臺灣博碩士論文加值系統

本研究中使用金屬茂觸媒系統(Dichloro[rac-ethylenebis(indenyl)]-Zirconium(IV))進行同位性聚 1-丁烯(Isotactic poly(1-Butene)，iP1B)之合成，透過加入鏈轉移劑(三乙基鋁)以末端官能化同位性聚 1-丁烯(形成鋁官能基末端)，並經由氧氣及雙氧水的氧化反應得到末端具有氫氧基的同位性聚 1-丁烯(hydroxyl-capped iP1B，iP1B-OH)，接著以tosylation反應將高分子末端之氫氧基轉換成活性更佳之甲苯磺氧基，最後利用偶合反應將以活性陰離子反應合成之poly(2-vinylpyridine)(P2VP)與iP1B-OTs結合，以成功合成iP1B-b-P2VP雙嵌段共聚物。
藉由凝膠滲透層析儀(GPC)、核磁共振儀(NMR)、小角度 X 光散射儀(Small Angle X-ray Scattering)及穿透式電子顯微鏡(TEM)的分析，我們可以確定此嵌段高分子自組裝所形成之奈米微結構並觀察其微觀相分離行為。而透過對前驅iP1B及P2VP高分子鏈段之分子量控制，亦發現此iP1B-b-P2VP嵌段高分子藉由其親疏水性與立體規則性相輔相成的影響，而有非常強之微觀相分離，進而具有小尺度的微結構，此一結果可以提供全新概念在製備出2奈米世代的奈米結構於高解析微影蝕刻的應用。
此外，本研究另一部分則收錄透過活性陽離子聚合方式合成含極性官能基之同位性立體規則性高分子，藉由起始系統CF3SO3H/ nBu4NCl/ ZnCl2在特定比例下所形成之counterion，限制N-vinylcarbazole單體往高分子鏈末端碳陽離子進攻之方向，以合成出isotactic poly(N-vinylcarbazole)(簡稱iPVK)。而透過不同的反應條件，我們也探討不同起始系統比例及溶劑對立體規則度之控制。藉由凝膠滲透層析儀(GPC)及核磁共振儀(NMR)之分析，我們可以證實此一同位性立體規則性之iPVK高分子能被成功的合成。最後我們亦透過加入極性之THF溶劑至CF3SO3H/nBu4NCl/ZnCl2起始系統，探討co-solvent之溶劑效應對iPVK高分子聚合起始系統及其立體規則度控制之影響。

In this research, we report that an aluminum-capped isotactic poly(1-butene) was generated as the exclusive chain transfer reaction product by using Dichloro[rac-ethylenebis(indenyl)]-zirconium(IV) to mediate the isospecific polymerization of 1-butene in the presence of triethylaluminum as the chain transfer agent. The resulting aluminum-capped iP1B can be treated with oxygen and hydrogen peroxide to provide the hydroxy-capped iP1B (iP1B-OH) as the end-functionalized prepolymer. Consequently, the resulting iP1B-OH can be converted into the tosyl-capped iP1B (iP1B-OTs) by treated it with p-toluenesulfonyl chloride. The resulting tosyl-capped iP1B(iP1B-OTs) can be used to undergo coupling reaction with the living anionic P2VP so as to give the iP1B-block-P2VP diblock with precise microstructural and block length controls. This synthetic method is able to provide various iP1B-block-P2VP diblock copolymer samples, which have various volume fraction and stereoregularity controls. Accordingly, these block copolymer samples are able to self-assemble into various nanomorphologies as evidenced by Small Angle X-ray Scattering and Transmission Electron Microscopy studies. The resulting self-assembled nanostructures have an extremely narrow length of boundary and have the potential for use as nanotemplates.
This research also focuses on the synthesis of isotactic poly(N-vinylcarbazole)(iPVK) through living cationic polymerization. In the presence of the initiating system consisting of CF3SO3H, nBu4NCl and ZnCl2, iPVK can be successfully prepared with good tacticity and molecular weight controls. We also demonstrated that the tacticity of iPVK can be precisely controlled by adding THF into the polymerization system.

謝辭 I
中文摘要 II
Abstract IV
目錄 VI
圖目錄 IX
表目錄 XIV
第一章、緒論 1
1.1前言 1
1.2 基本原理簡介 3
1.2-1 金屬觸媒茂介紹 3
1.2-2助觸媒(MAO)簡介 5
1.2-3助觸媒MAO在metallocene觸媒中提升活性機制 7
1.2-4 Metallocene觸媒的聚合反應機制 8
1.2-5 Metallocene觸媒的優點 12
1.3 聚1-丁烯高分子之介紹 14
1.3-1聚1-丁烯背景簡介 14
1.3-2聚 1-丁烯背景基本性質 15
1.3-3 聚1-丁烯製備方法及應用 17
1.4 陰離子聚合反應介紹 19
1.4-1起始劑種類及鏈起始反應 20
1.4-2 鏈成長反應 25
1.5 活性聚合反應介紹 26
1.6 嵌段共聚物(Block Copolymers)之介紹 27
1.6-1 合成嵌段共聚高分子的介紹 28
1.6-2 高分子自組裝(Macromolecular Self-Assembly) 33
1.7 高分子定向自組裝材料(Directed Self-Assembly Materials) 34
1.8 研究動機與實驗目的 36
第二章、實驗部分 39
2.1實驗藥品 39
2.2實驗設備與分析儀器 45
2.3 溶劑及單體純化步驟 52
2.4 實驗步驟 53
第三章、結果與討論 59
3.1 iP1B-b-P2VP嵌段共聚物之合成與分析 59
3.1-1 以Metallocene/MAO 觸媒系統合成 iP1B-OH高分子 59
3.1-2 iP1B-OH之1H NMR 分析與末端官能基鑑定 61
3.1-3 iP1B-OH之13C NMR 分析 64
3.1-4 iP1B-OH之 1H 對 13C-HMQC 分析 66
3.1-5 合成末端含甲苯磺氧基之iP1B前驅物(iP1B-OTs) 68
3.1-6 iP1B-b-P2VP嵌段共聚物之合成 70
3.1-7 iP1B-b-P2VP嵌段共聚物之分離與純化 72
3.1-8 iP1B-b-P2VP嵌段共聚物之1H NMR分析 74
3.1-9 iP1B-b-P2VP 雙嵌段高分子之應用與型態學 (morphology)分析 76
第四章、結論 94
第五章、參考文獻 96
第六章、附錄 101
6.1同位性立體規則性高分子isotactic poly(N-vinylcarbazole)之合成與分析 101
6.1-1 Poly(N-vinylcarbazole)高分子之介紹 101
6.1-2 研究動機與實驗目的 103
6.1-3 實驗方法 104
6.1-4 結果與討論 108
6.1-5 附錄總結 120

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