Multidimensional Control of Repeating Unit/Sequence/Topology for One-Step Synthesis of Block Polymers from Monomer Mixtures

Synchronously and thoroughly adjusting the chemical structure difference between two blocks of the diblock copolymer is very useful for designing materials but difficult to achieve via self-switchable alternating copolymerization. Here, we report self-switchable alternating copolymerization from a mixture of two different cyclic anhydrides, epoxides, and oxetanes, where a simple alkali metal carboxylate catalyst switches between ring-opening alternating copolymerization (ROCOP) of cyclic anhydrides/epoxides and ROCOP of cyclic anhydrides/oxetanes, resulting in the formation of a perfect block tetrapolymer. By investigating the reactivity ratio of these comonomers, a reactivity gradient was established, enabling the precise synthesis of block copolymers with synchronous adjustment of each unit’s chemical structure/sequence/topology. Consequently, a diblock tetrapolymer with two glass transition temperatures (Tg) can be easily produced by adjusting the difference in chemical structures between the two blocks.