Poly(arylene thioether-ketone) copolymer and production process thereof

A process for the production of a poly(arylene thioether-ketone) copolymer comprising (A) at least one poly(arylene thioether-ketone) segment and (B) at least one poly(arylene thioether) segment, which comprises at least the following three steps:

• i) heating in the presence of water an organic amide solvent containing a dihalogenated aromatic compound, which consists principally of a dihalobenzene, and an alkali metal sulfide, whereby a poly(arylene thioether) oligomer having at least 50 wt. % recurring units of the formula ##STR26## and at least one terminal thiolate group is synthesized, ii) heating in the presence of water an organic amide solvent containing a dihalogenated aromatic compound, which consists principally of at least one dihalobenzophenone selected from 4,4'-dichlorobenzophenone and 4,4'-dibromobenzophenone, and an alkali metal sulfide, whereby a poly(arylene thioether-ketone) oligomer having at least 50 wt. % recurring units of the formula ##STR27## wherein the --CO-- and --S-- are in the para position to each other, and terminal halogen atoms is synthesized, and
• iii) mixing and reacting the poly(arylene thioether) oligomer, which has been obtained in the step i), with poly(arylene thioether-ketone) oligomer obtained in the step ii) and optionally, water;
• said first through third steps i)-iii) being conducted under the following conditions (a)-(g):
• (a) in the first step i), the ratio of the water content to the amount of the charged organic amide solvent being 0.1-15 (mol/kg), the ratio of the amount of the charged dihalogenated aromatic compound to the amount of the charged alkali metal sulfide being 0.3-0.9 (mol/mol), and the polymerization being conducted until the number-average polymerization degree of the poly(arylene thioether) oligomer becomes higher than 1 but lower than 10,
• (b) in the second step ii), the ratio of the water content to the amount of the charged organic amide solvent being controlled within a range of 0.1-15 (mol/kg) and the reaction being conducted within a temperature range of 60.degree.-300.degree. C. with the proviso that the reaction time at 210.degree. C. and higher is not longer than 10 hours,
• (c) in the third step iii), the ratio of the water content to the amount of the charged organic amide solvent being 0.1-15 (mol/kg),
• (d) in the third step iii), the ratio of the total amount of the charged dihalogenated aromatic compound, said total amount being the amount of the whole dihalogenated aromatic compounds including the dihalobenzene and the dihalobenzophenone, to the total amount of the charged alkali metal sulfide, said latter total amount being the total amount of the alkali metal sulfide charged in the first step i) and that charged in the second step ii), being controlled within a range of 0.95-1.2 (mol/mol),
• (e) the ratio of the charged amount of the dihalogenated aromatic compound consisting principally of the dihalobenzene in the step i) to the charged amount of the dihalogenated aromatic compound consisting principally of the dihalobenzophenone in the step ii) being controlled within a range of 0.1-10 (mol/mol),
• (f) the reaction of the third step iii) being conducted within a temperature range of 150.degree.-300.degree. C. with the proviso that the reaction time at 210.degree. C. and higher is not longer than 10 hours, and
• (g) in the third step iii), the reaction being conducted until the melt viscosity of the resulting copolymer becomes 2-100,000 poises as measured at 350.degree. C. and a shear rate of 1,200/sec.