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Open AccessArticle

Synthesis of Highly Branched Polyolefins Using Phenyl Substituted α-Diimine Ni(II) Catalysts

1
Graduate School of Engineering, Hiroshima University, Kagamiyama 1-4-1, Higashi-Hiroshima 739-8527, Japan
2
State Key Lab of Chemical Fibers & Polymer Materials, College of Material Science & Engineering, Donghua University, Shanghai 201620, China
*
Author to whom correspondence should be addressed.
Academic Editor: Shin-ichi Yusa
Polymers 2016, 8(4), 160; https://doi.org/10.3390/polym8040160
Received: 28 March 2016 / Revised: 8 April 2016 / Accepted: 12 April 2016 / Published: 22 April 2016
A series of α-diimine Ni(II) complexes containing bulky phenyl groups, [ArN = C(Naphth)C = NAr]NiBr2 (Naphth: 1,8-naphthdiyl, Ar = 2,6-Me2-4-PhC6H2 (C1); Ar = 2,4-Me2-6-PhC6H2 (C2); Ar = 2-Me-4,6-Ph2C6H2 (C3); Ar = 4-Me-2,6-Ph2C6H2 (C4); Ar = 4-Me-2-PhC6H3 (C5); Ar = 2,4,6-Ph3C6H2 (C6)), were synthesized and characterized. Upon activation with either diethylaluminum chloride (Et2AlCl) or modified methylaluminoxane (MMAO), all Ni(II) complexes showed high activities in ethylene polymerization and produced highly branched amorphous polyethylene (up to 145 branches/1000 carbons). Interestingly, the sec-butyl branches were observed in polyethylene depending on polymerization temperature. Polymerization of 1-alkene (1-hexene, 1-octene, 1-decene and 1-hexadecene) with C1-MMAO at room temperature resulted in branched polyolefins with narrow Mw/Mn values (ca. 1.2), which suggested a living polymerization. The polymerization results indicated the possibility of precise microstructure control, depending on the polymerization temperature and types of monomers. View Full-Text
Keywords: α-diimine Ni(II) complex; chain-walking polymerization; branched polyolefins; living polymerization; 1-alkene α-diimine Ni(II) complex; chain-walking polymerization; branched polyolefins; living polymerization; 1-alkene
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Wang, F.; Tanaka, R.; Cai, Z.; Nakayama, Y.; Shiono, T. Synthesis of Highly Branched Polyolefins Using Phenyl Substituted α-Diimine Ni(II) Catalysts. Polymers 2016, 8, 160.

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