PROCESS FOR PRODUCTION OF POLY-PHENYLENE OXIDE COMPOUNDS

• Main Authors: SETO T,JA, NAKASHIO S,JA, MARUYAMA T,JA, TAKEMURA T,JA
• Format: Patent
• Language: English
• Published: 22.01.1974
• Subjects: CHEMISTRY; COMPOSITIONS BASED THEREON; MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVINGCARBON-TO-CARBON UNSATURATED BONDS; MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONSONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS; METALLURGY; ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP

1330326 Phenylene oxide polymers SUMITOMO CHEMICAL CO Ltd 16 Dec 1970 [16 Dec 1969] 59723/70 Heading C3R [Also in Division B1] Phenylene oxide polymers and copolymers are prepared by the oxidative polymerization of at least one phenol having the formula wherein each of R 1 , R 2 , R 3 , R 4 , R 5 is a hydrogen atom or a halogen atom or a hydrocarbyl, halogen-substituted hydrocarbyl, hydrocarbyloxy or halogen-substituted hydrocarbyloxy group having from 1 to 7 carbon atoms with the proviso that at least one of R 1 , R 2 , R 3 , R 4 , R 5 is a hydrogen atom and at least one of R 1 , R 2 , R 3 , R 4 , R 5 is not a hydrogen atom, in the presence of molecular oxygen and of catalyst prepared from (a) a manganese compound, (b) an alcohol and (c) a primary amine. The manganese compound may be a manganese halide, a manganese salt of an oxy-acid, a complex manganese salt, manganous acid or a salt thereof, manganic acid or a salt thereof, permanganic acid or a salt thereof, an oxygen-containing manganese complex, a solvated manganese complex or a manganese alkoxide. Polymerization may be effected at a temperature of from 0‹ to 150‹ C. under sub-atmospheric, atmospheric or superatmospheric pressure in the presence of liquid diluent and/or a dehydrating agent effective to remove water produced by the reaction; the molecular oxygen may be supplied as pure oxygen or in the form of air. The Specification lists numerous suitable phenols, manganese compounds, alcohols, primary amines, liquid diluents and dehydrating agents. According to specific examples, poly-(2,6-dimethyl-1,4-phenylene oxide) is prepared from 2,6-xylenol in the presence of catalysts prepared from manganese (II) chloride, methanol and one of methylamine, ethylamine, n - butylamine, n - propylamine, cyclohexylamine, ethylenediamine and ethanolamine; manganese (II) chloride, ethanol and either isopropylamine or n-hexylamine; manganese (II) sulphate, methanol and ethanolamine; manganese (II) acetate, methanol and ethanolamine; and potassium permanganate, methanol and methylamine (Examples 1 to 9); copolymer of 2,6-dimethyl-1,4-phenylene oxide and 2,5-dimethyl-1,4-phenylene oxide is prepared from 2,6-xylenol and 2,5-xylenol in the presence of catalyst prepared from manganese (II) chloride, methanol and ethanolamine (Example 10); and copolymer of 2,6-dimethyl-1,4- phenylene oxide and 2-methyl-1,4-phenylene oxide is prepared from 2,6-xylenol and o-cresol in the presence of catalyst prepared from manganese (II) chloride, methanol and ethanolamine (Example 11). According to comparative tests, poly - (2,6 - dimethyl - 1,4 - phenylene oxide) is prepared from 2,6-xylenol in the presence of catalysts prepared from manganese chloride, magnesium sulphate and tetramethylethylenediamine; cuprous chloride and pyridine; and cupric chloride, n-propanol and triethylamine. Reference is made to Specification 1,189,405.