臺灣博碩士論文加值系統

本研究一開始先合成不同間距基長度的主鏈用液晶單體4,4’-bis(n-hydroxyalkanoxy)azobenzene (n = 6,11) 及側鏈用液晶單體2,2-Bis(hydroxymethyl)propionic-(4-methoxy-azobenzene)alkane (n = 4,6,8,10)，再個別與飽和的二異氰酸酯H12MDI (4,4’-Methylenebis (cyclohexylisocyanate)) 與H6XDI (1.3-Bis(isocyanatomethyl)cyclo hexane) 合成出兩個系列含軟鏈段與不含軟鏈段聚胺基甲酸酯。第一系列的高分子則是將H6XDI與液晶單體以1：1的比例聚合而成。H12MDI 與 PTMO1000以莫耳數2：1的比例形成預聚合物，再導入液晶單體作為鏈延長劑，形成第二系列的液晶PU彈性體。所合成之主，側鏈液晶單體與高分子以FT-IR，NMR鑑定其結構，以DSC，偏光顯微鏡 (POM) 及WAXD分析其熱轉移性質與液晶相態，並以TGA測試高分子之熱烈解溫度。

結果發現，H6XDI系列之液晶聚胺基甲酸酯皆有液晶現象。主鏈型的液晶聚胺基甲酸酯皆為nematic liquid crystalline。側鏈型液晶聚胺基甲酸酯則呈現amorphous的高分子型態。合併型者則大部分傾向於形成nematic liquid crystalline。

至於含柔軟鏈段之H12MDI系列液晶高分子雖然彈性及成膜性很好，卻沒有呈現出液晶現象。有可能是因為H12MDI結構之複雜性導致結晶或液晶不易形成。此外，硬鏈段及軟鏈段之相混合較嚴重也是因素之一。在機械性質方面，合併型的液晶PU彈性體由於主、側鏈都受到液晶分子的增強作用(reinforcement)而呈現較為強韌的性質。

There are two series of azobenzene-based mesogenic diols were prepared, including 4,4’-bis(n-hydroxyalkanoxy)azobenzene/HAZBn (n = 6,11) and 2,2-Bis(hydroxymethyl)propionic-(4-methoxy-azobenzene) alkane/MAPn (n = 4,6,8,10). The first series of nonsegmented main chain, side chain and combined type liquid crystalline polyurethanes were then obtained from the isomolar polyaddition reaction of the above mesogenic diols and 1.3-Bis(isocyanatomethyl)cyclohexane (H6XDI). The preparation of the second series of polymer, the side chain and combined type liquid crystalline polyurethanes elastomers, used the two stage polymerization of H12MDI, PTMO 1000 and both of the mesogenic diols described above. The Fourier transform infrared spectroscopy, nucleus magnetic resonance spectrometer, differential scanning calorimetry, polarizing optical microscope, and wide angle X-ray diffractometer were used for characterizing these polyurethanes.

All the H6XDI based liquid crystalline polyurethanes exhibited enantiotropic nematic liquid crystalline behavior as major., except that the side chain LCPUs acted as amorphous polymers instead of showing liquid crystalline behavior.

As for the H12MDI based liquid crystalline polyurethanes elastomers, they showed good mechanical and elastic properties, especially the combined type, as refer to the biaxial reinforcement effect of the mesogenic group. However, no liquid crystalline behavior was observed under the POM investigation.

總目錄

中文摘要 I
英文摘要 II
誌謝 III
總目錄 IV
表目錄 VI
圖目錄 VII

第一章 緒論 1
1-1 液晶概述 1
1-2 液晶的分子排列 1
1-3 液晶的觀察方法與紋理 4
1-4 熱向型液晶高分子 5
1-4-1 主鏈液晶高分子 5
1-4-2 側鏈液晶高分子 6
1-4-3 合併型液晶高分子 6

第二章 文獻回顧 8
2-1 合併型液晶高分子 8
2-2 液晶聚胺基甲酸酯彈性體 12
2-3 研究方向 15

第三章 實驗部分 16
3-1 實驗藥品 16
3-2 實驗儀器: 17
3-3 實驗步驟 18
3-3-1 液晶單體HAZBn之合成 18
3-3-2 液晶單體MAPn之合成 18
3-3-3 H6XDI系列高分子之合成 20
3-3-4 H12MDI系列高分子之合成 21

第四章 結果與討論 27
4-1 液晶單體HAZBn之合成與性質探討 27
4-2 液晶單體MAPn之合成與性質探討 30
4-3 H6XDI系列液晶聚胺基甲酸酯之合成與鑑定 38
4-3-1 高分子結構之鑑定 39
4-3-2 高分子的熱轉移性質與晶相之探討 40
4-3-3 高分子之熱安定性 43
4-3-4 高分子之分子量 44
4-4 H12MDI系列液晶聚胺基甲酸酯彈性體之合成與鑑定 44
4-4-1 高分子結構之鑑定 45
4-4-2 高分子的熱轉移性質與晶相之探討 45
4-4-3 高分子之熱安定性 47
4-4-4 高分子之分子量拉力性質之探討 47

第五章 結論 50

參考文獻 114

自述 116

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