Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3525
標題: High Tg Polyimide Copolymers Containing 2,2'-Bipyridyl Units Coordinated With Nickel Malenonitriledithiolate(mnt)
含鎳錯合物聚亞醯胺合成鑑定及其熱穩定性之分析
作者: 許德紹
Hsu, Te-Shao
關鍵字: 聚亞醯胺;Polyimide
出版社: 化學工程學系
摘要: 
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.

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 ℃。
URI: http://hdl.handle.net/11455/3525
Appears in Collections:化學工程學系所

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