Compartmentalization in atom transfer radical polymerization (ATRP) in dispersed systems
Compartmentalization in atom transfer radical polymerization (ATRP) in dispersed systems
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DOI：
10.1002/mats.200600049
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发表时间：
2006-10-11
影响因子：
1.4
通讯作者：
Okubo, Mayayoshi
中科院分区：
文献类型：
--
作者：
Kagawa, Yasuyuki;Zetterlund, Per B.;Okubo, Mayayoshi
原子转移自由基的区隔化：在低转化率（< 10%）的分散体系中聚合（ATRP）已通过修正的Smith-Ewart方程进行了研究，重点研究了丙烯酸正丁酯/立方橡胶/4,4-二酰-2,2-二吡啶体系在110℃下的区隔化。模拟中考虑了扩散自由基和失活化剂的区隔化。当粒径(d)小于70 nm时，转化率为10%时聚合速率（R-p）相对于相应的本体体系增加，在60 nm处达到最大值，随后随着粒径(d)的进一步减小而急剧下降。这种行为是由区隔化（隔离和受限空间效应）对双分子终止和失活的单独影响引起的。对于小颗粒（d < 30 nm）， RP很低是由于伪一阶失活速率系数与d（-3）成正比。
Compartmentalization in atom transfer radical : polymerization (ATRP) in dispersed systems at low conversion (< 10%) has been investigated by means of a modified Smith-Ewart equation focusing on the system n-butyl acrylate/CuBr/4,4-dinonyl-2,2-dipyridyl at 110 degrees C. Compartmentalization of both propagating radicals and deactivator was accounted for in the simulations. As the particle diameter (d) decreases below 70 nm, the polymerization rate (R-p) at 10% conversion increases relative to the corresponding bulk system, goes through a maximum at 60 nm, and thereafter decreases dramatically as d decreases further. This behavior is caused by the separate effects of compartmentalization (segregation and confined space effects) on bimolecular termination and deactivation. The very low RP for small particles (d < 30 nm) is due to the pseudo first-order deactivation rate coefficient being proportional to d(-3).