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Ten years have passed since the conception of what was termed Lewis pair polymerization (LPP) that employs Lewis acid and base in pairs to not only activate monomers but also effect chain initiation, propagation, and transfer events. Compared to other polymerization methodologies, LPP’s cooperative and synergistic two-component catalytic mechanism empowers several unique or advantageous features, including extraordinary tunability of catalyst/initiator systems, compounded thermodynamic and kinetic control over comonomer sequences in one-pot LPP of monomer mixtures for highly resolved block copolymers, complete chemoselectivity in LPP of multifunctional vinyl monomers, independent tuning of polymerization activity and target polymer molecular weight, controlled heat dissipation in bulk polymerization with unactivated monomers functioning as solvent molecules, and coupled selectivity and livingness with immortality of the active species to produce ultrahigh molecular weight polymers and block copolymers with record-number (53) blocks. Focusing on four fundamental attributes of any polymerization methodology—mechanism, kinetics, control, and selectivity—this Perspective narrates the growth and development of LPP, tracing each innovation back to fundamental principles so that each concept can be strategically applied, and describes new frontiers fertile for future research.
McGraw et al. (Mon,) studied this question.