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We report the synthesis and temperature-dependent morphologies of a series of polylactide-block-poly (ฮต-decalactone)-block-polylactide (LDL) triblock copolymers with ๐๐=16.0โ18.1โขkg/mol and volume fractions ๐L=0.27โ0.31 and associated core-shell bottlebrush (csBB) polymers, which derive from enchaining LDL triblocks through a polymerizable midchain functionality. While the LDL triblocks form micellar Frank-Kasper A15 and ฯ phases due to the conformational asymmetry of this monomer pair, the csBB morphologies sensitively depend on the backbone degree of polymerization (๐bb). At low ๐bb values, micellar Frank-Kasper phases with the brush backbone situated in the matrix domain are stable, albeit with a modest reduction in the mean interfacial curvature evidenced by a ฯ to A15 order-to-order transition. However, larger ๐bb values drive csBBs to form hexagonally packed cylinders phases. This ๐bb-dependent phase behavior is rationalized in terms of a star-to-bottlebrush transition. At low ๐bb values, the csBBs are akin to star polymers with pointlike junctions that can support complex micelle packings. As ๐bb increases, the csBBs adopt cylindrical molecular geometries with extended backbones situated in the matrix domain that prefer hexagonally packed cylinders morphologies.more » « less
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Karavolias, Michael G.; Elder, Jack B.; Ness, Emily M.; Mahanthappa, Mahesh K. (, ACS Macro Letters)
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