Radical Polymerisation in the Associated Species of Ionogenic Surface-active Monomers in Water

The radical polymerisation in water of ionogenic monomers of the cationic and anionic type exhibiting surface-active properties is discussed. Together with kinetic phenomena, which can be accounted for within the framework of the hypothesis of a homophase course of the process, effects which require the assumption of the possibility of the association of the monomeric molecules are observed in the polymerisation of monomers with a low surface activity in aqueous solutions. The polymerisation of monomers with a high surface activity in micellar dispersions differs from the processes in solutions by a number of features associated with the influence of structure formation in the monomer on the kinetics of polymerisation and the macrostructure of the polymer formed. The kinetic effects induced by the increasing concentration and microviscosity of the monomer solutions and also by the change in the relative positions of its molecules in the associated species compared with the solution are discussed. Examples of the influence of processes involving the rearrangement of the associated speices on the process kinetics are presented. The possibility, in principle, of the fixation of the structure of the associated species (micelles) as a consequence of polymerisation is noted.
The kinetics of the polymerisation process in micellar and vesicular dispersions of two-chain surface-active monomers and also in monolayers at the water–gas interface are discussed.
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