Olefin polymerization is one of the most im portant chemical reactions in industry.This work presents a strategy that emphasizes the synergistic meta/poro-steric hindrance of N-aryl groups and electronic effects in ne...Olefin polymerization is one of the most im portant chemical reactions in industry.This work presents a strategy that emphasizes the synergistic meta/poro-steric hindrance of N-aryl groups and electronic effects in newly synthesized neutral salicylaldiminato nickel catalysts.These nickel(Ⅱ)catalysts exhibit exceptional thermostability,ranging from 30℃to 130℃,demonstrating enhanced catalytic activities and broadly regulated polyethylene molecular weights(3-341 kg·mol^(-1))and controlled polymer branch density(2-102 brs/1000C).The preferred catalyst Ni3 with concerted steric and electronic effects enables the production of solid-state semi-crystalline polyethylene materials at temperatures below 90℃.Notably,Ni3 exhibits an impressive tolerance of 110℃and can withstand even the challenging polymerization temperature of 130℃,leading to the production of polyethylene wax and oil.Also,functionalized polyethylene is produced.展开更多
Two types of salicylaldiminato-based nickel complexes,mono-ligated Ni(II)complexes([O-C_(6)H_(4)-o-C(H)=N-Ar]Ni(PPh_(3))(Ph)(5),[O-(3,5-Br_(2))C_(6)H_(2)-o-C(H)=N-Ar]Ni(PPh_(3))(Ph)(6),[O-(3-t-Bu)C_(6)H_(3)-o-C(H)=N-A...Two types of salicylaldiminato-based nickel complexes,mono-ligated Ni(II)complexes([O-C_(6)H_(4)-o-C(H)=N-Ar]Ni(PPh_(3))(Ph)(5),[O-(3,5-Br_(2))C_(6)H_(2)-o-C(H)=N-Ar]Ni(PPh_(3))(Ph)(6),[O-(3-t-Bu)C_(6)H_(3)-o-C(H)=N-Ar]Ni(PPh_(3))(Ph)(7))and bis-ligated Ni(II)complexes([O-(3,5-Br_(2))C_(6)H_(2)-o-C(H)=N-Ar]_(2)Ni(8),[O-(3,5-Br_(2))C_(6)H_(2)-o-C(H)=N-2-C_(6)H_(4)(PhO)]_(2)Ni(9),Ar=2,6-C_(6)H_(3)(i-Pr)_(2))were synthesized and characterized by Fourier transform infrared spectroscopy(FT-IR),nuclear magnetic resonance(NMR),mass spectrography(MS)and elemental analysis(EA).In the presence of methylaluminoxane(MAO)as cocatalyst,all the nickel complexes exhibited high activities for the polymerization of methyl methacrylate(MMA)and syndiotactic-rich poly(methyl methacrylate)(PMMA)was obtained.The complexes with less bulky substituents on salicylaldiminato framework possessed higher activities,while with the same salicylaldiminato,the mono-ligated nickel complexes showed higher catalytic activity than bis-ligated ones.展开更多
A series of neutral nickel complexes featuring N-fluorinated phenyl salicylaldiminato chelate ligands was syn- thesized, and the novel molecular structure of complex C14 was further confirmed by X-ray crystallographic...A series of neutral nickel complexes featuring N-fluorinated phenyl salicylaldiminato chelate ligands was syn- thesized, and the novel molecular structure of complex C14 was further confirmed by X-ray crystallographic analy- sis. The neutral nickel complexes showed high activity up to 9.96× 10^5 g oligomers/（mol Nioh） and high selectivity of C6 in catalyzing ethylene oligomerization using methylaluminoxane （MAO） as cocatalyst. It was observed that the strong electron-withdrawing effect of the fluorinated salicylaldiminato ligand was able to significantly increase the catalytic activity for oligomerization of ethylene. In addition, the influence of reaction parameters such as A1/Ni molar ratio, reaction temperature, a variety of cocatalyst and ethylene pressure on catalytic activity was investigated.展开更多
Emulsion copolymerization of styrene and ethylene catalyzed by a series of neutral nickel(Ⅱ) complexes was carried out in an aqueous system to give high-molecular-weight copolymers.The copolymers and emulsions were c...Emulsion copolymerization of styrene and ethylene catalyzed by a series of neutral nickel(Ⅱ) complexes was carried out in an aqueous system to give high-molecular-weight copolymers.The copolymers and emulsions were characterized by an array of techniques including NMR,GPC,TEM,WAXD and DSC.The results indicate that the copolymers obtained are mostly block copolymers of polyethylene with random insertion of styrene units,and their M_W is in the range of 10~5-10~6.By enhancing the electron withdrawing of the s...展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.22122110 and U23B6011 for Z.J.)the Jilin Provincial Science and Technology Department Program(No.20210101070JC for Y.C.)。
文摘Olefin polymerization is one of the most im portant chemical reactions in industry.This work presents a strategy that emphasizes the synergistic meta/poro-steric hindrance of N-aryl groups and electronic effects in newly synthesized neutral salicylaldiminato nickel catalysts.These nickel(Ⅱ)catalysts exhibit exceptional thermostability,ranging from 30℃to 130℃,demonstrating enhanced catalytic activities and broadly regulated polyethylene molecular weights(3-341 kg·mol^(-1))and controlled polymer branch density(2-102 brs/1000C).The preferred catalyst Ni3 with concerted steric and electronic effects enables the production of solid-state semi-crystalline polyethylene materials at temperatures below 90℃.Notably,Ni3 exhibits an impressive tolerance of 110℃and can withstand even the challenging polymerization temperature of 130℃,leading to the production of polyethylene wax and oil.Also,functionalized polyethylene is produced.
基金sponsored by the Scientific Research Foundation for the Returned Overseas Chinese Scholars,State Education Ministry of China,the Science and Technology Innovation Program of the China National Petroleum Corporation,and the Key Laboratory of Advanced Polymer Materials of Shanghai(Grant No.08DZ2230500)the Science and Technology Innovation Program of China National Petroleum Corporation.
文摘Two types of salicylaldiminato-based nickel complexes,mono-ligated Ni(II)complexes([O-C_(6)H_(4)-o-C(H)=N-Ar]Ni(PPh_(3))(Ph)(5),[O-(3,5-Br_(2))C_(6)H_(2)-o-C(H)=N-Ar]Ni(PPh_(3))(Ph)(6),[O-(3-t-Bu)C_(6)H_(3)-o-C(H)=N-Ar]Ni(PPh_(3))(Ph)(7))and bis-ligated Ni(II)complexes([O-(3,5-Br_(2))C_(6)H_(2)-o-C(H)=N-Ar]_(2)Ni(8),[O-(3,5-Br_(2))C_(6)H_(2)-o-C(H)=N-2-C_(6)H_(4)(PhO)]_(2)Ni(9),Ar=2,6-C_(6)H_(3)(i-Pr)_(2))were synthesized and characterized by Fourier transform infrared spectroscopy(FT-IR),nuclear magnetic resonance(NMR),mass spectrography(MS)and elemental analysis(EA).In the presence of methylaluminoxane(MAO)as cocatalyst,all the nickel complexes exhibited high activities for the polymerization of methyl methacrylate(MMA)and syndiotactic-rich poly(methyl methacrylate)(PMMA)was obtained.The complexes with less bulky substituents on salicylaldiminato framework possessed higher activities,while with the same salicylaldiminato,the mono-ligated nickel complexes showed higher catalytic activity than bis-ligated ones.
基金Acknowledgement The authors gratefully acknowledge the financial support subsidized by the National Basic Research Program of China （No. 2005CB623800）, the National Natural Science Foundation of China （NNSFC） （No. 21072128）.
文摘A series of neutral nickel complexes featuring N-fluorinated phenyl salicylaldiminato chelate ligands was syn- thesized, and the novel molecular structure of complex C14 was further confirmed by X-ray crystallographic analy- sis. The neutral nickel complexes showed high activity up to 9.96× 10^5 g oligomers/（mol Nioh） and high selectivity of C6 in catalyzing ethylene oligomerization using methylaluminoxane （MAO） as cocatalyst. It was observed that the strong electron-withdrawing effect of the fluorinated salicylaldiminato ligand was able to significantly increase the catalytic activity for oligomerization of ethylene. In addition, the influence of reaction parameters such as A1/Ni molar ratio, reaction temperature, a variety of cocatalyst and ethylene pressure on catalytic activity was investigated.
文摘Emulsion copolymerization of styrene and ethylene catalyzed by a series of neutral nickel(Ⅱ) complexes was carried out in an aqueous system to give high-molecular-weight copolymers.The copolymers and emulsions were characterized by an array of techniques including NMR,GPC,TEM,WAXD and DSC.The results indicate that the copolymers obtained are mostly block copolymers of polyethylene with random insertion of styrene units,and their M_W is in the range of 10~5-10~6.By enhancing the electron withdrawing of the s...
