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ETHYLENE POLYMERIZATION AND COPOLYMERIZATION WITH POLAR MONOMERS BY A NEUTRAL NICKEL CATALYST COMBINED WITH CO-CATALYST OF Ni(COD)2 OR AL(i-Bu)3
作者姓名:Yu-hua  Shan  Jun-quan  Sun~
摘    要:A neutral nickel (Ⅱ) catalyst D, { O-(3-cyclohexyl)(5-Cl)C6H2-ortho-C(H)=N-2,6-C6H3(i-Pr)2]Ni(Ph3P)(Ph)} has been synthesized and characterized by 1H-NMR, FTIR and elemental analysis. The results indicate that Al(i-Bu)3 is an effective cocatalyst for the neutral nickel catalyst. With bis(1,5-cyclooctadiene) nickel(0) Ni(COD)2] or Al(i-Bu)3 as a cocatalyst, the neutral nickel catalyst D is active for ethylene polymerisation and copolymerisation with polar monomers (tertbutyl 10-undecenoate(BU), methyl 10-undecenoate (MU), allyl alcohol (AA) and 4-penten-1-ol (PO)) under mild conditions.The resulting polymers were characterized by 1H-NMR, FTIR, DSC, and GPC. From the comparative studies, Ni(COD)2 is more active than Al(i-Bu)3 for ethylene homopolymerization, while Al(i-Bu)3 is more effective than Ni(COD)2 for ethylene copolymerisation with polar monomers. The polymerization parameters which affect both the catalytic activity and properties of the resulting polyethylene were investigated in detail. Under the conditions of 20 μmol catalyst D and Ni(COD)2/D = 3(molar ratio) in 30 mL toluene solution at 45℃, 12 × 105 Pa ethylene for 20 min, the polymerization activity reaches as High as7.29×105gPE.(mol.Ni·h)-1and Mηis 7.16×104g.mol-1.For ethylene copolymerization with polar monomers,the effect of comonomer concentrations was examined. As high as 0.97 mol% of MU, 1.06 mol% of BU, 1.04 mol% of AA and 1.37 mol% of PO were incorporated into the polymer, respectively, catalyzed by D/Al(i-Bu)3 system.

关 键 词:乙烯  聚合反应  共聚合作用    催化剂  
收稿时间:2004-03-30
修稿时间:2004-04-26

ETHYLENE POLYMERIZATION AND COPOLYMERIZATION WITH POLAR MONOMERS BY A NEUTRAL NICKEL CATALYST COMBINED WITH CO-CATALYST OF Ni(COD)2 OR AL(i-Bu)3
Yu-hua Shan Jun-quan Sun.ETHYLENE POLYMERIZATION AND COPOLYMERIZATION WITH POLAR MONOMERS BY A NEUTRAL NICKEL CATALYST COMBINED WITH CO-CATALYST OF Ni(COD)2 OR AL(i-Bu)3[J].Chinese Journal of Polymer Science,2005,0(3):301-310.
Authors:Yu-hua Shan  Jun-quan Sun  Yong-jin Xu  Yong-gang Cui  Feng Lin
Abstract: A neutral nickel (II) catalyst D, {O-(3-cyclohexyl)(5-Cl)C6H2-ortho-C(H)=N-2,6-C6H3(i-Pr)2]Ni(Ph3P)(Ph)} has been synthesized and characterized by 1H-NMR, FTIR and elemental analysis. The results indicate that Al(i-Bu)3 is an effective cocatalyst for the neutral nickel catalyst. With bis(1,5-cyclooctadiene) nickel(0) Ni(COD)2] or Al(i-Bu)3 as a co-catalyst, the neutral nickel catalyst D is active for ethylene polymerisation and copolymerisation with polar monomers (tert-butyl 10-undecenoate(BU), methyl 10-undecenoate (MU), allyl alcohol (AA) and 4-penten-1-ol (PO)) under mild conditions. The resulting polymers were characterized by 1H-NMR, FTIR, DSC, and GPC. From the comparative studies, Ni(COD)2 is more active than Al(i-Bu)3 for ethylene homopolymerization, while Al(i-Bu)3 is more effective than Ni(COD)2 for ethylene copolymerisation with polar monomers. The polymerization parameters which affect both the catalytic activity and properties of the resulting polyethylene were investigated in detail. Under the conditions of 20 mmol catalyst D and Ni(COD)2/D = 3 (molar ratio) in 30 mL toluene solution at 45℃, 12 × 105 Pa ethylene for 20 min, the polymerization activity reaches as high as 7.29 × 105 gPE·(mol·Ni·h)-1 and Mη is 7.16 × 104 g·mol-1. For ethylene copolymerization with polar monomers, the effect of comonomer concentrations was examined. As high as 0.97 mol% of MU, 1.06 mol% of BU, 1.04 mol% of AA and 1.37 mol% of PO were incorporated into the polymer, respectively, catalyzed by D/Al(i-Bu)3 system.
Keywords:Neutral nickel catalyst  Polar monomer  Copolymerization  Polyethylene  Functional polyolefins  COMBINED  NEUTRAL NICKEL CATALYST  POLAR  COPOLYMERIZATION  system  copolymerization  effect  concentrations  catalytic activity  High  toluene  solution  molar  parameters  affect  properties  polyethylene  comparative studies  polymers  characterized
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