Abstract
Three samples of poly(vinyl acetate) 36% hydrolysed, respectively, by saponification, transesterification and acid-equilibrium have been characterized through the refractive indices and light-scattering properties of their solutions in 10% aqueous methanol at 25°C. The original poly(vinyl acetate) sample and its iodine/iodide complex have been similarly characterized, respectively, in methanol at 5°C and in 9.1% methanolic water over the range 5–15°C. The apparent weight-average molecular weights of the vinyl polymers show that the three hydrolytic processes degrade the 130 000 average molecular weight of the original poly(vinyl acetate) macromolecules hardly at all. It is suggested that values of the apparent second virial coefficient might be used as criteria for the characterization of hydrolysed poly(vinyl acetate) specimens which have otherwise identical degrees of hydrolysis and blockiness of their residual acetate groups, but contrasting polydisperse characteristics and surface-active properties. The apparent average root-mean-square radius of gyration of the poly(vinyl acetate) macromolecules is reduced to ≈33% or less of its value on formation of the complex. The characteristics and structure of such complexes are discussed.
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