Supporting data for Core−Shell Gyroid in ABC Bottlebrush Block Terpolymers

These files contain primary data supporting all results reported in Cui et al. "Core−shell gyroid in ABC bottlebrush block terpolymers." A series of bottlebrush block polymers containing 24 PEP-PS diblock copolymers and 109 PEP-PS-PEO triblock terpolymers were synthesized by ring-opening metathesis polymerization (ROMP) of norbornene-functionalized poly(ethylene-alt-propylene) (PEP), poly(styrene) (PS), and poly(ethylene oxide) (PEO) macromonomers. The molecular weights of the three macromonomers were around 1 kg/mol. The relatively modest total backbone degrees of polymerization ranged from ca. 20 to 40. Morphologies of these bottlebrush block polymers were characterized by small-angle X-ray scattering (SAXS). The PEP-PS diblocks exhibited only cylindrical (HEX) and lamellar (LAM) morphologies; the desired network phases did not appear in these materials, consistent with previous experimental studies. However, adding variable-length bottlebrush PEO blocks to diblocks containing 30% to 50% PS led to a substantial core-shell double gyroid (GYR) phase window in the ternary phase portrait. Encouragingly, the GYR unit cell dimensions increased almost linearly with the backbone degree of polymerization, portending the ability to access larger network dimensions than previously obtained with linear block polymers. This finding demonstrates a periodic network phase in bottlebrush block polymers for the first time and highlights extraordinary opportunities associated with applying facile ROMP chemistry to multiblock bottlebrush polymers.