臺灣博碩士論文加值系統

本研究已成功置備一系列含有bipyridyl之聚亞醯胺及聚亞醯胺共聚合物。聚亞醯胺及聚亞醯胺共聚合物上具金屬鉗合性之2,2'-bipyridyl配位基與含有鎳金屬錯合物間以配位鍵之鍵結連接形成具有二次非線性性質之有機光學高分子材料。聚亞醯胺及聚亞醯胺共聚合物之玻璃轉移點隨bipyridyl之量降低而降低，但分子量卻隨bipyridyl之量降低而增加。由核磁共振儀之氫光譜測定結果得知，聚亞醯胺共聚合物中α,α'-Bis (4-aminophenyl)-1,4-diisorpropylbenzene (簡稱BAPDIPB)段之反應性高於4,4'-diamino-2,2'-bipyridyl段之反應性。而在溶解度方面，在接上含鎳金屬錯合物後，溶解度會有相當程度的降低。由元素分析結果可知，聚亞醯胺及聚亞醯胺共聚合物和含鎳金屬錯合物反應相當完全。此一系列具有二次非線性光學性質之高分子材料其熱穩定性高於370 ℃，聚亞醯胺及聚亞醯胺共聚合物之玻璃轉移點 (Tg)為260-300℃，而一般應用於二次非線性光學高分子之聚亞醯胺的玻璃轉移點 (Tg)大都低於250 ℃。聚亞醯胺及聚亞醯胺共聚合物接上含鎳金屬錯合物後，玻璃轉移點 (Tg)約增加10-25 ℃，熱裂解溫度(Td)約降低40-140 ℃。

Polyimides containing bipyridyl units were synthesized. The bipyridyl units were sucessfully incorporated by polymerization of bipyridyl diamine andα,α'-Bis(4-aminophenyl)-1,4-diisorpropyl benzene with hexafluoroisopropylidene-2,2'-bisphthalic anhydride. The resulting polyimides' Mws range from 4517 to 42526. The polymers are thermally stable up to 450 oC and show high glass transition temperatures (Tg) in a range between 260-300 oC dependent on the composition of the copolymers. The (2,2'-bipyridyl)(malenonitriledithiolato)Ni(II) containing polyimides possess glass transition temperatures (Tg) in a range between 270-325 ℃. It is important to note that known nonlinear optical polyimides often exhibit Tg's of less than 250 ℃. The 2,2'-bipyridyl containing polyimides in this study show Tg enhancement and better metal-binding capability after the coordination of nickel malenonitriledithiolate chromophore.

Abstract…..……………………………………………………………………………….I
摘要…..………………..…………………………………………………………………II
目錄………………………………………………………………………….…………..III
圖目錄………………………………………………………………………………….VII
表目錄…………………………………………………………...………………………X
一. 緒論…………………………………………………………………………………..1
1-1 前言…………………………………………………………………………………1
1-2 二次非線性光學性質…………………………………………………………..3
1-3 高分子材料之二次非線性光學性能……………………………………….5
1-4 非線性光學材料特性量測的基本原理……………………………………7
1-4-1以非線性光學技術診斷凝態材料特性的理論基礎………………….7
1-4-2晶體或非晶體薄片的非線性光學特性量測……………………………9
二. 文獻回顧及研究動機…………………………………………………………..11
2-1文獻回顧…………………………………………………………………………..11
2-1-1配位金屬錯合物之介紹…………………………………………………….11
2-1-2聚亞醯胺之合成………………………………………………………………12
2-1-3聚亞醯胺之特性………………………………………………………………12
2-2研究動機…………………………………………………………………………..13
三. 實驗…………………………………………………………………………………15
3-1化學藥品…………………………………………………………………………..15
3-2實驗儀器…………………………………………………………………………..19
3-3合成步驟流程……………………………………………………………………21
3-3-1 4.4'-diamino 2,2'-bipyridyl之合成流程…………………………………...21
3-3-2 Model compound之合成流程………..…………………………………….21
3-3-3 (NH3)2Ni(mnt)之合成流程……………....…………………………………...22
3-3-4 Model compound接上Ni(mnt)之合成流程……...……..……………….22
3-4-1 PI A, PI A-Nimnt1-5,PI G之合成流程……………….………………………23
3-4-2 PI B~PI F, PI B-Nimnt~PI F-Nimnt之合成流程………………………….24
3-5 4,4'-diamino 2,2'-bipyridyl之合成……………………………………………25
3-5-1 2,2'-bipyridyl N,N'-dioxide之合成………………………………………….25
3-5-2 4,4'-dinitro 2,2'-bipyridyl N,N-dioxide之合成…………………………....25
3-5-3 4,4'-dinitro 2,2'-bipyridyl之合成……………………………………………26
3-5-4 4,4'-diamino 2,2'-bipyridyl之合成………………………………………….26
3-6聚亞醯胺及接上含Ni(mnt) 聚亞醯胺之合成…………………………..27
3-6-1聚亞醯胺A之合成…………………………………………………..……….27
3-6-2 PI A-Nimnt1之合成……………………………………………………....……27
3-6-3 PI A-Nimnt2之合成……………………………………………………...…….28
3-6-4 PI A-Nimnt3之合成……………………………………………………...…….28
3-6-5 PI A-Nimnt4之合成……………………………………………………...…….28
3-6-6 PI A-Nimnt5之合成……………………………………………………...…….28
3-6-7 PI B之合成……………………………………………………………………..29
3-6-8 PI B-Nimnt之合成………………………………………………...…………..29
3-6-9 PI G之合成………………………….……………………………….…………30
3-6-10 PI C之合成………………………….…………………………….………….30
3-6-11 PI D之合成………………………….…………………………….………….31
3-6-12 PI E之合成………………………….……………………………..………….31
3-6-13 PI F之合成………………………….……………………………..………….31
3-6-14 PI C-Nimnt之合成……………………………………………………..…….32
3-6-15 PI D-Nimnt之合成……………………………………………………..…….32
3-6-16 PI E-Nimnt之合成……………………………………………………..…….32
3-6-17 PI F-Nimnt之合成……………………………………………………..…….32
四.結果與討論…………….………………………………………...……………….33
4-1-1 2,2'-bipyridyl N,N'-dioxide之合成……………………………………….…33
4-1-2 4,4'-dinitro 2,2'-bipyridyl N,N'-dioxide之合成……………………..…….33
4-1-3 4,4'-dinitro 2,2'-bipyridyl之合成…………………………………………...35
4-1-4 4,4'-diamino 2,2'-bipyridyl之合成…………………………….……………36
4-2-1聚亞醯胺A之合成…………………………………………………….……..43
4-2-2聚亞醯胺A接上Ni(mnt)之合成……………………...……….…….…….44
4-2-3聚亞醯胺B~F之合成…………………………………………….….………45
4-2-4聚亞醯胺B~F接上Ni(mnt)之合成…………………………….………….46
4-2-5聚亞醯胺G之合成……………………………………………….…….…….46
4-3聚亞醯胺A~G及接上Ni(mnt)後之溶解度探討……………….…………47
4-4聚亞醯胺B~G之1H-NMR鑑定……………………………………..…………49
4-5聚亞醯胺A~G之Inherent viscosity測定………………………..…………58
4-6聚亞醯胺B~G之分子量測定……………………………………..………….60
4-7-1聚亞醯胺A~G之IR光譜鑑定…………………………………..………….63
4-7-2聚亞醯胺A~F接上Ni(mnt)後之IR光譜鑑定……………….………….63
4-8 元素分析鑑定………………………………..…………………..……………..72
4-9-1聚亞醯胺A~G之DSC熱性質測試………………………….……………74
4-9-2聚亞醯胺A接上Ni(mnt)後之DSC熱性質測試………….…..……….75
4-9-3聚亞醯胺B~F接上Ni(mnt)後之DSC熱性質測試……..………..…...76
4-10-1聚亞醯胺A~G之TGA熱性質測試…………………….…..……………84
4-10-2聚亞醯胺A接上Ni(mnt)後之TGA熱性質測試…….….…………….85
4-10-3聚亞醯胺B~F接上Ni(mnt)後之TGA熱性質測試….….…………...86
五.結論…………………………………………………………………...…………….96
六.參考文獻…………………………………………………………..……..………..98

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