Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, China.
Macromol Rapid Commun. 2014 Aug;35(15):1332-9. doi: 10.1002/marc.201400204. Epub 2014 Jun 18.
A facile homogeneous polymerization system involving the iniferter agent 1-cyano-1-methylethyl diethyldithiocarbamate (MANDC) and copper(II) acetate (Cu(OAc)2 ) is successfully developed in bulk using methyl methacylate (MMA) as a model monomer. The detailed polymerization kinetics with different molar ratios (e.g., [MMA]0 /[MANDC]0 /[Cu(OAc)2 ]0 = 500/1/x (x = 0.1, 0.2, 0.5, 1.0)) demonstrate that this system has the typical "living"/controlled features of "living" radical polymerization, even with ppm level catalyst Cu(OAc)2 , first order polymerization kinetics, a linear increase in molecular weight with monomer conversion and narrow molecular weight distributions for the resultant PMMA. (1) H NMR spectra and chain-extension experiments further confirm the "living" characteristics of this process. A plausible mechanism is discussed.
一种简便的均相聚合体系，涉及引发剂 1-氰基-1-甲基乙基二乙基二硫代氨基甲酸盐（MANDC）和醋酸铜（Cu（OAc）2），在本体中成功地使用甲基丙烯酸甲酯（MMA）作为模型单体进行。详细的聚合动力学研究表明，不同摩尔比（例如，[MMA]0 / [MANDC]0 / [Cu（OAc）2]0 = 500/1/x（x = 0.1、0.2、0.5、1.0）），该体系具有“活性”/“受控”自由基聚合的典型特征，即使催化剂 Cu（OAc）2 的浓度为 ppm 级，聚合动力学仍为一级，分子量随单体转化率线性增加，所得 PMMA 的分子量分布较窄。（1）1H NMR 谱和链延伸实验进一步证实了该过程的“活性”特征。讨论了一种可能的机理。
