Interchain exchange in the anionic polymerization of hydroxyalkyl (meth) acrylates

The kinetics of chain propagation and interchain exchange reactions in the anionic polymerization of 2-hydroxyethyl acrylate initiated by lithium tert-butylate were compared. The kinetic parameters of the reactions under consideration were determined. An abnormal ratio between the activation energies of chain propagation and interchain exchange was revealed and explained by the involvement of hydroxyl groups in changes of reactivities of double bonds and ester groups of the initial monomer, the resulting polymer, and the growing active centers of polymerization. The effect of self-inhibition of polymerization was observed and attributed to the fact that ethylene glycol and its alkoxy alcoholate occurring as H-bonded cyclic complexes form at the beginning of the reaction.