Patent GB-576083-A (GB)
Title: Complex esters and their polymers
IPC: C08F2/00
Filed: 1941-09-11
Abstract: A complex monomeric ester is prepared by reacting an unsaturated alcohol chloroformate with a glycol, glycerol or polyvinyl alcohol or by reacting a chloroformate of a glycol, glycerol or polyvinyl alcohol with an unsaturated alcohol.  The chloroformate is prepared by the reaction of phosgene with the said alcohols.  The unsaturated alcohol may be allyl, methallyl, crotyl, 2-chloroallyl, chlorocrotyl, propiolic, cinnamyl, propargyl, methylvinylcarbinyl, oleyl or linoleyl alcohols or the alcohols derived from chinawood or coconut oils.  The glycols specified include tri-, tetra-, penta- and octa-methylene glycol, di-, tri- and tetraethyleneglycol, a -methyltetramethylene glycol, pinacol and 1.3-xylylene alcohol. Polymerization of the product gives a wide range of polymers.  A fusible polymer is obtained by interrupting polymerization before a gel is formed. Unpolymerized monomer may be removed from this by distillation or by the use of solvents or non-solvents and further polymerization of the purified product gives an infusible, insoluble polymer. The fusible polymers are soluble in solvents such as acetone, dioxane, benzene, chloroform, triacetin, glycolethers and carbontetrachloride.  Materials which may be incorporated in the polymer are plasticizers, softening agents or fillers such as dibutyl phthalate, dicyclohexyl phthalate, triacetin, tricresyl p  phosphate, resins, pigments including titanium oxide, carbon black, chromic oxide, lead chromate, organic dyes such as Methylene blue, Methyl orange.  Copolymers may be formed with, for example, acrylates, a -substituted acrylates, vinyl acetate, vinyl chloride, styrene, allyl esters such as the acetate, maleate, phthalate, succinate, oxalate, tartrate or other unsaturated alcohol esters, e.g. vinyl, crotyl, methallyl and 2-chlorallylesters.  The polymers may be incorporated in porous substances such as leather, paper and wood or used in coating compositions containing drying oils, safety glass, solvents, pharmaceuticals or plasticizers for vinyl, urea and phenol resins. They may be used in the production of laminated paper, linen or canvas and metal, glass and wood may be coated therewith. In the examples: (1) allyl chloroformate, prepared from allylalcohol and phosgene, is reacted with ethylene glycol in pyridine to give ethylene glycol bis-(allyl carbonate); (2) methallyl chloroformate, prepared from phosgene and methallylalcohol is reacted with ethylene glycol in pyridine to give ethylene bis-(methallyl carbonate); the following are prepared in an analogous manner: triethylene bis-(allyl carbonate), tetraethylene glycol bis-(allyl carbonate), diethylene glycol bis-(allyl carbonate), tetraethylene glycol bis-(methallyl carbonate), triethylene glycol bis-(methallyl carbonate), diethylene glycol bis-(methallyl carbonate), glyceryl tris-(allyl carbonate) and ethylene glycol bis - (2 - chloroallyl carbonate); (3) diethylene glycol dichloroformate (prepared from diethylene glycol and phosgene) is reacted with 2-chloroallyl alcohol in pyridine to give diethylene glycol di-(2-chloroallylcarbonate); ethylene glycol di-(2-chloroallylcarbonate) is prepared similarly; (4) allyl chloroformate is added to polyvinyl alcohol dissolved in pyridine and on pouring into acidified water, a gum is obtained which gives an infusible polymer on heating with benzoyl peroxide; (5) ethylene glycol bis-(allyl carbonate) is dissolved in dioxane and heated with benzoyl peroxide until viscous.  The mixture is cooled, methanol added and the polymer separated by decantation, then dissolved in acetone and reprecipitated.  The polymer, if further heated with benzoyl peroxide, gives a transparent sheet of infusible, insoluble polymer; (6) glyceryl tri-(allylcarbonate) is polymerized by heating with benzoyl peroxide.  Specification 540,938 is referred to.  The Specification as open to inspection under Sect. 91 comprises also the esterification of any polyhydric compound with an acid ester formed from an unsaturated alcohol and a polybasic acid. Polyhydric alcohols mentioned include: erythritol, pentaerythritol, polyglycerols, sorbitol, mannitol, glycerolmonochlorhydrin, resorcinol, pyrogallol, polyhydroxyanthracene and naphthalene, starch, sugar, phthalyl alcohol, 1 : 4-dioxanediol-2 : 3, polyallylalcohol, cellulose, cellulose mono- and diacetate, cellulose butyrates, cellulose ethers and mono-ethers of polyhydricalcohols.  In place of unsaturated alcohols, partial ethers of polyhydric alcohols with unsaturated alcohols may be used.  Partial esters of polyhydric alcohols with unsaturated acids are also mentioned.  The polybasic acids may be inorganic and organic, the following are mentioned: carbamic, thiocarbamic, thiocarbonic, diglycollic, dilactic, cyanuric, oxalic, malic, fumaric, dimethylmaleic, tartaric, succinic, malonic, phthalic, glutaric, adipic, pimelic, sebacic, itaconic, mesaconic, citraconic, citric, cyanuric, malic, terephthalic, acetonedicarboxylic, tricarballylic, sulphuric, sulphurous, phosphoric, phosphorous, boric, silicic, titanic and chromic acids. Further reactions mentioned include the following: (1) esters of hydroxyacids are reacted with aldehydes to form acetals, e.g. allyllactate may be reacted with formaldehyde, crotonaldehyde, acetaldehyde, acrolein or butyraldehyde; (2) hydroxyaldehydes are reacted with unsaturated alcohols and the resulting acetal esterified with a polybasic acid, e.g. b -hydroxy propionaldehyde may be treated with allyl or propargyl alcohol and esterified; (3) ester salts of polybasic acids are reacted with allyl type halides, e.g. a mono silver salt of phthalic or citraconic acid is esterified with glycol or glycerine and the product reacted with methallylchloride; (4) hydroxyamines, polyamines, thioglycols and thioamides are reacted with polybasic acids, e.g. ethylenediamine, phenylenediamine, aminophenol or melamine may be reacted with allyl acid phosphate or tartrate; (5) unsaturated esters of hydroxyacids are reacted with polybasic acids or phosgene, e.g. allyl lactate is treated with 2-chlorally-acid phthalate; (6) halo-acids or their salts or esters are reacted with alcohols or ether alcohols, e.g. glycerol allyl ether is treated with sodium chlorpropionate.  This subject-matter does not appear in the Specification as accepted.