Rapid Controlled Synthesis of Large Polymers by Frontal Ring-Opening Metathesis Polymerization

Tunable molecular weight and well-defined polydispersity are the hallmarks of a controlled polymerization. This process relies on vanishingly small termination rates, minimal chain transfer, and initiation rates faster than propagation rates. Ring-opening metathesis polymerization (ROMP) is a well-known controlled polymerization based on the opening of strained cyclic olefins. The exothermic nature of ROMP allows rapid conversion of neat monomers to polymers through frontal ROMP (FROMP). Unlike traditional ROMP, FROMP uses the exothermic heat from the opening of strained cyclic olefins to thermally activate the initiator that sustains the propagation of a cascading reaction front. Although the reaction mechanisms for ROMP and FROMP are the same, the reaction conditions differ greatly, especially in the temperature and monomer concentration. The ability to control the polymerization under FROMP conditions has yet to be investigated, as well as its potential in the synthesis of well-defined polymers without the use of solvents and with minimal energy input. Here, we show that FROMP rapidly transforms monomers into polymers of high-molecular weight (M_n) with good fidelity and low dispersity (Đ). Specifically, the synthesis of polymers with M_n up to 700 kg/mol and Đ of 1.5 was achieved with a rapid, solvent-free, and oxygen-tolerant frontal polymerization technique. Further control of the polymerization was possible with the addition of a phosphite ligand that lowered the Đ to 1.2. We anticipate that controlled FROMP will become a valuable macromolecular synthetic tool due to its reliability, speed, scalability, and simplicity.