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Compartmentalization in Atom Transfer Radical Polymerization (ATRP) in Dispersed Systems
Author(s) -
Kagawa Yasuyuki,
Zetterlund Per B.,
Minami Hideto,
Okubo Masayoshi
Publication year - 2006
Publication title -
macromolecular theory and simulations
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.37
H-Index - 56
eISSN - 1521-3919
pISSN - 1022-1344
DOI - 10.1002/mats.200600049
Subject(s) - atom transfer radical polymerization , chemistry , compartmentalization (fire protection) , polymerization , polymer chemistry , particle (ecology) , radical , butyl acrylate , acrylate , radical polymerization , atom (system on chip) , copolymer , photochemistry , polymer , organic chemistry , oceanography , computer science , embedded system , enzyme , geology
Summary: 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 °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 R p for small particles ( d < 30 nm) is due to the pseudo first‐order deactivation rate coefficient being proportional to d −3 .Simulated propagating radical concentration ([P•]) as a function of particle diameter ( d ) at 10% conversion for ATRP of n ‐butyl acrylate ([ n BA] 0 = 7.1 M , [PBr] 0 = [CuBr/dNbpy] 0 = 35.5 m M ) in a dispersed system at 110 °C. The dotted line indicates the simulated [P•] in bulk at 10% conversion.