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옥타하이드로-및 테트라하이드로-[1,10]펜안트롤린 지르코늄 및 하프늄 화합물의 합성 및 이를 이용한 올레핀 중합
- Alternative Title
- Eun Yeong Hwang
- Author(s)
- 황은영
- Alternative Author(s)
- Eun Yeong Hwang
- Advisor
- 이분열
- Department
- 일반대학원 분자과학기술학과
- Publisher
- The Graduate School, Ajou University
- Publication Year
- 2015-02
- Language
- eng
- Alternative Abstract
- Post-metallocenes were constructed for olefin polymerization using 1,2,3,4,7,8,9,10-octahydro[1,10]phenanthroline and 1,2,3,4-tetrahydro[1,10]phenanthroline derivatives. A series of zirconium complexes–LZrCl2(NHMe2)2 [L = 2,9-H2-C12H12N2 (4), 2,9-Me2-C12H12N2 (5), 2,9-nBu2-C12H12N2 (6), and 2,9-iPr2-C12H12N2 (7)]–and hafnium complexes–LHfCl2(NHMe2)2 [L = 2,9-H2-C12H12N2 (8), 2,9-Me2-C12H12N2 (9), 2,9-nBu2-C12H12N2 (10), and 2,9-iPr2-C12H12N2 (11)]–were synthesized via the reaction of octahydro[1,10]phenanthrolines (2,9-R2-C12H12(NH)2) with (Me2N)2MCl2·(DME). The reaction of 2,9-R2-C12H12(NH)2 with (PhCH2)2ZrCl2 in the presence of a small amount of THF afforded a series of THF adduct analogs, i.e., LZrCl2(THF)2 [L = 2,9-H2-C12H12N2 (12), 2,9-Me2-C12H12N2 (13), 2,9-nBu2-C12H12N2 (14), and 2,9-iPr2-C12H12N2 (15)]. Treatment of 12 and 13 with excess Me3Al resulted in the formation of unexpected complexes, i.e., L[ZrCl2(Me)][AlMe2] [L = 2,9-H2-C12H12N2 (16) and 2,9-Me2-C12H12N2 (17)], in which the Me2Al unit forms a five-membered ring through binding with the two nitrogen donors and the MeCl2Zr unit slips to an η4-binding mode containing N–C–C–N fragment. Treatment of tetrahydro[1,10]phenanthrolines [2,9-R2-C12NH9(NH)] with M(CH2Ph)4 afforded tribenzyl zirconium complexes LZr(CH2Ph)3–[L = 2,9-Me2-C12NH9N (18) and 2,9-nBu2-C12NH9N (19)]–and hafnium complexes–LHf(CH2Ph)3 [L = 2,9-Me2-C12NH9N (20), 2,9-nBu2-C12NH9N (21), and 2,9-iPr2-C12NH9N (22)]. The structures of 4, 5, 12, 17, and 22 were elucidated by X-ray crystallography. The newly prepared complexes were screened for ethylene/1-octene copolymerization activity: 12 and 16 were potent catalysts (activities of 74 × 106 g/mol-Zr·h at ~120 °C under 30 bar ethylene) for the production of wax-like low-molecular weight polyethylene (Mn: ~5000), which is widely used in industry.
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- Graduate School of Ajou University > Department of Molecular Science and Technology > 3. Theses(Master)
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