Stable vinyl polyperoxide: synthesis, characteristics and thermal initiation potentials of poly(α-phenylstyrene peroxide)

Abstract

The stable vinyl polyperoxide, namely, poly(-phenylstyrene peroxide) (PAPSP), an alternating copolymer of -phenylstyrene and oxygen, has been synthesized by the oxidative polymerization of α-phenylstyrene. It was characterized by ¹H and ¹³C NMR, FT-IR, DSC, GC-MS and GPC studies. The overall activation energy (E_d) for the degradation of PAPSP was found to be 45.0 kcal/mol. The stability of PAPSP was estimated from its isothermal degradation rate and compared with other related vinyl polyperoxides. Thermal initiating potentialities of PAPSP have been studied by polymerizing styrene at 80°C. The polymerization follows classical kinetics. The mechanism of polymerization has been discussed. The active polymer, which contains PAPSP segments in the polystyrene chain was confirmed by ¹H NMR study. The values of K² for PAPSP compared to that of 2,5-dimethyl-2,5-dihydroperoxyhexane and di-tert-butyl peroxide at 80°C indicate that PAPSP can be used as an effective high temperature initiator.