Solution properties of poly(fluorostyrene-co-chlorostyrene) copolymers. I. Light scattering, differential refractometry and viscometry

The weight‐average molecular weights (M̄w) of nominally random, unfractionated copolymers of ortho‐ and para‐fluorostyrene and ortho‐ and para‐chlorostyrene were determined by light scattering measurements in tetrahydro‐furan, toluene, carbon tetrachloride and chloroform. It was shown that there is no significant variation in measured M̄w in the various solvents, a finding indicating that the copolymers are not compositionally heterogeneous. Intrinsic viscosity measurements in the same solvents established a consistent relationship between [n] and M̄w despite the differences in copolymer compositions. It was not possible to establish a similar relationship between the second virial coefficient A2 and M̄w. It was concluded that measurements of the specific refractive index increment could be used for determining copolymer composition if the measurements were performed in thermodynamically poorer solvents. The results established for the Mark‐Houwink constant α, intrinsic viscosity, and A2 values indicated that these solvated copolymer molecules are in a less expanded conformation than are polystyrene molecules of similar molecular weights in a given solvent.