新型钴酞菁接枝温敏聚合物的制备及性能  

PREPARATION AND PROPERTIES OF A NOVEL THERMOSENSITIVE POLYMER CONTAINING COBALT PHTHALOCYANINE

作　　者：冯桂华[1] 申晓媛[1] 李楠[1] 赵宝艳[1] 姚玉元[1] 吕汪洋[1] 陈文兴[1] 

机构地区：[1]先进纺织材料与制备技术教育部霞点实验室浙江理工大学,杭州310018

出　　处：《高分子学报》2008年第6期567-573,共7页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号20574061);教育部“新世纪优秀人才支持计划”(项目号NCET-04-0559);教育部“长江学者与创新团队发展计划”(项目号IRT0654)资助项目

摘　　要：采用2,4,6-三氯-1,3,5-三嗪对四氨基钴酞菁进行改性,并以共价键接枝到聚N-异丙基丙烯酰胺上制得一种新型温敏性高分子催化剂——钴酞菁接枝温敏聚合物,并采用UV-Vis、TG等对其进行表征.对钴酞菁接枝温敏聚合物、温敏聚合物和小分子金属酞菁进行溶解性测试,结果表明与四氨基钴酞菁相比,所合成的钴酞菁接枝温敏聚合物能溶解于水和大多数有机溶剂,且该聚合物水溶液具有良好的温敏性,其最低临界溶解温度(LCST)为34.5℃.采用浊度法考察了不同比例的混合溶剂(乙醇/水、DMF/水)对LCST的影响,结果表明随着有机溶剂含量的增加,LCST先下降后升高,而当有机溶剂增加到一定程度时温敏性消失.本文还考察了钴酞菁接枝温敏聚合物对2-巯基乙醇的催化活性,结果表明随着温度升高,催化活性也不断提高,而当温度超过LCST时催化活性急剧下降,聚合物从溶液中析出.基于这些特性,该温敏聚合物负载酞菁作为一种新型的催化剂可实现均相催化、异相分离.Metallophthalocyanine has attracted considerable attention as oxidation catalyst because its structure similar to the active center of cytochrome P-450,and it can promote many reactions through oxidase-like,catalase-like,as well as peroxidase-like mechanism,whereas it has the following problems：low solubility,high aggregation tendency,difficulty in catalyst recovery and recycling,which restrict its further application as catalyst.Poly（N-isopropylacrylamide） （PNIPAAm） is a typical thermosensitive polymer,and it can be homogeneous below its lower critical solution temperature （LCST） and completely precipitated above LCST,which makes it become an attractive polymer support for catalyst.A novel reactive and aqueous soluble metallophthalocyanine derivative,cobalt tetra（2,4-dichloro-1,3,5-triazine）aminophthalocyanine （Co-TDTAPc）,was synthesized by the modification of cobalt aminophthalocyanine with 2,4,6-trichloro-1,3,5-triazine and immobilized on PNIPAAm by covalent bond to obtain a thermosensitive polymer catalyst,PNIPAAm-g-Co-TDTAPc.The polymer catalyst was characterized by UV-Vis spectrometer in ethanol and THF,and the results showed that PNIPAAm-g-Co-TDTAPc had characteristic absorption peaks of cobalt phthalocyanine （B band： 280～330 nm;Q band： 620～700 nm） in both ethanol and THF,while PNIPAAm had no absorption in these area,which proved that the Co-TDTAPc had been successfully grafted on PNIPAAm.The thermal stability of the polymers were also tested by heating from room temperature to 600℃ at a rate of 20 K/min in a nitrogen environment with flow rate of 100 mL/min.The results indicated that the beginning decomposition temperature of PNIPAAm-g-Co-TDTAPc was 407℃,which confirmed that the polymer catalyst had high thermal stability.The solubility of small molecular cobalt phthalocyanine,PNIPAAm and PNIPAAm-g-Co-TDTAPc was investigated in different solvents.The results showed that PNIPAAm-g-Co-TDTAPc could dissolve in water and most organic solvents,while the small molecule coba

关 键 词：聚合物 温敏性能 钴酞菁 共价接枝 

分 类 号：O631.3[理学—高分子化学]