臺灣博碩士論文加值系統

由於有機-無機混成材料是一具有高性能的新材料，不但具有有機高分子良好的韌性與加工性質，亦擁有無機材料高的強度與耐熱性質，為近年來材料研究發展的新領域。而溶膠－凝膠技術提供一相當吸引人之方法，用以製備三度空間之有機∕無機網狀高分子混成材料。本研究中除了利用矽氧烷化合物之溶-凝膠反應，形成SiO2鍵結外，亦利用含酚基之化合物與矽氧烷化合物反應形成phenoxysilicon linkage，以提升有機-無機材料之間的相容性與熱性質。因此本研究利用溶-凝膠技術製備了三種不同型態聚亞醯胺-無機混成材料。在全網狀互穿型混成材中，其熱裂解溫度隨無機含量的增加而上升，且當無機含量超過30％後，便有補強作用而提升了材料之熱性質。可見有機之網狀結構與無機之網狀結構因相互穿插，造就更緊密之網狀結構，進一步提升材料的熱性質。
在二次非線性光學有機高分子材料的研究上，雖然具有大的非線性光學係數、優越的光學透明性、快的應答速度、易加工成膜等優點，然而對於非線性高分子材料，在光電元件中要有實際應用的潛力，必須具備高的非線性光學係數、長期的高溫穩定性(100~125℃)、低光學損失以及250℃左右的加工溫度下具有短暫的時間穩定性等條件。因此研究利用溶-凝膠技術製備了三種不同型態聚亞醯胺-無機二次非線性光學材料。各系列之電光係數約介於2pm/V〜25pm/V之間，經過長時間（100小時）之熱處理（100℃）下，電光係數仍維持70％〜95％，其中以全網狀互穿型非線性光學有機高分子材料之熱穩定性最佳。可見加入芳香族聚亞醯胺可有效限制發色團基分子的運動，進一步提升其光學穩定性。

Organic-inorganic hybrid materials via the in-situ sol-gel reaction provide excellent thermal stability and good mechanical properties. In this work, the alkoxysilane was reacted with the rigid multiphenoxyl molecule to form a phenoxysilicon compound. These phenoxysilicon materials have been shown to possess excellent thermal and dimensional stability, and mechanical properties, in addition to excellent optical transparency. The phenoxysilicon materials were incorporated into respective polyimides to form a semi-interpenetrating polymer network (semi-IPN), silica-containing crosslinked polyimide, and full IPN. These materials exhibit excellent thermal properties, and excellent optical clarity.
Nonlinear optical (NLO) organic polymers have large optical nonlinearity, excellent processibility and fast response time. In order to meet application requirements of long-term NLO stability up to 100℃ and short excursion to the temperature of 250℃ or higher, sol-gel reaction of nonlinear optically active alkoxysilane dye (ASD) and the rigid multiphenoxyl molecule was utilized to grow a network in polyimide matrices or create a interpolymer network among polyimide chains. Electro-optical (EO) coefficients of a series of NLO polyimide -inorganic materials are in the range of 2pm/V〜25pm/V. Excellent long-term stability of EO coefficient at 100℃ was observed as well. Better temporal stability of EO coefficients were obtained from full-IPN.

目錄
摘要……………………………………………………………………….I
Abstract………………………………………………………………..…II
目錄…………………………………………………………………..…III
圖目錄…………………………………………………………..…… ..VII
表目錄…………………………………………………………………XI
壹、緒論…………………………………………………………………..1
1-1 前言……………………………………………………………….1
1-2 溶凝膠(sol-gel)的簡介…………………………………………...3
1-2-1 何謂溶凝膠………………………………………………….3
1-2-2 溶凝膠的優缺點…………………………………………….5
1-3 有機-無機混成材料之應用……………………………………6
1-4 有機非線性光學材料…………………………………………….7
1-5 非線性光學之波克效應………………………………………….8
1-6 二次非線性光學材料之應用…………………………………...10
貳、文獻回顧…………………………………………………………....12
2-1 溶-凝膠的歷史演進…………………………………………….12
2-2 非線性光學材料………………………………………………..13
參、研究動機……………………………………………………………17
3-1 有機-無機混成材料…………………………………………….17
3-2 非線性光學材料………………………………………………...20
肆、實 驗………………………………………………………………..23
4-1實驗流程…………………………………………………………23
4-2 化學藥品………………………………………………………...23
4-3 實驗儀器………………………………………………………...26
4-4 聚亞醯胺聚合物之合成………………………………………...28
4-4-1 聚亞醯胺聚合物（PI-A）之合成……………………………28
4-4-2 聚亞醯胺聚合物（PI-B）之合成……………………………28
4-4-3 聚亞醯胺聚合物（PI-C）之合成……………………………29
4-5 聚亞醯胺有機-無機材料之製備……………………………….30
4-5-1 THPE-TEOS預聚物………………………………………...31
4-5-2 半網狀互穿型有機-無機材料之製備……………………..31
4-5-3 網狀交聯型有機-無機材料之製備………………………..31
4-5-4 全網狀互穿型有機-無機材料之製備……………………..32
4-6 矽氧烷偶氮發色團（ASD）之合成……………………………...33
4-6-1 p-nitrosonitrobenzene之合成……………………………….33
4-6-2 Tris(4-aminophenyl)amine之合成……………………….....33
4-6-3 Bis(4-aminophenyl(4-(4-nitrophenyl)diazenyl)phenyl)amine（發色團基）之合成………………………………………..34
4-6-4 矽氧烷偶氮發色團（ASD）的合成 ……………………….35
4-7 非線性光學材料之製備………………………………………...36
4-7-1 THPE-ASD預聚物………………………………………….36
4-7-2 半網狀互穿型非線性光學材料之製備…………………...36
4-7-3 網狀交聯型非線性光學材料之製備……………………...37
4-7-4 全網狀互穿型非線性光學材料之製備…………………...38
4-8 二次非線性光學性質之檢測…………………………………...38
4-8-1 高分子薄膜之製備………………………………………...38
4-8-2 高分子薄膜極化配向……………………………………...39
4-8-3 波克效應之檢測原理……………………………………...39
4-8-4 電光係數(electro-optic coefficient)之測量………………...45
伍、結果與討論…………………………………………………………47
5-1 聚亞醯胺之特性分析…………………………………………...47
5-1-1 聚亞醯胺(PI-A)之化學結構鑑定與熱性質分析………….47
5-1-2 聚亞醯胺(PI-B)之化學結構鑑定與熱性質分析………….49
5-1-3 聚亞醯胺(PI-C)之化學結構鑑定與熱性質分析………….52
5-2 THPE-TEOS預聚物……………………………………………..55
5-2-1 化學結構鑑定與熱性質分析……………………………...55
5-2-2 形態學分析………………………………………………...59
5-2-3 結論………………………………………………………...59
5-3 半網狀互穿型有機-無機材料………………………………….61
5-3-1 化學結構鑑定與熱性質分析……………………………...61
5-3-2 形態學分析………………………………………………...64
5-4 網狀交聯型有機-無機材料…………………………………….66
5-4-1 化學結構鑑定與熱性質分析……………………………...66
5-4-2 形態學分析………………………………………………...69
5-5 全網狀互穿型有機-無機材料………………………………….71
5-5-1 化學結構鑑定與熱性質分析……………………………...71
5-5-2 形態學分析………………………………………………...75
5-6 三系統有機-無機混成材料之比較…………………………….77
5-7 Bis(4-aminophenyl(4-(4-nitrophenyl)diazenyl)phenyl) amine發色團基之結構鑑定及熱性質分析…………………………………79
5-8 矽氧烷偶氮發色團(ASD)之結構鑑定及熱性質分析…………81
5-9 THPE-ASD預聚物………………………………………………82
5-9-1 電光係數（r33）及動態熱行為、長時間熱穩定性之研究......82
5-9-2 TH2ASD5之其他性質……………………………………...85
5-10 半網狀互穿型非線性光學材料…………………………...…..88
5-10-1 化學結構鑑定與熱性質分析………………………….....85
5-10-2 形態學分析…………………………………………….....92
5-10-3 紫外-可見光光譜圖之分析……………………………....95
5-10-4 折射率與電光係數之量測……………………………….96
5-10-5 動態熱行為與長時間熱穩定性之研究………………….96
5-11 網狀交聯型非線性光學材料………………………………….99
5-11-1 化學結構鑑定與熱性質分析…………………………….99
5-11-2 形態學分析……………………………………………...103
5-11-3 紫外-可見光光譜圖之分析……………………………..106
5-11-4 折射率與電光係數之量測……………………………...107
5-11-5 動態熱行為與長時間熱穩定性之研究………………...107
5-12 全網狀互穿型非線性光學材料……………………………...110
5-12-1 化學結構鑑定與熱性質分析……………………………110
5-12-2 形態學分析………………………………………………114
5-12-3 紫外-可見光光譜圖之分析……………………………..117
5-12-4 折射率與電光係數之量測………………………………118
5-12-5 動態熱行為與長時間熱穩定性之研究…………………118
5-13 三系統非線性光學材料之比較…………………………...…120
陸、結論………………………………………………………………..123
柒、參考文獻…………………………………………………………..124

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