Polymer, Vol.38, No.6, 1323-1337, 1997
The Glass-Transition Temperature of Random Copolymers .2. Extension of the Gordon-Taylor Equation for Asymmetric T-G vs Composition Curves
It is obvious that asymmetric T-g vs composition curves of random copolymers cannot be adapted by the Gordon-Taylor equation based on volume additivity, even if instead of the model-specific additivity parameter KG-T = (rho(1)/rho(2))(Delta alpha(2)/Delta alpha(1)) a curve fitting parameter, K, is considered. Therefore contributions of diad- and triad-sequences to the copolymer T-g were considered. Assuming, by lack of copolymerization kinetics data, that the diad- and triad-sequence distribution can be related in a first approximation to the respective weight fractions of the copolymer components a concentration power equation is deduced for adapting the composition dependence of the glass temperature of copolymers. The two fitting parameters, K-1 and K-2, of this concentration power equation characterize the contributions to the copolymer T-g of the hetero-diads and -triads, respectively. Values of K-1 > 0 are generally typical for positive deviations of the copolymer T-g from additivity, suggesting stiffening effects induced by attractive interactions between the different repeating units of the copolymer. Negative values of K indicate negative deviations due to repulsions within the hetero-diads. The corresponding T-g vs composition curves may exhibit maxima or minima, respectively. The different influences on the copolymer T-g of hetero-triads, are characterized by values of K-2 different from zero. Depending on whether K-2 is smaller or larger than K-1 the results are either pronounced asymmetric or S-shaped T-g vs composition curves, suggesting that the influence on T-g of the hetero-triads is dependent on their composition, taking into account the hetero-triads may contain either two repeating units of the one or of the second component. Although fundamental relationships between the fitting parameters and a molecular property are not yet available, it is shown, that in a first approximation the values of K-1 are related to differences between the solubility parameters of the copolymer components. The T-g vs composition behaviour is analysed for copolymers of acrylates and methacrylates among each other and with styrene, acrylonitrile and vinyl chloride, respectively.
Keywords:POLYMER BLENDS