聚苯胺寡聚物及其導電性聚胺酯合成鑑定和物性探討

Synthesis, Characterization and Physical Property Investigation of Oligoanilines and Conductive Polyurethanes

張德楷(Te-Kai Chang)

指導教授 ： 芮祥鵬

國立臺北科技大學/工程學院/有機高分子研究所/碩士(2005年)

摘要

本研究將苯胺二聚體為單體利用氧化劑氯化鐵(FeCl3)合成苯胺四聚體，經過質子酸DBSA摻雜後有1.5*10-3 S/cm的導電度。實驗中第一部分以不同分子量的醚型聚氧四亞甲基二醇(軟鏈段)和二苯甲基二異氰酸鹽(硬鏈段)反應生成預聚合物，再以催化劑三乙基胺將苯胺四聚體接在預聚合物的頭尾端上形成共聚物，進而改善導電性高分子聚苯胺易碎裂的性質；另外預聚合物與鏈延長劑丁二醇反應合成聚胺酯。實驗第二部分將軟鏈段改用分子量2000的酯型聚己內酯二醇來合成共聚物及聚胺酯，來探討共聚物與聚胺酯高分子兩者性質差異。

經FTIR鑑定共聚物及聚胺酯的化學結構，兩者差異在urea官能基的特性峰，只有共聚物會有此一特性峰。而將共聚物和預聚合物的GPC分子量比較，共聚物的分子量大於預聚合物。

利用DMA研究共聚物和聚胺酯物性的物性，利用Burger’s modle來模擬兩者creep/recovery時，延遲時間(λret)共聚物會大於聚胺酯，因為含苯胺四聚體降低彈性，使得回復性變差。

利用TGA探討兩者的熱裂解溫度及殘餘量的關係，並利用小澤法(Ozawa’s method)計算熱裂解活化能。且共聚物可藉由UV/Vis得知摻雜效應及其性質。最後使用阻抗計量測摻雜後的共聚物薄膜，其導電度在10-4~10-6之間。

關鍵字

聚胺酯 ； 苯胺四聚體 ； 柏格模式 ； 導電薄膜

並列摘要

In this paper, tetraaniline was synthesized by using dianiline as monomer and FeCl3 as oxidant . The conductivity of the DBSA-doped tetraaniline was 1.5*10-3
S/cm.Firstly, prepolymer was synthesized with different molecular weights of poly(tetramethylene glycol)’s(PTMO) and 4,4-diphenylmethane diisocyanate(MDI),
ditetraaniline-capped copolymer was synthesized through reacting tetraaniline with prepolymer by catalyst of triethylamine, in order to improve the rigid of polyaniline.In addition and polyurethanes were synthesized with prepolymer and 1,4-butandiol.Secondly,we replaced the PTMO with the molecular weights of 2000 Polycaprolac-
-tone diol(PCL) to synthesize the copolymer and the polyurethane,to investigate the characterizations and properties of copolymers and polyurethanes.

Copolymers and polyurethanes chain structures have been characterized by FTIR,both of polymers were different in the urea groups, only copolymer owned the urea groups Moveover , GPC dates showed the copolymers large than prepolymers.

The physical properties of copolymers and polyurethanes were investigated by dynamic mechanical analysis(DMA),the dates of creep/recovery was fitted using
Burger’s model, retardation time(λret) of copolymers large than polyurethanes,because of tetraaniline reduced the elastic behavior.

The thermal degradation behavior of copolymers and polyurethanes were examined by the TGA analysis. The thermal degradation energy of polymers, estimated by Ozawa’s method. The electronic properties of the doped copolymers were studied by the use of UV/Vis instrument. At last we use the four-probe methed to measure the
conductivity of these conductive films around 10-4~10-6 S/cm.

並列關鍵字

Polyurethane ； Tetraaniline ； Conductive film

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