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研究生:蘇盟雄
研究生(外文):Meng-Hsiung Su
論文名稱:含第三丁基可溶性聚醯胺-醯亞胺之合成及性質研究
論文名稱(外文):Synthesis and Characterization of Soluble Polyamide-imides with tert-butyl group
指導教授:蔡三元
指導教授(外文):Sun-Yuan Tsay
學位類別:碩士
校院名稱:國立成功大學
系所名稱:化學工程學系碩博士班
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2002
畢業學年度:90
語文別:中文
論文頁數:99
中文關鍵詞:直接聚縮合法聚醯胺-醯亞胺苯偏三酸酐
外文關鍵詞:trimellitic anhydridepolyamide-imidedirect polycondensation
相關次數:
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摘 要

本研究先由1,4-雙對胺基苯氧基-2-第三丁基(BATB)和苯偏三酸酐(TMA)合成出具醯亞胺環的二羧酸類,再與不同的芳香族二胺類,利用三苯基亞磷鹽(TPP),以直接聚縮合法,形成含第三丁基可溶性的聚醯胺-醯亞胺。其本性黏度為0.53(dl/g)∼0.86(dl/g),成膜性佳,薄膜呈現柔軟及具韌性。
另外,合成出不含醯胺基的聚醯亞胺和不含第三丁基的聚醯胺-醯亞胺,可作為相互比較物性差異的對照組。可經由FTIR、H1-NMR、Instron、DSC、DMA及XRD來鑑定及分析。
結果顯示含第三丁基聚醯胺-醯亞胺呈現無結晶現象,對於極性溶劑(如NMP、DMF、DMAc)的溶解性比聚醯亞胺及無第三丁基的聚醯胺-醯亞胺較佳,改善良多。由DMA所觀察出的玻璃轉移溫度為243∼266℃。5﹪重量損失溫度在氮氣下為473∼480℃。與預期所需要的高性能材料性質相符合,即能同時能兼具穩定的熱性質及良好的溶解性。
Abstract

An imide ring-containing dicarboxylic acid was prepared by the condensation of 1,4-Bis(4-aminophenoxy)-2-tert-butyl benzene
(BATB) and trimellitic anhydride(TMA) .A series of soluble poly(amide-imide)s containing tert-butyl units were synthesized via the triphenyl phosphite-activated direct polycondensation of this diimide-diacid with various aromatic diamines.Four of the obtained polymer had inherent viscosities of 0.53(dl/g)∼0.86(dl/g) and afforded flexible films.
These compounds are discussed and compared with those of polyimides which do not contain amide units and also with the poly(amide-imide) which do not contain tert-butyl units .All the polymers were then characterized by FTIR、H1-NMR、Instron、DSC、DMA and XRD .Most of resulting poly(amide-imide)s containing tert-butyl units showed an amorphous nature and were readily soluble in polar solvents such as NMP、DMF and DMAc .The glass transition temperature could be determined with the help of DMA clearly,which were recorded in the range 243∼266℃.Their 5﹪weight loss temperature were recorded in the range 473∼480℃ in nitrogen.
These polymer exhibited a desired combination of propertiesrequiring high-performance materials that include excellent thermal stability and excellent solubility in organic solvents.
目錄
中文摘要……………………………………………………………….….Ⅰ
英文摘要………………………………………………………...….…..Ⅱ
誌謝…………………………………………………………………………Ⅲ
目錄…………………………………………………..……….…….……Ⅳ
表目錄……………………………………………………………….…….Ⅵ
圖目錄………………………………………………………………………Ⅶ
主文
第一章 緒論………………………………………………….…………….1
1-1前言…………………………………………………………………….1
1-2聚醯亞胺的合成與發展…………………………….….……….……2
1-3聚醯亞胺的優點及應用…………………………………………….…5
1-4研究方向……………………………………………………………….8

第二章 理論………………………………………….…………………….9
2-1聚醯胺-醯亞胺的合成與發展……………………………………….9
2-2聚醯胺-醯亞胺的改質………………………………………………13
2-3研究內容及合成途徑…………………………………………………17

第三章 實驗……………………………………………………………….24
3-1藥品……………………………………………………………………24
3-2合成裝置及分析儀器…………………………………………………25
3-3溶劑與二酸酐之純化…………………………………………………27
3-4單體的合成……………………………………………………………28
3-5聚醯胺-醯亞胺之合成………………………….………………….29
3-6聚醯胺-醯亞胺薄膜的製備…………………………………………30
3-7聚醯亞胺的之合成……………………………………………………30
3-8聚醯亞胺薄膜的製備…………………………………………………31
3-9結構及物性分析………………………………………………………32

第四章 結果與討論………………………………………….……………35
4-1二酸酐的純化…………………………………………………………35
4-2單體的合成……………………………………………………………36
4-3聚醯胺-醯亞胺的合成及分析………………………………………39
4-4聚醯亞胺的合成及分析………………………………………………41
4-5聚合物黏度之分析…………………………………….…………….41
4-6機械性質分析…………………………………………………………43
4-7吸濕性測定……………………………………………………………44
4-8聚合物的溶解性測試…………………………………………………44
4-9熱性質分析……………………………………………………………45
4-10 X-ray廣角繞射分析……………………………………………….48

第五章 結論……………………………………………………………….91

參考文獻……………………………………………………………………92

自述…………………………………………………………………………99

表目錄
表2-1 各種鹽類對聚醯胺黏度的效應………………………………….12
表2-2 單體的化學結構及簡稱………………………………………….21
表2-3 各類聚合物之代號、成份及結構式…………………………….23
表4-1 各類聚合物的黏度……………………………………………….49
表4-2 各類聚合物的機械性質………………………………………….50
表4-3 各類聚合物的吸濕率…………………………………………….51
表4-4 各類聚合物的溶解度…………………………………………….52
表4-5 各類聚合物在氮氣下的熱裂解溫度…………………………….53
表4-6 各類聚合物在空氣下的熱裂解溫度…………………………….54
表4-7 各類聚合物的玻璃轉移溫度…………………………………….55

圖目錄
圖1-1 聚醯亞胺在半導體元件應用之剖面圖……………………………7
圖2-1 各種鹽類含量對聚醯胺黏度的效應…………………………….13
圖4-1 PMDA純化前之紅外線吸收光譜圖……………………………….56
圖4-2 PMDA純化後之紅外線吸收光譜圖……………………………….56
圖4-3 PMDA純化前與純化後之DSC曲線圖……………………………..57
圖4-4 BNTB之紅外線吸收光譜圖……………………………………….58
圖4-5 BATB之紅外線吸收光譜圖……………………………………….59
圖4-6 BTTBB之紅外線吸收光譜圖………………………………………60
圖4-7 (p)BNB之紅外線吸收光譜圖…………………………………….61
圖4-8 (p)BAB之紅外線吸收光譜圖…………………………………….61
圖4-9 (m)BNB之紅外線吸收光譜圖…………………………………….62
圖4-10 (m)BAB之紅外線吸收光譜圖……………………………………62
圖4-11 PAI-BATB之紅外線吸收光譜圖…………………………………63
圖4-12 PAI-ODA之紅外線吸收光譜圖………………………………….64
圖4-13 PAI-(p)BAB之紅外線吸收光譜圖………………………………64
圖4-14 PAI-(m)BAB之紅外線吸收光譜圖………………………………65
圖4-15 PAI-ref之紅外線吸收光譜圖………………………………….65
圖4-16 PAI-BATB之H1-NMR光譜圖…………………………………….66
圖4-17 PAI-ODA之H1-NMR光譜圖………………………………………67
圖4-18 PAI-(p)BAB之H1-NMR光譜圖……………………………….…68
圖4-19 PAI-(m)BAB之H1-NMR光譜圖……………………………….…69
圖4-20 Ref1-BATB之紅外線吸收光譜圖……………………………….70
圖4-21 Ref2-ODA之紅外線吸收光譜圖…………………………………70
圖4-22 Ref3-(p)BAB之紅外線吸收光譜圖…………….………………71
圖4-23 Ref4-(m)BAB之紅外線吸收光譜圖…………………………….71
圖4-24 PAI-BATB在不同溫度下,本性黏度對時間作圖…………….72
圖4-25 PAI-BATB之應力與應變關係圖…………………………………73
圖4-26 PAI-ODA之應力與應變關係圖………………………………….73
圖4-27 PAI-(p)BAB之應力與應變關係圖………………………………74
圖4-28 PAI-(m)BAB之應力與應變關係圖………………………………74
圖4-29 Ref1-BATB之應力與應變關係圖……………………………….75
圖4-30 Ref2-ODA之應力與應變關係圖…………………………………75
圖4-31 Ref3-(p)BAB之應力與應變關係圖………….….………………76
圖4-32 各種聚醯胺-醯亞胺在氮氣下之TGA曲線圖….………………77
圖4-33 各種聚醯胺-醯亞胺在空氣下之TGA曲線圖….………………78
圖4-34 各種聚醯亞胺在氮氣下之TGA曲線圖…………….……………79
圖4-35 各種聚醯亞胺在空氣下之TGA曲線圖…………….……………80
圖4-36 PAI-BATB在氮氣及空氣下之TGA曲線圖………….……………81
圖4-37 各種聚醯胺-醯亞胺之DSC曲線圖……………….……………82
圖4-38 各種聚醯亞胺之DSC曲線圖……………………….……………83
圖4-39 PAI-BATB之Storage Modulus曲線圖………………………….84
圖4-40 PAI-ODA之Storage Modulus曲線圖……………………………84
圖4-41 PAI-(p)BAB之Storage Modulus曲線圖……………………….84
圖4-42 PAI-(m)BAB之Storage Modulus曲線圖…………………….…85
圖4-43 Ref1-BATB之Storage Modulus曲線圖…………………………85
圖4-44 Ref2-ODA之Storage Modulus曲線圖……………………….…85
圖4-45 Ref3-(p)BAB之Storage Modulus曲線圖………………………86
圖4-46 PAI-BATB之Tan delta曲線圖……………………………….…86
圖4-47 PAI-ODA之Tan delta曲線圖……………………………………86
圖4-48 PAI-(p)BAB之Tan delta曲線圖…………………………….…87
圖4-49 PAI-(m)BAB之Tan delta曲線圖…………………………….…87
圖4-50 Ref1-BATB之Tan delta曲線圖…………………………….….87
圖4-51 Ref2-ODA之Tan delta曲線圖………………………………….88
圖4-52 Ref3-(p)BAB之Tan delta曲線圖………………………………88
圖4-53 各種聚醯胺-醯亞胺之XRD繞射圖……………….……………89
圖4-54 各種聚醯亞胺之XRD繞射圖…………………..……………….90
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