Stereoblock polypropyienes bearing isotactic,atactic,and syndictactic polypropylene segments were successfully prepared by dry methylaluminoxane activated binary catalysts system,Ph2CFluCpZrCl2 and {Me2Si(2,5-Me2-3-(2...Stereoblock polypropyienes bearing isotactic,atactic,and syndictactic polypropylene segments were successfully prepared by dry methylaluminoxane activated binary catalysts system,Ph2CFluCpZrCl2 and {Me2Si(2,5-Me2-3-(2-MePh)-cyclopento[2,3-b]thiophen-6-yl)2}ZCl2,in the presence of iBu3Al as a chain shutting agent.by studying the catalyst activity,chain transfer efficiency,and reversility of chain transfer reaction of each catalyst system,as well as the molecular weight and polydispersity of the resulting polymers,the allyl exchange reactions between the zirconium catalyst and different main-group metal alky were estimated,respectvely.Based on the optimized react condition,the chain shuttling polymerization was conducted by binary catalyst system in the presence of iBu3Al under both atmospheric and high pressure.Resultant polymers were identified as stereoblock polypropylenes according to microstructure and physical properties analyses by 13C{1H}-NMR,DsC,and GPC.展开更多
In order to promote development of linear/branched block polyethylenes based on new catalytic systems,we synthesized a novel a.dimine nickel(Ⅱ)complex with isopropyl substituents on ortho-N-aryl and hydroxymethyl phe...In order to promote development of linear/branched block polyethylenes based on new catalytic systems,we synthesized a novel a.dimine nickel(Ⅱ)complex with isopropyl substituents on ortho-N-aryl and hydroxymethyl phenyl substituents on para-Naryl structures.The activity of a-dimine nickl(Ⅱ)catalyst was 3.02x10^(6)g-mol_(ni)^(-1)·h^(-1) at 70℃,and resultant polyethylene possessed 135/1000C branches.The linear/branched block polyethylenes were synthesized from ethylene polymerization catalyzed by the a-dimine nicke(Ⅱ)complex/bis(phenoxy-imine)zirconium in the presence of diethyI zinc.With the addition of ZnEtz(from 0 to 400),the melting peak of resultant polyethylene changed from a single melting peak to bimodal melting peaks.The molecular weights of resultant polyethylene ranging from 26.8 kg/mol to 17.1 kg/mol and PDI values varying gradually from 24.4 to 15.2 were obtained vla adjusting ZnEt;equiv.and molar ratio of two catalysts.In addition,the branching degree of the polyethylene increased from 13/1000C to 56/1000 with the increase of the proportion of a dimine nickel(Ⅱ)catalyst.Using this binary catalyst system,the reaction temperature of chain shutting polymerization can be carried out at 70℃,which is more conducive to industrial application.展开更多
基金the National Natural Science Foundation of China(No.21574097).
文摘Stereoblock polypropyienes bearing isotactic,atactic,and syndictactic polypropylene segments were successfully prepared by dry methylaluminoxane activated binary catalysts system,Ph2CFluCpZrCl2 and {Me2Si(2,5-Me2-3-(2-MePh)-cyclopento[2,3-b]thiophen-6-yl)2}ZCl2,in the presence of iBu3Al as a chain shutting agent.by studying the catalyst activity,chain transfer efficiency,and reversility of chain transfer reaction of each catalyst system,as well as the molecular weight and polydispersity of the resulting polymers,the allyl exchange reactions between the zirconium catalyst and different main-group metal alky were estimated,respectvely.Based on the optimized react condition,the chain shuttling polymerization was conducted by binary catalyst system in the presence of iBu3Al under both atmospheric and high pressure.Resultant polymers were identified as stereoblock polypropylenes according to microstructure and physical properties analyses by 13C{1H}-NMR,DsC,and GPC.
基金by the National Natural Science Foundation of China(Nos.21004017 and 21004043)the Natural Science Foundation of Hebei Provinee(No.B2015202049).
文摘In order to promote development of linear/branched block polyethylenes based on new catalytic systems,we synthesized a novel a.dimine nickel(Ⅱ)complex with isopropyl substituents on ortho-N-aryl and hydroxymethyl phenyl substituents on para-Naryl structures.The activity of a-dimine nickl(Ⅱ)catalyst was 3.02x10^(6)g-mol_(ni)^(-1)·h^(-1) at 70℃,and resultant polyethylene possessed 135/1000C branches.The linear/branched block polyethylenes were synthesized from ethylene polymerization catalyzed by the a-dimine nicke(Ⅱ)complex/bis(phenoxy-imine)zirconium in the presence of diethyI zinc.With the addition of ZnEtz(from 0 to 400),the melting peak of resultant polyethylene changed from a single melting peak to bimodal melting peaks.The molecular weights of resultant polyethylene ranging from 26.8 kg/mol to 17.1 kg/mol and PDI values varying gradually from 24.4 to 15.2 were obtained vla adjusting ZnEt;equiv.and molar ratio of two catalysts.In addition,the branching degree of the polyethylene increased from 13/1000C to 56/1000 with the increase of the proportion of a dimine nickel(Ⅱ)catalyst.Using this binary catalyst system,the reaction temperature of chain shutting polymerization can be carried out at 70℃,which is more conducive to industrial application.
