A neutral nickel(Ⅱ)catalyst D,{[O-(3-cyclohexyl)(5-Cl)C_6H_2-ortho-C(H)=N-2,6-C_6H_3(i-Pr)_2]Ni(Ph_3P)(Ph)}hasbeen synthesized and characterized by IH-NMR,FTIR and elemental analysis.The results indicate that Al(i-Bu...A neutral nickel(Ⅱ)catalyst D,{[O-(3-cyclohexyl)(5-Cl)C_6H_2-ortho-C(H)=N-2,6-C_6H_3(i-Pr)_2]Ni(Ph_3P)(Ph)}hasbeen synthesized and characterized by IH-NMR,FTIR and elemental analysis.The results indicate that Al(i-Bu)_3 is aneffective 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 (?)H-NMR,FTIR,DSC,and GPC.From the comparative studies,Ni(COD)_2 ismore active than Al(i-Bu)_3 for ethylene homopolymerization,while Al(i-Bu)_3 is more effective than Ni(COD)_2 for ethylenecopolymerisation with polar monomers.The polymerization parameters which affect both the catalytic activity and propertiesof 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 ashigh as 7.29×105 gPE.(mol.Ni.h)^(-1) and M_η,is 7.16×104 g.mol^(-1).For ethylene copolymerization with polar monomers,theeffect of comonomer concentrations was examined.As high as 0.97 mol% of MU,1.06 mol% of BU,1.04 mol% of AA and1.37 mol% of PO were incorporated into the polymer,respectively,catalyzed by D/Al(i-Bu)_3 system.展开更多
基金This work was supported by the NSFC(No.2007402820374043)SINOPEC(X500030).
文摘A neutral nickel(Ⅱ)catalyst D,{[O-(3-cyclohexyl)(5-Cl)C_6H_2-ortho-C(H)=N-2,6-C_6H_3(i-Pr)_2]Ni(Ph_3P)(Ph)}hasbeen synthesized and characterized by IH-NMR,FTIR and elemental analysis.The results indicate that Al(i-Bu)_3 is aneffective 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 (?)H-NMR,FTIR,DSC,and GPC.From the comparative studies,Ni(COD)_2 ismore active than Al(i-Bu)_3 for ethylene homopolymerization,while Al(i-Bu)_3 is more effective than Ni(COD)_2 for ethylenecopolymerisation with polar monomers.The polymerization parameters which affect both the catalytic activity and propertiesof 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 ashigh as 7.29×105 gPE.(mol.Ni.h)^(-1) and M_η,is 7.16×104 g.mol^(-1).For ethylene copolymerization with polar monomers,theeffect of comonomer concentrations was examined.As high as 0.97 mol% of MU,1.06 mol% of BU,1.04 mol% of AA and1.37 mol% of PO were incorporated into the polymer,respectively,catalyzed by D/Al(i-Bu)_3 system.
