臺灣博碩士論文加值系統

在本研究中，以原子轉移自由基活性聚合法（atom transfer radical polymerization, ATRP）合成兩性雙團聯式共聚和物poly(methyl methacrylate)-block-poly(2-hydroxyethyl methacrylate)，將此共聚和物與poly(ethylene oxide)利用THF為溶劑將其摻合，並且與PMMA/PEO摻合物之對照組比較其分析結果與差異。由於PMMA鏈段為疏水性而PHEMA鏈段為親水性，造成其相容性減低，因此可能引發的相分離行為在本研究中將進行討論。在許多研究中發現PMMA/PEO摻合系統之PMMA鏈段與PEO具有極佳的相容性，然而PHEMA與PEO之相容性在文獻中則較少被探討。因此本研究除了討論共聚和物與PEO分子間的作用力外，並分析共聚和物中PHEMA鏈段對摻合物特性之影響。除了討論PHEMA與PEO的相容性之外，PEO鏈段與共聚和物之間的作用力所造成PEO分子鏈之構型轉化也是本研究的另一個重點。PEO的結晶性由於無定形相存在的影響而受到抑制，並且在研究中發現copolymer/PEO中結晶相的結晶度Xc較PMMA/PEO摻合系統為低。研究中以掃瞄式熱差分析儀、偏光顯微鏡以及紅外光譜儀來觀察摻合物之相容性質，並且利用紅外光光譜證明了PMMA分子上的C=O與PHEMA上的-OH之間並無氫鍵存在。此外，存在於PHEMA與PEO之間的氫鍵可能提升copolymer/PEO摻合系統的相容性。

Poly(methyl methacrylate)-block-poly(2-hydroxyethyl methacrylate) (PMMA-b-PHEMA) diblock copolymer was synthesized through atom transfer radical polymerization（ATRP）. The diblock copolymer was then blended with poly(ethylene oxide)（PEO）by using THF as the solvent. The macroinitiator PMMA was also blended in the same way to compare the differences between the two systems. Since the PMMA block is hydrophobic and the PHEMA block is hydrophilic, the miscibility might decrease and the microphase separation behavior was discussed. The PMMA/PEO blend is known to a miscible system, but the compatibility between PHEMA chain and PEO chain was less discussed in literatures. Beside the discussion of the compatibility between PHEMA and PEO, the conformational transformation of the PEO chain caused by the interaction in this copolymer/PEO system was another point that we focused on. The crystallization of PEO is impeded by the amorphous phase, and in the copolymer/PEO system the crystallinity Xc is lower than that in PMMA/PEO. Differential scanning calorimetry, optical and atomic force microscopy, and infrared spectroscopy were performed to characterize and demonstrate miscibility in the copolymer/PEO system. The Fourier- transform infrared spectroscopy results revealed that no hydrogen bond formed between the C=O group of PMMA and -OH group of PHEMA. The hydrogen bond between PHEMA and PEO might exist and promoted the miscibility of the copolymer/PEO system.

中文摘要 I
英文摘要 II
誌謝 III
總目錄 IV
表目錄 VII
圖目錄 VIII
第一章 緒論 1
第二章 原理 4
2-1 雙團聯式共聚和物簡介 4
2-1.1 雙團聯式共聚和物 5
2-1.2 雙團聯共聚合物之製備-原子轉移自由基活性聚合法（ATRP） 6
2-1.3 ATRP法的優勢 9
2-2 PMMA-block-PHEMA與PEO摻合物之相容性及摻合物表面型態分析 10
2-2.1 PMMA-block-PHEMA的分析方法 10
2-2.2 摻合物的分析方法 11
第三章 實驗部分與儀器分析 16
3-1 實驗藥品與儀器設備 16
3-1.1 實驗藥品 16
3-1.2 實驗器材 17
3-1.3 分析儀器 18
3-2 實驗製備方法與步驟 19
3-2.1 實驗藥品之純化 19
3-2.2 雙團聯式共聚合物之合成與純化 22
3-2.3 PMMA-b-PHEMA與PEO摻合物的樣品製備 26
3-2.4 原子力顯微鏡之操作條件 27
第四章 結果與討論 28
4-1 PMMA與PMMA-block-PHEMA之分析 28
4-2 PMMA-b-PHEMA與PEO摻合物分析 31
4-2.1以偏光顯微鏡（POM）觀察共聚合物相容性及其摻合 物結晶形態 31
4-2.2 摻合物升溫處理後的結晶形態 36
4-2.3 copolymer/PEO摻合物與PMMA/PEO摻合物結晶形態之比較 37
4-3 摻合物的FTIR光譜分析 43
4-3.1 FTIR光譜鑑定 43
4-3.2 以FTIR光譜分析摻合物中PEO之構型轉化 51
4-3.3 作用力光譜（interaction spectrum）分析 59
4-4 摻合物之熱分析 60
4-4.1 摻合物熱分析結果討論 63
4-4.2 摻合物結晶性之分析 65
4-4.3 由玻璃轉化溫度分析摻合物相容性 69
4-5 摻合物之表面型態: AFM影像分析 72
4-5.1 摻合物之表面形態 73
4-5.2 改變摻合物比例對表面形態的影響 85
第五章 結論 91
參考文獻 94
自述 97

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