The catalytic properties of a series of (dppe) MCl2 [M = Fe(II), Co(II), Ni(II)] in combination with EAO (ethylaluminoxane) for ethylene oligomerization have been investigated. Treatment of the bidentate phosphine met...The catalytic properties of a series of (dppe) MCl2 [M = Fe(II), Co(II), Ni(II)] in combination with EAO (ethylaluminoxane) for ethylene oligomerization have been investigated. Treatment of the bidentate phosphine metal complexes with EAO in toluene generated in situ active catalysts which catalyze oligomerizaton of ethylene to low-carbon olefins. The effects of reaction temperature, ratios of n(Al) : n(M) and reaction periods on catalytic activity and product distribution have been studied. The activity of cobalt complex with EAO at 200C was 4021 g/g(Co)h, and the selectivity of C4-10 olefins is 95.5%.展开更多
The copolymerizations of ethylene with 1-hexene or 1-0ctene by using TiC14/MgCI2/THF catalysts modified with different metal halide additives （ZnCI2, SIC14, and the combined ZnC12-SiCl4） were investigated based on c...The copolymerizations of ethylene with 1-hexene or 1-0ctene by using TiC14/MgCI2/THF catalysts modified with different metal halide additives （ZnCI2, SIC14, and the combined ZnC12-SiCl4） were investigated based on catalytic activity and copolymer properties. It was found that the catalyst modified with mixed ZnC12-SiC14 revealed the highest activities for both ethylene/1-hexene and ethylene/1-0ctene copolymerization. The increase in activities was due to the formation of acidic sites by modifying the catalysts with Lewis acids. Based on the FTIR measurements, the characteristic C--O--C peaks of the catalysts modified with metal halide additives were slightly shifted to lower wavenumber when compared to the unmodified catalyst. This showed that the modified catalysts could generate more acid sites in the TiC14/MgC12/THF catalytic system leading to an increase in activities as well as comonomer insertion （as proven by IaC-NMR）. However, Lewis acid- modifications did not affect the microstructure of the copolymers obtained. By comparison on the properties of copolymers prepared with the unmodified catalyst, it was found that polymers with ZnC12 and/or SIC14 modification exhibited a slight decrease in melting temperature, crystallinity and density. It is suggested that these results were obtained based on the different amount of ct-olefins insertion, regardless of the types of Lewis acids and comonomer.展开更多
文摘The catalytic properties of a series of (dppe) MCl2 [M = Fe(II), Co(II), Ni(II)] in combination with EAO (ethylaluminoxane) for ethylene oligomerization have been investigated. Treatment of the bidentate phosphine metal complexes with EAO in toluene generated in situ active catalysts which catalyze oligomerizaton of ethylene to low-carbon olefins. The effects of reaction temperature, ratios of n(Al) : n(M) and reaction periods on catalytic activity and product distribution have been studied. The activity of cobalt complex with EAO at 200C was 4021 g/g(Co)h, and the selectivity of C4-10 olefins is 95.5%.
基金financially supported by the Dusadeepipat scholarship at Graduate school of Chulalongkorn Universitythe Thailand Research Fund(TRF)+1 种基金the Higher Education Promotion and National Research University Development(AM1088A)the office of the Higher Education Commission(CHE)
文摘The copolymerizations of ethylene with 1-hexene or 1-0ctene by using TiC14/MgCI2/THF catalysts modified with different metal halide additives （ZnCI2, SIC14, and the combined ZnC12-SiCl4） were investigated based on catalytic activity and copolymer properties. It was found that the catalyst modified with mixed ZnC12-SiC14 revealed the highest activities for both ethylene/1-hexene and ethylene/1-0ctene copolymerization. The increase in activities was due to the formation of acidic sites by modifying the catalysts with Lewis acids. Based on the FTIR measurements, the characteristic C--O--C peaks of the catalysts modified with metal halide additives were slightly shifted to lower wavenumber when compared to the unmodified catalyst. This showed that the modified catalysts could generate more acid sites in the TiC14/MgC12/THF catalytic system leading to an increase in activities as well as comonomer insertion （as proven by IaC-NMR）. However, Lewis acid- modifications did not affect the microstructure of the copolymers obtained. By comparison on the properties of copolymers prepared with the unmodified catalyst, it was found that polymers with ZnC12 and/or SIC14 modification exhibited a slight decrease in melting temperature, crystallinity and density. It is suggested that these results were obtained based on the different amount of ct-olefins insertion, regardless of the types of Lewis acids and comonomer.
