Viscoelastic properties of unsaturated polyesters were investigated in the glass‐rubber transition region in relation to the temperature dependence of specific volume. Polyesters which are homologous with respect to crosslinking density were prepared by using mixtures of succinic and fumaric acid as the dibasic acid component. The temperature dependence of the specific volume was determined by refractive index measurement, the specific refractivity being assumed to be independent of temperature. The temperature dispersion of dynamic viscoelasticity was measured at a constant frequency. Results are summarized as follows. Specific volume and glass temperature are linearly related to the logarithm of crosslinking density. The thermal expansion coefficient and steepness of viscoelastic dispersion decrease with increasing crosslinking density. Fractional free volume and expansion coefficient of free volume, both of which were calculated by WLF equation, are in good agreement with the temperature dependence of specific volume. The results indicate that the effect of crosslinking is largely attributable to the change in amount and distribution of free volume in polymer networks.

Copolymerization of vinyl and divinyl monomer is a typical method for preparing a network polymer. A multiple network structure, in which one network entangles with another, is supposed to be produced when a network polymer is swollen in the monomer mixture and then polymerization of absorbed monomer is carried out so as to superpose the second network on the first. Viscoelastic properties and degree of swelling in solvents were investigated for composite polymers prepared from styrene and divinylbenzene. Results were consistent with presumed characteristics of multiple network structures.