對含苯并雙噻唑為主要結構之側鏈發色團的非線性光學(NLO)聚醯亞胺已有一系列的探討，但其光電係數(r33)皆不如預期，所以本篇主要是基於實驗室學長所合成之VIII (光電係數r33 = 6.62 pm/V)為基礎，對含苯并雙噻唑為主要結構之側鏈發色團進行設計以期得到較佳之r33。如以往實驗室一樣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PI，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下合環成型。本篇重點主要在側鍵發色團上導入ethoxy group合成NLO-V-1以改善側鏈柔韌性使側鏈在電壓極化下能更容易配向排列，此方法所得之r33 = 7.4 pm/V， 確實比NLO-V-0來的高。另外導入phenyldiazene group合成NLO-V-2 以增加其共軛長度,從UV吸收上確實發現其λmax = 484 nm比VIII (λmax = 390 nm)增加94 nm，但其r33 = 5.8 pm/V卻只比NLO-V-0略為改善。

Based on a series of study to improve the electrooptic coefficient (r33) of nonlinear optical polyimides (NLO-PI) containing benzobisthiazole- based chromophores in our lab, this work concentrated on the modification of the benzobisthiazole-based chromophore VIII (r33 = 6.62 pm/V). At first, a hydroxyl-containing polyimide was first synthesized by using dianhydride and diamine as reactants via thermal imidization and the benzobisthiazole-based chromophores were synthesized by using DABDT as the starting monomer. The NLO precursors were obtained by the Mitsunobu reaction via ether linkage between PI and chromophore; it was then cured at 300℃ to result in the final NLO-PI. The benzobisthiazole-based chromophore of VIII was modified with an insertion of the ethoxy group between the NLO moiety and the main PI backbone to get the NLO-V-1. This method makes the chromophore easier to orient under the electric field during poling; thus a higher r33 (7.4 pm/V) is ensured. NLO-V-2 is another modified sample which had a phenyldiazene group inserted into the chromophore of VIII to increase the conjugated length; this results in a red shifts from 390 nm (VIII) to 484 nm in UV-abs spectrum but the r33 (5.8 pm/V) has only a slight improvement.

目錄
目錄………..……………………………………………….....i
表目錄……………………………………………………………….....iv
圖目錄……………………………………………………………….....v
圖解論目錄……………………………………………………………viii
壹、 緒論……………………………………………………………...1
1-1 前言……………………………………………………….....1
1-2 研究動機…………………………………………………….2
1-3 研究架構…………………………………………………….2
1-3-1 ethoxy group的導入……………………………………..2
1-3-2 phenyldiazene group的導入……………………………..4
貳、 文獻回顧............................................8
2-1 非線性光學簡介....................................8
2-2 非線性光學現象之原理..............................8
波克效應(Pockels effects)............................10
2-3 有機非線性光學材料................................11
2-3-1 有機非線性高分子.............................11
2-3-2 側鏈型高分子.................................16
叁、實驗內容.........................................................................................17
3-1 實驗流程.........................................17
3-2 實驗藥品與儀器...................................18
3-2-1 實驗藥品....................................18
3-2-2 實驗儀器....................................20
3-3 溶劑與二酸酐之純化................................23
3-4 實驗步驟..........................................23
3-4-1聚羥基醯亞胺之合成...........................23
3-4-2 發色團合成...................................25
3-4-2-1 DABDT之合成..........................25
3-4-2-2 monomer 1, 2, 3之合成........................................27
3-4-2-3 發色團之合成......................................................29
3-4-3 非線性光學聚醯亞胺之合成....................33
肆、結果與討論...................................................................................35
4-1 發色團之結構鑑定..................................................................35
4-1-1 發色團單體之結構鑑定.................................................35
4-1-2 monomer 1, 2之結構鑑定.................... ..........................39
4-1-3 發色團之結構鑑定.........................................................42
4-2聚羥基醯亞胺(Polyhydroxy-imide)之結構鑑定......................51
4-3非線性光學聚醯亞胺之結構鑑定............................................53
4-3-1 PI-V-1, 2之結構鑑定.......................................................53
4-3-2 NLO-V-1, 2之結構鑑定..................................................58
4-4接枝率量測.................................................................................61
4-5黏度量測….................................................................................64
4-6熱性質量測.................................................................................65
4-7紫外光-可見光(UV-Vis)吸收光譜之分析.................................68
4-7-1 PI和PI-V-1以及NLO-V-1之UV吸收分析.................68
4-7-2 PI和PI-V-2以及NLO-V-2之UV吸收分析.................70
4-8折射率( Refractive Index) n之量測…………………………...72
4-9電光係數(electrooptic coefficient)r33的量測………..…….......74
4-10 NLO-V-0, 1, 2與VIII[2]的性質比較…………………….….76
伍、結論與未來工作.......................................79
5-1 結論………………………………………………………........79
5-2 未來工作..……………………………………………....…....80
參考文獻................................................81附錄……………………......................................83
波克效應之量測………….…..………...............................................83
Ellipsometric method之原理………………………….............84


表目錄

Table 1.1共軛長度對μβ值的影響 6
Table 1.2 笨環數量對μβ值的影響 7
Table 2.1 LiNbO3,GaAs與有機高分子材料的性質比較 12
Table 2.2 NLO發色團(chromophores)之非線性光學特性之比較…....15
Table 4.1 DABDT上IR的特徵吸收峰 38
Table 4.2 IV之IR特徵吸收峰 45
Table 4.3 V-1之FT-IR特徵吸收峰 47
Table 4.4 V-2之FT-IR特徵吸收峰 50
Table 4.5聚羥基醯亞胺IR光譜的特徵吸收峰 51
Table 4.6 PI、PI-V-0, 1, 2之黏度 64
Table 4.7 VIII [2]和NLO-V-1, 2的結構和Td1, Tg之比較 67
Table 4.8 NLO-V-0, 1, 2之接技率與r33 75
Table 4.9 NLO-V-0, 1, 2之結構與性質比較 78


圖目錄
Fig 1.1 PI-1 [1]和VIII [2]以及NLO-V-1之結構示意圖 3
Fig 1.2 VIII [2]以及NLO-V-2之結構示意圖 5
Fig 2.1發色團結構 12
Fig 2.2 Benzobisthiazole 的合成………….…………….......................14
Fig 2.3藉由電場誘導所產生的非對稱中心結構 14
Fig 2.4側鏈型非線性光學高分子 16
Fig 3.1實驗流程圖 17
Fig 3.2旋轉塗佈機之示意圖 21
Fig 4.1 BTU之NMR結構鑑定 36
Fig 4.2 DABDT之NMR結構鑑定 37
Fig 4.3 DABDT之FT-IR之結構鑑定 38
Fig 4.4 Monomer 1之NMR結構鑑定 39
Fig 4.5 Monomer 2之NMR結構鑑定 41
Fig 4.6 Monomer 2及酸處理後之FT-IR比較 41
Fig 4.7Monomer 2之UV圖譜 42
Fig 4.8 III之NMR結構鑑定 43
Fig 4.9 Ⅳ之NMR圖 44
Fig 4.10 IV之FT-IR之結構鑑定 45
Fig 4.11Ⅴ-1之NMR結構鑑定 47
Fig 4.12Ⅴ-1之FT-IR之結構鑑定 47
Fig 4.13Ⅴ-2之NMR結構鑑定 49
Fig 4.14Ⅴ-2之FT-IR之結構鑑定 50
Fig 4.15 PI之FT-IR之結構鑑定 52
Fig 4.16 PI之NMR結構鑑定 54
Fig 4.17 PI-V-1之NMR結構鑑定 54
Fig 4.18 PI、V-1、PI-V-1之NMR對照圖 55
Fig 4.19 PI-V-1之FT-IR之結構鑑定 56
Fig 4.20 PI-V-2之NMR結構鑑定 57
Fig 4.21 PI-V-2之FT-IR之結構鑑定 57
Fig 4.22 NLO-V-1之FT-IR之結構鑑定 58
Fig 4.23 NLO-V-2之FT-IR之結構鑑定 59
Fig 4.24 PI-V-0 (VII [2] )和PI-V-1, 2之結構示意圖 60
Fig 4.25 NLO-V-0 (VIII [2] )和NLO-V-1, 2之結構示意圖 60
Fig 4.26 PI、V [2]、PI-V-0之NMR對照圖 62
Fig 4.27 PI-V-0, 1, 2之接技率計算 63
Fig 4.28 PI和NLO-V-1, 2之熱失重分析圖 66
Fig 4.29 PI和NLO-V-1, V-2之TMA壓縮測試圖 67
Fig 4.30 PI和PI-V-1之UV吸收光譜圖 68
Fig 4.31 PI-V-1和NLO-V-1之UV吸收光譜圖……………………...69
Fig 4.32 4.29 PI和PI-V-2之UV吸收光譜圖 70
Fig 4.33 PI-V-2和NLO-V-2之UV吸收光譜圖 71
Fig 4.34 NLO-V-1之折射率與波長對應圖 73
Fig 4.35 NLO-V-1之折射率與波長對應圖 73
Fig 4.36 r33在300V下對極化溫度的關係圖 75
Fig 4.37 r33 (t)/ r33 (0)在120oC下對時間的關係圖 76






















圖解目錄

Scheme 3.1 poly(hydroxyl-imide)之合成…………………….…….24
Scheme 3.2 DABDT的合成 26
Scheme 3.3 monomer 1, 2之合成 29
Scheme 3.4發色團之合成 31
Scheme 3.5 NLO-V-1的合成 34

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