臺灣博碩士論文加值系統

由Akira1之研究中，我們知道1,3丁二烯在CpTiCl3/MAO觸媒系統於低溫下聚合時具有living現象。值得注意的是，亦可使用CpTiCl3/MAO之機制來進行聚合對位性聚苯乙烯。由於兩種單體之觸媒中心相似，因此我們希望能運用CpTiCl3/MAO觸媒系統於-30℃低溫下，先聚合出末端帶有活性點的聚1,3丁二烯，再加入4-甲基苯乙烯或苯乙烯兩種單體，以成它X成出聚1,3丁二烯-對位性聚4-甲基苯乙烯以及聚1,3丁二烯-對位性聚苯乙烯之雙嵌段共聚物。由於上述的合成方法為living polymerization之方式能改善傳統配位聚合對位性聚苯乙烯非活性聚合而分子量分佈較寬之問題。此外，我們更能有效的控制其分子量與分子量成長的速率。
而所生成的PB-b-sPMS與PB-b-sPS聚合物則可經由臭氧氧化雙鍵的化學反應，將聚1,3丁二烯鏈段上的雙鍵全部氧化，而形成末端帶官能基(醛基)的sPMS或sPS聚合物。而此官能基則可被運用於進行藉陰離子偶合反應以合成含對位性聚4-甲基苯乙烯及對位性聚苯乙烯之雙嵌段共聚物。

This work reports our results on the preparation of sPS-based block copolymers by metallocene catalyst mediated block polymerization of butadiene and styrene. The first polybutadiene block was synthesized by using CpTiCl3/MAO catalyst to mediate the living polymerization of butadiene.Subsequently, para-methylstyrene or styrene monomers can be added for constructing the second block(sPS or sPMS). In this study, novel diblock copolymers including PB-b-sPMS and PB-b-sPS have been successfully prepared using the unprecedented living metallocene catalyst system.Our results indicate sPS or sPMS polymerization can be living at low temperature. Consequently, novel diblock copolymers including PB-b-sPMS and PB-b-sPS have been successfully prepared by this novel synthetic route.
We also demonstrate that the resulting PB-b-sPMS and PB-b-sPS can be used to undergo ozonization reaction,and this leads to generation of the result in aldehyde end-capped sPMS and sPS .Consequently,undergo coupling reaction in the presence of living anionic polymer(P2VP or aPS) to provide the novel sPMS-b-P2VP and sPS-b-aPS.
The resulting block copolymers have been characterized by GPC, 1H and 13C NMR to reveal that the styrene block still maintains a syndiotactic architecture.

中文摘要.........................................................................................................................i
Abstract..........................................................................................................................ii
目錄...............................................................................................................................iii
圖目錄...........................................................................................................................vi
表目錄.........................................................................................................................viii
第一章 緒論 1
1-1 前言 1
1-2 文獻回顧 4
1-2-1 聚1,3丁二烯簡介 4
1-2-2 聚苯乙烯簡介 9
1-3 原理介紹 15
1-3-1 有機金屬茂 (Metallocene)觸媒系統簡介 15
1-3-2 陰離子聚合反應簡介 25
1-3-2-1 起始劑的種類與起始反應 28
1-3-2-2 鏈成長反應 30
1-3-2-3 無終止反應(活性聚合)與其特色 30
1-3-3 嵌段共聚高分子簡介 31
1-4 研究大綱 33
第二章 實驗部分 34
2-1 實驗藥品 34
2-2 單體與溶劑之純化 38
2-3 實驗設備與分析儀器 41
2-4 分析儀器原理 43
2-4-1 調幅式微差掃描熱分析儀 43
2-4-2 凝膠滲透層析儀 48
2-4-3 熱重分析儀 51
2-4-2 核磁共振儀 51
2-5 藥品配製之方法 52
2-5-1 有機金屬茂觸媒配製 52
2-5-2 甲基氧化鋁（MAO）的配製 52
2-6 實驗步驟 53
2-6-1 在低溫下以Living polymerization合成含對位性聚4-甲基苯乙烯
烯及聚苯乙烯(以CpTiCl3 / MAO為觸媒) 53
2-6-2 合成末端帶醛基(aldehyde)對位性聚4-甲基苯乙烯及聚苯乙烯高
分子之官能化反應 56
2-6-3 利用陰離子反應合成出聚 2-乙烯基吡啶(poly2-vinylpridine)及聚
苯乙烯(atactic-polystyrene) 58
2-6-4 將末端醛基之對位性聚4-甲基苯乙烯及聚苯乙烯高分子與聚2-
乙烯基吡啶及聚苯乙烯高分子進行偶和反應 59
第三章 結果與討論 62
3-1 CpTiCl3/MAO反應機制之探討 62
3-1-1 聚1,3丁二烯-對位性聚4-甲基苯乙烯的雙嵌段共聚物之討論..66
3-1-2 聚1,3丁二烯-對位性聚苯乙烯的雙嵌段共聚物之分析 73
3-2 利用臭氧氧化(ozonizaiton)之官能化反應 79
3-2-1 對位性聚4-甲基苯乙烯(sPMS)官能化反應之分析 85
3-2-2 對位性聚苯乙烯(sPMS)官能化反應之分析 87
3-3 末端醛基之對位性聚4-甲基苯乙烯及聚苯乙烯高分子與陰離子聚合之
高分子合成出新型雙嵌段高分子之探討 92
3-3-1 對位性聚4-甲基苯乙烯-聚2-乙烯基吡啶(sPMS-b-P2VP)之分析93
3-3-2 對位性聚苯乙烯-聚苯乙烯(sPS-b-aPS)之分析 97
第四章 結論 102
參考文獻 104

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