Polyester resins containing phosphorus and process for their manufacture

Abstract

Abstract Polyester resins are obtained by copolymerizing an unsaturated polyester containing trivalent phosphorus attached by ester bonds and containing at least 1,5% by weight of phosphorus with another copolymerizable compound. The unsaturated polyester contains at least 5 mol. per cent of the residues of an unsaturated alcohol of the allyl type or an a :b - unsaturated polycarboxylic acid and is made by (a) reacting together an ester-forming derivative of phosphorus acid, a polyhydric alcohol and an a :b -unsaturated polycarboxylic acid, (b) reacting an ester-forming derivative of phosphorus acid with a polyhydric alcohol and reacting the product with an a :b -unsaturated polycarboxylic acid or (c) reacting an ester-forming derivative of phosphorus acid with a pre-formed unsaturated polyester containing free hydroxyl groups. The ester-forming derivative of phosphorus acid may be a phosphorous trihalide or a secondary or tertiary phosphorus acid ester. The unsaturated polycarboxylic acid may be maleic, fumaric, itaconic, mesaconic, citraconic or aconitic acid. A large number of polyhydric alcohols are specified including aliphatic, cycloaliphatic and aromatic dihydric alcohols and tri- and higher polyhydric alcohols. Modifying agents which may be included in the polyester forming reaction are (i) aliphatic, cycloaliphatic and aromatic di- and higher polycarboxylic acids, (ii) saturated or unsaturated aliphatic, cycloaliphatic, aromatic or heterocyclic monocarboxylic acids or hydroxycarboxylic acids or (iii) saturated or unsaturated aliphatic, cycloaliphatic or aromatic monohydric alcohols. Instead of the saturated or unsaturated polycarboxylic acids, their anhydrides, acid halides or esters may be used. The unsaturated polyester may be copolymerized with styrene, styrenes alkylated in the nucleus or side-chain, vinyl naphthalene, esters of vinyl phosphonic acid, vinyl acetate or propionate, acrylic and methacrylic acid and their esters and nitriles, allyl or methallyl esters of saturated or unsaturated mono- or polycarboxylic acids or carbonic acid, triallyl cyanate, allyl and methallyl phosphates or phosphonates or low molecular weight unsaturated polyesters (e.g. those of Specification 852,886 or those with combined chlorine). Suitable copolymerization catalysts are peroxy compounds, azoiisobutyronitrile, sulphinic acids, sulphonamines or sulphone carbinols, if desired in combination with cobalt octoate. The polymerizable compositions are useful as moulding compounds, impregnating or coating compounds or lacquers and may have incorporated into them chlorinated hydrocarbons, fillers or reinforcing fibres (e.g. glass fibres). Examples describe the manufacture of copolymerizable polyesters by reacting (1) A polyester from maleic anhydride and ethylene glycol with tricylodecane methylol and phosphorus trichloride; (2) A polyester from maleic anhydride, phthalic anhydride, glycerol and amyl alcohol with further amyl alcohol and phosphorus trichloride; (3) and (12) A condensate of ethylene glycol and diethyl phosphite with tricyclodecane methylol and maleic anhydride; (4) A condensate of ethylene glycol and diethyl phosphite with dimethyl maleate; (5) A condensate of diethylene glycol, dimethyl terephthalate and diethyl phosphite with dimethyl maleate; (6) A condensate of glycerol, ethylene glycol and diethyl phosphite first with dimethyl terephthalate and linseed oil fatty acids and then with maleic anhydride; (7) A condensate of maleic anhydride and ethylene glycol with diethyl phosphite; (8) A condensate of ethylene glycol and triethyl phosphite with dimethyl maleate; (9) A condensate of maleic anhydride and ethylene glycol with butanol and phosphorous trichloride; (16) A condensate of phthalic anhydride and ethylene glycol first with allyl alcohol and then with phosphorus trichloride. The polyester of Example 9 is copolymerized with 4-methyl styrene (Example 10) or diallyl phthalate (Example 11) and the polyester of Example 12 is copolymerized with styrene (Example 12), vinyl acetate (Example 13), diallyl terephthalate (Example 14) or cyclohexylphosphoric acid diallyl ester (Example 15)-in all cases using benzoyl peroxide as a catalyst.

Inventors

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