A silylated PNP ligand with asymmetric structure was synthesized using(γ-aminopropyl)triethoxysilane and chlorodiphenyl phosphine as raw materials.The optimal synthetic conditions of the PNP ligand were obtained by c...A silylated PNP ligand with asymmetric structure was synthesized using(γ-aminopropyl)triethoxysilane and chlorodiphenyl phosphine as raw materials.The optimal synthetic conditions of the PNP ligand were obtained by conditional experiments and were as follows:dichloromethane was solvent,triethylamine was acid acceptor,the mole ratio of chlorodiphenylphosphine and(γ-aminopropyl)triethoxysilane was 2.1∶1,the dropping temperature of chlorodiphenylphosphine was-5℃,the dropping time was 30 min,the reaction temperature was 25℃and the reaction time was 12 h.Under the conditions,the yield of the silylated PNP ligand was 91.20%.Based on grey correlation analysis,the dropping temperature was the main factor for the yield of the silylated PNP ligand.The single-active central chromium catalyst based on the silylated PNP ligand was synthesized by complexation reaction with the silylated PNP ligand and chromium chloride tetrahydrofuran complex as materials,and the yield was 95.25%.The chemical structures of the silylated PNP ligand and the corresponding chromium catalyst were confirmed by elemental analysis,FT-IR,^(1)H NMR,MS and ICP.The single-active central chromium catalyst based on the silylated PNP ligand had good catalytic activity for ethylene oligomerization,and the content of C_(8)olefin was 72.40%,which was superior to Si-Schiff-Cr based on intermolecular coordination.展开更多
PNP-type ligands showed very good property in the catalytic systems of PNP/Cr(Ⅲ)/methylaluminoxane(MAO)for ethylene selective tetramerization toward1-octene.In this research,two PNP analogues bis(diphenylphosphino)ph...PNP-type ligands showed very good property in the catalytic systems of PNP/Cr(Ⅲ)/methylaluminoxane(MAO)for ethylene selective tetramerization toward1-octene.In this research,two PNP analogues bis(diphenylphosphino)phenylborane and bis(diphenylphosphino)dimethylsilane have been synthesized and characterized.In combination with CrCl3(THF)3as active center and MAO as cocatalyst,these ligands produced a new catalytic systems for ethylene oligomerization to linear α-olefins with catalytic activities of up to 3.07 9 106g mol-1(cat)h-1.Herein,we report the effects of the reaction temperature,ethylene pressure,and the molar ratio of Al/Cr on the catalyst activities and product selectivities.展开更多
基金supported by Key Research and Development Project of Heilongjiang Province(JD22A026)
文摘A silylated PNP ligand with asymmetric structure was synthesized using(γ-aminopropyl)triethoxysilane and chlorodiphenyl phosphine as raw materials.The optimal synthetic conditions of the PNP ligand were obtained by conditional experiments and were as follows:dichloromethane was solvent,triethylamine was acid acceptor,the mole ratio of chlorodiphenylphosphine and(γ-aminopropyl)triethoxysilane was 2.1∶1,the dropping temperature of chlorodiphenylphosphine was-5℃,the dropping time was 30 min,the reaction temperature was 25℃and the reaction time was 12 h.Under the conditions,the yield of the silylated PNP ligand was 91.20%.Based on grey correlation analysis,the dropping temperature was the main factor for the yield of the silylated PNP ligand.The single-active central chromium catalyst based on the silylated PNP ligand was synthesized by complexation reaction with the silylated PNP ligand and chromium chloride tetrahydrofuran complex as materials,and the yield was 95.25%.The chemical structures of the silylated PNP ligand and the corresponding chromium catalyst were confirmed by elemental analysis,FT-IR,^(1)H NMR,MS and ICP.The single-active central chromium catalyst based on the silylated PNP ligand had good catalytic activity for ethylene oligomerization,and the content of C_(8)olefin was 72.40%,which was superior to Si-Schiff-Cr based on intermolecular coordination.
基金supported by the National Natural Science Foundation of China (U1162114,U1362110)the Program for New Century Excellent Talents in University (NCET-070142)
文摘PNP-type ligands showed very good property in the catalytic systems of PNP/Cr(Ⅲ)/methylaluminoxane(MAO)for ethylene selective tetramerization toward1-octene.In this research,two PNP analogues bis(diphenylphosphino)phenylborane and bis(diphenylphosphino)dimethylsilane have been synthesized and characterized.In combination with CrCl3(THF)3as active center and MAO as cocatalyst,these ligands produced a new catalytic systems for ethylene oligomerization to linear α-olefins with catalytic activities of up to 3.07 9 106g mol-1(cat)h-1.Herein,we report the effects of the reaction temperature,ethylene pressure,and the molar ratio of Al/Cr on the catalyst activities and product selectivities.
