由對位二苯胺(p-phenylenediamine)出發，經由兩個步驟製備出雜環型二胺-2,6-diaminobenzo〔1,2-d:4,5-d、〕bisthiazole (DABBT)。以DABBT為基礎，進一步合成出均聚醯亞胺和共聚醯亞胺，後者包含無規則和段式兩種。我們利用黏度、TGA、FTIR、x-ray和溶解度來鑑定分析聚醯亞胺的化性與物性。在單體方面，DABBT經由FTIR、NMR和EA的鑑定分析，證明DABBT被成功的合成出來。在聚醯胺酸方面，A系列使用的二酸酐單體為PMDA (pyromellitic dianhydride)，二胺單體為DABBT和ODA (4,4、-diaminodiphenyl ether)，其固有黏度值的範圍介於0.11∼1.04 dL/g之間，B系列使用的二酸酐單體為SDPA (4,4、-sulfonyldiphthalic dianhydride)，二胺單體為DABBT和SDPA，黏度值介於0.11∼0.31 dL/g之間。從吸收峰1780 cm-1、1720 cm-1和1380 cm-1的生成且由1650 cm-1 (amideⅠ) 和1550 cm-1 (amideⅡ)兩個吸收峰的消失，證明聚醯胺酸已經完全醯亞化成為聚醯亞胺。除了B-10 (ODA:DABBT=0:1)以外，所有PI在重量損失10%的裂解溫度在500℃以上，殘留灰燼率在50%以上。除了A-10和B-10有部分結晶外，全部的PI膜都是非結晶的。B系列高分子主鏈含有-SO2的柔曲鍵結，故其溶解性較A系列好。

Homopolyimides derived from a novel heterocyclic diamine, 2,6-diaminobenzo- [1,2-d:4,5-d]bisthiazole (DABBT), and either pyromellitic dianhydride (PMDA, A-series) or 4,4’-sulfonyldiphthalic dianhydride (SDPA, B-series), as well as copolyimides containing different molar ratios of DABBT and 4,4’-diaminodiphenyl ether (ODA), have been synthesized via soluble polyamic acids (PAA) followed by the thermal imidization. Polymer properties such as viscosity, thermal stability, crystallinity, and solubility were characterized and correlated to their monomer structure.
It is found that inherent viscosity of PAA increases with increasing molar ratio of ODA/DABBT; inherent viscosity of A-series ranges from 0.11 - 1.04 dL/g and the B-series from 0.11 - 0.31 dL/g. All the copolyimides can form flexible films; A transition from tough to brittle film is found as more DABBT is added. Results from thermal gravimetric analysis indicate that the degradation temperature at 10% weight loss locates from 561– 635 ℃ and char yield at 800 ℃ from 56 – 61% for A series; corresponding data of B-series are 489 – 560 ℃ and 47 – 52%, due primarily to the softer and more flexible solfone unit in SDPA. Also, the degradation temperature remains little changed with varying diamine ratios. X-ray diffractometry suggest all the copolyimides are amorphous and the PMDA/DABBT and SDPA/DABBT homopolyimides are semi-crystalline. The solubility tests indicate that solubility of B-series is better than that of A-series due to the flexible sulfone linkage; the solubility of block copolymers is better than that of random copolymers; in addition, the copolyimides with higher DABBT content have a better solubility.

目錄

致謝 Ⅰ
中文摘要 Ⅱ
英文摘要 Ⅳ
目錄 Ⅵ
表目錄 Ⅸ
圖目錄 Ⅹ
第一章 前言
1-1 背景說明 1
1-2 研究方向與研究動機 2
1-3 論文架構 3
第二章 文獻回顧
2-1 聚醯亞胺之性質與應用 5
2-2 聚醯亞胺之合成 6
2-3 增加聚醯亞胺加工性的方法 11
2-4 DABBT之PI相關文獻 14
第三章 實驗
3-1 藥品部分 16
3-2 儀器部分 18
3-3二酸酐之純化 19
3-4 單體合成 19
3-4-1 PBTU的合成反應 20
3-4-2 DABBT的合成反應 20
3-5 聚醯亞胺之合成 21
3-5-1 聚醯胺酸之合成 21
3-5-2 聚醯亞胺膜之製備 23
3-5-3無規則共聚醯胺酸之合成 23
3-5-4無規則共聚醯亞胺膜之製備 25
3-5-5段式共聚醯胺酸之製備 25
3-5-6段式共聚醯亞胺膜之製備 25
3-6 結構與物性分析 27
3-6-1 本性黏度測定 27
3-6-2 FTIR分析 27
3-6-3 熱重分析 30
3-6-4 溶解度測試 30
3-6-5 X光繞射分析 30

第四章 實驗結果與討論
4-1 單體之製備與分析 31
4-1-1 PBTU之合成與分析 31
4-1-2 DABBT之合成與分析 36
4-1-3 二酸酐純度鑑定 38
4-2 聚醯胺酸之合成與分析 47
4-2-1 黏度分析 44
4-2-2 FTIR分析 49
4-3 聚醯亞胺之合成與分析 49
4-3-1 PI膜分析分析 49
4-3-2 FTIR分析 53
4-3-3 TGA分析 53
4-3-4 X-ray分析 54
4-3-5溶解度分析 62
第五章 結論 67
第六章 未來工作與建議 69
參考文獻 71

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