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


ABSTRACT: 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.

SUBMITTER: Wang F 

PROVIDER: S-EPMC6432043 | biostudies-literature | 2016 Apr

REPOSITORIES: biostudies-literature

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

Wang Fuzhou F   Tanaka Ryo R   Cai Zhengguo Z   Nakayama Yuushou Y   Shiono Takeshi T  

Polymers 20160422 4


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  ...[more]

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