Control over bottlebrush polymer synthesis by ring-opening metathesis polymerization (ROMP) of macromonomers (MMs) is highly dependent on the competition between the kinetics of the polymerization and the lifetime of the catalyst. The anchor group–the configuration of atoms linking the polymer to a polymerizable norbornene–has shown to affect the propagation rate of various MMs. We calculated the energy of the highest-occupied molecular orbital (HOMO) containing the reactive norbornene olefin of a variety of nobornene-containing monomers with anchor group-like moieties. The kinetics of ROMP of ten monomers initiated by (H2IMes)(pyr)2(Cl)2Ru=CHPh (Grubbs third generation catalyst) were evaluated and compared to the respective HOMO energies. We observed a linear trend with HOMO energies less than -150 kcal mol-1 and a weaker dependence on HOMO energy for monomers with higher HOMO energies. To further evaluate the effect, the kinetics of ROMP of polystyrene MMs containing the same anchor groups as six of the previous ten monomers were investigated as well.

Effects of the anchor group in ROMP

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

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