电化学聚合漆酚铜配合物催化引发醋酸乙烯酯聚合的研究

STUDY ON CATALYZED POLYMERIZATION OF VAc BY COPPER ELECTROPOLYURUSHIOL

将电化学聚合方法得到的聚合漆酚 (EPU)与氯化铜异丙醇溶液作用生成电化学聚合漆酚铜配合物(EPU Cu2 + ) .采用顺磁共振波谱 (ESR)、红外光谱 (FT IR)、XPS光电子能谱、原子发射光谱 (AES)、元素分析及AES等手段进行表征 ,确定该配合物的结构即每个铜离子与EPU分子中二个链节单元的羟基发生配位 .配合物中铜含量达 8 6 3% .实验表明 ,电化学聚合漆酚铜 (EPU Cu2 + )配合物膜在室温下的Na2 SO3水体系 (pH =7)中能催化引发醋酸乙烯酯 (VAc)按自由基加聚反应历程进行聚合 .讨论了温度、Na2 SO3浓度、VAc浓度和EPU Cu2 + 膜用量对聚合速率、诱导时间的影响 ,求得聚合速率的表达式Rp=0 0 7e- 2 82 5 RT[VAc]1 54[Na2 SO3]0 5,实验结果表明 ,EPU Cu2 + 配合物膜催化引发醋酸乙烯酯 (VAc)聚合的诱导期为 12 2s ,反应 2 4h后PVAc得率为79% , Mw =1 2 6× 10 6 , Mn=2 6 3× 10 5,多分散性系数为 4 79.

The electroconductive polymer with new function and characteristic can be synthesized by the electrochemical polymerization. This new functional material can be widely used in catalyst, electrochemical sensor and electroanalysis etc. So the film of EPU Cu 2+ coordination polymer was obtained by the reaction between CuCl 2 in isopropyl alcohol solution and EPU. The EPU Cu 2+ film was characterized by ESR, FT IR, XPS, elemental analysis and AES, and the composition and structure of the film were determined. Each Cu 2+ ion is coordinated by hydroxyl from two units in EPU molecule. The Cu 2+ content in the coordination polymer is 8.63%. The experiments indicated that, the EPU Cu 2+ film activated by Na 2SO 3 can catalyze polymerization of VAc in water phase at room temperature. The effects of temperature, concentration of Na 2SO 3 and VAc, weight of copper electropolyurushiol complex membrane on the polymerization rate and induction time were investigated. The polymerization rate equation can be expressed as: R p=0.07 e -2825/ RT [VAc] 1 54 [Na 2SO 3] 0 5 The experimental results indicate: the induction period for polymerization is 122 s, the yield of VAc is equal to about 79% after 24 h, and w, n and w/ n of PVAc is 1 26×10 6, 2 63×10 5 and 4 79, respectively.