Dilute solution properties of poly(methyl methacrylate) in acetonitrile + carbon tetrachloride mixtures

Heterotactic poly(methyl methacrylate) (PMMA) is studied by light scattering and viscometry in the mixture acetonitrile + CCl₄. Both liquids are poor solvents of PMMA, but their mixture is a very good solvent of this polymer. The total sorption potential of the coil is calculated from second virial coefficient and intrinsic viscosity results. Unperturbed dimensions, Mark-Houwink exponent, Schulz-Blaschke constant, and coil expansion factor are also determined. The enhanced total solvent sorption is larger in this mixture than in any other cosolvent system of PMMA thus far studied. This is due to the strong repulsive interactions between acetonitrile and CCl₄. Such interactions also determine the inversion in preferential sorption that occurs close to equimolar composition. Acetonitrile can interact favourably with the ester group of PMMA and unfavourably with its methylene backbone. The role of such opposing interactions and of liquid order in acetonitrile are taken into account to discuss the results.