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옥타하이드로-및 테트라하이드로-[1,10]펜안트롤린 지르코늄 및 하프늄 화합물의 합성 및 이를 이용한 올레핀 중합
| DC Field | Value | Language |
|---|---|---|
| dc.contributor.advisor | 이분열 | - |
| dc.contributor.author | 황은영 | - |
| dc.date.accessioned | 2018-11-08T08:18:40Z | - |
| dc.date.available | 2018-11-08T08:18:40Z | - |
| dc.date.issued | 2015-02 | - |
| dc.identifier.other | 18907 | - |
| dc.identifier.uri | https://dspace.ajou.ac.kr/handle/2018.oak/12729 | - |
| dc.description | 학위논문(석사)--아주대학교 일반대학원 :분자과학기술학과,2015. 2 | - |
| dc.description.tableofcontents | 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 | - |
| dc.language.iso | eng | - |
| dc.publisher | The Graduate School, Ajou University | - |
| dc.rights | 아주대학교 논문은 저작권에 의해 보호받습니다. | - |
| dc.title | 옥타하이드로-및 테트라하이드로-[1,10]펜안트롤린 지르코늄 및 하프늄 화합물의 합성 및 이를 이용한 올레핀 중합 | - |
| dc.title.alternative | Eun Yeong Hwang | - |
| dc.type | Thesis | - |
| dc.contributor.affiliation | 아주대학교 일반대학원 | - |
| dc.contributor.alternativeName | Eun Yeong Hwang | - |
| dc.contributor.department | 일반대학원 분자과학기술학과 | - |
| dc.date.awarded | 2015. 2 | - |
| dc.description.degree | Master | - |
| dc.identifier.localId | 695618 | - |
| dc.identifier.url | http://dcoll.ajou.ac.kr:9080/dcollection/jsp/common/DcLoOrgPer.jsp?sItemId=000000018907 | - |
| dc.subject.keyword | Postmetallocene | - |
| dc.subject.keyword | Phenanthroline | - |
| dc.subject.keyword | Olefinpolymerization | - |
| dc.description.alternativeAbstract | 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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