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研究生:莊承樺
研究生(外文):Cheng-Huah Jueng
論文名稱:二液型淺色聚亞醯胺樹脂之研究
論文名稱(外文):The studies on two-liquid type of polyimide resin for transparent film
指導教授:林榮顯
指導教授(外文):Ring-Hsein Lin
學位類別:碩士
校院名稱:國立高雄應用科技大學
系所名稱:化學工程與材料工程系
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:2010
畢業學年度:98
語文別:中文
論文頁數:99
中文關鍵詞:聚亞醯胺透明電荷轉移複合物環氧樹脂
外文關鍵詞:polyimidetransmittancecharge transfer complexepoxy
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本研究是利用2,2-Bis(4-hydroxylphenylhexafluoropropane與2-Chloro-5-nitrobenzotrifluoride進行親核取代反應,先合成二硝基化合物,再將其硝基還原成胺基而得二胺單體2,2-Bis[4-(4-amino-2- trifluoromethylphenoxy)phenyl]hexafluoropropane,並且使用DSC測量其熔點、FTIR與NMR鑑定其結構。
將所合成的二胺及數種市售品二胺與二酐合成一系列主鏈結構不同的聚亞醯胺薄膜,不同結構包含醚基、碸基、三氟甲基、六氟異丙烯基等。利用FTIR鑑定其結構、GPC測量其分子量、UV-vis鑑定其光學特性如CIELAB座標、截止波長(cutoff wavelength)、黃色度(yellowness index),TGA測量其熱穩定性。發現活化基於酐側或去活化基於胺側可以降低聚亞醯胺顏色,而含氟單體也可以有效降低聚亞醯胺顏色。在二胺固定的情況之下,酐側的基團影響聚亞醯胺膜的顏色由深至淺的順序是:-SO2- > - > -C(CF3)2- > -O-;在二酐固定的情況之下,胺側的基團影響聚亞醯胺膜的顏色由深至淺的順序是:-O- > -CH2- > -SO2- > siloxane。
比較其顏色後,選擇合適的單體配製二液型淺色聚亞醯胺樹脂,並且使用FTIR鑑定其結構、GPC測定其分子量。使用環氧樹脂與配製出來的聚亞醯胺溶液交聯,可得高透光性之聚亞醯胺交聯膜。並且使用FTIR鑑定其結構、UV-vis鑑定其光學特性、TGA測定其熱穩定性。發現其膜透明性佳,且有足夠的耐熱性。
A new diamine monomer, 2,2-bis[4-(4-amino-2-trifluoromethyl phenoxy)phenyl]hexafluoropropane, was successfully synthesized from 2,2-bis(4- hydroxylphenyl)hexafluoropropane and 2-chloro-5- nitrobenzotrifluoride via two-step method which underwent nucleophilic substitution and oxdation- reduction reaction. The synthesized diamine was identified by DSC, FTIR and 1H NMR.
PI films with different functional groups, such as ether, sulfone, trifluoromethyl, hexafluoropropyl, on the backbone were synthesized from several purchased dianhydrides and diamines (including a newly synthesized one) via a typical two-step method. Completely imidized PIs were identified by FTIR. The properties such as molecular weight, thermal ability and optical properties as CIE color space, cutoff wavelength, and yellowness indices of the PI films were determined by GPC, TGA and UV-vis, respectively. Light color of PI films was observed when the activing group in anhydride side of PI or the deactiving group in amine side of PI. Fluoride-containing monomer also may lighten the color of PI films. In the system for the same diamine, influence order of varied group in anhydride side on color of the PI films was as follows: -SO2- > - > -C(CF3)2- > -O- (from deep to light); In the system for the same dianhydride, influence order of varied group in amine side on color of the PI films was as follows: -O- > -CH2- > -SO2- > siloxane (from deep to light).
Suitable monomers were choiced from preciously studied cases to undergo the synthesis of soluble PI with light color. The partially imidized PI solution was crosslinked with epoxy to form a transmittant PI-epoxy film, and the properties of the resulting film was investigated by FTIR, UV-Vis and TGA. The PI-epoxy film was highly transparent and bared a good thermal ability.
誌謝 I
摘要 II
Abstract III
總目錄 IV
流程目錄 VI
表目錄 VII
圖目錄 VIII
第一章 前言 1
第二章 基本原理與文獻回顧 2
2-1 聚亞醯胺簡介與特性 2
2-2 聚亞醯胺種類 3
2-2-1 縮合型聚亞醯胺(condensation type of polyimide) 3
2-2-2 加成型聚亞醯胺(addition type of polyimide) 4
2-3 聚醯胺酸亞醯胺化 5
2-3-1 物理環化 5
2-3-2 化學環化 6
2-3-3 UV光環化 6
2-4 無色聚亞醯胺簡介 6
2-4-1 電荷轉移錯合物 7
2-4-2 CIE色彩空間 7
2-4-3 黃色度 9
2-5 二液型樹脂簡介 10
2-6 環氧樹脂簡介 10
2-7 文獻回顧 11
2-7-1 二胺單體合成 12
2-7-2 淺色聚亞醯胺 14
2-8 研究動機與目的 20
第三章 研究方法與實驗步驟 22
3-1 材料 22
3-2 儀器 24
3-3 實驗步驟及方法 26
第四章 結果與討論 28
4-1 二胺單體合成與鑑定 28
4-1-1 二硝基化合物Dinitro-12F-bis-A之合成與鑑定 28
4-1-2 二胺基化合物Diamino-12F-bis-A之合成與鑑定 29
4-2 不同主鏈結構之PI膜的合成與性質 30
4-2-1 主鏈結構不同之PI膜合成與鑑定 30
4-2-2 聚亞醯胺性質 33
4-2-3 聚亞醯胺膜顏色 34
4-3 二液型淺色PI樹脂合成與其顏色 42
4-3-1 二液型淺色聚亞醯胺樹脂單體選擇 42
4-3-2 二液型淺色PI樹脂其與環氧樹脂交聯膜合成與結構鑑定 42
4-3-3 PI-epoxy交聯膜性質 47
第五章 結論 49
5-1 不同主鏈結構的PI膜顏色與其他性質探討 49
5-2 二液型淺色聚亞醯胺樹脂與其交聯膜之顏色與熱穩定性 50
第六章 參考文獻 52
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