An Arbitrarily Regulated Monomer Sequence in Multi-Block Copolymer Synthesis by Frustrated Lewis Pairs

Rapid access to sequence-controlled multi-block copolymers (multi-BCPs) remains as a challenging task in the polymer synthesis. Here we employ a Lewis pair (LP) composed of organophosphorus superbase and bulky organoaluminum to effectively copolymerize the mixture of methacrylate, cyclic acrylate, and two acrylates, into well-defined di-, tri-, tetra- and even a hepta-BCP in one-pot one-step manner. The combined livingness, dual-initiation and CSC feature of Lewis pair polymerization enable us to achieve not only a trihexaconta-BCP with the highest record in 8 steps by using four-component monomer mixture as building blocks, but also the arbitrarily-regulated monomer sequence in multi-BCP, simply by changing the composition and adding order of the monomer mixtures, thus demonstrating the powerful capability of our strategy in improving the efficiency and enriching the composition of multi-BCP synthesis.

Automated summary

This study presents a strategy using a Lewis pair composed of organophosphorus superbase and bulky organoaluminum as catalyst to successfully synthesize sequence-controlled multi-block copolymers in a one-pot one-step manner. By utilizing the livingness, dual-initiation, and CSC feature of the Lewis pair polymerization, di-, tri-, tetra-, and even a hepta-BCP were obtained with the highest record in 8 steps. The monomer sequence in multi-BCP can be regulated by changing the composition and adding order of the monomer mixtures, showcasing the efficient and versatile capability of this strategy.