Patent GB-595056-A (GB)
Title: Production of complex esters and their polymers
IPC: C08G63/21
Filed: 1942-04-13
Abstract: Two molecular proportions of an acid ester derived from a dicarboxylic acid or its chloride and an unsaturated alcohol are esterified with one molecular proportion of an aliphatic dihydroxy compound.  The latter may be an ester of a simple aliphatic dihydroxy compound with a hydroxy carboxylic acid, and instead of using an acid ester of a dicarboxylic acid with an unsaturated alcohol, two molecules of the dicarboxylic acid itself, or the chloride may be esterified with one molecule of the aliphatic dihydroxy compound to give a diacid ester, and the product then esterified with an unsaturated alcohol.  In further modifications, one molecular proportion of an aliphatic dihydroxy compound is reacted with either two molecular proportions of an acid ester formed from a hydroxy carboxylic acid and an acid ester of an unsaturated alcohol with a dicarboxylic acid or with one molecular proportion of an acid ester of a simple dicarboxylic acid and an unsaturated alcohol together with one molecular proportion of an acid ester formed from a hydroxy carboxylic acid and an acid ester of an unsaturated alcohol with a simple dicarboxylic acid.  In examples: (1) ethyleneglycol dihydrogen diphthalate is esterified with allyl alcohol; (2) the same components are used in the presence of benzene and small quantities of hydroquinone and benzenesulphonic acid; (3) allylacid succinate is converted into the chloride with thionyl chloride and esterified in benzene with glycol; (4) allyl acid succinate is esterified with the ester derived from diethyleneglycol (1 mol.) and glycollic acid (2 mols.) in the presence of carbon tetrachloride; (5) allylphthalylchloride (2 mols.) is esterified with ethyleneglycol dilactate (1 mol.) in benzene; the product is worked up by adding pyridine and evaporating at reduced pressure.  The resulting polyesters readily polymerize, preferably in the presence of oxygen, ozone and organic peroxides such as lauroyl, benzoyl and acetone peroxide. Aliphatic dihydroxy compounds mentioned include: butyleneglycol, trimethyleneglycol, di-, tri- and tetrapropyleneglycol, bis-(hydroxy ethyl) carbonate, glycolmonoglycollate and diethyleneglycol bis-(hydroxyethylcarbonate) and instead of allyl alcohol, vinyl, isopropanyl, methallyl, crotyl, isocrotyl, a - and b -ethylallyl, tiglyl, butadienyl, propargyl, chlorallyl, chlorcrotyl, bromallyl and linallyl alcohols and methyl allyl carbinol, citronellol, diallylcarbinol and isopropylethynyl carbinol may be used.  Oxalic, adipic, maleic, fumaric, diphenyl dicarboxylic, naphthalic, quinolinic, cinchomeronic, cotarinic dilactic, methoxysuccinic, ethylene oxide dicarboxylic acids and glycollylacidmalonate may be used as dicarboxylic acids.  The products are plasticisers for styrene, cellulose derivatives and urea, protein, phenolic and acrylic resins.  They are also insecticides and solvents being miscible with acetone, alcohol, chloroform, dioxane and hydrocarbons.  The Specification as open to inspection under Sect. 91 comprises also the production of esters from polyacidic compounds and polyhydroxy compounds and includes the use of the following components: glycerine, methylglycerol, erythritol, pentaerythrite, glycose, lactose, sucrose, maltose, pyrogallol, hydroquinone, 2 : 5-bis-(oxymethyl) furan, 3 : 5-dioxycumaron, dioxandiols, dihydroxydiphenylether, citric acid, tartaric acid, saccharic acid, malic acid, glyceric acid, salicylic acid, gallic acid, resorcylic acid, coumaric acid, furylglycollic acid and 3 - oxycumaroncarboxylic acid.  This subject-matter does not appear in the Specification as accepted.