Self-assembled complex micelle phase stability in ABA-type triblock copolymers and related core-shell bottlebrushes

Karavolias, Michael G.; Mahanthappa, Mahesh K.

doi:10.1103/PhysRevMaterials.8.015603

Title: Self-assembled complex micelle phase stability in ABA-type triblock copolymers and related core-shell bottlebrushes

Journal Article · 30 January 2024 · Physical Review Materials

DOI: https://doi.org/10.1103/PhysRevMaterials.8.015603 · OSTI ID:2283488

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We report the synthesis and temperature-dependent morphologies of a series of polylactide--poly (-decalactone)--polylactide (LDL) triblock copolymers with $M_{n} = 16.0 - 18.1 kg / mol$ and volume fractions $f_{L} = 0.27 - 0.31$ 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 phases due to the conformational asymmetry of this monomer pair, the csBB morphologies sensitively depend on the backbone degree of polymerization ( $N_{bb}$ ). At low $N_{bb}$ 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 to A15 order-to-order transition. However, larger $N_{bb}$ values drive csBBs to form hexagonally packed cylinders phases. This $N_{bb}$ -dependent phase behavior is rationalized in terms of a star-to-bottlebrush transition. At low $N_{bb}$ values, the csBBs are akin to star polymers with pointlike junctions that can support complex micelle packings. As $N_{bb}$ increases, the csBBs adopt cylindrical molecular geometries with extended backbones situated in the matrix domain that prefer hexagonally packed cylinders morphologies. Published by the American Physical Society 2024

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Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2283488

Journal Information:: Physical Review Materials, Journal Name: Physical Review Materials Journal Issue: 1 Vol. 8; ISSN PRMHAR; ISSN 2475-9953

Publisher:: American Physical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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