STUDY ON NOVEL PHOTORESPONSIVE POLYMER MATERIAL

新型光响应高分子材料的研究

• 批准号: 62550669
• 负责人: KAMOGAWA Hiroyoshi
• 金额: $ 1.47万
• 依托单位: University of Yamanashi
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1987
• 资助国家: 日本
• 起止时间: 1987 至 1989
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-62550669/
• 关键词: Photoresponsive Vinyl Polymer; Photosynthesis model; Polymer bearing Porphyrin Dimer; Photo trans-cis Isomerization; Azobenzene having Chelating ability; 光感性ビニルポリマ-; ポルフイリン二量体ポリマ-; ポルフィリン二量体ポリマー; キレート化アゾベンゼン; 光感応性ビニルポリマー; ポルフイリンニ量体; 光トランスーシス異性化

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

1.为了获得光合成中镁叶绿素a的合成模型，通过与H_2N(CH_2)_nNH_2缩合，通过酰胺键将内消旋四(羧基苯基)卟啉转化为二聚体。然后将所得二聚体的剩余羧基用苄基卤酯化以提供单乙烯基化合物，其与大量过量的N-乙烯基-2-吡咯烷酮共聚以提供带有卟啉二聚体作为侧基的水溶性聚合物。还合成了在卟啉环中带有中心金属（例如Mg、Zn、Co(II)、Ni(II)和CU(II)）的可聚合二聚体并共聚以提供水溶性共聚物。注意到将这些共聚物添加到光氧化还原系统：FRA - H_2O 中的 L-抗坏血酸中的效果。因此，具有侧垂二聚体（其中两个卟啉或金属卟啉环与最短链连接）的共聚物作为光氧化还原催化剂是最有效的。具有悬垂镁卟啉二聚体的聚合物是所有聚合物中最有效的，超过具有悬垂单体的聚合物。对于除Mg以外的金属的作用，Zn较有效，而其他金属则几乎没有效果。2．利用光反式-顺式异构化和由此产生的偶氮苯的空间结构变化。因此，使用亚氨基二乙酸向偶氮苯的3,3'-位提供金属螯合性能。苯乙烯部分也被引入到5-位或3-位以提供可聚合单体，将其共聚以提供带有作为侧链的螯合功能的苯或水溶性共聚物。将上述带有亚氨基二乙酸部分的偶氮苯的酸酐与二胺进行缩聚，得到具有分离的羧基并在主链上带有偶氮苯单元的水溶性聚酰胺。这些聚合物的金属离子萃取能力随着光反式-顺式异构化而改变，并且取决于金属的种类，Zn是所研究的金属中最好的。较少的

项目成果

鴨川博美: J. Polymer Science, Polym. Chem. Ed.25. 967-977 (1987)

鸭川宏美：《高分子科学》，《高分子化学》，第 967-977 版（1987 年）。

鴨川博美: "N-Methyl-N-nitroso-p-Styrenesulfonamide and p-Styrensulfinic Acid Polymer" Bull.Chem.Soc.Jpn.62. 189-192 (1989)

Hiromi Kamokawa：“N-甲基-N-亚硝基-对苯乙烯磺酰胺和对苯乙烯亚磺酸聚合物”Bull.Chem.Soc.Jpn.62 (1989)。

鴨川博美 他: "Function of Vinyl Copolymens with Pendant Porphyrin or Metalloporphyrin Dimers as Photoredox Catalyst" J.Polymar Science,A.

Hiromi Kamokawa 等人：“带有卟啉或金属卟啉二聚体的乙烯基共聚物作为光氧化还原催化剂的功能”J.Polymar Science，A。

鴨川博美 他: Bull,Chem,Soc,Jpn.62. 189-192 (1989)

Hiromi Kamokawa 等人：Bull，Chem，Soc，Jpn.62（1989）。

Hiroyoshi Kamogawa: "Preparation of Vinyl Polymer Bearing Synthetic Porphyrin and Mg-Porphyrin Dimers as Pendant" Macromolecules, 22, 1989, 2123-2126.

Hiroyoshi Kamokawa：“带有合成卟啉和镁卟啉二聚体作为悬垂物的乙烯基聚合物的制备”《高分子》，22，1989，2123-2126。