负载型原子转移自由基聚合配体的合成及应用

Synthesis & Application of Immobilized Ligand of Atom Transfer Radical Polymerization

用丙烯酸甲酯(MA)与负载到纳米二氧化硅有机/无机杂化粒子上的三乙烯四胺(TETA)进行Michael加成反应,合成了负载型原子转移自由基聚合(ATRP)配体。将其用于甲基丙烯酸甲酯(MMA)的ATRP,结果表明,动力学曲线表现为ln[c(M0)/c(Mt)](c(M0)为单体起始浓度,c(Mt)为反应时间t时单体浓度)与时间线性相关,分子量随转化率线性增加。可以通过离心轻易将催化体系从聚合物中分离出来,回收的催化体系可再次用于MMA的ATRP,且聚合反应仍具有可控/活性的特性,克服了传统ATRP中聚合后去除含过渡金属催化体系的困难。

Immobilized ligand was synthesized via the Michael addition reaction between methyl acrylate （MA） and triethylenetetramine（TETA） on the surfaces of nano-silica organic/inorganic hybrid particles. The resulting immobilized ligand was utilized for the atom transfer radical polymerization （ ATRP ） of methyl methacrylate（MMA）. Kinetic curves show the linear dependence of ln [c（ M0 ） /c（ Mt ）]on time,and the molecular mass of poly （ methyl methacrylate） increases linearly with monomer conversion. Compared with traditional ATRP processes,the immobilized catalyst could be easily separated and collected from final product by centrifugation. The activity of reclaimed catalyst could be retained and the catalyst can be reused for the ATRP of MMA with controllable polymerization reaction.