Switchable Polymerization Organocatalysis: From Monomer Mixtures to Block Copolymers

Abstract 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 ofO‐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 CO2liberated 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 % CO2conversion 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.