Superior Cascade Ring-Opening/Ring-Closing Metathesis Polymerization and Multiple Olefin Metathesis Polymerization: Enhancing the Driving Force for Successful Polymerization of Challenging Monomers.

Recently, our group successfully developed two new polymerization methodologies for monomers containing two cycloalkene moieties. These polymerization methods yielded well-defined polymers via a combination of ring-opening and ring-closing metathesis (cascade polymerization) or ring-opening, ring-closing, and cross-metathesis (multiple olefin metathesis polymerization (MOMP)) using a second monomer. However, cascade polymerization had some limitations such as low polymerization efficiency (maximum turnover number (TON) of 250) and narrow monomer scope. Furthermore, one-shot MOMP also showed a very narrow monomer scope because of certain undesired side reactions. To overcome these problems, we designed various new monomers containing cyclopentene and even more challenging ring-strain-free cyclohexene moieties, so that polymerization would produce a thermodynamically favored six-membered-ring backbone repeat unit. With this enhanced driving force for polymerization, these new monomers successfully underwent cascade polymerization with a high polymerization efficiency, leading to a maximum TON of 1940 and maximum number-average molecular weight ( Mn) of 343 kDa. Lastly, one-shot MOMP, which uses all three types of metathesis transformations in a single step, was possible with these monomers and gave highly A,B-alternating copolymers with high selectivity as well. This was possible because the newly designed monomers with the appropriate thermodynamic and kinetic preferences suppressed undesired polymerization pathways and reduced defects in the polymer microstructures. In short, we present our strategies for achieving superior cascade polymerization and MOMP using these new monomers.