The synthesis of sodium poly(styrene sulfonate) via aqueous atom transfer radical polymerization has been demonstrated with control over polymerization kinetics and final polymer properties. This was achieved through an interplay of several reaction variables; addition of nonsolvent, type and concentration of deactivator species, type of ligand, ratio of catalyst to initiator, and pH were explored in order to suppress unwanted side reactions. Kinetic control over the reaction, determined by the rate of monomer conversion, was calculated from 1H NMR, and both molecular weight and polydispersity were determined by gel permeation chromatography coupled multi angle light scattering. In certain cases an order of magnitude difference was observed in the molecular weight by altering a single reaction variable without changing the monomer to initiator ratio. Kinetic and molecular weight data were correlated, as higher conversions led to larger molecular weights. Polydispersity values ranged from 1.05 to 1.25 for polymers ranging from approximately 2 × 10<sup>4</sup> to 5 × 10<sup>5</sup> g/mol which are characteristic values for living polymerizations. Polymer architecture was analyzed by assessing the relationship between Rg and Rh, as well as the dimensionless parameter, ρ, which was found to be on the order of 1.7-1.8, good solvent conditions, and was invariant with molecular weight. Conformation plots showed that v was 0.65 ± 0.04, as averaged across all samples, again proof of a linear random coil polymer in good solvent conditions.

Multivariate study of the synthesis of sodium poly(styrene sulfonate) by aqueous atom transfer radical polymerization

255th National Meeting (2018)

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