Premium
Compartmentalization in TEMPO‐Mediated Radical Polymerization in Dispersed Systems: Effects of Macroinitiator Concentration
Author(s) -
Zetterlund Per B.,
Okubo Masayoshi
Publication year - 2007
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.200600085
Subject(s) - compartmentalization (fire protection) , polymerization , radical , styrene , radical polymerization , nitroxide mediated radical polymerization , chemistry , polymer chemistry , photochemistry , chemical engineering , copolymer , polymer , organic chemistry , engineering , enzyme
The influence of the initial macroinitiator concentration ([PT] 0 ) on compartmentalization effects (segregation effects and confined space effects) in 2,2,6,6‐tetramethylpiperidinyl‐1‐oxy (TEMPO)‐mediated radical polymerization of styrene in a dispersed system at 125 °C has been investigated by simulations employing modified Smith‐Ewart equations. The modeling approach accounts for compartmentalization of both propagating radicals and nitroxide, as well as the generation of radicals by thermal initiation of styrene. The manifestation of compartmentalization effects occurs at significantly greater particle diameters ( d ) for low [PT] 0 ; at [PT] 0 = 0.002 M , the polymerization rate, control and livingness are affected by compartmentalization for d < 120 nm, whereas the system behaves as in the corresponding bulk system for d > 45 nm at [PT] 0 = 0.2 M . The results are discussed with regards to the specific effects of compartmentalization on deactivation and bimolecular termination.