Synthesis of Silylene-Bridged Thiophene-Fused Cyclopentadienyl ansa-Metallocene Complexes for High-Performance Supported Catalyst

DC Field Value Language
dc.contributor.advisor이분열-
dc.contributor.author정선미-
dc.date.accessioned2022-11-29T03:01:11Z-
dc.date.available2022-11-29T03:01:11Z-
dc.date.issued2022-02-
dc.identifier.other31473-
dc.identifier.urihttps://dspace.ajou.ac.kr/handle/2018.oak/20845-
dc.description학위논문(석사)--아주대학교 일반대학원 :분자과학기술학과,2022. 2-
dc.description.tableofcontents1. 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.isoeng-
dc.publisherThe Graduate School, Ajou University-
dc.rights아주대학교 논문은 저작권에 의해 보호받습니다.-
dc.titleSynthesis of Silylene-Bridged Thiophene-Fused Cyclopentadienyl ansa-Metallocene Complexes for High-Performance Supported Catalyst-
dc.typeThesis-
dc.contributor.affiliation아주대학교 일반대학원-
dc.contributor.department일반대학원 분자과학기술학과-
dc.date.awarded2022. 2-
dc.description.degreeMaster-
dc.identifier.localId1245109-
dc.identifier.uciI804:41038-000000031473-
dc.identifier.urlhttps://dcoll.ajou.ac.kr/dcollection/common/orgView/000000031473-
dc.subject.keywordethylene polymerization-
dc.subject.keywordmetallocene catalyst-
dc.subject.keywordmethylaluminoxane-
dc.subject.keywordsilica-
dc.subject.keywordslurry process-
dc.subject.keywordsupported catalyst-
dc.description.alternativeAbstractA 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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Graduate School of Ajou University > Department of Molecular Science and Technology > 3. Theses(Master)
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