Precise Synthesis of Bottlebrush Block Copolymers from ω-End-Norbornyl Polystyrene and Poly(4-tert-butoxystyrene) via Living Anionic Polymerization and Ring-Opening Metathesis Polymerization

A facile and efficient synthetic grafting-through strategy for preparing well-defined bottlebrush block copolymers (BBCPs) was developed through a combination of living anionic polymerization (LAP) and ring-opening metathesis polymerization (ROMP). ω-End-norbornyl polystyrene (NPSt) and poly(4-tert-butoxystyrene) (NPtBOS) were synthesized by LAP using terminator of chlorine moiety containing silane-protecting amine and coupled with a subsequent amidation using norbornyl activated ester. Bottlebrush homopolymers of NPSt were obtained by ROMP with ultrahigh molecular weights (MWs, M_w = 2928 kDa) and narrow molecular weight distributions (MWDs, Đ = 1.07) at high degree of polymerizations (DP_w = 1084). Well-defined BBCPs with ultrahigh MWs (M_w ∼ 3055 kDa) and narrow MWDs (Đ ∼ 1.13) were synthesized through sequential ROMP of NPSt with NPtBOS. The effect of ultrahigh MWs was investigated by self-assembly of the BBCPs in which the phase-separated BBCPs presented periodic lamellar structures and exhibited structural colors from blue to pink.