Patent GB-893674-A (GB)
Title: Phosphorus-containing resinous polyesters, polymers and copolymers thereof and a process for their manufacture
IPC: C08G79/04
Filed: 1958-07-21
Abstract: Phosphorus-containing resinous polyesters are prepared by condensing at least one phosphonous acid derivative of the formula <FORM:0893674/IV (a)/1> (wherein R is an aliphatic, cycloaliphatic or aromatic hydrocarbon radical which may contain substituents and X is Cl, Br, an alkyl radical of 1-8 carbon atoms, a cycloalkyl or an aryl radical) with at least one polyhydric alcohol and at least one polybasic carboxylic acid, or ester, anhydride or halide thereof. All three ingredients may be reacted together or the polyhydric alcohol may be reacted with one of the acid compounds and the intermediate product reacted with the other acid compound. Dihalides of the phosphoric acid may be used in presence of a solvent, e.g. a hydrocarbon, cyclic ether or chlorbenzene. Hydrogen halide liberated can be removed by reduced pressure, raised temperature or a current of inert gas or bound, e.g. by a base such as triethylamine, or dimethylaniline.  The polybasic acid may be saturated or unsaturated. Suitable ones are listed. Monobasic acids may be used in addition. Suitable polyhydric alcohols are also listed.  Preferred ones contain at most 3 carbon atoms between the hydroxyl groups.  Monohydric alcohols may be used in addition to an alcohol containing at least 3 hydroxyl groups.  Unsaturated phosphorus-containing polyesters may be polymerized, e.g. with benzoyl or lauryl peroxide, or copolymerized, e.g. with a monomer which may be a solvent. Polymerization catalysts are listed.  They include peroxide, hydroperoxides, azo-nitriles, sulphinic acids, sulphone-amines, sulphone carbinols and para-chlorphenyl carbinol.  Suitable monomers for copolymerization are styrene, alkylated styrene, vinyl esters, acrylic or methacrylic acid or their esters or nitriles, allyl or methallyl esters of carboxylic or phosphorus acids, esters of vinyl-phosphonic acid, triallyl cyanurate, triallyl trimesinate, and low molecular weight unsaturated polyesters especially those containing allyl or methallyl groups. In the Examples, (1) maleic anhydride is reacted with a condensate from diethylene glycol and phenylphosphorus dichloride, (2) phenyl-phosphorus dichloride is reacted with a condensate of ethylene glycol and phthalic anhydride, (3) phenylphosphonous chloride is reacted with a polyester from ethylene glycol, maleic anhydride and phthalic anhydride, (4) the polyester of Example (3) is polymerized with benzoyl peroxide, (5) and (6) phenyl-phosphonous dichloride is condensed with ethylene glycol and the product reacted with phthalic and maleic anhydrides, (7) the condensate from glycerine and phenyl-phosphonous dichloride is reacted with phthalic anhydride and linseed oil fatty acid, (8) a polyester from ethylene glycol, phthalic and maleic anhydride is reacted with phenyl-phosphonous dichloride and in Example (9) the product is copolymerized with styrene and benzoyl peroxide.  Examples (10 and (11) use styrene-phosphonous dichloride to produce unsaturated polyesters which are copolymerized with styrene, methyl ethyl ketone peroxide in one case with octadecyl isocyanate.  (12) iso-octenyl-phosphonous dichloride is used to produce an unsaturated polyester which in Example (13) is copolymerized with styrene using methyl ethyl ketone peroxide and octadecyl isocyanate.  (14) Phenyl phosphonous dibromide is reacted with a polyester from ethylene glycol, and maleic and phthalic anhydride and the resulting polyester is polymerized in Example (15) using benzoyl peroxide.  (16) A condensate of phenyl-phosphonous dichloride and ethylene glycol is heated with hexane-triol, butanol and phthalic anhydride.  (17) Terephthalic acid dimethyl ester is heated with ethylene glycol in presence of calcium oxide and the product condensed with phenyl-phosphonous dichloride. (18) Phenyl-phosphonous acid diethyl ester is trans-esterified with glycerol in presence of calcium oxide, and the product further esterified with fumaric acid.  (19) Phenyl-phosphonous diethyl ester is heated with a polyester from glycerine and phthalic anhydride.  (20) and (21) Polyesters from phenyl-phosphonous dichloride, ethylene glycol, maleic and phthalic anhydrides were polymerized with benzoyl peroxide.  (22) A polyester as in Examples (20 or 21) was mixed with styrene and copolymerized using benzoyl peroxide.  (23) A polyester from phenyl-phosphonous dichloride, ethylene glycol, phthalic anhydride and fumaric acid was mixed with vinyl toluene and copolymerized in presence of cobalt naphthenate and methyl ethyl ketone peroxide.  (24) A polyester from phenyl-phosphonous dichloride, diethylene glycol and maleic anhydride was copolymerized with diallyl terephthalate using benzoyl peroxide. (25) A polyester from phenyl-phosphonous dichloride, ethylene glycol, diethylene glycol, phthalic anhydride and fumaric acid was mixed with styrene and copolymerized with benzoyl peroxide.  The products of the invention are useful as flame-proofing additives to paper, textiles, glass fibres, as adhesives, coating compositions or stabilizers for polyvinyl chloride.  Especially when used with unsaturated monomers they are useful for self-extinguishing shaped bodies with or without fillers.  They are generally transparent and colourless and useful for optical purposes.