STUDY ON NOVEL PHOTORESPONSIVE POLYMER MATERIAL

1.为了得到光合成中叶绿素a的合成模型，通过与H_2N(CH_2)_nNH_2的缩合反应，通过酰胺键将四(羧基苯基)卟啉转化为二聚体，然后将生成的二聚体中剩余的羧基与卤代苄进行酯化反应，得到单烯类化合物，再与过量的N-乙烯-2-吡咯烷酮进行共聚，得到以卟啉二聚体为侧基的水溶性聚合物。还合成了含中心金属镁、锌、钴(II)、镍(II)和铜(II)的可聚合二聚体，并进行了共聚反应，得到了水溶性的共聚物。将这些共聚物加入到光氧化还原体系中，观察到了它们在水中的光氧化还原作用。因此，以最短的链连接两个卟啉或金属卟啉环的侧链二聚体的共聚物是最有效的光氧化还原催化剂。含侧基镁-卟啉二聚体的聚合物是最…的最有效的是，超过了带有吊坠单体的产品。至于除镁以外的其他金属的影响，锌是有效的，而其他金属几乎不起作用。利用了偶氮苯的光反顺式异构化和由此产生的空间结构变化。因此，使用亚氨基二乙酸对偶氮苯的3，3‘-位提供了金属螯合性能。还在5-位或3-位引入了苯乙烯部分，以提供可聚合的单体，该单体被共聚以提供具有螯合功能的苯基或水溶性共聚物作为侧链。将上述含亚氨基二乙酸基的偶氮苯的酸酸酐与二胺缩聚，得到主链上含有偶氮苯单元的具有孤立羧基的水溶性聚酰胺。这些聚合物对金属离子的萃取能力随光反式异构化反应的不同而不同，并与金属的种类有关，其中锌的萃取率最高。较少

1. In order to get a synthetic model for Mg-chlorophyll a In photo- synthesis, meso-tetra(carboxyphenyl)porphyrin was converted to its dimers via amide linkage by condensation with H_2N(CH_2)_nNH_2. The remaining carboxyl groups of the resulting dimers were then esterified with benzyl halides so as to afford monovinyl compounds, which were copolymerized with a large excess of N-vinyl-2-pyrrolidone to afford water-soluble polymers bearing porphyrin dimer as pendant. Polymerizable dimers bearing central metals such as Mg, Zn, Co(II), Ni(II), and CU(II) in porphyrin rings were also synthesized and copolymerized to provide water-soluble copolymers. The effect of addition of these copolymers to a photo-redox system: FRA - L-Ascorbic acid in H_2O ,was noted. Thus, copolymers with the pendant dimers in which two porphyrin or metalloporphyrin rings were linked with the shortest chains were the most effective as photoredox catalyst. Polymers with pendant magnesium- porphyrin dimers was the most … More effective of all, exceeding those with pendant monomers. As for the effect of metals other than Mg, Zn was effective but other metals were hardly effective.2. The photo trans-cis isomerization and the resulting sterical structure change of azobenzenes were utilized. Thus, the metal-chelating property was provided to 3,3'-positions of azobenezene using iminodiacetic acid. Styrenic moiety was also introduced to either the 5- or 3-position to afford a polymerizable monomer, which was copolymerized to provide either benzene- or water-soluble copolymers bearing chelating function as pendant. Acid anhydrides from the above-mentioned azobenzene with the iminodiacetic acid moiety were subjected to polycondensation with diamine to provide a water soluble polyamide with the isolated carboxyl group and bearing the azobenzene unit in the principal chain. The metal ion-extracting ability of these polymers was changed with photo trans-cis isomerization and dependent on the kind of metal, Zn being the best among metals investigated. Less