Design, Synthesis, and Self-Assembly of Polymers with Tailored Graft Distributions

Grafting density and graft distribution impact the chain dimensions and physical properties of polymers. However, achieving precise control over these structural parameters presents long-standing synthetic challenges. In this report, we introduce a versatile strategy to synthesize polymers with tailored architectures via grafting-through ring-opening metathesis polymerization (ROMP). One-pot copolymerization of an ω-norbornenyl macromonomer and a discrete norbornenyl comonomer (diluent) provides opportunities to control the backbone sequence and therefore the side chain distribution. Toward sequence control, the homopolymerization kinetics of 23 diluents were studied, representing diverse variations in the stereochemistry, anchor groups, and substituents. These modifications tuned the homopolymerization rate constants over 2 orders of magnitude (0.36 M–1 s–1 < khomo < 82 M–1 s–1). Rate trends were identified and elucidated by complementary mechanistic and density functional theory (DFT) studies. Building ...