臺灣博碩士論文加值系統

在本研究裡，我們利用數種Metallocene觸媒(包含(t-butylamido) (tetramethyl-cyclopentadienyl)-dimethylsilane titanium dichloride、(diphenylmethylene) (9-fluorenyl) cyclopentadienyl zirconium dichloride和我們實驗室自行研發的新觸媒系統)來共聚合乙烯和非共軛雙烯(包括5-ethylidene-2-norbornene和 dicyclopentadiene)。利用新觸媒系統行共聚合反應時，顯現出了較高的活性和高分子中的雙烯單體含量。經由實驗證明，當5-ethylidene-2-norbornene 的含量高達62.8mole %時，高分子的玻璃轉移溫度可達209.98℃，而當dicyclopentadiene的含量高達73.9mole %時，高分子的玻璃轉移溫度為273.22℃。5-ethylidene-2-norbornene和 dicyclopentadiene為非共軛的雙烯類單體，其工業上的主要用途為合成EPDM橡膠之共聚單體，由於5-ethylidene-2-norbornene和dicyclopentadiene和乙烯共聚後可留下較不反應之雙鍵作為官能化之用途，因此若能有效的共聚此類單體將可借由其特殊之環化結構生成具備官能基之高玻璃轉移溫度材料，並應用於深紫外光阻做為基本素材。由本研究之相關實驗證實使用新觸媒系統可以有效共聚高含量之雙烯單體，由於富含雙烯單體之高玻璃轉移溫度材料是先前技術未曾被報導的，因此相關材料已著手申請專利中。

This study relates to the copolymerization of 5-ethylidene-2- norbornene or dicyclopentadiene with ethylene by Metallocene catalysts (Including: (t-butylamido) (tetramethyl-cyclopentadienyl)-dimethylsilane titanium dichloride, (diphenylmethylene) (9-fluorenyl) cyclopentadienyl zirconium dichloride and a new catalyst developed by our laboratory). The results of our studies indicate that the new catalyst system has higher activities and provides higher diolefins contents in the copolymer corresponding to the commercial available catalysts. Our experiments indicate that the glass transition temperature of poly(ethylene- co-5-ethylidene-2-norbornene) is at 209.98℃ as the incorporation of 5-ethylidene-2-norbornene in the copolymer is 62.8 mole% ; whereas the glass transition temperature of poly(ethylene-co- dicyclopentadiene) is up to 273.22℃ when the incorporation of dicyclopentadiene is 73.9 mole%. After polymerization, the resulting polymer will contain double bonds in the side chain. Thereby, these double bonds can be functionalized to provide the potential high glass transition temperature and functional group containing transparent polymers. Because the diolefins (5-ethylidene-2-norbornene and dicyclopentadiene) enriched copolymers has never been reported by prior technology, the preparation of these novel polymers is currently filed for a patent application by Eteral Chemical Corporation.

第一章 緒論.........................................1
1.1 Norbornen於環狀烯烴共聚物的應用....................1
1.2 Norbornen的雙烯衍生物於官能化傳統烯烴聚合物的應
用.................................................6
1.3 Norbornen的雙烯衍生物於EPDM橡膠中的應用...........10
1.4 Norbornen的雙烯衍生物於光阻材料上的應用...........13
1.5 Metallocene觸媒聚合反應原理.......................19
1.6 研究目的..........................................24
第二章 結果與討論..................................25
2.1 乙烯與5-ethylidene-2-norbornene的共聚合反應
探討..............................................25
2.2 聚合反應於trans和cis-5-ethylidene-2-norbornene
的立體選擇性......................................43
2.3 乙烯與5-ethylidene-2-norbornene的共聚合高
分子的官能化......................................48
2.4 利用乙烯與5-ethylidene-2-norbornene的共聚合
高分子製造深紫外光光阻材料........................61
2.5 乙烯與dicyclopentadiene的共聚合反應...............63
2.6 乙烯與dicyclopentadiene的共聚合高分子的官
能化..............................................86
2.7 加入氫氣對高分子分子量影嚮的探討..................94
2.8 聚合反應於exo-和endo-dicyclopentadiene的立
體選擇性..........................................98
第三章 實驗部份..................................106
3.1 實驗設備與分析儀器...............................106
3.2 實驗藥品.........................................108
3.3 實驗步驟及方法...................................110
3.3.1 乙烯與5-ethylidene-2-norbornene的共聚合
反應.............................................110
3.3.2 乙烯與5-ethylidene-2-norbornene共聚物之
氫硼化-氧化反應..................................110
3.3.3 光阻材料的製作...................................111
3.3.4 乙烯與dicyclopentadiene的共聚合反應..............112
3.3.5 臭氧裂解反應.....................................112
3.3.6 Exo-dicyclopetadiene的製作.......................113
第四章 結論......................................117
參考文獻...............................................119
名詞縮寫對照表.........................................121
附圖...................................................122

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