可见光活性[艹北]铜配位聚合物网络催化甲基丙烯酸甲酯原子转移自由基聚合

Atom Transfer Radical Polymerization of Methyl Methacrylate Catalyzed by Visible Light Active Perylene-Copper Coordination Polymer Network

以具有可见光活性的[艹北]-铜配位聚合物网络(Cu-PTC)为催化剂,实现了甲基丙烯酸甲酯(MMA)的原子转移自由基聚合。研究了催化剂/单体比例对MMA聚合行为的影响,优化了聚合条件。动力学研究显示,聚合过程符合"活性"自由基聚合特征;并且核磁共振氢谱(^(1 )H-NMR)结果表明,Cu-PTC的微孔结构可诱导MMA的光聚合,使聚合物的立构规整性提升。进一步采用紫外光谱(UV)、电子顺磁共振波谱(EPR)及电化学研究了Cu-PTC作为光诱导催化剂催化MMA聚合的机理,结果显示,Cu-PTC受光激发产生光生电子和空穴,通过光生电子活化α-溴苯乙酸乙酯(EBP)引发剂以实现"活性"聚合。

Atom transfer radical polymerization of methyl methacrylate(MMA)was carried out by using perylene-copper coordination polymer network(Cu-PTC)with visible light activity as catalyst.The effect of catalyst/monomer ratio on the polymerization behavior of MMA was studied,and the polymerization conditions were optimized.The kinetic study shows that the polymerization process is consistent with the living radical polymerization characteristics.Moreover,the results of^1H-NMR show that the microporous structure of Cu-PTC can induce the photopolymerization of MMA and improve the stereoregularity of the polymer.UV-spectroscopy(UV),electron paramagnetic resonance spectroscopy(EPR)and electrochemical studies were carried out to investigate the mechanism of Cu-PTC as photoinduced catalyst for the polymerization of MMA.The results show that Cu-PTC is excited by photoexcitation to generate photogenerated electrons and holes.Photogenerated electrons activate an alpha-bromophenylacetate(EBP)initiator to achieve living polymerization.