Cationic Bottlebrush Polymers from Quaternary Ammonium Macromonomers by Grafting-Through Ring-Opening Metathesis Polymerization

Cationic bottlebrush homopolymers are polymerized using a grafting-through approach by ring-opening metathesis polymerization (ROMP) to afford well-defined polymers. Quaternary ammonium macromonomers (MMs) are prepared by quaternizing tertiary amine MMs synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. The quaternary ammonium MMs undergo ROMP to target molecular weights (M-n = 30 000-100 000 g mol(-1)) and a low dispersity (D = 1.10-1.30). Halide-ligand exchange between the third generation Grubbs catalyst (G3) and halide counter ions (bromide and iodide ions) of MMs changes the catalyst activity throughout ROMP, causing it to deviate from pseudo-first order kinetic behavior; however, the polymerization still follows controlled behavior without significant catalyst termination. Increasing steric bulk of the MMs decreases the polymerization rate as well. Amphiphilic block copolymers are synthesized by sequential polymerization of quaternary ammonium MMs and polystyrene (PS) MMs. Using a PS macroinitiator affords block copolymers with lower D values as compared to the less active cationic macroinitiator.