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

Michael G. Karavolias, Jack B. Elder, Emily M. Ness, Mahesh K. Mahanthappa

Research output: Contribution to journalArticle

1 Scopus citations

Abstract

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 (Mn = 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 Nbb = 8-43. Temperature-dependent small-angle X-ray scattering (SAXS) studies indicate that the critical triblock arm degree of polymerization (Narm) required for melt segregation decreases with increasing Nbb, 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 (χNarm)ODT and Nbb 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.

Original languageEnglish (US)
Pages (from-to)1617-1622
Number of pages6
JournalACS Macro Letters
Volume8
Issue number12
DOIs
StatePublished - Dec 17 2019

How much support was provided by MRSEC?

  • Partial

Reporting period for MRSEC

  • Period 6

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  • Projects

    University of Minnesota MRSEC (DMR-1420013)

    Lodge, T. P.

    11/1/1410/31/20

    Project: Research project

    MRSEC SEED Projects

    11/1/14 → …

    Project: Research project

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