St-MMA-BuA terpolymerization in emulsion: II. The kinetic azeotropy and the problem of homogeneity in composition

An analysis of the kinetic azeotropy of the terpolymer from styrene(St)-methyl methacrylate(MMA)-butyl acrylate(BuA) in emulsion polymerization is effectuated. The objective is to determine the conditions for obtaining terpolymers uniform in composition. In this regard, a composition near to the unitary azeotrope is used in batch, semicontinuous and seeded emulsion polymerization processes. As expected, the monomer partition between the different phases modifies the terpolymer composition, in particular at the beginning of the semicontinuous processes. It is also observed that the unitary azeotrope in batch and semicontinuous emulsion polymerization is conserved in a large range of conversion due to the constancy of monomer concentration and radicals in the particle. In this way, a terpolymer with almost an accumulated constant composition is obtained in the seeded process. A thermodynamic analysis of the kinetic azeotropy is also made. The correspondence between the azeotropes of the binary copolymers and the values of the Flory interaction parameters of the monomers χ ιj is correlated. It is found that the lesser repulsion of the St-MMA pair respect to that of St-BuA provoked that the composition of the terpolymer tends to the copolymer azeotrope of St-MMA.