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Solvent Influence on Propagation Kinetics in Radical Polymerizations Studied by Pulsed Laser Initiated Polymerizations
Author(s) -
Beuermann Sabine
Publication year - 2009
Publication title -
macromolecular rapid communications
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 154
eISSN - 1521-3927
pISSN - 1022-1336
DOI - 10.1002/marc.200900131
Subject(s) - kinetics , steric effects , supercritical fluid , solvent , intermolecular force , chemistry , photochemistry , activation energy , ionic bonding , solvent effects , radical polymerization , polymerization , polymer chemistry , materials science , organic chemistry , molecule , polymer , ion , physics , quantum mechanics
The influence of the reaction medium (organic solvents, water, ionic liquids, supercritical CO 2 ) on the propagation rate in radical polymerizations has very different causes, e.g., hindered rotational modes, hydrogen bonding or electron pair donor/acceptor interactions. Depending on the origin of the solvent influence propagation rate coefficients, k p , may be enhanced by up to an order of magnitude associated with changes in the pre‐exponential or the activation energy of k p . In contrast, non‐specific interactions, size and steric effects lead to rather small changes in the vicinity of the radical chain end and are reflected by modest variations in k p .