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