Patent GB-984099-A (GB)
Title: Dicarboxylic acid esters and polymers and copolymers thereof
IPC: C07D317/24
Filed: 1963-05-21
Abstract: The invention comprises compounds of general formula <FORM:0984099/C2/1> in which X is CH2 = attached to C1 by a double bond and Y is hydrogen attached to C2, or X is hydrogen attached to C1 and Y represents an additional bond between C2 and C1, R is hydrogen, a saturated aliphatic hydrocarbon radical (1-8C) or R1, and when X is H and Y a bond between C1 and C2 R is also an olefinic unsaturated hydrocarbon radical (1-8C), R1 is an alkylene dioxolone radical <FORM:0984099/C2/2> n=1 to 4, and a process for the preparation thereof by reacting a compound <FORM:0984099/C2/3> in which Z or Z1 is OR where R is H or an alkyl group with not above seven carbon atoms, or Z or Z1 is a halogen atom, Z and Z1 being the same or different or Z and Z1 represent an oxygen atom bonded to C3 and C4 and completing an anhydride ring structure, with a compound of formula <FORM:0984099/C2/4> and if the product is a monoester, esterifying the product to a di-ester of formula I.  Specific compounds are mono and di itaconic esters of the 1,2 carbonates of 1,2,3-propane-triol, 1,2,4-butane-triol and 1,2,5-pentane triol and 1,2,6-hexane triol, and the mono and di maleic and fumaric esters of 1, 2 carbonate of 1,2,3 propane triol.  The reaction may be carried out in an inert solvent and the mono-ester may be converted to an alkali metal salt and reacted with a dialkyl sulphate to form the diester, and when an acid chloride is used an acceptor such as tributyl amine or sodium carbonate may be present.  The products are polymerizable and may form copolymers with vinyl, vinylidene or vinylene containing compounds (see Division C3), and may be used as foaming agents for preformed polymers.ALSO:Dicarboxylic esters of general formula <FORM:0984099/C3/1> in which X is CH2= attached to C1 by a double bond and Y is hydrogen attached to C2 or X is hydrogen attached to C1 and Y represents an additional bond between C1 and C2, R is hydrogen, a saturated aliphatic hydrocarbon radical (1-8 C) or R1, and when X is H and Y a bond between C1 and C2, R also is an olefinic unsaturated hydrocarbon radical containing (1- C), R1 is an alkylene dioxolone radical of structure <FORM:0984099/C3/2> where n is 1-4 (see Division C2) are polymerized, or copolymerized in admixture or with monomers with a vinyl, vinylidene or vinylene group.  Specific compounds mentioned are itaconic, mono or diesters of the 1,2-carbonates of 1,2,3-propane triol, 1,2,4-butane triol, 1,2,5-pentane triol and 1,2,6-hexane triol and the mono- and di-maleic and fumaric esters of 1,2-carbonate of 1,2,3-propane triol. Acrylic and methacrylic esters, e.g. methyl, ethyl, hexyl, allyl, phenyl benzyl, and methyl-a -chloroacrylates, methyl, ethyl, propyl, methallyl methacrylate, ethylene dimethacrylate; vinyl esters, e.g. vinyl chloride, acetate, stearate, benzoate, chloroacetate, divinyl phthalate and divinyl succinate; acrylamide, hydroxymethylacrylamide, methacrylamide, itaconic mono- and diamides, acrylonitrile and methacrylonitrile; alkenyl aryl compounds, e.g. styrene, o-, p-, or a -methyl styrene, chlorostyrenes, divinyl and diallyl benzenes; mono- and polyallyl esters, e.g. allyl acetate, diallyl succinate, phthalate, maleate and fumarate; vinylidene compounds, e.g. vinylidene chloride, cyanide and methylene malonic esters; vinylene compounds, e.g. vinylene carbonates, maleic anhydride, mono- and di-esters, itaconic anhydride, mono- and di-esters; and dienes, e.g. butadiene, isoprene, or 2-chlorobutadiene-1,3 may be copolymerized with the compounds.  Bulk, solution in an organic solvent, emulsion or suspension methods with or without initiators, e.g. peroxides or azo compounds, may be used and examples describe the copolymerization of the itaconic and maleate ester of glyceryl carbonate with styrene, vinyl acetate, methyl acrylate and methacrylate.  The compounds with a free carboxylic group liberate carbon dioxide on heating and may be used as foaming agents.  The monomers on heating may also evolve carbon dioxide and may be used added alone or with modifiers such as H3PO4, Na2CO3, NaHCO3, ZnCl2 and FeSO4, to preformed polymers.