A Novel Synthesis of Poly(styrene peroxide) with Controlled Peroxy Linkages at Room Temperature

Abstract

The present report provides an elegant technique for the oxidative polymerization of vinyl monomers at room temperature using a 5,10,15,20-tetraphenyl-21H-23H-porphine cobalt(II) pyridine complex [CoTPP(Py)] (a reversible oxygen carrier). The content of peroxy linkages in the poly(styrene peroxide) (PSP) copolymer is controlled by varying the reaction time. The presence of peroxy linkages in the PSP copolymer has been substantiated using Fourier transform infrared spectroscopy (FT-IR), gel permeation chromatographic (GPC) techniques and nuclear magnetic resonance (NMR) spectroscopy. The sequence of the peroxy linkages in PSP is determined from an in-depth study of high-resolution 1 H and 13 C NMR spectra. Moreover, we have attempted to study the thermal degradation of PSP having a low concentration of peroxy linkages, using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The measured dissociation energy of PSP was found to be 211± 12 kJ.mol -1 . The synthesis of the PSP copolymer containing active peroxide segments as demonstrated here, could help in understanding the mechanism of the generation and degradation of peroxides instinctively formed during the polymer processing.