Facile synthesis of asymmetric tetrablock copolymer by dual thermal and photochemical initiator

Vesicles obtained by the self-assembly of asymmetric tetrablock copolymers are a class of materials with fascinating properties. However, simple strategies to synthesize asymmetric tetrablock copolymers are limited. Herein, we have designed and synthesized an initiator which generates radicals by either heating or photoirradiation. Taking the advantages of organocatalyzed reversible complexation mediated radical polymerization which has lower energy requirements, milder reaction conditions, and reduced generation of hazardous byproducts, a three steps synthetic route following "photo-photo-thermal" initiation condition for the preparation of asymmetric CABC tetrablock copolymers with controllable molecular weight, precise block composition and low polydispersity was developed.