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고활성의 이산화탄소-에폭사이드 고분자 중합 촉매에 관한 구조 해석
| DC Field | Value | Language |
|---|---|---|
| dc.contributor.advisor | 이분열 | - |
| dc.contributor.author | 나성재 | - |
| dc.date.accessioned | 2018-11-08T07:19:43Z | - |
| dc.date.available | 2018-11-08T07:19:43Z | - |
| dc.date.issued | 2010-02 | - |
| dc.identifier.other | 10322 | - |
| dc.identifier.uri | https://dspace.ajou.ac.kr/handle/2018.oak/5889 | - |
| dc.description | 학위논문(박사)--아주대학교 일반대학원 :분자과학기술학과,2010. 2 | - |
| dc.description.tableofcontents | ABSTRACT. 1 1. Elucidation of the Structure of A Highly Active Catalytic System for CO2/Epoxide Copolymerization: A Salen-Cobaltate Complex of An Unusual Binding Mode. 3 1.1 Introduction. 4 1.2 Results and Discussion. 6 1.2.1 NMR Studies.. 6 1.2.2 Proposal for uncoordinated imine Structure.. 12 1.2.3 DFT Calculations. 15 1.2.4 Status of DNP Ligands 16 1.2.5 Analysis of the NMR spectra in dmso-d6 20 1.2.6 Cyclic Voltammetric Studies. 21 1.2.7 Initiation Reaction.. 22 1.2.8 CO2/Propylene Oxide Copolymerization Studies.. 25 1.2.9 Dinitrophenol-Dinitrophenolate Homoconjuation as the Initiating Anion... 27 1.2.10 Preparation of Trichlorophenolate Complexes 29 1.2.11 Preparation of 4-Nitrophenolate Complex. 34 1.2.12 Preparation of 2,4-Dichlorophenolate Complex 35 1.2.13 Preparation of Homoconjugate Complexes. 36 1.3 Summary and Conclusion 38 1.4 Experimental Section. 42 1.5 Reference 81 APPENDIX 2. New Cyclic Olefine Copolymer. 88 2.1 Introduction 89 2.2. Results and Discussion 91 2.2.1 Preparation of dihydrotricyclopentadiene monomer. 97 2.2.2 Copolymerization reactions. 99 2.3 Summary and Conclusions. 105 2.4 Experimental Section. 106 2.5 Reference. 125 3. Two Components in a Molecule: Highly Efficient and Thermally Robust Catalytic System for CO2/Epoxide Copolymerization. 128 4. A Highly Active and Recyclable Catalytic System for CO2/Propylene Oxide Copolymerization. 136 ABBREVIATION 146 PUBLICATION LIST 148 | - |
| dc.language.iso | eng | - |
| dc.publisher | The Graduate School, Ajou University | - |
| dc.rights | 아주대학교 논문은 저작권에 의해 보호받습니다. | - |
| dc.title | 고활성의 이산화탄소-에폭사이드 고분자 중합 촉매에 관한 구조 해석 | - |
| dc.type | Thesis | - |
| dc.contributor.affiliation | 아주대학교 일반대학원 | - |
| dc.contributor.department | 일반대학원 분자과학기술학과 | - |
| dc.date.awarded | 2010. 2 | - |
| dc.description.degree | Master | - |
| dc.identifier.localId | 568275 | - |
| dc.identifier.url | http://dcoll.ajou.ac.kr:9080/dcollection/jsp/common/DcLoOrgPer.jsp?sItemId=000000010322 | - |
| dc.subject.keyword | 고활성 | - |
| dc.subject.keyword | 이산화탄소-에폭사이드 | - |
| dc.subject.keyword | 고분자 | - |
| dc.subject.keyword | 종합 촉매 | - |
| dc.subject.keyword | 구조 해석 | - |
| dc.description.alternativeAbstract | 1. Salen-type ligands comprised of ethylenediamine or 1,2-cyclohexenediamine, along with an salicylaldehyde bearing a methyl substituent on its 3-position and -[CR(CH2CH2CH2N+Bu3)2] (R = H or Me) on its 5-position, unexpectedly afford cobalt(III) complexes with uncoordinated imines. In these complexes, two Salen-phenoxys and two 2,4-dinitrophenolates (DNPs), which counter the quaternary ammonium cations, coordinate persistently with cobalt while two other DNPs are fluxional between a coordinating and an uncoordinated state in THF at room temperature. The complexes of this binding mode show excellent activities in CO2/propylene oxide copolymerization (TOF, 83000-13000 h-1), but with some fluctuation in induction times (1 - 10 hours) depending on how dry the system is. The induction time is shortened (< 1.0 h) and activity is increased ~1.5 times upon replacement of the two fluxional DNPs with 2,4-dinitrophenol-2,4-dinitrophenolate homoconjugation ([DNP...H...DNP]-). Imposing steric congestion by either replacing the methyl substituent on salicylaldehyde with tert-butyl or employing H2NCMe2CMe2NH2 instead of ethylenediamine or 1,2-cyclohexenediamine results in conventional imine-coordinating complexes, which show lower activities than imine-not-coordinating complexes. Anion exchange of BF4- occurs by stirring a cobalt(III) complex of Salen-type ligand tethered by four quaternary ammonium BF4- salts over a slurry of NaX in CH2Cl2, affording a complex containing four X's per cobalt (X = 2,4,5-trichlorophenolate, X = 4-nitrophenolate, X = 2,4-dichlorophenolate). The 1H and 13C NMR spectra are in agreement with an unusual imine uncoordinated structure. 2. Regioselective partial hydrogenation of tricyclopentadiene (TCPD) is achieved with a high TON (turnover number) up to 10000 by employing a N-heterocyclic carbene palladium complex as a catalyst. Copolymerization of ethylene and the partial hydrogenated product, dihydrotricyclopentadiene (HTCPD) is realized using a catalytic system of [8-(？？5-C5Me4)-2-Me(C9H8N)-？？N]TiMe2 (C9H10NH = 1,2,3,4-tetrahydroquinoline) activated with (Ph3C)+[B(C6F5)4]-. The copolymer is unambiguously characterized through analysis of one- and two-dimensional NMR spectra. The monomer reactivity ratios, rethylene and rHTCPC, determined through the Fineman-Ross plot, are 2.8 and 0.025, indicating successive insertion of two HTCPD is negligibly allowed. A nearly alternating copolymer of HTCPD content of 45 mol% is obtained with a satisfactory activity (4.7 ？e106 g/molTi？？h) whose Tg is 177oC, significantly higher than those of other cycloolefin-derived copolymer at the same cycloolefin content. | - |
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