树形聚合物表面大环载双金属纳米粒子催化二烯类聚合物氢化改性

项目名称： 树形聚合物表面大环载双金属纳米粒子催化二烯类聚合物氢化改性

项目编号： No.51273071

项目类型： 面上项目

立项/批准年度： 2013

项目学科： 一般工业技术

项目作者： 彭晓宏

作者单位： 华南理工大学

项目金额： 80万元

中文摘要： 本项目拟基于双金属纳米粒子的协同电子效应更有利于含双键底物催化反应的特性，利用聚丙烯亚胺为核、表面含十五元三烯大环配体的杂化树形聚合物载体和过渡金属络合物（Ru(PPh3)3、Rh(PPh3)4、Pd2(dba)4、Pt2(dba)4、Pd(PPh3)4、Pt(PPh3)4），通过两种过渡金属络合物配体与大环配体的同步交换反应制备出一系列杂化树形聚合物表面负载的双金属RuRh 和PdPt纳米粒子(DTNs)。探讨双金属DTNs形成过程和结构的关系，考察双金属DTNs催化剂在二烯类聚合物氢化反应过程中的氢化度、催化活性、选择性和循环使用次数，研究二烯类聚合物中碳碳双键催化加氢反应的变化规律、作用机理及其氢化二烯类聚合物的物理化学性能。为建立高选择性、高催化活性、稳定性好、易于回收和循环使用的新型表面负载型双金属DTNs催化体系及其催化二烯类聚合物氢化改性提供理论依据。

中文关键词： 杂化树形聚合物；十五元三烯大环；双金属催化剂；氢化；二烯类聚合物

英文摘要： This project is based on the characteristic of synergistic electronic effect in bimetallic nanoparticles that can be more beneficial to the catalytic reaction of substrate having a double bond. Accordingly, a series of bimetallic RuRh and PdPt dendrimer-templated nanoparticles (DTNs), stabilized by hybrid dendrimers containing a poly(propyleneimine) core and 15-membered triolefinic macrocycles in periphery, will be prepared by using the simultaneous ligand-exchange reaction between the macrocycles and two transition-metal complexes (Ru(PPh3)3/Rh(PPh3)4, Pd2(dba)4/Pt2(dba)4 or Pd(PPh3)4/Pt(PPh3)4). The relationships between formation process and structure of the bimetallic DTNs will be discussed. The hydrogenation degree, catalytic activity, hydrogenation selectivity, and cycle times of the process for hydrogenating diene polymers with the bimetallic DTNs as catalysts will be investigated. The change regularity and mechanism of catalytic hydrogenation of the C=C in diene polymers, as well as the physical and chemical performance of the hydrogenated products will also be researched. It can be expected to provide the theory basis for not only the establishment of novel surface-loaded type of bimetallic DTN catalytic systems, which are of high selectivity, high catalytic activity, good stability, easy recovery, and

英文关键词： Hybrid dendrimer；15-Membered triolefinic macrocycle；Bimetallic catalyst；Hydrogenation；Diene polymer