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ABSTRACT:The use of self-propagating frontal polymerization to produce polymer blends has been investigated. A homogeneous solution of monomer, polymer (of a second monomer), and initiator is initially heated at a specific location to start a polymerization front that propagates along the system. The obtained polymerization reaction is very fast compared with diffusion, so that the two types of macromolecules remain homogeneously distributed, as in the original monomer/polymer solution. In the case of two incompatible polymers, the system has no time to reach the equilibrium condition where phase separation occurs and a polymer blend is obtained in the form of a metastable solution. Applications to two incompatible pairs (methyl methacrylatestyrene and methyl methacrylate-methacrylic acid) are discussed. Moreover, it has been found that the presence of inert polymer in the initial mixture improves the process performance, leading to more stable propagation fronts, lower front temperatures, and higher monomer conversions.

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Traveling polymerization fronts in unstirred solutions of methylmethacrylate, methacrylic acid, or acrylamide with some free radicals initiators (through thermal decomposition) have been observed experimentally. A local heating of the initial reactant mixture, under suitable conditions, leads to a reaction front that propagates along the space coordinate with a constant velocity. In this article, a physical interpretation of this phenomenon is provided through a mathematical model that accounts for the depolimerization reaction and is based on the constant pattern approach. Moreover, an approximate explicit analytic expression for the velocity of propagation of the polymerization front is proposed. The theoretical values are compared with those measured experimentally as a function of the initiator concentration for different addition polymerization systems. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35:1047–1059, 1997