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

doi:10.1021/acsmacrolett.9b00782

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 journal › Article › peer-review

18 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 (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.

Original language	English (US)
Pages (from-to)	1617-1622
Number of pages	6
Journal	ACS Macro Letters
Volume	8
Issue number	12
DOIs	https://doi.org/10.1021/acsmacrolett.9b00782
State	Published - Dec 17 2019

Bibliographical note

Funding Information:
This work was supported by National Science Foundation DMR-1708874, supplemented by a partial graduate fellowship from 3M Foundation (J.B.E.), and funding from the Research Experiences for Undergraduates (REU) Program of the National Science Foundation under Award Number DMR-1559833 and through the University of Minnesota MRSEC under Award Number DMR-1420013 (E.M.N.). Preliminary SAXS analyses were acquired in the Characterization Facility at the University of Minnesota, which also receives partial support from NSF through the UMN MRSEC (DMR-1420013). Synchrotron SAXS experiments were conducted at the 12-ID-B beamline of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated by Argonne National Laboratory under Contract No. DE-AC02-06CH11357.

Funding Information:
This work was supported by National Science Foundation DMR-1708874, supplemented by a partial graduate fellowship from 3M Foundation (J.B.E.), and funding from the Research Experiences for Undergraduates (REU) Program of the National Science Foundation under Award Number DMR-1559833 and through the University of Minnesota MRSEC under Award Number DMR-1420013 (E.M.N.). Preliminary SAXS analyses were acquired in the Characterization Facility at the University of Minnesota, which also receives partial support from NSF through the UMN MRSEC (DMR-1420013). Synchrotron SAXS experiments were conducted at the 12-ID-B beamline of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated by Argonne National Laboratory under Contract No. DE-AC02-06CH11357.

Publisher Copyright:
Copyright © 2019 American Chemical Society.

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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; {\D} = 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.",

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note = "Funding Information: This work was supported by National Science Foundation DMR-1708874, supplemented by a partial graduate fellowship from 3M Foundation (J.B.E.), and funding from the Research Experiences for Undergraduates (REU) Program of the National Science Foundation under Award Number DMR-1559833 and through the University of Minnesota MRSEC under Award Number DMR-1420013 (E.M.N.). Preliminary SAXS analyses were acquired in the Characterization Facility at the University of Minnesota, which also receives partial support from NSF through the UMN MRSEC (DMR-1420013). Synchrotron SAXS experiments were conducted at the 12-ID-B beamline of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Funding Information: This work was supported by National Science Foundation DMR-1708874, supplemented by a partial graduate fellowship from 3M Foundation (J.B.E.), and funding from the Research Experiences for Undergraduates (REU) Program of the National Science Foundation under Award Number DMR-1559833 and through the University of Minnesota MRSEC under Award Number DMR-1420013 (E.M.N.). Preliminary SAXS analyses were acquired in the Characterization Facility at the University of Minnesota, which also receives partial support from NSF through the UMN MRSEC (DMR-1420013). Synchrotron SAXS experiments were conducted at the 12-ID-B beamline of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Publisher Copyright: Copyright {\textcopyright} 2019 American Chemical Society.",

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

Abstract

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