负载型铜催化剂的制备及在反向自由基聚合反应中的应用

Synthesis and application of Cu-supported catalyst in the atom transfer radical polymerization

以ZSM-5和Al2O3为载体,通过浸渍法合成铜负载催化剂Cu-ZSM-5和Cu-Al2O3,将该负载催化剂应用于甲基丙烯酸甲酯（MMA）和苯乙烯（Sty）的反向原子转移自由基聚合反应（R-ATRP）,考察了聚合反应的动力学规律.实验结果表明,Cu-ZSM-5和Cu-Al2O3中的铜含量分别为0.55和0.59mmol/g,以CuCl2和CuO形式存在.Cu-ZSM-5和Cu-Al2O3参与的聚合反应均满足一级动力学反应规律,为可控聚合.负载催化剂的使用减少了聚合物中的铜含量,Cu-ZSM-5催化所得的PMMA中的铜残留量为0.0294mg/g,而在Cu-Al2O3催化所得产物中未检测到铜.负载催化剂可以通过简单的离心进行分离回收,活化后仍具有良好的活性.

The supported catalysts Cu-ZSM-5 and Cu-Al2O3 were synthesized firstly by an immersion method with ZSM-5 and Al2O3 as carrier and employed in the reverse atom transfer radical polymerization（R-ATRP）of methyl methacrylate（MMA）or styrene（Sty）.The copper content in the supported catalyst was 0.55 and0.59 mmol/g for Cu-ZSM-5 and Cu-Al2O3,respectively,which exists in the forms of CuCl2 and CuO.The studies on the kinetics indicated the polymerizations catalyzed by supported catalyst Cu-ZSM-5 or Cu-Al2O3 have the features of controllable polymerization.The use of supported catalysts reduces obviously the copper content in the polymer.The copper residue in the polymer catalyzed by Cu-ZSM-5 was 0.029 4 mg/g,while no copper was detected in the product catalyzed by Cu-Al2O3.The supported catalyst can be recycled with a good activity by simple centrifugation and activation.