Ideal Copolymers and the Second-Order Transitions of Synthetic Rubbers. I. Noncrystalline Copolymers

Theoretical and practical evidence is put forward to show that copolymers can be treated like solutions of small molecules in the interpretation of packing phenomena, and that ideal volume-additivity of the repeating units in copolymers is frequently realized. On this basis equations are derived for predicting θ, the second-order transition temperature, of binary copolymers from the two second-order transition temperatures of the pure polymers and their coefficients of expansion in the glassy and rubbery states. Previous mechanistic theories of the second-order transition temperature of such copolymers are thus superseded by a general reduction of the problem to the mechanism of thermal expansion. Practical applications to the choice of monomers in producing synthetic rubbers are outlined, and attention is drawn to the importance of second-order transitions in kinetic measurements on the reactions of polymers.