Spontaneous polymerization is defined as the thermally initiated polymerization of pure monomers without initiators being added in the dark. The present review concerns with the spontaneous polymerizations of vinyl monomers in three kinds of anisotropic systems :
a micellar solutions of some amphiphilic monomers capable of forming micelles,
b emulsion of oil-soluble monomers such as styrene and methyl methacrylate with conventional surfactants, and c aqueous suspension of the oil-soluble monomers in the presence of water-soluble polymers (polysoaps). In
a, as a feature of the polymerization systems, the monomer aggregation state has a very important role in controlling the generation of initiating radical species. In
b and
c, the monomers solubilized in the micelles formed by the surfactants or the polysoaps are assumed to be active for the radical formation. The generalized initiation mechanisms are discussed.
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