Patent GB-575386-A (GB)
Title: Improvements in or relating to complex esters and polymers thereof and methods of preparing same
IPC: C07C69/96
Filed: 1942-02-12
Abstract: Complex esters are prepared by reacting (a) an alkenyl ester of an aliphatic hydroxy carboxylic acid with an acid ester of a polybasic carboxylic acid and an unsaturated aliphatic monohydric alcohol or with an acid halide of said acid ester or (b) an alkenyl ester of an aliphatic halogen carboxylic acid with a salt of an acid ester of a polybasic carboxylic acid and an unsaturated aliphatic monohydric alcohol.  In examples: (1) sodium alkylphthalate is treated with vinyl or allyl chloracetate; polymers are obtained from the resulting esters by heating with benzoyl peroxide; (2) allylchlorformate is treated with allyl or vinyl lactate; (3) allyl acid carbonate is treated with allylacetate; the ester gives a fusible polymer by heating while passing a stream of air through the monomer and precipitating by means of methanol: a colourless resin is obtained by moulding the fusible polymer with benzoyl peroxide and heating; (4) methallylformate is treated with methallyl lactate; (5) potassium allylsuccinate is treated with allylchloracetate.  The following polybasic acids are also mentioned: diglycollic, dilactic, oxalic, maleic, phenylmalonic, fumaric, glutaric, adipic, pimelic, sebasic, tricarballylic, itaconic, mesaconic, citraconic, citric, terephthalic, and acetylenedicarboxylic acids, and the following hydroxycarboxylic acids; hydroxybutyric, citric, malic, hydroxyvaleric, hydroxyfumaric, hydroxyacrylic, glyceric, hydroxyvinylacetic, hydroxycaproic, ricinoleic, tartaric, mucic and gluconic acids.  Among the unsaturated alcohols used to esterify the carboxylic acids are: isopropenyl, butenyl: methylvinyl carbinyl, ethylallyl, tiglyl, butadienyl, proparyl, angelyl, oleyl, elaidyl, linoleyl, chloralkyl and chlorcrotyl alcohols.  Alkaline reagents such as pyridine, quinoline, dimethylaniline, alkalies or quaternary ammonium bases, and solvents such as acetone or dioxane may be used in the esterification.  The monomers are miscible with acetone, alcohol, chloroform, dioxane, benzene, toluene, xylene, ether and paraffin hydrocarbons, and may be used as solvents, e.g. for paints, pharmaceuticals and plasticisers for cellulose, vinyl, urea, phenol, acrylic and styrene resins.  Polymers may be formed by polymerisation of the ester products, especially those containing more than one double bond or solutions thereof.  A solid gel may be formed directly which may be moulded and then completely polymerised.  It is desirable to separate the monomer, e.g. by distillation or adding a solvent before continuing polymerisation of the partial polymers. The latter may be obtained by interruption of polymerisation; they are fusible and soluble in the usual resin solvents.  The soft insoluble gel may be dried and converted into a moulding powder.  The monomers, fusible polymers or solutions thereof may be used to impregnate paper, linen, canvas, leather, and wood.  By heating or otherwise curing the impregnated material, laminated products having improved water proof and electrical properties may be obtained.  For use in lacquers and coating compositions, the resins may be used in combination with drying oils or resins.  Moulding powders may be produced by emulsifying the monomer or syrupy polymer in an aqueous medium containing polyvinyl, polyallyl or polymethallyl alcohol as emulsifying agents, and after polymerisation separating the polymer.