原子转移自由基聚合合成(甲基)丙烯酸酯类模型聚合物及其动力学研究

Synthesis of (Meth)acrylates Model Polymers and the Keinetics Study of Atom Transfer Radical Polymerization (ATRP)

本文采用一种新颖的活性自由基聚合—原子转移自由基聚合（ＡＴＲＰ）的方法，以１－溴代苯乙烷作为引发剂，过渡金属卤化物与配位剂络合物（ＣｕＢｒ／２，２’－联吡啶）为催化体系，环己酮为溶剂，进行了甲基丙烯酸正丁酯（ＢＭＡ）和丙烯酸正丁酯（ＢＡ）的活性聚合。得到具有指定分子量和窄分子量分布（１．２＜Ｍｗ／Ｍｎ＜１．５）的模型聚合物。

The general principle and the mechanism of novel living radical polymerization -Atom Transfer Radical Polymerization (ATRP) have been attained in this paper. Butyl Methacrylate (BMA) and Butyl acrylate (BA) were chosen as monomers. A simple alkyl halide, 1-phenylethyl bromine, was used as the initiator, and a transition metal species CuBr complexed by suitable ligand 2,2'-bipyridine, was used as the catalyst system. ATRP was carried out at 110℃, the molecular weight and its distribution of polymers taken at different time were measured by GPC. The GPC results showed that the molecular weights of the model polymers were very closed to the designed values (M n,th =△/ 0×(MW) 0). The molecular weight distribution (MWD) become narrower with prolonging the polymerization time. The MWD of the model polymers of PBMA and PBA are 1.35,1.28 respectively. The major factors affecting the ATRP processes, the structures of monomers and polymerization temperature were discussed. Several kinetical constants, e.g. concentration of propagating radical species were also estimated. All results suggested that ATRP of (meth)acrylates have been successfully achieved.