Efficient Synthesis of Narrowly Dispersed Brush Polymers via Living Ring-Opening Metathesis Polymerization of Macromonomers

Various macromonomers (MMs) were efficiently synthesized through the copper-catalyzed “click” coupling of a norbornene moiety to the chain end of poly(methylacrylate), poly(t-butylacrylate), and polystyrene that were prepared using atom transfer radical polymerization. Ring-opening metathesis polymerization (ROMP) of these MMs was carried out using the highly active, fast-initiating ruthenium catalyst (H_2IMes)(pyr)_2(Cl)_2RuCHPh in THF at room temperature. ROMP of MMs was found to be living with almost quantitative conversions (>90%) of MMs, producing brush polymers with very low polydispersity indices of 1.01−1.07 and high Mn’s of 200−2600 kDa. The efficient ROMP of such MMs provides facile access to a variety of brush polymers and overcomes previous difficulties in the controlled polymerization of MMs. Atomic force microscopy of the brush polymer products revealed extended, wormlike shapes as a result of significant steric repulsion of densely grafted side chains