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 d...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.展开更多
基金The project was successively supported by the National Natural Science Foundation of China (No. 50073022, No 59773030, No. 59543002 and No. 5880104).
文摘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.
