- 學位論文
含三苯胺結構之新型聚醯胺及聚醯亞胺之合成與性質研究
Synthesis and Properties of Polyamide and Polyimide containing Triphenylamine Structures
摘要
本研究利用對甲苯胺與對氟硝基苯，並以氟化銫做催化劑於DMSO溶劑下，進行芳香親核置換反應得4-nitro-N-(4-nitrophenyl)-N-p-tolyl-benzenamine 之結構，更進一步將二硝基以鈀(Pd/C)做為觸媒以及聯胺做為還原劑，然後製得含有二胺之三苯胺結構N1-(4-aminophenyl)-N1-p-tolylbenzene-1,4-diamine單體。再利用上述製得的二胺單體與各種芳香族二羧酸及二酐聚合成兩系列新型主鏈具有三苯胺結構的芳香族聚醯胺和聚醯亞胺。 以FT-IR和NMR鑑定其結構；UV及PL光譜分析其光學性質；以TGA和DSC測定其熱性質。這些聚合物具有優異的特性，聚醯胺在NMP溶液中，於316~362 nm有UV-vis吸收峰，而410~449 nm有PL放射峰，玻璃轉移溫度介於286~318 ℃之間，5％重量損失溫度為459~492 ℃，在氮氣下加熱至 800 ℃ 時的焦炭殘餘率超過 55%，黏度為0.48~1.05 dL/g；聚醯亞胺在NMP溶液中，於304~317 nm有UV-vis吸收峰，而395~417 nm有PL放射峰，玻璃轉移溫度介於295~323 ℃之間，在氮氣下5％重量損失溫度為477~556 ℃，加熱至 800 ℃ 時的焦炭殘餘率超過 55%，黏度為0.51~1.10 dL/g。聚合物塗佈在 ITO玻璃上的薄膜的階段伏安 (CV) 圖皆顯示出ㄧ對可逆的氧化還原峰，聚醯胺及聚醯亞胺於1.05~1.15 V和1.30 V下顏色分別由淡綠色轉變為深綠色及淡黃色變深藍色。
並列摘要
N’-(4-aminophenyl)-N’-p-tolylbenzene-1,4-diamine to get was synthesized by cesium fluoride –mediate nucleophilic displacement reaction of 1-fluoro-4-nitro-benzene with p-toluidine in dimethyl sulfoxide, followed by palladium-catalyzed hydrazine reduction. This newly synthesized diamine monomer was reacted with various aromatic dicarboxylic acids and tetracarboxylic dianhydrides to produce two series of novel triphenylamine-based polyamides and polyimides. The confirmations of polyamide and polyimide structures were determined by FT-IR and NMR. The optical properties of the polymers were analyzed by UV-Vis and PL spectroscopies. The thermal properties were measured by TGA and DSC. These polymers showed excellent properties. The polyamides exhibited UV-Vis absorption band at 316~362 nm and showed PL maxim emission peak at 410~449 nm in NMP solution. The glass-transition temperature were from 268 to 318 ℃, and 5％ weight loss temperatures were 459~492℃ under nitrogen, and char yields higher than 55%. The inherent viscosity of the polyamides were 0.48~1.05 dL/g. The polyimides exhibited UV-Vis absorption band at 304~317 nm and showed PL maxim emission peaks at 395~417 nm in NMP solution. The glass-transition temperature were from 295 to 323 ℃, and 5％ weight loss temperatures were 477~556 ℃ under nitrogen, and char yields higher than 55%. The inherent viscosity of the polyimides was 0.51~1.10 dL/g. Cyclic voltammetry curves of the polymer films on an indium-tin oxide (ITO)-coated glass substrate showed one pair of reversible redox peak, these polyamides and polyimides with the color change from light green neutral form to dark green and light yellow neutral form to dark blue under 1.05~1.15 V and 1.30 V, respectively.