ANALYSIS OF THE PRODUCTS OF THERMAL-DEGRA DATION OF POLY(2-VINYLPYRIDINE) AND PECULIARITIES OF THE MECHANISM OF 2-VINYLPYRIDINE POLYMERIZATION USING TRIS(PI-ALLYL)CHROMIUM

The products of thermal degradation of poly(2-vinylpyridine)s and olig o(2-vinylpyridine)s prepared with tris(pi-allyl)chromium at various te mperatures and concentration ratios were studied using mass spectromet ric thermal analysis. The pattern and intensity of the peaks in the ma ss spectrum of ion fragments depend on the monomer-to-initiator ratio, the temperature of the synthesis of the above compounds, and the regi me of thermal degradation. Analysis of the obtained data and their com parison with the data on thermal degradation of poly(2-vinylpyridine) prepared by radical polymerization made it possible to elucidate the d etails of the mechanism of reactions in 2-vinylpyridine-tris(pi-allyl) chromium systems. Specifically, the dependence of relative contributio ns of the reactions of the monomer with chromium-carbon and chromium-n itrogen active bonds (they appear when initiator or a growing chain re act with pyridine rings) on the starting conditions of the experiment was estimated.