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研究了由N,N,N′,N′-对四甲基苯二胺(TMPD)/电子受体组成的光致电子转移变色体系,及其在溶液中和高分子膜中的光反应和热稳定性。实验结果表明这类光致变色体系具有较高速度的光响应能力。在不同芳胺/碘鎓盐(DPIOC)组成的体系中,可观察到电子转移速度随芳胺的氧化还原电位下降而增加:TMPD>N,N-二甲基苯胺>三苯胺>二苯胺。光反应速度和反应物浓度具有一定指数关系,分别为0.66(TMPD)和0.16(二苯基碘铕盐)。在TMPD/卤代烃(RX)组成的体系中,发现卤代烃的C—X键较弱时,体系的光致生色反应速度较快。显然,这是由于反应中间产物(RX~-)的分解有利于减少电子逆转移反应的缘故。在聚甲基丙烯酸甲酯高分子膜中的光致生色反应效率显著地高于溶液中的反应效率,并能获得较高的光密度。热稳定性结果表明,温度对色稳定性有显著影响,每经过一次生色/褪色循环,体系的发色能力下降一半左右。
The photoelectron transfer colorimetric system consisting of N, N, N ’, N’-p-tetramethylphenylenediamine (TMPD) / electron acceptor and its photoreaction in solution and in polymer film and Thermal stability. The experimental results show that these photochromic systems have a higher speed of light response. In the systems of different aromatic amines / iodonium salts (DPIOCs), the electron transfer rate was observed to increase with the decrease of the redox potential of aromatic amines: TMPD> N, N-dimethylaniline> triphenylamine> diphenylamine. There was a certain exponential relationship between the photoreaction rate and the reactant concentration, which was 0.66 (TMPD) and 0.16 (diphenyliodonium europium salt), respectively. In the system consisting of TMPD / halogenated hydrocarbon (RX), the photochromatic reaction of the system was found to be faster when the C-X bond of the halogenated hydrocarbon was found to be weaker. Obviously, this is because the reaction intermediates (RX ~ -) decomposition is conducive to reducing the electronic reverse transfer reaction sake. The photochromic reaction efficiency in the polymethylmethacrylate polymer membrane is significantly higher than the reaction efficiency in the solution, and a higher optical density can be obtained. The results of the thermal stability show that the temperature has a significant effect on the color stability, and the color rendering ability of the system drops by about half after each color / fading cycle.