Patent GB-547854-A (GB)
Title: Manufacture and polymerisation of ªúª-unsaturated esters of carbonic acid and of orthoformic acid and its derivatives
IPC: C08F2/00
Filed: 1941-03-12
Abstract: 547,854. Esters, ethers, resinous polymerization products. DU PONT DE NEMOURS & CO., E.I. March 12, 1941, No. 3362. Convention date, March 13, 1940. [Class 2 (iii)] #:γ-Unsaturated esters of carbonic acid and of orthoformic acid and its derivatives are obtained by heating with an excess of the #:γ- unsaturated alcohol an ester of the acid with a volatile saturated alcohol. Specified #:γ-unsaturated alcohols are allyl, #-methallyl, furfuryl, crotyl, tiglyl, propargyl and cinnamyl alcohols and 3-chlorobutene-2-ol-1. Specified derivatives of orthoformic acid are the ortho acids corresponding to acetic, propionic, butyric, isobutyric, valeric, chloroacetic, oxalic, malonic, succinic, adipic, crotonic, acrylic, methacrylic, benzoic, phthalic, terephthalic, chlorobenzoic, nitrobenzoic, toluic, naphthoic, phenylacetic, toluylacetic, phenylpropionic and naphthylacetic acids. Specified volatile saturated alcohols are methyl, ethyl, propyl, isopropyl, butyl, sec. butyl and isobutyl alcohols. The reaction may be accelerated by the use of an ester interchange catalyst, such as sodium, a sodium alcoholate, litharge or an organic base. The products are capable of homopolymerization or of interpolymerization, especially with vinyl or vinylidene compounds of the general formula CH 2 =C#<SP>R</SP> A , wherein R represents H, alkyl, aryl, aralkyl, cycloalkyl or halogen and A represents halogen, aryl, cyano, acyloxy, vinyl or -CO-X (wherein X represents H, hydroxy, halogen, alkyl, alkoxy or aryloxy), -N#<SP>CO</SP> CO #R<SP>1</SP> (wherein R<SP>1</SP> represents a bivalent hydrocarbon residue) or -CO-N#<SP>R2</SP> R3  (wherein R 2 , R 3  represent H or alkyl), the products being resinous. Specified vinyl and vinylidene compounds are vinyl esters, e.g. vinyl acetate and halides, acrylic and α-alkylacrylic acids and their amides, halides and esters, e.g. methacrylic acid, methyl and ethyl methacrylates, methacrylamide and methacryl chloride, vinyl succinimide, acrolein, N - methylacrylamide, N- ethyl-methacrylamide, N - dipropyl - acrylamide, N - methylethyl - acrylamide, styrene, butadiene, chloroprene and methylvinyl ketone. The polymerization may be accelerated by the use of polymerization catalysts, such as organic peroxides, hydrogen peroxide or acidic salts, or of actinic light. In examples of the preparation of the monomers, (1) diethyl carbonate is heated under reflux with excess of #-methallyl, allyl, crotyl or furfuryl alcohol in presence of sodium and the ethyl alcohol formed and,excess unsaturated alcohol removed by distillation ; (2) ethyl orthoformate is similarly reacted with #-methallyl or allyl alcohol; (3) ethyl orthoacetate is similarly reacted with #-methallyl alcohol; on further fractionation diethyl methallyl orthoacetate and ethyl dimethallyl orthoacetate are obtained. In examples of the preparation of the polymers, (4) dimethallyl carbonate is heated for 20 hours at 65C. in presence of 1 per cent. of benzoyl peroxide to form a soft gel-like polymer, insoluble in organic solvents ; diallyl carbonate may be similarly polymerized ; (5) a mixture of methyl methacrylate and dimethallyl carbonate is heated for 6 days at 65C. to obtain a clear, colourless, hard, tough, glass-like interpolymer, insoluble in organic solvents ; an addition of 0.05 per cent. of benzoyl peroxide enables the polymerization to be effected in 1 day; to prepare a granular interpolymer from the same components the heating is effected for 40 minutes on a steam bath in presence of benzoyl peroxide and of an aqueous solution of a neutralized interpolymer from methyl methacrylate and methacrylic acid ; (6) a mixture of vinyl acetate and dimethallyl carbonate is heated for 3¢ hours on a steam bath in presence of benzoyl peroxide and of an aqueous solution as in (5) to obtain a granular interpolymer insoluble in organic solvents ; the use of the dimethallyl carbonate raises the softening point of the resin; (7) a mixture of styrene and dimethallyl carbonate is heated for 6 hours as in (6) to obtain a granular interpolymer; a clear hard interpolymer, soluble in organic solvents, is obtainable by heating a mixture of the monomers for 4 days at 60C. ; (8) a mixture of methyl methacrylate and diallyl carbonate is heated for 5 days at 65C. to obtain a clear hard tough interpolymer insoluble in organic solvents ; (9) a mixture cf vinyl acetate and diallyl carbonate is converted as in (6) into a granular interpolymer; (10) a mixture of methyl methacrylate and dicrotyl or difurfuryl carbonate is converted into a cast or granular interpolymer; (11) a mixture of methyl methacrylate and methallyl orthoformate containing 1 per cent. of benzoyl peroxide is heated for 50 minutes on a steam bath with an aqueous solution of a neutralized methyl methacrylate-methacrylic acid interpolymer to obtain a granular interpolymer, mouldable to a clear hard mass and insoluble in organic solvents ; (12) a mixture of methyl methacrylate and ethyl dimethallyl orthoacetate is heated for 2 days at 60C. to obtain a clear, hard, cast. interpolymer, difficulty soluble in toluene, dioxane or butyl acetate ; corresponding interpolymers from methyl methacrylate and diethyl methallyl orthoacetate are soluble in such solvents. The Specification as open to inspection under Sect. 91 comprises also the use as unsaturated alcohols of 1:2-butadiene-ol-4, hexadiene-2:4-ol- 1 and 3:7-dimethyloctadiene-2:7-ol-1. This subject-matter does not appear in the Specification as accepted.