Order-to-Disorder Transitions in Lamellar Melt Self-Assembled Core–Shell Bottlebrush Polymers

We report the synthesis and melt self-assembly behaviors of densely grafted, core–shell bottlebrush (csBB) polymers derived from covalently linking narrow dispersity, symmetric composition ABA-type triblock polymers through their chain midpoints. Derived from sequential ring-opening polymerizations of ε-decalactone and rac-lactide initiated from 5-norbornene-2-exo,3-exo-dimethanol, poly­(lactide-block-ε-decalactone-block-lactide) macromonomers (M n = 9.2–17.8 kg/mol; Đ = 1.19–1.25) were enchained by living ring-opening metathesis polymerization (ROMP) into csBBs with backbone degrees of polymerization N bb = 8–43. Temperature-dependent small-angle X-ray scattering (SAXS) studies indicate that the critical triblock arm degree of polymerization (N arm) required for melt segregation decreases with increasing N bb, leading to reductions in the accessible ordered lamellar microdomain (d) spacings. We derive a phenomenological relationship between the critical triblock arm segregation strength at the order–disorder transition (χN arm)ODT and N bb to enable the future design of microphase separated core–shell bottlebrushes, which self-assemble at sub-10 nm length scales for nanolithography and nanotemplating applications.