Macromolecules, Vol.31, No.18, 6010-6013, 1998
Active center aggregation in lithium-based anionic polymerization. Are very large aggregates present?
Active chain association is the dominant feature of lithium-based anionic polymerization in nonpolar solvents. This must have an influence on reaction rates. The dissociation mechanism maintains that under normal conditions, chain propagation is carried out by the dissociated species that are present as only a very small fraction of the whole. This requires that the kinetic order be the reciprocal of the association number. A recent paper in this journal has mounted a vigorous attack on the dissociation hypothesis, maintaining that the kinetic order is variable and not constant in each system and hence there can be no relation between association number and kinetic order. Moreover, the claim is made that besides dimers very large active center aggregates are present in all the solutions in large amounts. It seems obvious, however, that variability in kinetic order can only be caused by differences in the rigor of experimental procedures carried out on highly moisture and air sensitive systems at high dilutions. The evidence for the presence of very large aggregates of active centers is totally unconvincing and contrary to existing data previously obtained by the authors themselves and others.
Keywords:HYDROCARBON SOLVENTS;ASSOCIATION;POLYBUTADIENYLLITHIUM;POLYISOPRENYLLITHIUM;POLYSTYRYLLITHIUM;UNREACTIVITY;MECHANISM;BEHAVIOR;LIGHT