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Ligand Steric Effects on Naphthyl-α-diimine Nickel Catalyzed α-Olefin Polymerization
作者单位:Advanced Catalysis and Green Manufacturing Collaborative Innovation Center, School of Pertrochemical Engineering, Changzhou University, Changzhou 213164, China Chinese Academy of Sciences Key Laboratory of Soft Matter Chemistry, Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei 230026, China
基金项目:This work was financially supported by the Fundamental Research Funds for the Central Universities,Advanced Catalysis and Green Manufacturing Collaborative Innovation Center,Yixing Taodu Ying Cai Program
摘    要:Naphthyl-α-diimine nickel complexes with systematically varied ligand sterics, activated by modified methylaluminoxane(MMAO), were tested in the polymerization of higher α-olefin(1-hexene, 1-decene and 1-hexadecene) under suitable conditions. The polymerization results indicated the possibility of precise microstructure control, depending on catalyst structure, polymerization temperature, monomer concentration and types of monomers, which in turn strongly affects the resultant polymer properties. Naphthyl-α-diimine nickel complex bearing chiral bulky sec-phenethyl groups in the o-naphthyl position showed good catalytic activity, and resulted in branched polymers(42-88/1000 C) with high molecular weights(M_n:(4.3-15.2) × 10~4 g·mol~(-1)) and narrow molecular weight distribution(M_w/M_n = 1.13-1.29, RT), which suggested a living polymerization. The increasing steric hindrance of catalyst leads to enhance insertion for 2,1-insertion of α-olefin and the chain-walking reaction.

关 键 词:Naphthyl-α-diimine  nickel  complex  Chain-walking  polymerization  Higher  α-olefin  Steric  effect  Naphthyl-α-diimine  nickel  complex  Chain-walking  polymerization  Higher  α-olefin  Steric  effect

Ligand steric effects on naphthyl-α-diimine nickel catalyzed α-olefin polymerization
Authors:Wang  Fu-Zhou  Tian  Su-Su  Li  Rui-Ping  Li  Wei-Min  Chen  Chang-Le
Abstract:Naphthyl-α-diimine nickel complexes with systematically varied ligand sterics,activated by modified methylaluminoxane (MMAO),were tested in the polymerization of higher α-olefin (l-hexene,l-decene and 1-hexadecene) under suitable conditions.The polymerization results indicated the possibility of precise microstructure control,depending on catalyst structure,polymerization temperature,monomer concentration and types of monomers,which in turn strongly affects the resultant polymer properties.Naphthyl-α-diimine nickel complex bearing chiral bulky sec-phenethyl groups in the o-naphthyl position showed good catalytic activity,and resulted in branched polymers (42-88/1000C) with high molecular weights (Mn∶ (4.3-15.2) × 104 g·mo1-1) and narrow molecular weight distribution (Mw/Mn =1.13-1.29,RT),which suggested a living polymerization.The increasing steric hindrance of catalyst leads to enhance insertion for 2,1-insertion of α-olefin and the chain-walking reaction.
Keywords:
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