Hydroplasticization of polymers: model predictions and application to emulsion polymers.

The plasticization of a polymer by solvent has a dramatic impact on both its thermal and mechanical behavior. With increasing demand for zero volatile organic compound materials and coatings, water is often the sole solvent used both in the polymer synthesis and in formulation and application; latex colloids derived from emulsion polymerization are a good example. The impact of water on the glass transition temperature of a polymer thus becomes a critical physical property to predict. It has been shown here that in order to do so, one simply needs the dry state glass transition temperature (T(g)) of the (co)polymer, the T(g) of water, and the saturated weight fraction of water for the sample in question. Facile calculation of the later can be achieved using water sorption data and the group additivity method. With these readily available data, we show that a form of the Flory-Fox equation can be used to predict the hydroplasticized state of copolymers in exceptional agreement with direct experimental measurement. Furthermore, extending the prediction to include the impact of the degree of ionization for pH responsive components, only with extra knowledge of the pK(a), was also validated by experiment.

Probing the surface of polymer colloids by conductometric surfactant titration.

This work revisits the use of surfactant titrations for the characterization of latex particle surfaces. Experiments were performed to study the effect of comonomer composition and the effect of acid comonomers, and the technique is applied to the characterization of particle morphology in composite latices for several different systems. It is confirmed that the packing density of surfactant on a polymer surface is a linear function of copolymer composition. Inclusion of acid comonomers has the expected effect of decreasing the amount of surfactant adsorbed on the polymer surfaces. The usefulness of the technique in the determination of particle morphology is demonstrated, in particular toward the detection of thin layers of either seed or second-stage polymer on the particle surface which are not easily detected by other techniques such as transmission electron microscopy (TEM). Finally, it is shown that the use of acid comonomers in composite particles greatly reduces the usefulness of the surfactant titration technique for morphology characterization. A possible explanation for this effect is proposed.