Mechanism of Spatial and Temporal Control in Precision Cyclic Vinyl Polymer Synthesis by Lewis Pair Polymerization

In typical cyclic polymer synthesis via ring-closure, chain growth and cyclization events are competing with each other, thus affording polymers uncontrolled molecular weight or ring size high dispersity. Here we uncover a mechanism by which Lewis pair polymerization (LPP) operates on polar vinyl monomers that allows the control of where when takes place, thereby achieving spatial temporal to afford precision block copolymers predictable low dispersity (≈1.03). A combined experimental theoretical study demonstrates occurs only after all have been consumed (when) conjugate addition propagating end specific site initiating (where), allowing formation steps be regulated executed in space time.