合成含蒽之聚醯亞胺與聚醯胺及其性質研究｜國立臺灣科技大學博碩士論文系統

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研究生：	李至為 Chih-wei Lee
論文名稱：	合成含蒽之聚醯亞胺與聚醯胺及其性質研究 Synthesis and Characterization of Polyimides and Polyamides Based on Anthracene
指導教授：	陳燿騰 Yaw-terng Chen
口試委員:	江選雅江選雅陳志堅陳志堅
學位類別：	碩士 Master
系所名稱：	工程學院 - 化學工程系 Department of Chemical Engineering
論文出版年：	2006
畢業學年度：	94
語文別：	中文
論文頁數：	84
中文關鍵詞：	聚醯亞胺、聚醯胺、蒽
外文關鍵詞：	polyimide, polyamide, anthracene
相關次數：	點閱：258 下載：5
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以含蒽環之9,10-Bis(4-aminophenyl)Anthracene之剛硬二胺單體與多種芳香族二酸酐單體製備成一系列的聚醯亞胺，而其聚醯胺酸之固有黏度介於0.85至1.34 dL/g之間，經高溫熱閉環後可形成堅硬且透明的薄膜，抗張強度範圍在51~152 MPa之間，斷裂伸長率介於5.7~12.8％間。經動態熱機械分析儀量測它們具有相當高的玻璃轉移溫度，介於396~403℃；另外經由熱重量損失分析在氮氣與空氣下10％重量損失範圍分別在540~594℃和540~584℃之間。
另一方面，考慮到蒽環具有良好之穩定發光特性，以此含蒽之二胺單體與數種二酸單體製備成一系列的聚醯胺。這些聚醯胺都具有良好的溶解度，它們可以溶在NMP(N-methyl-2-pyrrolidone)、 DMAc (N,N’-Dimethylacetamide)與THF(Tetrahydrofuran)等之中，經溶液塗佈後可形成具韌性且透明的薄膜。這些薄膜的抗張強度範圍在54~137 MPa之間，而斷裂伸長率值為6.5~18.5％，其經動態熱機械分析儀量測它們具有高的玻璃轉移溫度範圍在318~350℃，而經由熱重量損失分析在氮氣與空氣下10％重量損失的範圍分別在528~546℃和
524~559℃之間。另外光學性質方面由紫外光/可見光分光譜儀可測得其最大吸收峰在290 nm左右，而利用螢光光譜儀以290 nm激發出波長為447 nm左右之發光特性，約為可見光範圍內之藍光。

A series of polyimides were synthesized by poly-
condensation of rigid diamine based on Anthracene, 9,10-bis -(4-aminophenyl)Anthracene, with various aromatic tetracarboxylic dianhydrides. The poly(amic acid)s had viscosities of 0.85~1.34dL/g, which can form a tough and transparent film after cyclodehydration. The films had tensile stress of 51~152 MPa, and elongation to breakage values of 5.7~12.8％. They had high glass transition temperatures of 396~403℃. In addition, the temperatures of the 10％ weight loss in nitrogen and the air ranged on 540~594℃ and 540~584℃,respectively.
Considered that Anthracene exhibits a blue fluorescence under ultraviolet light, another series of polyamides were synthesized by polycondensation of the diamine based on Anthracene and various diacids. The polyamides which have inherent viscosities of 0.39~0.83dL/g were soluble in common solvent such as NMP(N-methyl-2-pyrrolidone)、DMAc(N,N’-Dimethylacetamide)、THF(Tetrahydrofuran and so on. This kind of polyamides can form transparent films with good toughness by solvent-casting. They had tensile stress of 54~137 MPa, and elongation to breakage values of 6.5~18.5％. They had high glass transition temperatures of 318~350℃. The temperatures of the 10％ weight loss in nitrogen and the air ranged on 528~546℃ and 524~559℃,respectively. In addition, a series of aromatic polyamides have fluorescence emissions in the blue region.

摘要………………………………………………………………………I
Abstract………………………………………………………………III
目錄……………………………………………………………………V
Table索引……………………………………………………………VII
Figure索引…………………………………………………………VIII
第一章	 緒論……………………………………………………………1
1-1	 聚醯亞胺簡介…………………………………………………1
1-1-1	聚醯亞胺之合成方式…………………………………3
1-1-2	聚醯亞胺之改質與應用………………………………7
1-2	 聚醯胺簡介………………………………………………12
1-2-1	聚醯胺之改質與應用………………………………14
1-3	 蒽環之應用…………………………………………………20
1-4	 剛硬結構之文獻回顧…………………………………………22
1-5	 擬進行之研究………………………………………………24
第二章	 實驗……………………………………………………………26
2-1	 實驗藥品………………………………………………………26
2-2	 實驗藥品的純化………………………………………………29
2-3	 合成單體………………………………………………………30
2-4	 合成聚醯亞胺…………………………………………………32
2-5	 合成聚醯胺……………………………………………………34
2-6	 單體鑑定及聚合物的物性與化性分析………………………36
第三章	 結果與討論……………………………………………………39
3-1	 9,10-bis(4-aminophenyl)Anthracene……………………39
3-2	 聚醯亞胺之合成………………………………………………40
3-2-1	化學環化……………………………………………40
3-2-2	熱環化………………………………………………42
3-3	 聚醯胺之合成…………………………………………………43
3-4	 聚合物之物性分析……………………………………………45
3-4-1	聚醯亞胺方面………………………………………45
3-4-2	聚醯胺方面…………………………………………48
第四章	 結論……………………………………………………………52
聚醯亞胺方面………………………………………………………52
聚醯胺方面…………………………………………………………53
參考文獻………………………………………………………………55
作者簡介………………………………………………………………80

Table索引

Table 1  Solubility of Polyimide 2d’……………………………40
Table 2  The Inherent Viscosities of Poly(amic acid)………42
Table 3  Inherent Viscosities of  Polyamides…………………44
Table 4  Solubility of Polyimides………………………………45
Table 5  Mechanical Properties of Polyimides Films…………46
Table 6  Thermal Properties of Polyimides……………………46
Table 7  Solubility of Polyamides………………………………48
Table 8  Mechanical Properties of Polyamides…………………49
Table 9  Thermal Properties of Polyimides………………………49
Table 10  Optical Properties of Polyamides……………………51











Figure索引

Figure 1.  FTIR spectra of 9,10-bis(4-aminophenyl)-    Anthracene……………………………………………60
Figure 2.  MASS spectrum of 9,10-bis(4-aminophenyl)- Anthracene……………………………………………60
Figure 3.  Single crystal structure for 9,10-bis(4-amino- phenyl)Anthracene…………………………………61
Figure 4.  TGA curve of polyimide 2b in nitrogen atmosphere at a heating rate of 10℃/min…………………………61
Figure 5.  TGA curve of polyimide 2c in nitrogen atmosphere at a heating rate of 10℃/min…………………………62
Figure 6.  TGA curve of polyimide 2d in nitrogen atmosphere at a heating rate of 10℃/min…………………………62
Figure 7.  TGA curve of polyimide 2e in nitrogen atmosphere at a heating rate of 10℃/min…………………………63
Figure 8.  TGA curve of polyimide 2b in air atmosphere at a heating rate of 10℃/min……………………………63
Figure 9.  TGA curve of polyimide 2c in air atmosphere at a heating rate of 10℃/min……………………………64
Figure 10.  TGA curve of polyimide 2d in air atmosphere at a heating rate of 10℃/min……………………………64
Figure 11.  TGA curve of polyimide 2e in air atmosphere at a heating rate of 10℃/min……………………………65
Figure 12.  DSC thermogram of polyimide 2b in nitrogen atmosphere at rate of 20℃/min……………………65
Figure 13.  DSC thermogram of polyimide 2c in nitrogen atmosphere at rate of 20℃/min……………………66
Figure 14.  DSC thermogram of polyimide 2d in nitrogen atmosphere at rate of 20℃/min……………………66
Figure 15.  DSC thermogram of polyimide 2e in nitrogen atmosphere at rate of 20℃/min……………………67
Figure 16.  DMA curve for polyimide 2b in nitrogen atmosphere at a heating rate of 5℃/min………………………67
Figure 17.  DMA curve for polyimide 2c in nitrogen atmosphere at a heating rate of 5℃/min………………………68
Figure 18.  DMA curve for polyimide 2d in nitrogen atmosphere at a heating rate of 5℃/min………………………68
Figure 19.  DMA curve for polyimide 2e in nitrogen atmosphere at a heating rate of 5℃/min………………………69
Figure 20.  TGA curve of polyamide 3a in nitrogen atmosphere at a heating rate of 10℃/min………………………69
Figure 21.  TGA curve of polyamide 3c in nitrogen atmosphere at a heating rate of 10℃/min………………………70
Figure 22.  TGA curve of polyamide 3a in air atmosphere at a heating rate of 10℃/min……………………………70
Figure 23.  TGA curve of polyamide 3c in air atmosphere at a heating rate of 10℃/min……………………………71
Figure 24.  DSC thermogram of polyamide 3a in nitrogen atmosphere at rate of 20℃/min……………………71
Figure 25.  DSC thermogram of polyamide 3c in nitrogen atmosphere at rate of 20℃/min……………………72
Figure 26.  DMA curve for polyamide 3a in nitrogen atmosphere at a heating rate of 5℃/min………………………72
Figure 27.  DMA curve for polyamide 3c in nitrogen atmosphere at a heating rate of 5℃/min………………………73
Figure 28.  UV/Visible spectrum of Polyamide 3a in 10-4M NMP solution………………………………………………74
Figure 29.  UV/Visible spectrum of Polyamide 3b in 10-4M NMP solution………………………………………………75
Figure 30.  UV/Visible spectrum of Polyamide 3c in 10-4M NMP solution………………………………………………76
Figure 31.  PL spectrum of polyamide 3a in 10-6M NMP solution………………………………………………77
Figure 32.  PL spectrum of polyamide 3b in 10-6M NMP solution………………………………………………78
Figure 33.  PL spectrum of polyamide 3c in 10-6M NMP solution………………………………………………79

                                

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