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| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 陳竹亭(Jwu-Ting Chen) | |
| dc.contributor.author | Hsin-Wei Lin | en |
| dc.contributor.author | 林欣微 | zh_TW |
| dc.date.accessioned | 2021-06-15T05:24:43Z | - |
| dc.date.available | 2010-07-21 | |
| dc.date.copyright | 2010-07-21 | |
| dc.date.issued | 2010 | |
| dc.date.submitted | 2010-07-16 | |
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| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/46709 | - |
| dc.description.abstract | 一系列在甲苯胺陰離子上帶有不同取代基之甲苯胺陰離子-胺基雙牙配位基以(C2H5)2NC(CH3)2CCH3N(Ar) [Ar = p-methoxyphenyl, p-methylphenyl, Phenyl, p-fluorophenyl, p-chlorophenyl] 形式，以及甲苯胺陰離子-吡啶雙牙配位基以 (C5H5N) C(CH3)2NH(Ar) [Ar'= Phenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl] 形式被成功地合成與鑑定。
這些衍生物呈現扭曲的四角錐構型並且可以在沒有任何輔助的起始劑情況下，有效地活化環己內酯的開環聚合反應。合成出的高分子聚合物，具有良好的分子量散佈趨勢。 除此之外，加入具有輔助效應的醇類起始劑，除了可以在更短時間內催化環己內酯的開環聚合反應，亦可以得到分子量分佈均勻的高分子聚合物。 本論文除了鑑定以及合成高分子聚合物以外，利用電子效應的調控以及Hammett plot來探討反應機構。 電子效應有效地反應在催化活性上，並得到OMe >CH3 > H > Cl近線性的Hammett plot。表示推電子的基團可以有效增強甲苯胺陰離子的親核能力並加快整體聚合的反應速率。 利用不同的技術可以達到鑑定的效果外，本論文結合了末端基分析法，利用光譜分析以及聚合結果的趨勢來進行反應機構的推論。 | zh_TW |
| dc.description.abstract | A numbers of organoaluminum complexes bearing nitrogen-donating bidentate ligands of amido-amine such as (C2H5)2NC(CH3)2CCH3N(Ar) [Ar = p-methoxyphenyl, p-methylphenyl, Phenyl, p-fluorophenyl, p-chlorophenyl, 2,6-diisopropylphenyl] and anilido-pyridine ligands with formula of (C5H5N)C(CH3)2NH(Ar') [Ar' = Phenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl] are synthesized and characterized.
These mononuclear complexes are found in distorted tetrahedral geometry. The aluminum complexes are able to activate the ring-opening polymerization(ROP) of ε-caprolactone without using activators in toluene. The resulting polyester products show comparable activity and acceptable molecular weights distribution. (Mw/Mn<2). With assistance of benzyl alcohol, ROP could undergo with acceptable activity and controlable molecular weight distribution (Mw/Mn <2). Mechanistic studies for such ROP reactions particularly in terms of ligand effect are thus investigated. | en |
| dc.description.provenance | Made available in DSpace on 2021-06-15T05:24:43Z (GMT). No. of bitstreams: 1 ntu-99-R97223160-1.pdf: 3533823 bytes, checksum: e9c8132257a9d0894a51c9112c057350 (MD5) Previous issue date: 2010 | en |
| dc.description.tableofcontents | 1. Introductions 1
1-1 Biodegradable Polymer – Polyesters 1 1-2 Polycaprolactone (PCL) 2 1-3 General mechanisms for ROP of lactones 4 1-4 Catalyst Selection for ROP of ε-CL 6 1-5 The distinguishing features of Aluminum-based catalyst for ROP 7 1-6 The development of ROP of ε-CL using Al-based catalyst 7 1-7 The concept of ligand design 13 1-8 The purpose of this thesis 13 2. Synthesis and Characterization 15 2-1 Synthesis of Ligands 15 2-1-1 Synthesis of Bidentate amino-imine ligands 15 2-1-2 Synthesis of Bidentate imino-pyridine ligands 16 2-2 Characterization of Ligands 17 2-2-1 Characterization of Bidentate amino-imine ligands 17 2-3 Synthesis of Neutral Aluminum (III) Complex 19 2-3-1 Synthesis of amido-amine aluminum complexes 19 2-3-2 Synthesis of Amido-pyridine aluminum complexes 21 2-4 Characterization of Neutral Aluminum (III) Complex 22 2-4-1 Characterization of Amido-amine aluminum complexes 22 2-4-2 Amido- pyridine aluminum complexes 33 3. ROP of ε-Caprolactone 37 3-1 Development of alkylaluminum Catalyzed ROP 37 3-2 Typical Procedure for ROP of ε-CL 37 3-3 Characterization of PCL (polycaprolactone 38 3-3-1 NMR 38 3-3-2 GPC (Gel Permeation Chromatography) 39 3-3-3 Mass spectroscopy 40 3-4 Amido-amine dimethylaluminum catalyzed ROP ofε -CL 41 3-4-1 Concentration effect 41 3-4-2 Electronic effect in the polymerization 43 3-4-3 Hammett plot 47 3-4-4 Solvent effect 51 3-4-5 Monomer tolerance 53 3-5 Amido-pyridine dimethylaluminum catalyzed ROP ofε -CL 54 3-6 ROP of ε -CL along with benzyl alcohol 56 IX 3-6-1 Electronic effect 56 3-6-2 Stoichiometry 58 4. Mechanistic study 60 4-1 Mechanistic studies of alkylaluminum catalyzed ROP in present 60 4-2 Characterization of polymer 62 4-2-1 Mass Spectroscopy 63 4-2-2 NMR 68 4-3 From end group analysis to mechanism 74 4-4 Discussions for multi-modal in GPC 79 5. Conclusion 81 6. Experimental Section 84 6-1 Analysis Instruments 84 6-2 General Considerations 87 6-3 Synthesis and Characterization 87 6-4 Typical Procedure for ROP of ε-CL 101 6-5 Switch quenchers 102 Reference 103 Appendix 108 | |
| dc.language.iso | en | |
| dc.title | 有機鋁化物之胺陰離子-胺基雙牙配位基的電子效應及
其催化環己內酯開環聚合反應的研究 | zh_TW |
| dc.title | Ring-Opening Polymerization of ε-caprolactone Using
Organoaluminum-based Complexes Bearing Amido-amine Bidentate Ligand and A Study of Ligand Effect | en |
| dc.type | Thesis | |
| dc.date.schoolyear | 98-2 | |
| dc.description.degree | 碩士 | |
| dc.contributor.oralexamcommittee | 劉緒宗(Shiuh-Tzung Liu),張啟光(Chi-Kwong Chang) | |
| dc.subject.keyword | 鋁,電子效應,環己內酯,開環聚合, | zh_TW |
| dc.subject.keyword | Aluminum,electronic effect,caprolactone,polyester,ring-opening polymerization,ROP, | en |
| dc.relation.page | 111 | |
| dc.rights.note | 有償授權 | |
| dc.date.accepted | 2010-07-19 | |
| dc.contributor.author-college | 理學院 | zh_TW |
| dc.contributor.author-dept | 化學研究所 | zh_TW |
| 顯示於系所單位： | 化學系 | |
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