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Preparation of Pyridylamido Hafnium Complexes for Olefin Polymerization
- Author(s)
- 박경리
- Advisor
- 이분열
- Department
- 일반대학원 분자과학기술학과
- Publisher
- The Graduate School, Ajou University
- Publication Year
- 2020-08
- Language
- eng
- Keyword
- coordinative chain transfer polymerization; dialkylzinc; post-metallocene; pyridylamido hafnium complex
- Alternative Abstract
- The pyridylamido hafnium complex (I) discovered at Dow is a flagship catalyst among postmetallocenes, which are used in the polyolefin industry for PO-chain growth from a chain transfer agent, dialkylzinc. In the present work, with the aim to block a possible deactivation process in prototype compound I, the corresponding derivatives were prepared. A series of pyridylamido Hf complexes were prepared by replacing the 2,6-diisopropylphenylamido part in I with various 2,6-R2C6H3N- moieties (R = cycloheptyl, cyclohexyl, cyclopentyl, 3-pentyl, ethyl, or Ph) or by replacing 2-iPrC6H4C(H)- in I with the simple PhC(H)- moiety. The isopropyl substituent in the 2-iPrC6H4C(H)- moiety influences not only the geometry of the structures (revealed by X-ray crystallography) but also catalytic performance. In the complexes bearing the 2-iPrC6H4C(H)- moiety, the chelation framework forms a plane; however, this framework is distorted in the complexes containing the PhC(H)- moiety. The ability to incorporate a-olefin decreased upon replacing 2-iPrC6H4C(H)- with the PhC(H)- moiety. The complexes carrying the 2,6-di(cycloheptyl)phenylamido or 2,6-di(cyclohexyl)phenylamido moiety (replacing the 2,6-diisopropylphenylamido part in I) showed somewhat higher activity with greater longevity than did prototype catalyst I.
- Fulltext
- Appears in Collections:
- Graduate School of Ajou University > Department of Molecular Science and Technology > 3. Theses(Master)
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