Taranekar Prasad, Fulghum Timothy, Baba Akira, Patton Derek, Advincula Rigoberto
Department of Chemistry, University of Houston, Houston, Texas 77204-5003, USA.
Langmuir. 2007 Jan 16;23(2):908-17. doi: 10.1021/la061820d.
A comparative analysis of the copolymerization behavior between an electro-active terthiophene and a carbazole moiety of a conjugated polymer precursor was investigated using electrochemical and hyphenated electrochemical methods. Five different precursor polymers were first synthesized and characterized using NMR, IR, and GPC. The polymers include homopolymers of individual electro-active groups (P3T, P-CBZ) and different compositions of 25, 50, and 75% (P3TC-25, P3TC50, and P3TC-75) with respect to the two electro-active groups. Since the oxidation potentials of terthiophene and carbazole lie very close to each other, highly cross-linked copolymer films of varying extent were produced depending on the composition. The copolymerization extent was found to be dependent primarily on the amount of the terthiophene, which in this case provided for a more efficient carbazole polymerization and copolymerization than with just carbazole alone (homopolymer). The extent of copolymerization, electrochromic properties, and viscoelastic changes was quantitatively investigated using a number of hyphenated electrochemistry techniques: spectro-electrochemistry, electrochemical quartz crystal microbalance studies (EC-QCM), and electrochemical surface plasmon resonance spectroscopy (EC-SPR). Each technique revealed a unique aspect of the electrocopolymerization behavior that was used to define structure-property relationships and the deposition/copolymerization mechanism.
采用电化学和联用电化学方法，对一种电活性三联噻吩与共轭聚合物前体咔唑部分之间的共聚行为进行了对比分析。首先合成了五种不同的前体聚合物，并利用核磁共振（NMR）、红外光谱（IR）和凝胶渗透色谱（GPC）对其进行了表征。这些聚合物包括单个电活性基团的均聚物（P3T、P-CBZ）以及两种电活性基团不同组成比例（25%、50%和75%）的聚合物（P3TC-25、P3TC50和P3TC-75）。由于三联噻吩和咔唑的氧化电位非常接近，根据组成不同会生成不同程度的高度交联共聚物薄膜。发现共聚程度主要取决于三联噻吩的量，在这种情况下，三联噻吩比单独的咔唑（均聚物）能使咔唑的聚合和共聚更有效。利用多种联用电化学技术对共聚程度、电致变色性能和粘弹性变化进行了定量研究：光谱电化学、电化学石英晶体微天平研究（EC-QCM）和电化学表面等离子体共振光谱（EC-SPR）。每种技术都揭示了电共聚行为的一个独特方面，这些方面被用于定义结构-性能关系以及沉积/共聚机理。
