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研究生： 曾敬哲
Tseng - Ching Che
論文名稱： 合成新型含三苯胺及金剛烷之聚醯亞胺與聚醯胺及其性質研究
Synthesis and Characterization of New Polyimides and Polyamides with Triphenylamine and Adamantane Groups
指導教授： 陳燿騰
Yaw-Terng Chern
口試委員: 江選雅
none
陳志堅
none
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： 2007
畢業學年度： 95
語文別： 中文
論文頁數： 90
中文關鍵詞： 三苯胺 、金剛烷 、聚醯亞胺 、聚醯胺
外文關鍵詞： triphenylamine, adamantane, polyimide, polyamide
相關次數： 點閱：220  下載：1 
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    • 以含有三苯胺及金剛烷的二胺單體與芳香族酸酐所合成的聚醯亞胺其固有黏度範圍在0.38 ~ 1.34 dL/g，其聚醯胺酸黏度範圍在0.94 ~ 2.03 dL/g，且具有不錯的溶解度，這些聚醯亞胺可溶於NMP 、o-chlorophenol和chloroform。經DMA測定之後，其玻璃轉移溫度在362 ~ 453℃之間。經TGA測定後，其10%熱重損失於空氣下介於513 ~ 542℃，氮氣下介於521 ~ 536℃，在氮氣下600℃燃燒殘餘率在65 ~ 75%之間。經紫外光譜儀(UV/Vis)測試所合成之聚醯亞胺之光學性質，其主要的UV吸收峰在320 nm左右，而由光激發所產生的螢光主要發生在530 nm左右，這是屬於綠光範圍。經電化學分析後，再配合紫外光譜，求得聚醯亞胺其能階差(LUMO -HOMO)的範圍在3.08 ~ 3.58 eV之間。
    以含有三苯胺及金剛烷的二胺單體與芳香族二酸所合成的聚醯胺其固有黏度範圍在0.54 ~ 0.69 dL/g，且具有不錯的溶解度，這些聚醯亞胺可溶於NMP 、o-chlorophenol、DMAc、cyclohexanone。經DMA測定之後，其玻璃轉移溫度在331 ~ 356℃之間。經TGA測定後，其10%熱重損失於空氣下介於479 ~ 511℃，氮氣下介於494 ~ 507℃，在氮氣下600℃燃燒殘餘率在60 ~ 67%之間。經紫外光譜儀(UV/Vis)測試所合成之聚醯亞胺之光學性質，其主要的UV吸收峰在333 nm左右，而由光激發所產生的螢光主要發生在530 nm左右，這是屬於綠光範圍。經電化學分析後，再配合紫外光譜，求得聚醯胺其能階差(LUMO -HOMO)的範圍在3.10 ~ 3.16 eV之間。

    The polyimides derived from N,N-bis(4-aminophenyl)-4-adamantylaniline, had inherent viscosities of 0.38 ~ 1.34 dL/g and the poly(amic acid) had inherent viscosities of 0.94 ~ 2.03dL/g. The polyimides were readily soluble in NMP, o-chlorophenol and chloroform. The dynamic mechanical analysis(DMA) reveals that the glass transition temperatures(Tg) ranged on 362 ~ 453℃. In addition, the temperature of 10% weight loss in air and nitrogen ranged on 513 ~ 542℃ and 521 ~ 536℃ by the thermal gravity analyzer(TGA). These polymers exhibited strong UV-vis absorption bands about 320 nm in NMP 10-4M solution. The photoluminescence spectra showed maximum bands around 530 nm in the green region. The energy gap of polyimides ranged on 3.08 ~ 3.58 eV.
    The polyamides derived from N,N-bis(4-aminophenyl)-4-adamantylaniline, had inherent viscosities of 0.54 ~ 0.69 dL/g. The polyamides were readily soluble in NMP, o-chlorophenol, DMAc and cyclohexanone. The dynamic mechanical analysis(DMA) reveals that the glass transition temperatures(Tg) ranged on 331 ~ 356℃. In addition, the temperature of 10% weight loss in air and nitrogen ranged on479 ~ 511℃ and 494 ~ 507℃ by the thermal gravity analyzer(TGA). These polymers exhibited strong UV-vis absorption bands about 333 nm in NMP 10-4M solution. The photoluminescence spectra showed maximum bands around 530 nm in the green region. The energy gap of polyamides ranged on 3.10 ~ 3.16 eV.

    目錄 Abstract ………………………………………………………………Ⅰ 摘要 ………………………………………………………………Ⅱ 目錄 ………………………………………………………………Ⅳ Scheme 索引……………………………………………………………Ⅶ Table 索引………………………………………………………………Ⅷ Figure 索引 ……………………………………………………………Ⅸ 第一章 緒論 ……………………………………………………………1 1-1 前言 ……………………………………………………………1 1-2 聚醯亞胺簡介……………………………………………………1 1-3 聚醯亞胺的合成方法……………………………………………3 1-4 聚醯亞胺的改質及其應用………………………………………9 1-5 聚醯胺簡介………………………………………………………13 1-6 聚醯胺合成………………………………………………………14 1-7 聚醯胺的改質與應用……………………………………………20 1-8 三苯胺的應用與文獻回顧………………………………………23 1-9 金剛烷的應用與文獻回顧………………………………………29 1-10 擬進行之研究……………………………………………………29 第二章 實驗………………………………………………………………31 2-1 實驗藥品…………………………………………………………31 2-2 實驗程序…………………………………………………………34 2-2-1 單體製備………………………………………………………34 2-2-2 聚醯亞胺的合成………………………………………………37 2-2-3 聚醯胺的合成…………………………………………………39 第三章 結果與討論 ……………………………………………………44 3-1 聚醯亞胺的合成…………………………………………………44 3-2 聚醯亞胺的物性分析……………………………………………47 3-2-1 溶解度測試……………………………………………………47 3-2-2 熱性質測試……………………………………………………48 3-2-3 電化學性質及光學性質測試…………………………………49 3-2-4 螢光性質測試…………………………………………………50 3-3 聚醯胺合成………………………………………………………50 3-4 聚醯胺物性分析…………………………………………………53 3-4-1 溶解度測試……………………………………………………53 3-4-2 熱性質測試……………………………………………………54 3-4-3 電化學性質光學性質測試……………………………………55 3-4-4 螢光性質測試…………………………………………………56 第四章 結論………………………………………………………………57 4-1 聚醯亞胺…………………………………………………………57 4-2 聚醯胺……………………………………………………………58 參考文獻……………………………………………………………………5 Scheme 索引 Scheme 1 合成聚醯亞胺之反應…………………………………………37 Scheme 2 合成聚醯胺之反應……………………………………………39 Table 索引 Table 1 The Inherent Viscosities of Soluble Polyimides and Poly(amic acid)s. ………………………………………………47 Table 2 Solubility of Polyimides. ………………………………………48 Table 3 Thermal Properties of Polyimides.………………………………48 Table 4 Optical and Electrochemical Properties for Polyimides. ………49 Table 5 PL Properties of Polyimides. ……………………………………50 Table 6 The Inherent Viscosities of Soluble Polyamides. ………………52 Table 7 Solubility of Polyamides. ………………………………………53 Table 8 Thermal Properties of Polyamides. ……………………………54 Table 9 Optical and Electrochemical Properties for Polyamides. ………55 Table10 PL Properties of Polyimides. …………………………………56 Figure 索引 Figure 2-1 FTIR spectrum of N,N-bis(4-aminophenyl)-4-adamantylaniline(6) ……………64 Figure 3-1 DMA curve of polyimide 8a in nitrogen atmosphere at a heating rate of 5℃/min ………………………………………………64 Figure 3-2 DMA curve of polyimide 8b in nitrogen atmosphere at a heating rate of 5℃/min ………………………………………………65 Figure 3-3 DMA curve of polyimide 8c in nitrogen atmosphere at a heating rate of 5℃/min ………………………………………………65 Figure 3-4 DMA curve of polyimide 8c in nitrogen atmosphere at a heating rate of 5℃/min ………………………………………………66 Figure 3-5 DMA curve of polyimide 8e in nitrogen atmosphere at a heating rate of 5℃/min ………………………………………………66 Figure 3-6 TGA curve of polyimide 8b in nitrogen atmosphere at a heating rate of 10℃/min………………………………………………67 Figure 3-7 TGA curve of polyimide 8c in nitrogen atmosphere at a heating rate of 10℃/min………………………………………………67 Figure 3-8 UV/Visible curve of polyimides 8a ~ 8e in NMP solvent 10-4 M. ………………………………………………68 Figure 3-9 CV curve of Ferrocene in 0.1M TBAP/CH3CN at a scanning rate of 100mV/s …………………………………………………68 Figure 3-10 CV curve of the casting film of polyimide 8b on an ITO-coated glass substrate. ………………………………………………69 Figure 3-11 CV curve of the casting film of polyimide 8d on an ITO-coated glass substrate. ………………………………………………69 Figure 3-12 CV curve of the casting film of polyimide 8e on an ITO-coated glass substrate. ………………………………………………70 Figure 3-13 PL curve of polyimides 8a ~ 8e in NMP solvent 10-6 M. ……70 Figure 3-14 DMA curve of polyamide 9a in nitrogen atmosphere at a heating rate of 5℃/min………………………………………………71 Figure 3-15 DMA curve of polyamide 9b in nitrogen atmosphere at a heating rate of 5℃/min………………………………………………71 Figure 3-16 DMA curve of polyamide 9c in nitrogen atmosphere at a heating rate of 5℃/min………………………………………………72 Figure 3-17 DMA curve of polyamide 9d in nitrogen atmosphere at a heating rate of 5℃/min………………………………………………72 Figure 3-18 TGA curve of polyamide 9a in nitrogen atmosphere at a heating rate of 10℃/min………………………………………………73 Figure 3-19 TGA curve of polyamide 9b in nitrogen atmosphere at a heating rate of 10℃/min………………………………………………73 Figure 3-20 TGA curve of polyamide 9c in nitrogen atmosphere at a heating rate of 10℃/min………………………………………………74 Figure 3-21 UV/Visible curve of polyamides 9a ~ 9d in NMP solvent 10-4 M solvent 10-4 M…………………………………………………74 Figure 3-22 CV curve of the casting film of polyamide 9b on an ITO-coated glass substrate. ………………………………………………75 Figure 3-23 CV curve of the casting film of polyamide 9c on an ITO-coated glass substrate. ………………………………………………75 Figure 3-24 CV curve of the casting film of polyamide 9d on an ITO-coated glass substrate. ………………………………………………76 Figure 3-25 PL curve of polyamides 9a ~ 9d in NMP solvent 10-6 M. ……76

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