Styrene‐methyl acrylate copolymers and acrylate homopolymers in solution

Abstract

Abstract Molecular weight determinations by light scattering and osmometry and intrinsic viscosity measurements were made in various solvents on fractions of styrene–methyl acrylate copolymers with different compositions and on acrylate homopolymers prepared by free‐radical reaction. Relations between intrinsic viscosity [η] and molecular weight M thus established are compared with those reported by other authors. 2‐Methylcyclohexanol was found to be a theta solvent for the copolymers and both parent homopolymers, and isoamyl acetate was a theta solvent for poly(methyl acrylate). From theta point viscosity data obtained with these solvents, unperturbed chain dimensions were estimated. The results are compared with the unperturbed dimensions estimated from the [η]–M relations obtained in good solvents. On the basis of the experimental data it was found that the unperturbed dimension depends linearly on the copolymer composition, in contrast to the case of styrene–methyl methacrylate copolymers. Composition dependences of the theta temperature and of the parameter describing the long‐range interactions between nonadjacent segments in polymer chains were investigated. The result implies that long‐range interactions between monomeric units never disappear even when those between the same monomeric units vanish. The Huggins constant for copolymer is discussed in terms of the excluded volume variable.