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Preparation of Extremely Active Ethylene Tetramerization Catalyst [iPrN(PAr2)2−CrCl2]+[B(C6F5)4]– (Ar = −C6H4-p-SiR3)
| DC Field | Value | Language |
|---|---|---|
| dc.contributor.advisor | 이분열 | - |
| dc.contributor.author | 이정현 | - |
| dc.date.accessioned | 2022-11-29T03:01:31Z | - |
| dc.date.available | 2022-11-29T03:01:31Z | - |
| dc.date.issued | 2022-02 | - |
| dc.identifier.other | 31340 | - |
| dc.identifier.uri | https://dspace.ajou.ac.kr/handle/2018.oak/21267 | - |
| dc.description | 학위논문(석사)--아주대학교 일반대학원 :분자과학기술학과,2022. 2 | - |
| dc.description.tableofcontents | 1. Introduction 1 2. Results and Discussion 2 2.1 Preparation of Ligand 2 2.2 Preparation of Chromium Complexes 8 2.3 Oligomerization studies 10 3. Experimental Section 13 3.1 General remarks 13 3.2 (1-Octyl)3SiCl 13 3.3 BrC6H4-p-Si(1-octyl)3 14 3.4 Et2NP[C6H4-p-Si(1-octyl)3]2 14 3.5 ClP[C6H4-p-Si(1-octyl)3]2 15 3.6 iPrN(PAr2)2 (Ar = - C6H4-p-Si(1-octyl)3) 15 3.7 Preperation of [iPrN(PAr2)2-CrCl2]+[B(C6F5)4]- Using [CrCl2(NCCH3)4]+ [B(C6F5)4]- 16 3.8 Attempt to Prepare [iPrN(PAr2)2-CrCl2]+[B(C6F5)4]– Using [PhN(H)Me2]+ [B(C6F5)4]– and [CrCl2(μ-Cl)(thf)2] 16 3.9 [CrCl2(NCCH3)4]+[B(C6F5)4]– 17 3.10 Ethylene Tetramerization 17 4.Conclusions 18 5. Patent 18 6. References 19 | - |
| dc.language.iso | eng | - |
| dc.publisher | The Graduate School, Ajou University | - |
| dc.rights | 아주대학교 논문은 저작권에 의해 보호받습니다. | - |
| dc.title | Preparation of Extremely Active Ethylene Tetramerization Catalyst [iPrN(PAr2)2−CrCl2]+[B(C6F5)4]– (Ar = −C6H4-p-SiR3) | - |
| dc.type | Thesis | - |
| dc.contributor.affiliation | 아주대학교 일반대학원 | - |
| dc.contributor.department | 일반대학원 분자과학기술학과 | - |
| dc.date.awarded | 2022. 2 | - |
| dc.description.degree | Master | - |
| dc.identifier.localId | 1245099 | - |
| dc.identifier.uci | I804:41038-000000031340 | - |
| dc.identifier.url | https://dcoll.ajou.ac.kr/dcollection/common/orgView/000000031340 | - |
| dc.subject.keyword | 1-octene production | - |
| dc.subject.keyword | Ethylene tetramderization | - |
| dc.subject.keyword | bis(phosphine)ligand | - |
| dc.subject.keyword | chromium catalyst | - |
| dc.subject.keyword | tetrakis(pentafluorophenyl)borate | - |
| dc.description.alternativeAbstract | Numerous efforts have been made to achieve “on-purpose” 1-octene production since Sasol discovered a Cr-based selective ethylene tetramerization catalyst in the early 2000s. By preparing a series of bis(phosphine) ligands iPrN(PAr2)2 where the Ar contains a bulky –SiR3 substituent (Ar = -C6H4-p-Si(nBu)3 (1), -C6H4-p-Si(1-hexyl)3 (2), -C6H4-p-Si(1-octyl)3 (3), -C6H4-p-Si(2-ethylhexyl)3 (4), -C6H4-p-Si(3,7-dimethyloctyl)3 (5)), we obtained an extremely active catalyst that meets the criteria for commercial utilization. The Cr complexes [iPrN(PAr2)2-CrCl2]+[B(C6F5)4]–, obtained by reacting ligands 1-5 with [(CH3CN)4CrCl2]+[B(C6F5)4]–, showed high activity exceeding 6000 kg/g-Cr/h, when combined with the inexpensive iBu3Al, thus avoiding the use of expensive modified methylaluminoxane (MMAO). The bulky –SiR3 substituents played a key role in the success of catalysis by blocking the formation of inactive species (Cr complexes coordinated by two iPrN(PAr2)2 ligands, that is, [(iPrN(PAr2)2)2-CrCl2]+[B(C6F5)4]–). Among the complexes prepared, [3-CrCl2]+[B(C6F5)4]– exhibited the highest activity (11,100 kg/g-Cr/h, 100 kg/g-catalyst) with high 1-octene selectivity (75 wt%), and, moreover, mitigated the generation of undesired > C10 fractions (10.7 wt%). A 10-g-scale synthesis of 3 was developed, as well as a facile and low-cost synthetic method for [(CH3CN)4CrCl2]+[B(C6F5)4]–. | - |
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