phosphorous, boric, silicic, titanic or chromic acids. Suitable esters are those derived from lactic, a -, b - or g -hydroxy-butyric, glycollic, citric, m- or p-hydroxy-benzoic, malic, hydroxy-valeric, hydroxy-fumaric, hydroxy-cinnamic, salicylic, hydroacrylic, mandelic, glyceric, a -hydroxy-vinylacetic, hydroxycaproic and ricinoleic acids and vinyl, allyl, methallyl, ethyl-allyl, cinnamyl, crotyl, 2-chloroallyl, chlorocrotyl, propargyl, methylvinyl-carbinyl, tiglyl- or isopropenyl-vinyl-carbinyl-alcohols, 3 - chlorobutene - 2 - ol - 1, 3 - hydroxybutene - 1,3 - hydroxy - pentadiene - 1.4, 1-hydroxy-hexadiene-2.4, 1-hydroxy-2-methylhexene-2.  Oleyl or linoleyl alcohols or alcohols obtained by the reduction of chinawood oil acids may be used.  Suitable catalysts are benzene or toluene sulphonic acid.  The reaction may be conducted in water, acetone or dioxane in the presence of pyridine or sodium, potassium, calcium, barium, strontium or magnesium carbonates, bicarbonates or hydroxides.  Polymerization inhibitors such as hydroquinone may be used.  Purification of the reaction mixture may be effected by distillation or by washing with water and dehydrating with calcium chloride.  The esters may be used as solvents or plasticisers for cellulose derivatives and synthetic resins, e.g. polyvinyl or polyacrylic plastics, polystyrene, urea-aldehyde and phenol-aldehyde resins.  The esters may be polymerized in the presence of heat, light, oxygen, ozone or lauryl or benzoyl peroxide.  Polymerization may be effected in solution in acetone, dioxane, chloroform, toluene, benzene, carbon tetrachloride, dichlorethyl ether, xylene, tetrahydronaphthalene, dibutyl phthalate, trichlorethylene, tetrachlorethane, glycol monomethyl ether acetate or glycol monophenyl ether.  Fusible polymers are formed by interrupting polymerization before a gel is formed by separating unchanged monomer by the addition of methyl or ethyl alcohol, petroleum ether, water or ethylene glycol in which the polymer is insoluble, by lowering the temperature of the reaction mixture, or by addition of inhibitors, e.g. pyrogallol, hydroquinone, aniline, phenylene diamine, sulphur and thiophenol.  Monomer may be removed from the polymer by distillation in vacuo, by solvent extraction or by solution of monomer and polymer in a common solvent and adding a non-solvent to precipitate the polymer.  The fusible polymers are converted to infusible and insoluble products by heating above the softening point, if desired in the presence of light, oxygen, ozone, air, hydrogen peroxide, benzoyl peroxide or basic or acidic catalysts. The surface only may be hardened by local heating, by applying catalysts to the surface only or by incorporating inhibitors in the interior of the moulding.  The moulding composition may comprise plasticisers, e.g. dibutyl- or dicyclohexyl-phthalate, triacetin and tricresyl phosphate, natural or synthetic resins, pigments, e.g. titanium dioxide, carbon black, chromic oxide and lead chromate and dyestuffs, e.g. methylene blue and methyl orange.  Copolymers may be prepared with acrylates, methyl-, allyl- or glycol-methacrylates, vinyl chloride, styrene, allyl acetate, maleates, fumarates, phthalates, succinates, oxalates or tartrates or the corresponding vinyl, crotyl, methallyl or 2-chlorallyl esters.  The products may also be used in making laminated materials including laminated glass, for impregnating leather, paper and wood, as coating compositions, and as adhesives for cementing granular material on roofing tiles and shingles.  In an example phosgene was passed into a cooled mixture of allyl ricinoleate, pyridine and benzene, which was heated to 40 DEG C. and diluted with water.  The oily layer was washed successively with water, dilute hydrochloric acid and again with water.  Volatile products were removed by vacuum distillation at 20 mm. pressure and 100 DEG  C.  The light yellow oily carbonate of allyl ricinoleate polymerized to a transparent gel on heating at 70 DEG  C. with benzoyl peroxide.