以壳聚糖为模板的对苯二酚氧化聚合反应表观动力学研究  

AN APPARENT KINETICS STUDY ON THE OXIDATIVE POLYMERIZATION OF p-DIHYDROXYBENZENE USING CHITOSAN AS TEMPLATE

作　　者：贺剑[1] 关英[1] 张拥军[1] 

机构地区：[1]南开大学化学学院高分子化学研究所功能高分子材料教育部重点实验室,天津300071

出　　处：《高分子学报》2009年第6期572-575,共4页Acta Polymerica Sinica

基　　金：科技部国际科技合作项目(基金号2007DFA50760);教育部博士点基金新教师项目(基金号20070055079)资助

摘　　要：以壳聚糖为模板在酸性溶液中实现了对苯二酚的氧化聚合.该反应必须在氧气存在的条件下才能进行.动力学研究表明该氧化聚合反应是以选取机理进行的模板聚合反应.当壳聚糖残基与对苯二酚的摩尔比小于0.8时,反应速度与壳聚糖浓度成正比.当壳聚糖残基与对苯二酚的摩尔比大于0.8时,反应速度不再随壳聚糖浓度提高而提高.反应对对苯二酚而言是一个一级反应.反应的活化能为71.6kJ/mol.The oxidative polymerization of hydroquinone in acidic solutions in the presence of chitosan was studied. The reaction rate was facilely represented by the increase rate of absorption at 470 nm and measured under various conditions. The reaction does not proceed in the absence of oxygen. The presence of chitosan increases the reaction rate significantly, suggesting chitosan works as a template for the oxidative polymerization of hydroquinone. Kinetic studies reveal that the reaction is first-order for hydroquinone, while the reaction rate increases linearly with chitosan concentration when molar ratio of chitosan/hydroquinone is less than 0.8, but keeps constant beyond that point. These results suggest a pick-up mechanism for the template polymerization of hydroquinone.The energy, of activation was calculated to be 71.6 kJ/mol. Preliminary results also show that the reaction mixture gelates in certain cases. Further investigation on the structure, molecular weight and its distribution of the resultant poly（hydroquinone） is still on-going. These redox-active hydrogels may find applications in electrochemical biosensor.

关 键 词：模板聚合 氧化聚合反应 聚对苯二酚 壳聚糖 

分 类 号：O631.5[理学—高分子化学] O625.312[理学—化学]