Synthesis and characterization of copoly(arylene sulfide)s

Copolymerizations of p-dichlorobenzene (DCB)/4-bromophenyl ether (BPE), DCB /4,4'-dibromobiphenyl (DBB), and DBB/BPE pairs with sodium sulfide under hi gh temperature (270-290 degrees C) utilizing N-methyl-2-pyrrolidinone (NMP) as solvent were carried out to give C(DCB/BPE), C(DCB/DBB), and C(DBB/BPE) copolymers, respectively. The reactivity of dihaloaromatic monomers toward thiolate anion in the polycondensation reaction followed the order DBB > D CB > BPE. The reactivity gap between DBB and DCB toward thiolate anion seem ed to be smaller than that between BPE and DCB, resulting in both high yiel d and high molecular weight in the C(DCB/DBB) copolymers compared to C(DCB/ BPE) copolymers. The copolymerization of DBB/BPE pair with sodium sulfide, which has larger reactivity gap than the DCB/ DBB or DCB/BPE pair, gave mix tures of PBS and PPSE homopolymers especially in the range of 50-80 mol % B PE in the feed. The C(DCB/DBB) and C(DCB/BPE) copolymers, however, exhibite d random copolymer character in all comonomer ratios in the feed as evidenc ed by copolymer composition and DSC data. (C) 1999 John Wiley & Sons, Inc.