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REACTION mechanism OF BENZOPHENONE-PHOTOINITIATED CROSSLINKING OF POLYETHYLENE

Chinese Journal of Polymer Science 2002年第4期20卷 291-307页

作者： Bao-jun Qu State Key Laboratory of Fire Science and Department of Polymer Science and Engineering University of Science and Technology of China Hefei 230026 China Univ Sci & Technol China State Key Lab Fire Sci Hefei 230026 Peoples R China Univ Sci & Technol China Dept Polymer Sci & Engn Hefei 230026 Peoples R China

The radical intermediates, the crosslink microstructures, and the reaction mechanism of benzophenone (BP)-photoinitiated crosslinking of low-density polyethylene (LDPE) and model compounds (MD) have been reviewed in detail. The spin-trapping electron spin resonance (ESR) spectra obtained from the LDPE/BP systems with spin-trap agents show that two kinds of polymer radical intermediates are mainly formed: tertiary carbon and secondary carbon radicals. The spin-trapping ESR studies of MD/BP systems give further evidence that photocrosslinking reactions of PE predominantly take place a sites of tertiary carbon, secondary carbon, and especially allylic carbon when available. The high resolution C-13-NMR spectra obtained from LDPE and MD systems show that the crosslink microstructures have H- and Y-type links and that their concentrations are of the same order. The fluorescence, ESR, C-13 and H-1-NMR spectra from the PE and MD systems demonstrate that the main photoreduction product of BP (PPB) is benzpinacol formed by the recombination of two diphenylhydroxymethyl (K-.) radical intermediates. Two new PPB products: an isomer of benzpinacol with quinoid structure, 1-phenylhydroxymethylene-4-diphenylhydroxymethyl-2,5-cyclobexadiene and three kinds of alpha-alkyl-benzhydrols have been detected and identified. These results provide new experimental evidence for elucidating the reaction mechanism in the BP-photoinitiated crosslinking of polyethylene.

关键词： photocrosslinking mechanism polymer radical intermediates crosslink microstructures photolytic products of benzophenone polyethylene model compound

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