臺灣博碩士論文加值系統

本研究乃利用不同之介相性基團(BP、HHB、HHBP)與各種二醇(N10、BPA、BPO、BPOO、MeHQ、PhHQ、isosorbide)單體，以三光氣(triphosgene)、啶(pyridine)，利用溶液聚合法合成出一系列的熱向型液晶聚碳酸酯。並利用DSC、TGA、含加熱裝置的偏光顯微鏡、x-ray繞射等測定其性質，並探討結構對液晶性質的影響。
本研究中發現，聚碳酸酯的液晶相呈現與否與所選擇的介相性基團有密切關係。BP系列之聚碳酸酯，當bisphenol中的鍵角小於120。或含有較長柔軟間隔基，則不利於呈現液晶相，而含有較小取代基(MeHQ)，則可呈現明顯的液晶行為。而HHB、HHBP系列中，由於其介相性基團中含有酯基結構，因此即使聚合物中含有非線性結構或較長之間隔基，所合成之聚碳酸酯皆具有穩定且呈現溫度範圍寬廣之液晶相，其液晶呈現溫度也較BP系列來的低。
本研究也嘗試利用isosorbide為旋光性二醇單體(chiral diol monomer)進行共聚碳酸酯反應，合成出新穎之膽固醇型液晶共聚碳酸酯。研究中發現，當導入isosorbide的含量高達50%時，所合成的液晶共聚碳酸酯在寬廣的溫度範圍內，不但不會破壞液晶相，反而利於膽固醇液晶相之呈現，可呈現均一顏色的Grandjean圖形，且顏色會隨溫度而變化，形成藍色、綠色或紅色的液晶相。此外，將其Grandjean 圖形迅速驟冷於室溫時，可使圖形固定住，不僅不會破壞其螺旋狀結構並且可以保存下來，而保留其光學特性。其在反射光下為均一的色彩，而在穿透光下則呈現黃色或橘色的現象。

Four series of thermotropic liquid crystalline polycarbonates were prepared by solution polycondensation of 4,4'-dihydroxybiphenyl(BP), 4'-hydroxyphenyl-4-hydroxybenzoate(HHB) or 4-hydroxyphenyl-4''-hydroxybiphenyl-4'-carboxylate(HHBP), as mesogenic unit, with 1,10-bis(p-hydroxyphenoxy)decane, bisphenol A, 4,4'-dihydroxydiphenyl ether, 4,4'-[phenylbis(oxy)]bisphenol, methylhydroquinone, phenylhydroquinone or isosorbide. All of the polycondensations were conducted in pyridine as the HCl absorbent and using triphosgene as the carbonation reagent. The thermotropic liquid crystalline properties of synthesized polycarbonates were investigated by DSC, TGA , thermo-optical polarized microscopy , and WAXD powder pattern.
In this study, the liquid crystalline properties of synthesized polycarbonates are strongly depended on the chosen mesogenic unit. The aspect ratio, rotary freedom and the polarity of mesogenic unit dominates LC properties. BP-series possesses worst LC stability, while HHBP-series shows widest mesophase range. HHBP-series exhibits stable LC phase even containing 50% of BPA. BPA is V-shape structure and usually destroys LC properties. In addition, homo-polycarbonate with HHBP structure possesses extraordinary low phase transition temeprature and wide LC phase range due to its asymmetric structure. This asymmetric structure causes H-T, H-H and T-T random conformation of polymer chain. Therefore, HHBP could be an excellent mesogenic unit for the LC polycarbonates.
A series of cholesteric polycarbonates were also prepared in this study by using isosorbide as the chiral monomer. The results revealed that all isosorbide-containing polycarbonates formed cholesteric phase and stable homogeneous blue, green, or red Grandjean texture upon shearing. The Grandjean texture could be frozen while quenching the sample to the room temperature rapidly. With the strong mesogenic characteristic of HHBP, polycarbonate containing 50% of isosorbide, which is non-linear structure, can also exhibit stable cholesteric phase over wide temperature range.

目錄
中文摘要…………………………………………………………………….Ⅰ
英文摘要……………………………………………………………..……...Ⅱ
目 錄……………………………………………………………………….Ⅳ
圖目錄……………………………………………………………………….Ⅵ
表目錄………………………………………………………………..……...Ⅷ
流程圖目錄………………………………………………………………….Ⅸ
第一章 緒論1
1.1液晶聚合物簡介1
1.1-1 液晶之發展1
1.1-2 液晶相之分類2
1.1-3 熱向型液晶高分子3
1.2聚碳酸酯6
1.3 熱向型聚碳酸酯7
1.4 文獻回顧8
1.5 研究動機15
第二章 實驗部份16
2.1 藥品及純化16
2.2 儀器設備及物性測試17
2.3 單體之合成20
2.4 聚合物之合成25
第三章 結果與討論28
3.1 單體之合成28
3.2 聚合物之合成34
3.3 聚碳酸酯之熱性質39
3.4 結論64
3.5 參考文獻66

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