Bernhard A. Wolf

Interpolymer Complexes and Polymer Compatibility

A reliable method to decide whether two polymers A and B are miscible or incompatible would be very helpful in many ways. In this contribution we demonstrate why traditional procedures cannot work. We propose to use the intrinsic viscosities [η] of the polymer blends instead of the composition dependence of the viscosities as a criterion for polymer miscibility. Two macromolecules A and B are miscible because of sufficiently favorable interactions between the two types of polymer segments. For solutions of these polymers in a joint solvent, this Gibbs energetic preference of dissimilar intersegmental contacts should prevail upon dilution and lead to the formation of interpolymer complexes, manifesting themselves in deviations from the additivity of intrinsic viscosities.

Liquid/gas and liquid/liquid phase equilibria of the system water/bovine serum albumin.

The thermodynamic behavior of the system H2O/BSA was studied at 25 °C within the entire composition range: vapor pressure measurements via head space sampling gas chromatography demonstrate that the attainment of equilibria takes more than one week. A miscibility gap was detected via turbidity and the coexisting phases were analyzed. At 6 °C the two phase region extends from ca. 34 to 40 wt % BSA; it shrinks upon heating. The polymer rich phase is locally ordered, as can be seen under the optical microscope using crossed polarizers. The Flory-Huggins theory turns out to be inappropriate for the modeling of experimental results. A phenomenological expression is employed which uses three adjustable parameters and describes the vapor pressures quantitatively; it also forecasts the existence of a miscibility gap.

Thermodynamics of copolymer solutions: how the pair interactions contribute to the overall effect.

Vapor pressure measurements were performed for solutions of poly(methyl methacrylate-ran-tert-butyl methacrylate) with different weight fractions of tert-butyl methacrylate units, and their parental homopolymers in chloroform at 323 K, over a large domain of concentrations. The Flory-Huggins interaction parameters obtained from these experimental investigations show complex dependences of the Flory-Huggins interaction parameter on concentration and copolymer composition. This behavior can be modeled by taking into account an approach which considers the ability of the polymers to rearrange in a response to changes in their molecular surroundings [Adv. Polym. Sci. 2011, 238, 1-66]. According to this concept, the mixing process is subdivided into two clearly separable steps and accounts for the specific interactions between the solvent and copolymer segments.

Joint aqueous solutions of dextran and bovine serum albumin: coexistence of three liquid phases.

The phase diagram of the system water/dextran (DEX)/BSA was measured as well as modeled. On the experimental side, cloud points were determined and the coexisting phases were analyzed. The theoretical calculations use an approach capable of describing solutions of chain polymers and of globular proteins with the same formalism. The required thermodynamic input comes from experiments concerning the binary subsystems, except for the polymer blend for which one interaction parameter had to be adjusted. Both sources of information yield the same essential features: the existence of a large composition area of immiscibility, starting from the subsystem DEX/BSA and extending well into the region of dilute polymer solutions. This range is subdivided into three sections: one two-phase area at high polymer content, a two-phase area at low polymer content, and a three-phase region located in between. Measured and calculated phase diagrams match qualitatively; the reasons for the quantitative discrepancies are being discussed.