Regular Mixing Thermodynamics of Hydrogenated Styrene–Isoprene Block–Random Copolymers

Abstract

Random copolymerization of A and B monomers represents a versatile method to tune interaction strengths between polymers, as ArB random copolymers will exhibit a smaller effective Flory interaction parameter χ (or interaction energy density X) upon mixing with A or B homopolymers than upon mixing A and B homopolymers with each other, and the ArB composition can be tuned continuously. This approach can also be used to tune the segregation strength in A–ArB “block–random” copolymers. Simple models of polymer mixing thermodynamics suggest that the effective interaction energy density in such block–random copolymers should follow XA–ArB = fB2XA–B, but this prediction has not been tested quantitatively. The present work systematically assesses the validity of this rule for thermally stable hydrogenated derivatives of styrene–isoprene block copolymers, through measurements of the order–disorder transition (ODT) temperature on near-symmetric diblock and diblock–random copolymers of varying composition and suitab...