具光致變偶氮苯分子結構之電活性高分子合成與性質研究

Synthesis and Property Studies of Azo-Based Chromophore-Containing Electroactive Polymers

黃琇嫈(Hsiu-Ying Huang)

指導教授 ： 葉瑞銘

中原大學/理學院/化學研究所/博士(2013年)

https://doi.org/10.6840/cycu201300230

摘要

本論文主要是從分子設計著手，透過改變光活性偶氮苯基團在電活性高分子鏈中的位置，得到一系列具主鏈型、側鏈型光活性基團的多功能性高分子電活性材料。本論文分三部分進行討論：首先以氧化聚合方式製備出與聚苯胺相似結構的偶氮苯胺高分子。第二部分則是製備出光活性與電活性皆在主鏈的聚醯胺高分子。最後則是側鏈含光活性偶氮苯分子而主鏈含苯胺寡聚體的電活性高分子。
第一部分以Friedel-Crafts acylation reaction之方式改質奈米碳管，使碳管表面帶有胺基，將其導入偶氮苯胺高分子中，因偶氮苯胺分子與苯胺之結構相似，同樣擁有胺基可進行氧化聚合以形成共價鍵結，並進一步提升電性。此外並針對其光學性質與電致變色做進一步討論。
第二部分是將含偶氮苯寡聚體ACAO與對苯二胺以氧化偶合法聚合出兼具光活性與電活性的聚醯胺。並在特定波長紫外光和可見光的交互照射下，以紫外光可見光光譜儀(UV-Vis)和液態核磁共振儀(1H NMR)進行監測，觀察其偶氮苯光學異構化轉換情形。另一方面，可由循環伏特安培儀(CV)偵測聚醯胺之電活性。
第三部分則是導入苯胺五聚體在偶氮苯分子中使其成為同時具有光活性與電活性之高分子(Electroactive poly(azine-azo) (EPAA))。並以CV研究偶氮苯光學異構化對此電活性高分子的影響，再分別用以下兩種途徑進行偶氮苯異構化回復探討：(1)利用照光回復；(2)利用熱恢復。同時，我們並針對其光學性質與電致變色做進一步討論。

關鍵字

光活性高分子 ； 偶氮苯 ； 電活性高分子 ； 聚醯胺 ； 電致變色 ； 光致變

並列摘要

In this dissertation, a series of new photoactively conducting polymers have been synthesized, characterized and applied. The basic concept of this dissertation is to use light-driven chromophore moiety of azobenzene as a ‘‘trigger’’ to induce morphological changes in the backbone or side chain of polymers. Basically, this dissertation can be divided into three parts. First of all, chemical oxidative polymerization of 4-aminoazobenzene was studied under oxidative polymerization with ammonium peroxodisulfate as oxidant. Secondly, a new polyamide with azobenzene in the main chain was synthesized. Finally, a novel polymer contained alternating phenyl-capped aniline pentamer in the main chain and azo chromophores in the side chain was synthesized and characterized.
Firstly, the structure of polyaniline and poly(4-aminoazobenzene) are similar. Amino-functionalized MWCNTs grafted with 4-aminobenzoyl groups was obtained by Friedel-Crafts acylation of MWCNTs by direct electrophilic substitution reaction with 4-aminobenzonic acid (4-ABAD) using a mild and noncorrosive medium of polyphosphoric acid (PPA)/phosphorous pentoxide (P2O5). The as-prepared 4-aminobenzoyl- functionalized CNTs (AF-CNTs) can be expected to provide reactive sites for obtaining oligoanilines by polymerization and hence improve the electrical conductivity of polymer. At the same time, electrochromic performance of polymer was investigated by measuring electrochromic photographs and UV-Vis spectra.
Subsequently, photoactively electroactive polyamide was synthesized through reacting ACAO with p-phenylenediamine by oxidative coupling polymerization. After alternate irradiation with UV and visible light, the azobenzene exhibited obvious photochemical switching properties. The reversible photoisomerization (i.e., cis trans) behaviour of the backbone azobenzene moieties existed in as-prepared photoactively electroactive polyamide was by in-situ monitoring through systematic studies of UV-Vis spectra and 1H NMR spectroscopies. On the other hand, electrochemical activity (i.e., redox capability) of the as-prepared polyamide was explored by cyclic voltammetry (CV) measurements.
Finally, an electroactive polymer with good solubility containing alternating phenyl-capped aniline pentamer in the main chain and azo chromophores in the side chain was synthesized. In this study, we present reversible example of photochemically induced switching of electroactivity by performing electrochemical CV in two ways: (i) in that the photochemical reaction switch can be photochemically reverted by re-irradiation at a different wavelength (ii) in that a photoreaction is used that is thermally reversible. Moreover, the electrochromic performance of EPAA was investigated by measuring electrochromic photographs and UV-Vis spectrum.

並列關鍵字

electroactive polymer ； polyamide ； electrochromic ； photochromism ； photoactive polymer ； azobenzene

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