Patent GB-883754-A (GB)
Title: Polyesters containing phosphorus and process for their manufacture
IPC: C08G79/04
Filed: 1957-12-02
Abstract: Polymers containing both carboxylate and phosphate groups are made by reacting (a) a dihalide or a lower aliphatic diester of a phosphonic acid having directly attached to phosphorous, a monovalent alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl or alkaryl group, or such a group substituted by a halogen, hydroxyl or alkoxy radical or, in the case of an aromatic group, in addition to the aforesaid substituents a nitro and/or amino radical, with (b) a polyhydric alcohol containing up to 14 carbon atoms and (c) a polycarboxylic aliphatic, cycloaliphatic or aromatic polycarboxylic acid or an anhydride, ester or acid halide of such an acid.  All three components (a), (b) and (c) may be reacted simultaneously or alternaitvely a polymeric phosphonate or polycarboxylate may first be prepared from components (a) and (b) or (b) and (c) respectively and these polymers further reacted with the other acid and possibly additional alcohol.  When using a halide as reactant, reaction may be effected in the presence of a tertiary amine or a metal; when using an ester as reactant, an ester-intercharge catalyst (many specified) may be used. Specified polycarboxylic acids are malonic, succinic, chlorosuccinic, adipic, sebacic, phthalic, isophthalic, terephthalic, tetrachlorophthalic, chlorendic, maleic, fumaric, itaconic, metaconic, citraconic, malic, tartaric, trimseric, tricarballylic, aconitic, citric, hemimeltitic and pyromellitic acids.  Specified polyhydric alcohols are ethylene glycol, polyethylene glycols, propylene glycol, polypropylene glycols, butylene glycol, hexanediol, butenediol, pinacone, 1:2-diphenyl ethylene glycol, phthalyl alcohol, tricyclodecane di- or tri-methylol, glycerine, hexanetriol, trimethylol propane, pentaerythritol, dipentaerythritol and sorbitol, halogenated derivatives of those polyhydric alcohols, and partial ethers or esters of higher polyhydric alcohols.  The polymers may be modified with monohydric alcohols (e.g. methyl, ethyl, propyl, butyl, ethylhexyl, allyl, oleyl or chloroethyl alcohols) or with monocarboxylic acids (e.g. acetic, butyric, crotonic, sorbic, benzoic, chlorobenzoic, furanecarboxylic, furfuracrylic, cinnamic, nicotinic, lactic, hydroxybutyric chloroacetic, chlorbutyric, brombenzoic or linseed fatty acids).  The polymers are soluble in hydrocarbons, cyclic ethers, the mono-ethyl ether of ethylene glycol, esters of glycolic acid and phenols and may be used as flame-proofing impregnating materials, adhesives and lacquers.  When the polymers are unsaturated e.g. when maleic acid, fumaric acid, crotonic acid, allyl alcohol or vinyl phosphates are used, they may be homopolymerized or copolymerized with monomer such as styrene, alkylated styrenes, vinyl naphthalene, vinyl acetate, acrylic and methacrylic acid and the esters and nitriles thereof, alkyl and methalkyl esters of saturated or unsaturated mono- or poly-carboxylic acids, allyl and methallyl carbonates, allyl and methallyl phosphates or phosphonates, esters of vinyl phosphonic acid, triallyl cyanurate, polyesters containing allyl or methallyl groups and halogen substituted derivatives thereof; polymerization is effected by irradiation and/or heating and/or a polymerization catalyst (many specified).  The addition polymers may be admixed with highly chlorinated hydrocarbons and strengthened with organic or inorganic fibres.  In Examples (1) and (15) Diethylene glycol and phenyl phosphonic acid dichloride are reacted and the product reacted with maleic anhydride to provide a polymer polymerizable by benzoyl peroxide; (2) Diethylene glycol is reacted with vinyl phosphonic acid dichloride and the product reacted with maleic anhydride to provide a polymer polymerizable by a peroxide; (3) Hexanetriol and phenyl phosphonic acid dichloride are reacted and the product reacted with ethylene glycol and maleic anhydride to provide a polymer polymerizable by peroxides; (4) Ethylene glycol and phenyl phosphonic acid dichloride are reacted and the product reacted with hexanetriol, butanol and maleic anhydride; (5) Dimethyl maleate and ethylene glycol are reacted and the product reacted with phenyl phosphonic acid dichloride to provide a polymer polymerizable by peroxides; (6) Glycerine and cyclohexane phosphonic acid dichloride are reacted and the product reacted with terephthalic acid and linseed fatty acids; (7) Glycerine and cyclohexyl phosphonic acid dimethyl ester are reacted and the product reacted with fumaric acid to provide a polymer polymerizable by benzoyl peroxide; (8) Butylene glycol and phenyl phosphonic acid dimethyl ester are reacted and the product reacted with maleic anhydride to provide a polymerizable polymer; (9) Ethylene glycol, glycerine and propyl phosphonic acid dimethyl ester are reacted and the product reacted with succinic acid; (10) Glycerine, cyclohexane phosphonic acid dimethyl ester and linseed oil fatty acid are reacted and the product reacted with fumaric acid; (11) Hexanetriol, benzyl phosphonic acid and linseed fatty acids are reacted and the product reacted with maleic anhydride; (12) Hexane triol and cyclohexane phosphonic acid diallyl ester are reacted and the product reacted with maleic anhydride and butanol to provide a polymer polymerizable by heat (and possibly in the presence of an initiator); (13) Glycerine and phthalic anhydride are reacted and the product reacted with phenyl phosphonic acid dimethyl ester; (14) Glycerine, cyclohexane phosphonic acid dimethyl ester and linseed fatty acids are reacted and the product reacted with dimethyl terephthalate and fumaric acid; the resin may be made into a lacquer by dissolving it in a solvent and adding phosphoric and/or perchloric acid; (16)-(18) A polymer from ethylene glycol, dimethyl maleate and phenyl phosphonic acid dichloride is copolymerized with styrene, vinyl toluene, or diallyl terephthalate in the presence of benzoyl peroxide; (19) A polymer from butylene glycol, cyclohexyl phosphonic acid, dimethyl ester and maleic anhydride is copolymerized with vinyl acetate in the presence of p-toluene sulphonic acid and copper acetyl acetonate.