옥타하이드로-및 테트라하이드로-[1,10]펜안트롤린 지르코늄 및 하프늄 화합물의 합성 및 이를 이용한 올레핀 중합
Preperation of octahydro- and tetrahydro-[1,10]phenanthroline zirconium and hafnium complexes for olefin polymerization
- 주제(키워드) Postmetallocene , Phenanthroline , Olefinpolymerization
- 발행기관 아주대학교
- 지도교수 이분열
- 발행년도 2015
- 학위수여년월 2015. 2
- 학위명 석사
- 학과 및 전공 일반대학원 분자과학기술학과
- 실제URI http://www.dcollection.net/handler/ajou/000000018907
- 본문언어 영어
- 저작권 아주대학교 논문은 저작권에 의해 보호받습니다.
초록/요약
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.
more목차
Abstract……………………………………………………6
1. Introduction……………………………………………7
2. Results and discussion
2. 1 Synthesis ……………………………………………8
2. 2 X-Ray Crystallographic Studies…………………13
2. 3 Polymerization Studies……………………………15
3. Conclusions……………………………………………18
4. Experimental Section
4. 1 General remarks……..………………………………18
4. 2 Ethylene/1-Octene Copolymerization……………27
4. 3 X-Ray Crystallography………………………………27
4. 4 Acknowledgements…………………………………29
5. Reference…………………………………………………34
6. Supporting information…………………………………38
