STUDIES OF THE MECHANISM OF FORMATION OF POLY(1,4-PHENYLENE SULFIDE) FROM COPPER(I) 4-BROMOBENZENETHIOLATE

The mechanism of formation of poly(1,4-phenylene sulfide) (PPS) by solution polymerisation of copper(I) 4-bromobenzenethiolate (CBT) at 200-degrees-C in quinoline under nitrogen at atmospheric pressure has been investigated. The polymerisation has been monitored as a function of reaction time by electron spin resonance (ESR) spectroscopy and by evaluating the yield and molar mass of the PPS formed. The ESR spectra provided direct evidence for the operation of a mechanism involving single electron transfer processes. The results are discussed in terms of possible mechanisms for polymerisation of CBT, leading to the conclusion that a S(RN)1-type mechanism predominates and that a free-radical mechanism also may be involved.