在此篇研究中，苯并雙噻唑的剛硬性與共軛性被運用並擴展到二次非線性光學的應用。新型含苯并雙噻唑為主要結構之側鏈發色團的非線性光學(NLO)聚醯亞胺已被合成出來。首先，利用雙胺酚塩與雙酐作為起始單體以熱環化法合成出含有羥基的可溶型聚醯亞胺。然後NLO發光基團由DABDT作為起始單體合成出含苯并雙噻唑為主要結構之側鏈發色團的預聚物，再藉由Mitsunobu 反應形成醚基鍵結接到聚醯亞胺主鏈上，最後含苯并雙噻唑NLO發光基團於300 oC及真空條件下成型。在聚醯亞胺主鏈與發色團間導入醚基預期將可改善側鏈柔韌性使側鏈在電壓極化下能更容易配向排列。而由FTIR與UV-vis光譜分析，已確認苯并雙噻唑結構的形成。由TGA與TMA的分析結果顯示這些NLO聚醯亞胺具有優越的熱性質，在主鏈熱裂解時溫度高達576 oC及玻璃轉化溫度為324 oC。最後，以雷射波長為630nm 所量側出此一新型非線性光學聚醯亞胺的電光係數(r33) = 6.62 pm/V。

In this study, we extend the rigidity and resonance of benzobisthiazo-
le for the application as second-order nonlinear optics. A novel nonlinear optical polyimide (NLO-PI) containing side-chained benzobisthiazole-
based chromophore has been synthesized. A hydroxyl- containing PI (PHI) was first prepared using direct thermal imidization of 2,4-diaminophenol dihydrochloride and 4,4’-(hexafluoroisopropylidene)diphthalic anhydride; the benzobisthiazole-based chromophore was then prepared using 2,5-diamino- 1,4-benzenedithiol dihydrochloride as the starting monomer. The final NLO-PI was obtained by the Mitsunobu reaction via ether linkage between PHI and the chromophore. This ether linkage is expected to provide chain flexibility for better orientation under electric field during poling. Formation of benzobisthiazole-based chromophore and the corresponding NLO-PI was evidenced by FTIR and UV-vis spectra. TGA and TMA reveal a thermal decomposition temperature and a glass transition temperature as high as 576 and 324oC, respectively. The electrooptic coefficient of the NLO-PI at a wavelength of 630nm was found to be r33 = 6.62 pm/V.

目錄
目錄…………………………………………….. i
表目錄………………………………………….. iv
圖目錄………………………………………….. vi
圖解目錄……………………………………….. ix
壹、緒論.............................................................. 1
1-1前言 1
1-2 研究動機 2
1-2-1發色團分子的選擇 2
1-2-2主鏈高分子的選擇 8
貳、文獻回顧………………………………….. 9
2-1非線性光學簡介 9
2-2 非線性光學材料之介紹 10
2-2-1 無機非線性光學材料 10
2-2-2 有機非線性光學材料 11
2-2-3 有機非線性高分子 14
2-3 非線性光學現象之原理 18
2-4 波克效應(Pockels effects) 19
2-5 波克效應之量測 20
2-6 Ellipsometric method之原理 21
叁、實驗內容………………………………….. 24
3-1 實驗流程 24
3-2 實驗藥品與儀器 25
3-2-1實驗藥品 25
3-2-2實驗儀器 26
3-3 溶劑與二酸酐之純化 30
3-4實驗步驟 31
3-4-1聚羥基醯亞胺之合成(Ⅱ)(scheme 3.1) 31
3-4-2-1 2,5-Diamino-1,4-benzenedithiol dihydrochloride(DABDT)之合成(Scheme 3.2) 33
3-4-2-2 發色團之合成 (Scheme 3.3) 36
3-4-3 非線性光學聚醯亞胺之合成(Scheme 3.5) 40
肆、結果與討論……………………………….. 42
4-1聚羥基醯亞胺(Polyhydroxy-imide)之結構鑑定 42
4-2 發色團單體之結構鑑定 45
4-3 非線性光學聚醯亞胺之結構鑑定 65
4-4 黏度測量 68
4-5 紫外光-可見光(UV-Vis)吸收光譜之分析 69
4-6熱性質量測 78
4-7 折射率之量測 84
4-8 膜厚之觀測 86
4-9 電光係數(electrooptic coefficient)r33的量測 87
4-10 比較 90
伍、結論與未來工作…………………………… 97
5-1、結論 97
5-2、未來工作 98
參考文獻……………………………………….. 100
附錄…………………………………………….. 102
A-1 Ellipsometric method之原理 102
A-2 折射率與波長關係之計算 107

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