高分子刷负载TEMPO催化体系的可控制备及其选择性氧化性能研究

项目名称： 高分子刷负载TEMPO催化体系的可控制备及其选择性氧化性能研究

项目编号： No.21304030

项目类型： 青年科学基金项目

立项/批准年度： 2014

项目学科： 数理科学和化学

项目作者： 刘少杰

作者单位： 河北科技大学

项目金额： 25万元

中文摘要： 均相催化剂的负载化是解决催化剂分离与回收的一条有效途径，其中表面接枝高分子刷的功能性微球因其独特的结构使其用作催化剂载体具有诱人的应用前景。本课题拟通过表面引发的ARGET ATRP，制备以交联聚苯乙烯（PS）微球为基质，含甲基丙烯酸-2,2,6,6-四甲基-4-哌啶基酯（TMPM）结构单元的结构可控的高分子刷。再用3-氯过氧苯甲酸将哌啶基氧化为氮氧自由基，生成负载有机小分子催化剂2,2,6,6-四甲基哌啶-N-氧自由基（TEMPO）的高分子刷（PTMA）。本课题首次制备了高分子刷负载TEMPO催化体系，且通过对高分子刷长度、TMPM含量及位置的调控实现对TEMPO负载数量和位置的调控。以高分子刷负载TEMPO/CuBr2作为醇选择性氧化的催化体系，使得聚合物中残留的CuBr2得到再利用。借助线形高分子刷的可溶性及交联PS球的不溶性实现均相催化与异相分离的有机统一。

中文关键词： 高分子刷；ARGET ATRP；负载；TEMPO；选择性氧化

英文摘要： Immobilization of a homogeneous catalyst can in principle facilitate its separation and recycling, and therefore is of considerable interest to both academia and industry. The spherical polymer brush as catalyst carrier is promising for its characteristic microstructure. This study will apply ARGET (Activators Regenerated by Electron Transfer) ATRP (Atom Transfer Radical Polymerization) to prepare the polymer brushes having TMPM(2,2,6,6-Tetramethyl-4-piperidyl Methacrylate) on cross-linked PS (Polystyrene) microspheres with controlled structure. TEMPO (2,2,6,6-tetramethyl-piperidyl-1-oxy1) as an organocatalyst can be immobilized on the polymer brushes through oxidation of PTMPM with m-Chloroperoxybenzoic acid. The application of ARGET ATRP makes the process of preparing polymer brushes green, effective and controllable. The control of TEMPO immobilization is achieved by controlling the polymer brush structure. The residua CuBr2 in polymer is reused through using TEMPO/CuBr2 as a catalyst system. The combination of homogeneous reaction and heterogeneous separation for the catalyst system can be realized by means of the soluble linear polymer brush and insoluble cross-linked PS core.

英文关键词： Polymer brush；ARGET ATRP；Support；TEMPO；Selective oxidation