臺灣博碩士論文加值系統

在本實驗中我們利用活性陰離子聚合製備兩種均聚物高分子，分別是poly(methyl methacrylate) (PMMA) 及在側鏈含有多面體矽氧烷寡聚物 (POSS)的PMMA衍生物 (PMAPOSS)。我們使用了微差掃描熱卡儀 (DSC)、傅立葉紅外線光譜儀 (FTIR) 及廣角度X光繞射儀 (WAXD) 來量測PMMA與PMSPOSS分別與三種氫鍵予體分子: Poly(vinyl phenol) (PVPh), phenolic resin, bisphenol A (BPA) 之間的相容性及特殊的作用行為。經由DSC的量測可以發現PVPh/PMMA、phenolic/PMMA及BPA/PMMA 的混摻展現出了相容性系統的特性，這是由於PMMA上的C=O官能基與三種氫鍵予體分子上的OH官能基產生氫鍵作用力所導致(FTIR鑑定結果)，而相反的所有PMAPOSS的混摻系統都由於高強度屏蔽效應的緣故而產生不相容的行為。由實驗結果可知道POSS會對氫鍵予體產生屏蔽效果，且PMMA對於氫鍵予體分子也有良好的相容性，因此我們更進一步的用活性陰離子聚合法合成出PMMA-b-PMAPOSS的嵌段共聚物，此嵌段共聚物會形成長程有序的微相分離結構，接著我們將其與phenolic做混摻，藉由phenolic與PMMA形成氫鍵作用且改變PMMA基底的體積分率而達到結構的轉變，在PMAPOSS的部分由於POSS產生的屏蔽效應與無機物的聚集性，使得phenolic無法與PMAPOSS上的C=O官能基產生作用，不會進入到PMAPOSS的基底中，我們利用穿透式電子顯微鏡 (TEM)及小角度X光散射 (SAXS)來觀察結構轉變的詳細過程。

In this study we used living anionic polymerization to prepare two different homopolymers: a poly(methyl methacrylate) (PMMA) and a PMMA derivative presenting polyhedral oligomeric silsesquioxane (PMAPOSS) units as its side chains. We then employed differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy, and wide-angle X-ray diffraction (WAXD) to investigate the miscibility and specific interactions of PMMA and PMAPOSS with three hydrogen bonding donor compounds: poly(vinyl phenol) (PVPh), phenolic resin, and bisphenol A (BPA). DSC revealed that all of the PVPh/PMMA, phenolic/PMMA, and BPA/PMMA blends exhibited characteristic of miscible systems from hydrogen bonding interactions between the C=O groups of PMMA and the OH groups of these three hydrogen bonding donor compounds (FTIR). In contrast, all of the PMAPOSS blend systems were immiscible arising from strong screening effects. Depending on the strong screening effect, the diblock copolymers, namely PMMA-b-PMAPOSS were synthesized by living anionic polymerization exhibit microphase-separated structures. The structures were transformed by blending phenolic resin to change the volume fraction of PMMA domain, as evidenced consistently by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS).

主目錄
摘要 i
Abstract ii
主目錄 iii
表目錄 vi
圖目錄 vii
第一章 緒論 1
1-1 前言 1
1-2 研究動機 4
1-3 文獻回顧 5
1-3-1 活性陰離子聚合(Living Anionic Polymerization) 5
1-3-2多面體矽氧烷寡聚物(Polyhedral Oligomeric Silsesquioxanes , POSS) 7
1-3-3 氫鍵混摻系統原理 8
1-3-4 摻合原理 9
1-3-5 嵌段共聚物 10
第二章 實驗內容 11
2-1 實驗內容及流程 11
2-2 實驗藥品 12
2-3 實驗步驟 13
2-3-1.1 合成 Poly(methylmethacrylate) (PMMA) 13
2-3-1.2 合成Poly(methacrylIsobutyl POSS) (PMAPOSS) 13
2-3-1.3 合成Poly(methylmethacrylate)-block-Poly(methacrylIsobutylPOSS) (PMMA-b-PMAPOSS) 14
2-3-2.1 混摻PMMA/Bisphenol-A, Poly(4-vinyl phenol) (PVPh), Phenolic 16
2-3-2.2 混摻PMAPOSS/Bisphenol-A, Poly(4-vinyl phenol) (PVPh), Phenolic 16
2-3-2.3 混摻PMMA-b-PMAPOSS/ Phenolic 16
2-4 儀器介紹 17
2-4-1 傅立葉紅外線光譜儀(Fourier Transform Infrared Spectrometer, FT-IR 型號：Bruker Tensor-27 17
2-4-2 核磁共振分析儀(Nuclear Magnetic Resonance, NMR)型號：Varian® Unity Inova-500 17
2-4-3 微差掃瞄熱卡儀(Differential Scanning Calorimeter, DSC) 型號：TA Q-20 18
2-4-4 凝膠滲透層析儀(Gel Permeation Chromatography , GPC) 型號: Jasco PU-980 19
2-4-5 廣角X光繞射儀 (Wide Angle X-Ray Diffraction, WAXD) 型號: NSRRC BL17A 19
2-4-6 多角度雷射光散射儀 (Multi Angle Laser Light Scattering) 型號: Wyatt miniDAWN 20
2-4-7 小角度Ｘ光散射儀(Small Angle X-ray Scattering, SAXS) 型號：Bruker AXS VANTEC-2000 22
2-4-8穿透式電子顯微鏡(Transmission Electron Microscope, TEM) 型號：JEOL-2100 22
第三章 結果與討論 23
3-1 PMAPOSS 在氫鍵混摻系統之分析 23
3-1-1 PMAPOSS及PMMA 合成鑑定 23
3-1-2 PMAPOSS 及 PMMA 混摻之熱分析 29
3-1-3 PMAPOSS 及 PMMA 混摻之紅外線光譜分析 35
3-1-4 PMAPOSS 混摻之廣角度X光散射分析 48
3-2 PMMA-b-PMAPOSS 在Phenolic氫鍵混摻系統之分析 51
3-2-1 PMMA-b-PMAPOSS 合成鑑定 51
3-2-2 Phenolic/PMMA-b-PMAPOSS 混摻之熱分析 55
3-2-3 Phenolic/PMMA-b-PMAPOSS之紅外線光譜分析 58
3-2-4 Phenolic/PMMA-b-PMAPOSS之小角度X光散射分析 66
3-2-5 Phenolic/PMMA-b-PMAPOSS之穿透式電子顯微鏡分析 70
3-2-6 Phenolic/PMMA-b-PMAPOSS之廣角度X光散射分析 73
第四章 結論 75
第五章 參考文獻 76

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