Morphological consequences of frustration in ABC triblock polymers

Madalyn R. Radlauer; Christophe Sinturel; Yusuke Asai; Akash Arora; Frank S. Bates; Kevin D. Dorfman; Marc A. Hillmyer

doi:10.1021/acs.macromol.6b02112

Morphological consequences of frustration in ABC triblock polymers

Madalyn R. Radlauer, Christophe Sinturel, Yusuke Asai, Akash Arora, Frank S. Bates, Kevin D. Dorfman, Marc A. Hillmyer

Research output: Contribution to journal › Article › peer-review

17 Scopus citations

Abstract

Three poly(styrene)-block-poly(isoprene)-block-poly-(lactide) (PS-b-PI-b-PLA, SIL) triblock terpolymers were synthesized and characterized in the bulk and as thin films. The pronounced incompatibility of the covalently connected PI and PLA led to significant frustration and the tendency to minimize their intermaterial dividing surface area. This resulted in the formation of a core-shell cylinder morphology with exaggerated nonconstant mean curvature from triblock polymers with equal block volume fractions rather than the more typical lamellar morphology. The effect of frustration was magnified in thin films by both confinement and interfacial interactions such that the PI domains became discontinuous. Self-consistent field theory (SCFT) calculations emphasize that the marked difference in the PS/PI and PI/PLA interaction parameters promotes the formation of nonlamellar morphologies. However, SCFT predicts that lamellar morphology is more stable than the observed cylindrical morphology, demonstrating a limitation that arises from the underlying assumptions.

Original language	English (US)
Pages (from-to)	446-458
Number of pages	13
Journal	Macromolecules
Volume	50
Issue number	1
DOIs	https://doi.org/10.1021/acs.macromol.6b02112
State	Published - Jan 10 2017

Bibliographical note

Funding Information:
This work was supported by the National Science Foundation (DMR-1333669). M.R.R. holds the Camille and Henry Dreyfus Foundation Postdoctoral Fellowship in Environmental Chemistry. Y.A was financially supported by the Program for Leading Graduate Schools "Integrative Graduate Education and Research in Green Natural Sciences", MEXT, Japan. rac-Lactide was generously provided by Ortec. Parts of this work were carried out in the Characterization Facility, University of Minnesota, which receives partial support from NSF through the MRSEC program. SAXS data were obtained at the DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science user facility operated for the DOE Office of Science by Argonne National Laboratory under Contract DE-AC02-06CH11357.

Publisher Copyright:
© 2016 American Chemical Society.

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title = "Morphological consequences of frustration in ABC triblock polymers",

abstract = "Three poly(styrene)-block-poly(isoprene)-block-poly-(lactide) (PS-b-PI-b-PLA, SIL) triblock terpolymers were synthesized and characterized in the bulk and as thin films. The pronounced incompatibility of the covalently connected PI and PLA led to significant frustration and the tendency to minimize their intermaterial dividing surface area. This resulted in the formation of a core-shell cylinder morphology with exaggerated nonconstant mean curvature from triblock polymers with equal block volume fractions rather than the more typical lamellar morphology. The effect of frustration was magnified in thin films by both confinement and interfacial interactions such that the PI domains became discontinuous. Self-consistent field theory (SCFT) calculations emphasize that the marked difference in the PS/PI and PI/PLA interaction parameters promotes the formation of nonlamellar morphologies. However, SCFT predicts that lamellar morphology is more stable than the observed cylindrical morphology, demonstrating a limitation that arises from the underlying assumptions.",

author = "Radlauer, {Madalyn R.} and Christophe Sinturel and Yusuke Asai and Akash Arora and Bates, {Frank S.} and Dorfman, {Kevin D.} and Hillmyer, {Marc A.}",

note = "Funding Information: This work was supported by the National Science Foundation (DMR-1333669). M.R.R. holds the Camille and Henry Dreyfus Foundation Postdoctoral Fellowship in Environmental Chemistry. Y.A was financially supported by the Program for Leading Graduate Schools {"}Integrative Graduate Education and Research in Green Natural Sciences{"}, MEXT, Japan. rac-Lactide was generously provided by Ortec. Parts of this work were carried out in the Characterization Facility, University of Minnesota, which receives partial support from NSF through the MRSEC program. SAXS data were obtained at the DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science user facility operated for the DOE Office of Science by Argonne National Laboratory under Contract DE-AC02-06CH11357. Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

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AU - Radlauer, Madalyn R.

AU - Sinturel, Christophe

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AU - Arora, Akash

AU - Bates, Frank S.

AU - Dorfman, Kevin D.

AU - Hillmyer, Marc A.

N1 - Funding Information: This work was supported by the National Science Foundation (DMR-1333669). M.R.R. holds the Camille and Henry Dreyfus Foundation Postdoctoral Fellowship in Environmental Chemistry. Y.A was financially supported by the Program for Leading Graduate Schools "Integrative Graduate Education and Research in Green Natural Sciences", MEXT, Japan. rac-Lactide was generously provided by Ortec. Parts of this work were carried out in the Characterization Facility, University of Minnesota, which receives partial support from NSF through the MRSEC program. SAXS data were obtained at the DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science user facility operated for the DOE Office of Science by Argonne National Laboratory under Contract DE-AC02-06CH11357. Publisher Copyright: © 2016 American Chemical Society.

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N2 - Three poly(styrene)-block-poly(isoprene)-block-poly-(lactide) (PS-b-PI-b-PLA, SIL) triblock terpolymers were synthesized and characterized in the bulk and as thin films. The pronounced incompatibility of the covalently connected PI and PLA led to significant frustration and the tendency to minimize their intermaterial dividing surface area. This resulted in the formation of a core-shell cylinder morphology with exaggerated nonconstant mean curvature from triblock polymers with equal block volume fractions rather than the more typical lamellar morphology. The effect of frustration was magnified in thin films by both confinement and interfacial interactions such that the PI domains became discontinuous. Self-consistent field theory (SCFT) calculations emphasize that the marked difference in the PS/PI and PI/PLA interaction parameters promotes the formation of nonlamellar morphologies. However, SCFT predicts that lamellar morphology is more stable than the observed cylindrical morphology, demonstrating a limitation that arises from the underlying assumptions.

AB - Three poly(styrene)-block-poly(isoprene)-block-poly-(lactide) (PS-b-PI-b-PLA, SIL) triblock terpolymers were synthesized and characterized in the bulk and as thin films. The pronounced incompatibility of the covalently connected PI and PLA led to significant frustration and the tendency to minimize their intermaterial dividing surface area. This resulted in the formation of a core-shell cylinder morphology with exaggerated nonconstant mean curvature from triblock polymers with equal block volume fractions rather than the more typical lamellar morphology. The effect of frustration was magnified in thin films by both confinement and interfacial interactions such that the PI domains became discontinuous. Self-consistent field theory (SCFT) calculations emphasize that the marked difference in the PS/PI and PI/PLA interaction parameters promotes the formation of nonlamellar morphologies. However, SCFT predicts that lamellar morphology is more stable than the observed cylindrical morphology, demonstrating a limitation that arises from the underlying assumptions.

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Morphological consequences of frustration in ABC triblock polymers

Abstract

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Morphological consequences of frustration in ABC triblock polymers

Abstract

Bibliographical note

MRSEC Support

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MRSEC IRG-3: Hierarchical Multifunctional Macromolecular Materials

MRSEC Program DMR-1420013

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