SynopsisA thermodynamic analysis of polymer particle morphology highlights the role of interfacial tensions in controlling particle structure. The influence of the surfactant and the nature of the incompatible polymers is seen through their individual and collective effects upon these interfacial tensions. It has been found that by simply changing the type of surfactant used in the emulsion the particle morphology can change from core-shell to hemispherical, in agreement with thermodynamic predictions. Several apparently different morphologies (hemispherical, sandwich, multiple lobes) have been found to coexist a t the same time within a single emulsion, suggesting that they may be simply different states of phase separation and not thermodynamically stable, unique morphologies. The thermodynamic analyses are independent of particle size and method of emulsion processing. Experimental evidence shows that the morphology of particles formed via in situ polymerization ( a s in a synthetic latex) is controlled by interfacial tensions in the same manner as those particles formed via solvent evaporation from a solution of an incompatible polymer pair (as in a n artificial latex or microencapsulation).

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SynopsisIt is well known that the reaction rate and molecular weight of vinyl polymers can change markedly during the course of polymerization and that these changes are due to the influence of diffusion on the termination reaction. The chain length dependence of the termination rate constant has been considered in this work and has resulted in a general method of treating the polymerization kinetics and molecular weight distribution. This method is independent of the form of the chain length dependency and is capable of dealing with both disproportionation and recombination modes of termination. A specific model for the termination rate constant with chain length dependence is proposed and is based on free volume theory and entanglement coupling. Master curves for the characteristics of the reaction rate and molecular weight distribution are presented with the application of this model.

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.

Monte Carlo simulation methods are suitable for free radical polymerizations (FRP) even when there is significant chain length dependence of the reactions. For each simulation step the probability of each possible reaction is determined at that point in time. In FRP modeling most of the computation time is spent on radical propagation. We demonstrate a hybrid simulation method where the propagation reaction is treated using differential equations and other reactions (e.g. termination and initiation reactions) are treated stochastically. This allows significant reductions in simulation time while maintaining the features of complete Monte Carlo methods. This approach can be applied to more complex polymerization reactions like branching and crosslinking using Monte Carlo methods within manageable times.

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Carboxylic acid monomers are commonly used at low concentrations as functional additives in emulsion polymerization. Being quite water-soluble, they partition between the aqueous and polymer particle phases in complex manners. We have studied of the partitioning behavior of both acrylic (AA) and methacrylic (MAA) acids between water and a variety of individual styrene, acrylate, and methacrylate monomers. The distribution coefficients strongly depend upon the hydrogen-bond acceptor characteristics of the organic phase and the pH of the aqueous phase. AA and MAA behave similarly, but AA distributes much less strongly to the organic phase than does MAA. The logs of the distribution coefficients for both vinyl acids correlate linearly with the molar volume of the (meth)acrylate monomers, and these values decrease as the molecular weight of the monomer increases. Vinyl acid distributions to styrene monomer are nearly completely determined by the dimerization of the acids in the monomer phase and, as such, are quite sensitive to the concentration of the acid in the water phase. The effects of ionic strength and temperature are minimal for the usual emulsion polymerization reaction conditions.