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完整後設資料紀錄
DC 欄位 | 值 | 語言 |
---|---|---|
dc.contributor.advisor | 陸天堯(Tien-Yau Luh) | |
dc.contributor.author | Te-Chung Wei | en |
dc.contributor.author | 魏德忠 | zh_TW |
dc.date.accessioned | 2021-06-16T16:25:17Z | - |
dc.date.available | 2018-02-01 | |
dc.date.copyright | 2013-02-01 | |
dc.date.issued | 2013 | |
dc.date.submitted | 2013-01-22 | |
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dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/63152 | - |
dc.description.abstract | 本篇論文主要探討單體分子中含有不同可聚合基團化合物的先後聚合,我們以降冰片烯分子連接含有間亞苯二酯基團的分子作為單體,以Grubbs-1催化劑進行開環歧化聚合反應 (ROMP) 得到單股高分子聚合物,以此單股降冰片烯高分子為複製反應的模板,另一端的間亞苯二酯官能基以克萊森酯縮合反應 (Claisen condensation) 進行縮合聚合反應,可以得到不對稱結構的雙股高分子,之後在鹼性條件下水解,得到子鏈高分子寡聚-間亞苯丙酮(Oligo(m-phenylene)acetonylene)。更重要的是,經由GPC的測試結果得知,水解下來的子鏈高分子的分子量可以經由模板來準確的控制,且有良好的分子量分布 (PDI)。此外,我們還研究無模板系統的間苯二乙酯衍生物的縮合聚合反應,其GPC測試結果與模板聚合產物相比,直接縮合聚合後的產物分子量不可控制,且分子量分佈很廣,此控制實驗的結果充分顯示了模板聚合突出的優點:我們能夠經由模板聚合得到分子量分佈窄、且分子量可控制的寡聚-間亞苯丙酮。此寡聚物是一條嶄新的高分子鏈,可供做為石墨烯寡聚物的前驅物。
關鍵字:開環歧化聚合反應;模板聚合;先後聚合;降冰片烯;寡聚-間亞苯丙酮 | zh_TW |
dc.description.abstract | This thesis describes the sucessesful sequential polymerization of a monomer containing two different polymerizable groups, which can undergo polymerization under different conditions. N-arylpyrrolidine-fused norbornene connected with m-phenylene diacetate moiety is chosen as the starting monomer. This monomer contains norbornene group which can undergo ring-opening metathesis polymerization (ROMP) under various conditions to give well-defined single-stranded polynorbornene skeletons. This polynorbornene backbone can then serve as a template to control Claisen condensation reaction of m-phenylene diacetate moieties to afford the corresponding β-keto ester. This protocols is executed and unsymmetrical ladderphanes are obtained with different degree of polymerization. After hydrolysis under basic conditions, oligo(m-phenylene)acetonylenes with control molecular weight and narrow polydispersity index (PDI) are obtained. It is noteworthy that Claisen condensation of m-phenylene diacetate moiety without templation generated corresponding oligo(m-phenylene)acetonylene with uncontrolled molecular weight and polydispersity index (PDI).
Key words: ROMP; Templated polymerization; Sequential polymerization; Norbornene; Oligo(m-phenylene)acetonylene | en |
dc.description.provenance | Made available in DSpace on 2021-06-16T16:25:17Z (GMT). No. of bitstreams: 1 ntu-102-R99223122-1.pdf: 11861694 bytes, checksum: 589302abf0645dc24c116357aaa19800 (MD5) Previous issue date: 2013 | en |
dc.description.tableofcontents | 章節目錄
中文摘要………………….…………………………………………………….….......I 英文摘要……………………………………………………………………………...II 章節目錄……………………………………………………………………………..III 圖目錄…………………………………………………………………………….......V 表目錄………………………………………………………………………………VII 縮寫對照表………………………………………………………………………...VIII 第一章 緒論………………………………………………………………..…………1 1.1 前言…………………………………………………………………..………...1 1.2 降冰片烯高分子的立體化學結構…………………………………….....……3 1.2.1 雙股螺旋與雙股超螺旋…………………………………………..……3 1.2.2 降冰片烯高分子的排列方式…………………………………….....….4 1.2.3 降冰片烯高分子的立體規整度 (Tacticity)…................……….……..5 1.3複製反應-模板聚合………………………………………………………..…...9 1.3.1 經由非共價鍵結的模板聚合…………………………………..…...….9 1.3.2 經由共價鍵結的模板聚合………………………………………..…..14 1.4研究目的…………………………………………………………………........18 第二章 結果與討論……………………………………………………………..…..19 2.1 文獻回顧………………………………………………………………….…..19 2.2 設計、合成與光譜鑑定…………………………………………………...…..22 2.2.1 策略……………………………………………………………….…...22 2.2.2 逆合成分析…………………………………………………….……...22 2.2.3 懸掛基團56之合成 (linker) ……………………………………..…..23 2.3 克萊森酯縮合聚合反應 (Claisen condensation polymerization) 初探-……… . ..無模板系統-對比高分子74nt之合成與光譜鑑定…………………...…......29 2.4 單體化合物之合成與光譜鑑定…...........…………………….………….…..32 2.4.1 降冰片烯衍生物55之合成.....……………………….…………….....32 2.4.2 單體化合物54之合成 (Monomer).…………..…………….……...32 2.5 開環歧化聚合反應-降冰片烯高分子.…..……….………….………….…....34 2.5.1 單股高分子72a、72b與72c的合成與GPC鑑定....…………..…...34 2.5.2 單股高分子72a、72b與72c的1H核磁共振光譜鑑定.…….……...36 2.5.3 單股高分子72a、72b與72c的13C核磁共振光譜鑑定…….……..38 2.6 不對稱雙股高分子- Claisen condensation polymerization …..……….…….40 2.6.1 雙股高分子73初步探討……………………………………………..40 2.6.2 反應條件測試………………………………………………………....42 2.6.3 雙股高分子73a、73b與73c的合成與GPC鑑定…………………..43 2.6.4 雙股高分子73a、73b與73c的1H核磁共振光譜鑑定…………….....46 2.6.5 雙股高分子73a、73b與73c的13C核磁共振光譜鑑定…………..…..49 2.7 子鏈高分子探討……………………………………………………………...52 2.7.1 子鏈高分子74a、74b與74c的合成與GPC鑑定………………….....52 2.7.2 子鏈高分子74a、74b與74c的1H核磁共振光譜鑑定…………….....54 2.7.3 子鏈高分子74a、74b與74c的13C核磁共振光譜鑑定…………..…..55 2.8 後續發展………………………………………………………………….…..57 第三章 結論………………………………………………………………………....58 第四章 實驗部分………………………………………………………………..…..59 4.1 實驗之一般敘述……………………………………………………………...59 4.2 實驗步驟……………………………………………………………………...61 第五章 參考文獻………………..…………………………………………………..80 附錄…………………………………………………………………………………..85 部分化合物之1H NMR光譜、13C NMR光譜與GPC結果 | |
dc.language.iso | zh-TW | |
dc.title | 寡聚-間亞苯丙酮:以降冰片烯為基礎之先後聚合反應 | zh_TW |
dc.title | Oligo(m-phenylene)acetonylene:
Sequential ROMP and Claisen Condensation of Norbornene Derivatives | en |
dc.type | Thesis | |
dc.date.schoolyear | 101-1 | |
dc.description.degree | 碩士 | |
dc.contributor.oralexamcommittee | 梁文傑(Man-kit Leung),詹益慈(Yi-Tsu Chan) | |
dc.subject.keyword | 開環歧化聚合反應,模板聚合,先後聚合,降冰片烯,寡聚-間亞苯丙酮, | zh_TW |
dc.subject.keyword | ROMP,templated polymerization,sequential polymerization,norbornene,Oligo(m-phenylene)acetonylene, | en |
dc.relation.page | 148 | |
dc.rights.note | 有償授權 | |
dc.date.accepted | 2013-01-22 | |
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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