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Well‐Controlled Synthesis of Poly (phenylene sulfide) (PPS) Starting from Cyclic Oligomers
Author(s) -
Horiuchi Syunsuke,
Yamamoto Daisuke,
Kaiho Shu,
Yamashita Kohei,
Yokoe Makito,
Osato Keiko,
Yamauchi Koji
Publication year - 2015
Publication title -
macromolecular symposia
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.257
H-Index - 76
eISSN - 1521-3900
pISSN - 1022-1360
DOI - 10.1002/masy.201300221
Subject(s) - sulfide , polymerization , sodium sulfide , polymer chemistry , chemistry , molar mass distribution , phenylene , ring opening polymerization , nucleophilic substitution , polymer , organic chemistry
Summary The mixture of cyclic PPS oligomers ( c ‐PPS) with more than 99% of purity, less than 15 ppm of metal content and more than 4 of repeating units was prepared by the nucleophilic substitution reaction between dichlorobenzene (DCB) and sodium sulfide (Na 2 S) in relatively dilute solution. Melt polymerization of the c ‐PPS in the absence of initiator at high temperature resulted in P( c ‐PPS) having high molecular weight, relatively narrow molecular weight distribution and extremely low weight loss at high temperature. Results from MALDI‐TOF‐MS, GPC and in ‐ situ ESR analysis of the polymerization intermediates suggested that the polymerization of c ‐PPS proceeded by a sulfide exchanging polymerization. In addition, the sulfide exchanging polymerization of c ‐PPS in the presence of bis(4‐substituted phenyl) sulfides (BPS‐X) such as bis(4‐aminopheny) sulfide (BPS‐NH 2 ), bis(4‐carboxyphenyl) sulfide (BPS‐COOH), and bis(4‐chlorophenyl) sulfide (BPS‐Cl) produced end‐group modified and ring‐opened P( c ‐PPS)s. Comparison of polymerization rate in the presence of BPS‐X suggested that the BPS‐X acted as both initiator and chain transfer agent, and the sulfide exchanging polymerization was accelerated by the addition of BPS‐NH 2 and BPS‐COOH due to the activation of sulfide linkage through the substitution effect.