Synthesis of Silylene-Bridged Thiophene-Fused Cyclopentadienyl ansa-Metallocene Complexes for High-Performance Supported Catalyst
DC Field | Value | Language |
---|---|---|
dc.contributor.advisor | 이분열 | - |
dc.contributor.author | 정선미 | - |
dc.date.accessioned | 2022-11-29T03:01:11Z | - |
dc.date.available | 2022-11-29T03:01:11Z | - |
dc.date.issued | 2022-02 | - |
dc.identifier.other | 31473 | - |
dc.identifier.uri | https://dspace.ajou.ac.kr/handle/2018.oak/20845 | - |
dc.description | 학위논문(석사)--아주대학교 일반대학원 :분자과학기술학과,2022. 2 | - |
dc.description.tableofcontents | 1. Introduction 1 2. Results and Discussion 2 2.1 Preparation of ansa-metallocene complexes 2 2.2 Preparation of the supported catalyst and ethylene/1-hexene copolymerization 12 3. Conclusions 14 4. Experimental Section 15 4.1 General remarks 15 4.2 Synthesis of ligands and complexes 15 4.3 Preparation of supported catalysts 19 4.4 Ethylene/1-hexene polymerization 19 4.5 X-ray crystallography 19 5. Reference 20 | - |
dc.language.iso | eng | - |
dc.publisher | The Graduate School, Ajou University | - |
dc.rights | 아주대학교 논문은 저작권에 의해 보호받습니다. | - |
dc.title | Synthesis of Silylene-Bridged Thiophene-Fused Cyclopentadienyl ansa-Metallocene Complexes for High-Performance Supported Catalyst | - |
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 | 1245109 | - |
dc.identifier.uci | I804:41038-000000031473 | - |
dc.identifier.url | https://dcoll.ajou.ac.kr/dcollection/common/orgView/000000031473 | - |
dc.subject.keyword | ethylene polymerization | - |
dc.subject.keyword | metallocene catalyst | - |
dc.subject.keyword | methylaluminoxane | - |
dc.subject.keyword | silica | - |
dc.subject.keyword | slurry process | - |
dc.subject.keyword | supported catalyst | - |
dc.description.alternativeAbstract | A series of Me2Si-bridged ansa-zirconocene complexes coordinated with thiophene-fused cyclopentadienyl ligand and fluorenyl ligand [Me2Si(2-R1-3-R2-4,5-Me2C7S)(2,7-R32C13H6)]ZrMe2 (9, R1 = Me, R2 = H, R3 = H; 10, R1 = Me, R2 = Me, R3 = H; 11, R1 = H, R2 = H, R3 = H; 12, R1 = Me, R2 = H, R3 = tBu; 13, R1 = Me, R2 = H, R3 = Cl) were synthesized with an aim to prepare a supported catalyst adoptable in a commercial process. Fluorenyl anion is more basic than thiophene-fused cyclopentadienyl, and sequence of reaction order to Me2SiCl2 was crucial to achieve high yield; successive addition of fluorenyl-Li and thiophene-fused cyclopentadienyl-Li to Me2SiCl2 resulted in high yield (87%) while addition in the reverse sequence afforded the ligand precursor in low yield (27%). X-ray crystallography studies of 9 revealed that fluorenyl ligand adopts an 3-binding mode. Related Me2Si-bridged ansa-zirconocene complex 15 was also prepared replacing fluorenyl ligand in 9 with 2-methyl-4-(4-tert-butylphenyl)indenyl ligand, although it was obtained as a mixture of two diastereomers. Furthermore, ansa-metallocene complexes 20 and 23 containing tBuO(CH2)6- were prepared by replacing Me2Si-bridge in 12 and 15 with tBuO(CH2)6(Me)Si-bridge. Silica supported catalysts prepared with 12 showed two times higher productivity than the one prepared with the conventional (THI)ZrCl2 (26 vs. 12 kg-PE/g-(supported catalyst)) with polymers with comparable molecular weight (Mw, 330 vs. 300 kDa) but containing higher amount of 1-hexene content (1.3 and 1.0 mol%) being produced, although the bulk density of generated polymer particles was rather inferior (0.35 vs. 0.42 g/mL). | - |
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