含金屬酞菁之聚醯亞胺之合成與物性研究

Synthesis and Properties of Novel Copolyimides Containing Metal Phthalocyanine

蕭雅文(Ya-Wen Hsiao)

指導教授 ： 汪昆立

國立臺北科技大學/工程學院/化學工程研究所/碩士(2011年)

https://doi.org/10.6841/NTUT.2011.00024

摘要

本實驗成功合成三種含金屬酞菁之聚醯亞胺共聚物，首先合成新型雙胺
3-(4-(bis(4-aminophenyl)amino)phenoxy)-6-(hexyloxy)phthalonitrile後，與4,4'-(Hexafluoroisopropylidene)diphthalic Anhydride分別聚合成聚醯胺酸（PAA-6FDA）及聚醯亞胺（PI-6FDA），聚醯胺酸與鄰苯二甲腈合成含金屬酞菁之聚醯胺酸共聚物高分子，再進行脫水反應合成聚醯亞胺共聚物（PI-ZnPc-1），另一方面，聚醯亞胺則直接與鄰苯二甲腈反應合成含金屬酞菁之聚醯亞胺共聚物高分子（PI-ZnPc-2、PI-CuPc），並探討其熱性質、光電性質以及溶解性。在可見光區600~700nm之間具有強烈的UV-Vis吸收可證明聚醯亞胺結構中有酞菁的存在，最大放光波長範圍在660~700nm之間。這些共聚物的玻璃轉移溫度在226~238℃之間，在氮氣下的5%及10%重量損失分別在338~419℃及431~501℃之間。聚合物的循環伏安圖（CV）皆顯示出一對可逆的氧化還原峰。

關鍵字

聚醯胺酸 ； 聚醯亞胺 ； 酞菁

並列摘要

Three novel copolyimides （PI-6FDA）containing Zn, Cu- phthalocyanine were successfully synthesized. First, 3-(4-(bis(4-aminophenyl)amino)phenoxy)-6-(hexyloxy)phthalonitrile was prepared and polymerized with 4,4'-(Hexafluoroisopropylidene)diphthalic anhydride to form polyamic acid （PAA-6FDA）and polyimide（PI-6FDA）. Polyamic acid （PAA-6FDA）was condensed with 1,2-dicyanobenzene to form copolyamic acid containing Zn- phthalocyanine and then chemical imidization was carry out to obtain copolyimide, followed by chemical imidization. On the other hand, polyimide（PI-6FDA）was directly condensed with 1,2-dicyanobenzene to form copolyimides containing Zn, Cu- phthalocyanine. The thermal properties, optical properties and solubility of the copolyimides were investigated and discussed. The presence of phthalocyanine was confirmed by the absorption band at 669nm and 671 nm in the visible range. These copolyimides showed photoluminescence maximum at 660~680nm. These copolyimides showed glass transition temperatures between 226~238℃, and they showed 5% and 10% weight-loss temperatures in nitrogen atmosphere were record in the range of 338~419℃ and 431~501℃, respectively. Cyclic voltammetry curves of the polymers showed one pair of reversible redox peak.

並列關鍵字

polyamic acids ； polyimides ； phthalocyanine

參考文獻

1. Abadie, M. J. M. and Sillion, B., Polyimides and Other High Temperature Polymers. 1991, Amsterdam: Elsevier.

3. Sroog, C. E., "Polyimides". Prog Polym Sci, 1991. 16, 561-694.

4. Sawada, T. and Ando, S., "Synthesis, Characterization, and Optical Properties of Metal-Containing Fluorinated Polyimide Films". Chem. Mater., 1998. 10, 3368-3378.

5. Kim, Y. K., Park, H. B., and Lee, Y. M., "Synthesis and characterization of metal-containing sulfonated polyimide membranes and their gas separation properties". Desalination, 2002. 145, 389-392.

6. Meador, M. A. B., Cubon, V. A., Scheiman, D. A., and Bennett, W. R., "Effect of Branching on Rod-Coil Block Polyimides as Membrane Materials for Lithium Polymer Batteries". Chem. Mater., 2003. 15, 3018-3025.