期刊
ACS CATALYSIS
卷 8, 期 2, 页码 1104-1113出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.7b03282
关键词
nickel catalyst; chain walking; ethylene; polyethylene; long-chain branching; controlled branching
资金
- National Natural Science Foundation of China (NSFC) [21674130]
- Natural Science Foundation of Guangdong Province [2017A030313254, 2017A030310349]
- Fundamental Research Funds for the Central Universities [17lgjc02]
- PetroChina Innovation Foundation [2017D-5007-0505]
- Key Laboratory Opening Fund of PCFM
The synthesis of polyethylenes with precise branching, especially long-chain branching (LCB), using ethylene monomer as a single feedstock is of a significant academic and industrial interest. On the basis of the ortho-aryl effect, a series of adiimine nickel complexes with monoaryl-substituted anilines has been designed and prepared for the synthesis of the polyethylenes with controlled branching. The introduction of the ortho-aryl on aniline moieties enhanced the branching control ability of the adiimine nickel catalysts. A different mechanistic model was proposed to interpret the presence of methyl and LCB but absence of other short branches in the obtained polyethylenes. LCB was formed by ethylene insertion into the primary Ni-alkyl species originating from nickel migration to methyl terminal of the growing chain because of restricted ethylene insertion into secondary Ni-alkyl species with an alpha-ethyl or a bulkier alkyl group.
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