Block Copolymer Thermodynamics: Theory and Experiment

Block copolymers are macromolecules composed of sequences, or blocks, of chemically distinct repeat units. The development of this field originated with the discovery of termination-free anionic polymerization, which made possible the sequential addition of monomers to various carbanion-ter­ minated (living) linear polymer chains. Polymerization of just two dis­ tinct monomer types (e.g. styrene and isoprene) leads to a class of materials referred to as AB block copolymers. Within this class, a variety of molec­ ular architectures is possible. For example, the simplest combination, obtained by the two-step anionic polymerization of A and B monomers, is an (A-B) dioblock copolymer. A three-step reaction provides for the preparation of (ABA) or (BAB) triblock copolymer. Alternatively, living diblock copolymers can be reacted with an n-functional coupling agent to produce (A-B)n star-block copolymers, where n = 2 constitutes a triblock copolymer. Several representative (A-B)n block copolymer architectures