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Published January 23, 2018 | Supplemental Material
Journal Article Open

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.

Additional Information

© 2018 American Chemical Society. Received: November 20, 2017; Revised: December 19, 2017; Published: January 9, 2018. This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT and Future Planning (NRF-2015R1A2A1A01002493) and by the GIST Research Institute (GRI) grant funded by the GIST in 2017. The authors declare no competing financial interest.

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