Development of Polymer Materials with Solar Energy Storage-Exchange Property

本课题研究开发具有太阳能储能交换性能的高分子材料。我们成功地大规模合成了3-苯基-2,5- nbd -2-羧酸（PNCA），它在太阳能储能交换系统中具有优异的光化学反应性。在适宜的反应条件下，将聚甲基丙烯酸缩水甘油酯中的环氧化物悬垂基团与PNCA进行大规模加成反应，制备了含PNCA悬垂基团的聚合物。然后，研究了聚合物的光化学反应性、热能储存性能、热稳定性和其他性能。此外，采用一些新的合成方法合成了各种主链或侧链含有NBD基团的聚合物。以2,5-NBD-2,3-二羧酸二甘油酯醚与二酰基氯化物加成，再以季铵盐为催化剂，用光敏性化合物对聚合物进行化学改性，得到主链NBD基团，侧链悬垂光敏性基团的高光化学反应活性聚酯。采用二环氧化合物与2,5-NBD-2,3-二羧酸衍生物的聚加成反应，合成了主链上含有NBD基团的聚（酯酰胺）s。以PNCA和其他NBD化合物与环氧氯丙烷、羧酸酐为原料，将含NBD基团的环氧化合物开环共聚，合成了含悬垂NBD基团的聚酯。用含NBD基团的环氧化合物和含光敏基团的环氧化合物与羧酸酸酐开环共聚制备了高性能NBD聚酯。然后，在膜态和溶液态下评价了这些聚合物的光化学反应性和储热性能。

This research project investigated to develop polymeric materials with solar energy storage-exchange property. We succeeded the synthesis of 3-phenyl-2,5-NBD-2-carboxylic acid (PNCA), which have excellent photochemical reactivity for solar energy storage-exchange system, in large scale. Polymers containing pendant PNCA groups were prepared by the addition reaction of pendant epoxide groups in poly (glycidyl methacrylate) s with PNCA under appropriate reaction conditions in large scale. Then, photochemical reactivity, thermal-energy storage property, thermal stability, and other properties of the polymers were investigated. Furthermore, various polymers containing NBD moieties in the main chain or the side chain were synthesized using some novel synthetic methods. That is, polyesters with NBD moieties in the main chain and pendant photosensitizing groups in the side chain, which have high photochemical reactivity, were synthesized by the polyaddition of diglycidyl ether of 2,5-NBD-2,3-dicarboxylic acid with diacyl chlorides followed by the chemical modification of the resulting polymers with photosensitizing compounds using quaternary onium salts as catalysts. Poly(ester-amide) s with NBD moieties in the main chain were synthesized by the polyaddition of bisepoxides with of 2,5-NBD-2,3-dicarboxylic acid derivatives. Polyesters containing pendant NBD moieties were synthesized by the ring-opening copolymerization of epoxy compounds containing NBD moieties, which were synthesized by the reaction of PNCA and other NBD compounds with epichlorohydrin, with carboxylic acid anhydrides. High performance NBD polyesters were also synthesized by the ring-opening copolymerization of the epoxy compounds containing NBD moieties and epoxy compounds containing photosensitizing groups with carboxylic acid anhydrides. Then, photochemical reactivity and thermal energy storage property of these polymers were evaluated in the film state or in solution.