臺灣博碩士論文加值系統

　　本研究經由有機胺dodecylamine(DOA)及4-phenoxyaniline(POA)和鈉-蒙脫土(Na+-montmorillonite)進行離子交換反應，製成膨潤化的有機黏土(oganoclay) 。再利用2,2-bis(3-amino-4-hydroxyphenol)hexafluoropropane(BisAPAF)、4,4-oxydiphthalic anhydride(ODPA) 與isophthaloyl dichloride(IC)三種單體進行低溫聚縮合反應，合成固有黏度為0.21dL/g 的可溶性聚苯噁唑- 聚亞醯胺共聚物『poly(benzoxazole-imide) copolymer』的前趨物(precursor)－聚羥醯胺-聚醯胺酸『poly(hydroxyamide-amic acid)』。再將不同比例有機黏土和PHA-PAA precursor 混合，經過高溫加熱環化反應後，製成一種新型的PBO-PI copolymer/clay nanocomposites。由熱機械(TMA)分析得知，PBO-PI copolymer 的玻璃轉移溫度(Tg)為331℃。X-ray 繞射分析與TEM 分析顯示，DOA-clay 添加至7wt%與POA-clay 添加至3wt%時，呈奈米脫層型分散，當POA-clay 添加量超過3wt%時，黏土開始出現聚集或者插層分散。熱機械(TMA)分析指出，PBO-PI copolymer的熱膨脹係數隨著黏土的增加而降低，添加7wt%可以降低33~35%。由熱重量(TGA)分析可以看出添加有機黏土，可以略為增加PBO-PIcopolymer 的熱裂解溫度。由機械性質分析可以看出，有機黏土可以增加PBO-PI copolymer 的彈性模數，添加7wt%可以增加68~95%，但其伸長率則隨著黏土增加而降低。由吸水性實驗可以看出添加黏土可以降低PBO-PI copolymer 的吸水率，添加7wt%可以降低16~23%。從可見度分析可看出，隨著黏土的添加會降低PBO-PI copolymer 的可見度，但由熱安定性較好的POA-clay 所製成的薄膜，具有較佳的透光率。

　　Poly(benzoxazole-imide) (PBO-PI) copolymer/clay nanocomposites have been prepared from a PBO-PI precursor－poly(hydroxyamide-amic acid) (PHA-PAA) and two different organoclays. The PBO-PI precursor was made by a polycondensation reaction between 2,2-bis(3-amino-4-hydroxyphenol) hexafluoropropane (BisAPAF), 4,4-oxydiphthalic anhydride (ODPA) and isophthaloyl dichloride (IC). The organoclays were formed by a cation exchange reaction between a Na+-montmorillonite clay and an ammonium salt of dodecylamine (DOA) or 4-phenoxyaniline (POA). The glass transition temperature (Tg) of PBO-PI copolymer is 331℃. Both X-ray diffraction (XRD) and transmission electron microscope (TEM) analyses showed that the
organoclays were dispersed in PBO-PI copolymer matrix in a nanoscale. The in-plane coefficient of thermal expansion (CTE) of PBO-PI copolymer/clay film was decreased with the increasing amount of organoclay. The CTE of PBO-PI copolymer/clay film which contained 7 wt % DOA-clay was decreased 35% compared to the pure PBO-PI film and the CTE of PBO-PI copolymer/clay film which contained 7 wt % POA-clay was decreased 33%. The thermal decomposition temperatures of PBO-PI copolymer/clay films increased with the increasing amount of organoclay. The tensile modulus of PBO-PI copolymer/clay films increased with the increasing amount of organoclay. The tensile modulus of PBO-PI copolymer/clay film which contained 7 wt % DOA-clay was increased 95% compared to the pure PBO-PI copolymer film and the tensile modulus of PBO-PI copolymer/clay film which contained 7 wt % POA-clay was increased 68%. The water absorption of PBO-PI copolymer/clay film was decreased with the increasing amount of organoclay. From UV-Vis spectra, the PBO-PI copolymer/POA-clay film showed a better transparency than the PBO-PI copolymer/DOA-clay film. That could be due to the fact that POA has a higher thermal stability than DOA.

摘要.............................................Ⅰ
Abstract ........................................Ⅲ
誌謝.............................................Ⅴ
目錄.............................................Ⅹ
圖目錄...........................................XI

第一章 緒論.......................................1
1-1 前言..........................................1
1-2 研究動機與目的................................3
1-3 研究架構......................................5
第二章 文獻回顧...................................6
2-1 引言..........................................6
2-2 黏土之介紹....................................9
2-3 聚苯噁唑之介紹...............................13
2-4 聚亞醯胺之介紹...............................16
2-5聚苯噁唑-聚亞醯胺共聚物之介紹.................19
2-6 黏土/高分子奈米複合材料之介紹................21
2-6-1 黏土/高分子奈米複合材料之製備方法..........21
2-6-2 黏土/高分子奈米複合材料之型態..............23
2-6-3 奈米高分子複合材料之特性...................25
2-6-4 奈米高分子複合材料之應用...................25
2-7 奈米材料未來發展趨勢.........................28
第三章 實驗方法與步驟............................33
3-1 實驗材料.....................................33
3-2 實驗儀器.....................................34
3-3 實驗步驟.....................................35
3-3-1 黏土之改質.................................35
3-3-2 聚羥醯胺-聚醯胺酸前趨物之合成..............36
3-3-3 聚苯噁唑-聚亞醯胺共聚物/黏土奈米複合材料薄
膜之製備.........................................37
3-4 性質測試與分析...............................38
3-4-1 固有黏度測定...............................38
3-4-2 傅立葉紅外線光譜儀分析(FT-IR)..............39
3-4-3 核磁共振光譜儀分析(1H-NMR) ................39
3-4-4 元素分析(EA) ..............................40
3-4-5 聚苯噁唑-聚亞醯胺/黏土奈米複合材料之型態分析.................................................40
3-4-5-1 X-ray繞射分析(XRD) ......................40
3-4-5-2 穿透式電子顯微鏡觀察(TEM) ...............40
3-4-6 熱性質分析.................................41
3-4-6-1 熱重損失分析(TGA)........................41
3-4-6-2 熱機械分析(TMA)..........................41
3-4-7 薄膜機械性質分析...........................41
3-4-8 吸水性實驗.................................42
3-4-9 可見度測試.................................42
第四章 結果與討論................................47
4-1 聚苯噁唑-聚亞醯胺共聚物之分析................47
4-1-1 共聚物之合成...............................47
4-1-2 固有黏度測定...............................48
4-1-3 玻璃轉移溫度之測定.........................48
4-1-4 傅立葉紅外線光譜分析.......................49
4-1-5 核磁共振光譜分析...........................50
4-1-6 元素分析...................................50
4-2 有機黏土之分析...............................51
4-2-1 有機黏土之製備.............................51
4-2-2 傅立葉紅外線光譜分析.......................52
4-2-3 熱重損失分析...............................53
4-2-4 X-ray繞射分析..............................53
4-3 聚苯噁唑-聚亞醯胺共聚物/黏土奈米複合材料之分
析...............................................55
4-3-1 奈米複合材料之製備.........................55
4-3-2 X-ray繞射分析..............................56
4-3-3 穿透式電子顯微鏡分析.......................57
4-3-4 熱膨脹係數分析.............................58
4-3-5 熱重損失分析...............................59
4-3-6 機械性質分析...............................60
4-3-7 吸水性分析.................................62
4-3-8 可見度分析.................................62
第五章 結論......................................96
參考文獻.........................................99
自述............................................104

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