臺灣博碩士論文加值系統

中文摘要
sPS材料是一種高熔點之結晶性材料，其具有高堅硬度、低吸濕度、高尺寸穩定度、良好的高化學組抗、及高耐熱溫度等優異性質，可是由於材料不具備任何極性官能基，因此限制了sPS材料的應用空間。為了改善相關問題，本研究中先利用metallocene 觸媒【Cp*Ti(OCH3)3 /MAO】聚合出對位聚4-甲基苯乙烯(syndiotactic poly-4-methylstyrene, sPMS)，再利用陰離子起始劑n-BuLi對sPMS聚合物進行金屬化反應（Metallation）, 以生成在4-甲基苯乙烯上之甲基位置帶有陰離子的反應活性點，而利用此反應活性點我們可以進行多種極性單體之接枝共聚反應，(e.g., poly hexamethylcyclotrisiloxane, poly-2-vinylpyridine, poly-4-vinylpyridine, and polyphenylisocyanate)並應用於合成多種新型對位聚4-甲基苯乙烯-接枝-極性鏈段之新型材料。由於相關材料嵌入了極性鏈段，因此其應用於sPS材料與含極性官能基高分子的摻混值得期待，據此我們選用sPS與nylon6之摻混並藉由使用本實驗合成之新共聚物sPS-g-poly-4-vinylpyridine為助溶劑來提升sPS與nylon6之相容性，以尋求改善sPS材料之缺點，並進一步提升sPS材料之可能商用空間。

Abstract:
Sydiotactic polystyrene, a stereoregular crystalline polymer with high melting temperature, has been the focus of research in recent years for its outstanding physical properties including high stiffness, low water intake, excellent dimensional stability, good chemical resistance and high heat resistance etc. Unlike most engineering plastics, the chemical structure of sPS contains neither heteroatoms nor polar functional groups. Clearly, the high mechanical strength in sPS is owing to its high crystallinity. The combination of high crystallinity and the lack of any polar functional group in sPS results in the low compatibility of sPS with other material, and hence limits its commercial applications. In order to circumvent this deficiency, sPS grafting copolymers with grafting arms synthesized from grafting polymerization of polar monomers were prepared. In our studies, the preparations of syndiotactic polystyrene or poly-4-methylstyrene were conducted in bulk polymerization by using Cp*Ti(OMe)3 as catalyst and MAO as cocatalyst. On the other hand, the grafting copolymerizations of polar monomers were conducted by using anionic polymerization methods. In this work, four new sPS grafting copolymers have been successfully prepared that include sPS-graft-polyphenylisocyanate, sPS-graft-poly- 4-vinylpyridine, sPS-graft-poly-2-vinylpyridine and sPS-graft-polysiloxane. The syntheses and characterizations of these new copolymers were reported in this study. Finally in order to exam the feasibility of these novel polymers, polymer blends between sPS and nylon 6 was studied by using the sPS-graft-poly-4-vinylpyridine as the compatilizer.

第一章 緒論 1
1-1前言 1
1-2文獻回顧1~27 3
1-2-1何謂sPS 3
1-3研究大綱 10
第二章 原理介紹 11
2-1 metallocene觸媒系統簡介:28~44 11
2-2 陰離子聚合反應簡介:45~47 17
2-2-1 起始劑種類與起始反應 18
2-2-2 鏈成長反應 19
2-2-3無終止反應與其特色 20
第三章 實驗部分 21
3-1實驗藥品 21
3-2單體與溶劑之純化 25
3-3實驗設備與分析儀器 28
3-4分析儀器原理 30
3-4-1調幅式微差掃描熱分析儀(見圖3.5) 30
3-4-1-1 工作原理 30
3-4-1-2 調幅式微差掃描熱分析儀與微差掃描熱分析儀的比較 31
3-4-2 凝膠滲透層析儀 (Gel Permeation Chromatography 36
3-4-3 顯微結構觀察(SEM) 39
3-4-4 X射線能量散佈分析儀(EDS) 41
3-4-5 核磁共振儀 43
3-4-6 傅立葉轉換紅外線光譜儀(FTIR) 43
3-5實驗步驟及高分子純化方法 44
3-5-1 有機茂金屬觸媒與助觸媒的配置 44
3-5-2 使用有機金屬茂觸媒對4-甲基苯乙烯進行配位聚合 45
3-5-3 4-甲基苯乙烯聚合物之純化部份 46
3-5-4 使用n-BuLi將4-甲基苯乙烯聚合物金屬化 47
3-5-5 使用n-BuLi將4-甲基苯乙烯聚合物金屬化後接枝 poly-2-vinylpyridine (sPMS-g-poly-2-vinylpyridine) 47
3-5-6 使用n-BuLi將4-甲基苯乙烯聚合物金屬化後接枝 poly-4-vinylpyridine (sPMS-g-poly-4-vinylpyridine) 48
3-5-7 使用n-BuLi將4-甲基苯乙烯聚合物金屬化後接枝聚異氰酸苯酯(sPMS-g-polyphenylisocyanate) 49
3-5-8使用n-BuLi將4-甲基苯乙烯聚合物金屬化後接枝 polysiloxane(sPMS-g-polysiloxane) 50
3-5-9 sPS與nylon6的摻混 51
3-5-10甲基苯乙烯聚合物及其共聚物之後處理裝置 52
第四章 結果與討論 53
4-1 利用metallocene catalyst聚合對位性4-甲基苯乙烯……….53
4-1-1對位性聚4-甲基苯乙烯（sPMS）之分子量分佈探討 54
4-1-2 對位性 4-甲基苯乙烯（sPMS）之DSC探討 56
4-1-3 使用n-BuLi將4-甲基苯乙烯聚合物金屬化與金屬化 後的接枝數之探討 58
4-1-4 對位性4-甲基苯乙烯聚合物之1H-NMR 61
4-1-5 對位性4-甲基苯乙烯聚合物之13C-NMR 62
4-2 使用n-BuLi將4-甲基苯乙烯聚合物金屬化後接枝 poly-2-vinylpyridine ( sPMS-g-P2VP) 64
4-2-1使用n-BuLi將4-甲基苯乙烯聚合物金屬化後接枝 poly-2-vinylpyridine (sPMS-g-P2VP)之分子量探討 65
4-2-2使用n-BuLi將4-甲基苯乙烯聚合物金屬化後接枝 poly-2-vinylpyridine (sPMS-g-P2VP)之DSC探討 67
4-2-3使用n-BuLi將4-甲基苯乙烯聚合物金屬化後接枝 poly-2-vinylpyridine (sPMS-g-P2VP)之1H-NMR 探討 68
4-2-4使用n-BuLi將4-甲基苯乙烯聚合物金屬化後接枝 poly-2-vinylpyridine (sPMS-g-P2VP)之13C-NMR…….70
4-3 使用n-BuLi將4-甲基苯乙烯聚合物金屬化後接枝poly-4-vinylpyridine (sPMS-g-P4VP)……….………….72
4-3-1 使用n-BuLi將4-甲基苯乙烯聚合物金屬化後接枝 poly-4-vinylpyridine (sPMS-g-P4VP)之分子量探討 73
4-3-2 使用n-BuLi將4-甲基苯乙烯聚合物金屬化後接枝 poly-4-vinylpyridine (sPMS-g-P4VP)之DSC探討 76
4-3-3 使用n-BuLi將4-甲基苯乙烯聚合物金屬化後接枝 poly-4-vinylpyridine(sPMS-g-P4VP)之1H-NMR 探討 77
4-3-4 使用n-BuLi將4-甲基苯乙烯聚合物金屬化後接枝 poly-4-vinylpyridine (sPMS-g-P4VP) 之13C-NMR 79
4-4 使用n-BuLi將4-甲基苯乙烯聚合物金屬化後接枝聚異氰苯酯 (sPMS-g-polyphenylisocyanate) 81
4-4-1 使用n-BuLi將4-甲基苯乙烯聚合物金屬化後接枝 polyphenylisocyanate(sPMS-g-polyphenylisocyanate) 之FT-IR圖譜探討 82
4-4-2 使用n-BuLi將4-甲基苯乙烯聚合物金屬化後接枝 polyphenylisocyanate(sPMS-g-polyphenylisocyanate)之DSC探討 83
4-5 使用n-BuLi將4-甲基苯乙烯聚合物金屬化後接枝polysiloxane (sPMS-g-polysiloxane) 85
4-5-1 使用n-BuLi將4-甲基苯乙烯聚合物金屬化後接枝 polysiloxane(sPMS-g-polysiloxane)之GPC, DSC, 及NMR 88
4-6對位性聚苯乙烯接枝poly-4-vinylpyridine之合成與應用…..92
4-6-1使用sPS —g-P4PY 為sPS與nylon6摻混助溶劑之DSC分析 96
4-6-2使用sPS —g-P4PY 為sPS與nylon6摻混助溶劑之SEM與EDS分析 99
第五章 結論 102
附 圖 103
縮 寫 對 照 表 120
參 考 文 獻……………………………………………………...... 121

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