Rapid and Scalable Access to Sequence‐Controlled DHDM Multiblock Copolymers by FLP Polymerization

Abstract

An immortal N-(diphenylphosphanyl)-1,3-diisopropyl-4,5-dimethyl-1,3-dihydro-2H-imidazol-2-imine/diisobutyl (2,6-di-tert-butyl-4-methylphenoxy) aluminum (P(NIⁱ Pr)Ph₂ /(BHT)Alⁱ Bu₂ )-based frustrated Lewis pair (FLP) polymerization strategy is presented for rapid and scalable synthesis of the sequence-controlled multiblock copolymers at room temperature. Without addition of extra initiator or catalyst and complex synthetic procedure, this method enabled a tripentacontablock copolymer (n=53, k=4, dp_n =50) to be achieved with the highest reported block number (n=53) and molecular weight (M_n =310 kg mol^-1 ) within 30 min. More importantly, this FLP polymerization strategy provided access to the multiblock copolymers with tailored properties by precisely adjusting the monomer sequence and block numbers.