Coordination Polymerization of Renewable 3‐Methylenecyclopentene with Rare‐Earth‐Metal Precursors

Abstract

AbstractCoordination polymerization of renewable 3‐methylenecyclopentene has been investigated for the first time using rare‐earth metal‐based precursors bearing various bulky ligands. All the prepared complexes catalyze controllable polymerization of 3‐methylenecyclopentene into high molecular weight polymers, of which the NPN‐ and NSN‐tridentate non‐Cp ligated lutetium‐based catalytic systems exhibited extremely high activities up to 11 520 kg/(molLu⋅h) in a dilute toluene solution (3.2 g/100 mL) at room temperature. The resultant polymers have pure 1,4‐regioregularity (>99 %) and tailorable number average molecular weights (1–20×104) with narrow molecular weight distributions (polydispersity index (PDI)=1.45–1.79). DFT simulations were employed to study the polymerization mechanism and stereoregularity control.