Switchable Polymerization Organocatalysis: From Monomer Mixtures to Block Copolymers

One‐pot production of sequence‐controlled block copolymer from mixed monomers is a crucial but rarely reached goal. Using a switchable Lewis‐pair organocatalyst, we have accomplished sequence‐selective polymerization from a mixture of O‐carboxyanhydride (OCA) and epoxide. Polymerization of the OCA monomer occurs first and exclusively because of its exceedingly high polymerizability. When OCA is fully consumed, alternating copolymerization of epoxide and CO2 liberated in OCA polymerization is triggered from the termini of the first block. The two polymerizations thus occur in tandem, both in chemoselective fashion, so that a sequence‐controlled block polymer with up to 99 % CO2 conversion is furnished in this one‐pot protocol. Calculations and experimental results demonstrate a chemoselective and cooperative mechanism, where the high polymerizability of the OCA monomers guarantees exquisite sequence selectivity and the cooperative decarboxylation partly arose from the stabilization effect by triethylborane, which facilitates the smooth transformation of the chain end from carbonate to alkoxide. One‐pot synthesis of sequence‐controlled block polymers from the monomer mixture comprising O‐carboxyanhydride (OCA) and epoxide has been realized using a Lewis‐pair organocatalyst. The experimental and computational results highlighted the pivotal roles played by the high polymerizability of the OCA monomer for guaranteeing the exquisite sequence selectivity and the synergistic decarboxylation for facilitating the smooth transformation of the chain end from carbonate to alkoxide during the switching period.