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

20 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.

MRSEC Support

Partial

Publisher link

10.1021/acsmacrolett.9b00782

Find It

Find It at U of M Libraries

Cite this

@article{5a558d626f5846e5b6a9edd895129be8,

title = "Order-to-Disorder Transitions in Lamellar Melt Self-Assembled Core-Shell Bottlebrush Polymers",

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.",

author = "Karavolias, {Michael G.} and Elder, {Jack B.} and Ness, {Emily M.} and Mahanthappa, {Mahesh K.}",

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.",

year = "2019",

month = dec,

day = "17",

doi = "10.1021/acsmacrolett.9b00782",

language = "English (US)",

volume = "8",

pages = "1617--1622",

journal = "ACS Macro Letters",

issn = "2161-1653",

publisher = "American Chemical Society",

number = "12",

}

TY - JOUR

T1 - Order-to-Disorder Transitions in Lamellar Melt Self-Assembled Core-Shell Bottlebrush Polymers

AU - Karavolias, Michael G.

AU - Elder, Jack B.

AU - Ness, Emily M.

AU - Mahanthappa, Mahesh K.

N1 - 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.

PY - 2019/12/17

Y1 - 2019/12/17

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=85075620739&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85075620739&partnerID=8YFLogxK

U2 - 10.1021/acsmacrolett.9b00782

DO - 10.1021/acsmacrolett.9b00782

M3 - Article

C2 - 35619390

AN - SCOPUS:85075620739

SN - 2161-1653

VL - 8

SP - 1617

EP - 1622

JO - ACS Macro Letters

JF - ACS Macro Letters

IS - 12

ER -

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

Abstract

Bibliographical note

MRSEC Support

Publisher link

Find It

Other files and links

Fingerprint

REU Site: University of Minnesota MRSEC in Nanomaterials

MRSEC SEED Projects DMR-1420013

University of Minnesota MRSEC (DMR-1420013)

Cite this