a.Hebei Key Laboratory of Functional Polymers, Institute of Polymer Science and Engineering, Hebei University of Technology, Tianjin 300130, China
b.State Key Laboratory of Separation Membranes and Membrane Processes, School of Material Science and Engineering, Tiangong University, Tianjin 300160, China
houyh1977@163.com (Y.H.H.)
polyym@163.com (M.Y.)
收稿:2021-04-19,
修回:2021-6-28,
录用:2021-6-29,
网络首发:2021-08-26,
纸质出版:2021-10-18
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Zhao, D. D.; Hou, Y. H.; Zong, K. N.; Cui, M. M.; Liu, B. Y.; Yang, M. Linear/branched block polyethylene produced by α-diimine nickel(II) catalyst and bis(phenoxy-imine) zirconium binary catalyst system in the presence of diethyl zinc. Chinese J. Polym. Sci. 2021, 39, 1581–1589
Ding-Ding Zhao, Yan-Hui Hou, Ke-Ning Zong, et al. Linear/branched Block Polyethylene Produced by
Zhao, D. D.; Hou, Y. H.; Zong, K. N.; Cui, M. M.; Liu, B. Y.; Yang, M. Linear/branched block polyethylene produced by α-diimine nickel(II) catalyst and bis(phenoxy-imine) zirconium binary catalyst system in the presence of diethyl zinc. Chinese J. Polym. Sci. 2021, 39, 1581–1589 DOI: 10.1007/s10118-021-2629-5.
Ding-Ding Zhao, Yan-Hui Hou, Ke-Ning Zong, et al. Linear/branched Block Polyethylene Produced by
In order to promote development of linear/branched block polyethylenes based on new catalytic systems
we synthesized a novel
α
-diimine nickel(II) complex with isopropyl substituents on
ortho
-
N
-aryl and hydroxymethyl phenyl substituents on
para
-
N
-aryl structures. The activity of
α
-diimine nickel(II) catalyst was 3.02×10
6
g·mol
Ni
−1
·h
−1
at 70 °C
and resultant polyethylene possessed 135/1000C branches. The linear/branched block polyethylenes were synthesized from ethylene polymerization catalyzed by the
α
-diimine nickel(II) complex/bis(phenoxy-imine) zirconium in the presence of diethyl zinc. With the addition of ZnEt
2
(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
via
adjusting ZnEt
2
equiv. and molar ratio of two catalysts. In addition
the branching degree of the polyethylene increased from 13/1000C to 56/1000C with the increase of the proportion of
α
-diimine nickel(II) catalyst. Using this binary catalyst system
the reaction temperature of chain shuttling polymerization can be carried out at 70 °C
which is more conducive to industrial application.
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