The Order–Disorder Transition in Graft Block Copolymers

Michael J. Maher; Seamus D. Jones; Aristotelis Zografos; Jun Xu; Haley J. Schibur; Frank S. Bates

doi:10.1021/acs.macromol.7b02262

The Order–Disorder Transition in Graft Block Copolymers

Michael J. Maher, Seamus D. Jones, Aristotelis Zografos, Jun Xu, Haley J. Schibur, Frank S. Bates

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

18 Scopus citations

Abstract

The order-disorder transitions of diblock copolymers grafted to a common backbone were examined by oscillatory shear rheology and small-angle X-ray scattering. The effect of grafting density, graft molecular weight, number of grafts, and backbone dispersity were studied using poly[(styrene-alt-N-hydroxyethylmaleimide)-random-(styrene-alt-N-ethylmaleimide)]-graft-poly(4-methylcaprolactone-block-d,l-lactide) [PSHE-g-(P4MCL-PLA)] as a model graft block copolymer. At high grafting densities (25-50%), the order-disorder temperature (T _ODT) of the graft polymers was nearly identical to the analogous linear diblock. At lower grafting densities (<25%), the T _ODT was found to systematically decrease. The number of grafts did not significantly change the value of the T _ODT; however, increasing the number of grafts resulted in broad, ill-defined transitions. Backbone dispersity was found to have little impact on the T _ODT. Ordered morphologies were imaged by transmission electron microscopy. Long-range order was observed in polymers with at least 10 grafts/chain.

Original language	English (US)
Pages (from-to)	232-241
Number of pages	10
Journal	Macromolecules
Volume	51
Issue number	1
DOIs	https://doi.org/10.1021/acs.macromol.7b02262
State	Published - Jan 9 2018

Bibliographical note

Funding Information:
The authors thank Debbie Schneiderman for generously providing TOC artwork. The background of the TOC image is an original piece of artwork by Debbie Schneiderman. The images on the left and right were inspired by the paintings of Piet Mondrian and Jackson Pollock, respectively. This work was funded by the NSF through the Center for Sustainable Polymer (CHE-1413862). Parts of this work were carried out in the Characterization Facility, University of Minnesota, which receives partial support from NSF through the MRSEC program. This research used resources of the Advanced Photon Source (APS), 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. Part of this work was performed at the DuPont− Northwestern−Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the APS. DND-CAT is supported by E.I. DuPont de Nemours & Co., The Dow Chemical Company, and Northwestern University.

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© 2017 American Chemical Society.

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10.1021/acs.macromol.7b02262

http://pubs.acs.org/doi/10.1021/acs.macromol.7b02262

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title = "The Order–Disorder Transition in Graft Block Copolymers",

abstract = "The order-disorder transitions of diblock copolymers grafted to a common backbone were examined by oscillatory shear rheology and small-angle X-ray scattering. The effect of grafting density, graft molecular weight, number of grafts, and backbone dispersity were studied using poly[(styrene-alt-N-hydroxyethylmaleimide)-random-(styrene-alt-N-ethylmaleimide)]-graft-poly(4-methylcaprolactone-block-d,l-lactide) [PSHE-g-(P4MCL-PLA)] as a model graft block copolymer. At high grafting densities (25-50%), the order-disorder temperature (T ODT) of the graft polymers was nearly identical to the analogous linear diblock. At lower grafting densities (<25%), the T ODT was found to systematically decrease. The number of grafts did not significantly change the value of the T ODT; however, increasing the number of grafts resulted in broad, ill-defined transitions. Backbone dispersity was found to have little impact on the T ODT. Ordered morphologies were imaged by transmission electron microscopy. Long-range order was observed in polymers with at least 10 grafts/chain. ",

author = "Maher, {Michael J.} and Jones, {Seamus D.} and Aristotelis Zografos and Jun Xu and Schibur, {Haley J.} and Bates, {Frank S.}",

note = "Funding Information: The authors thank Debbie Schneiderman for generously providing TOC artwork. The background of the TOC image is an original piece of artwork by Debbie Schneiderman. The images on the left and right were inspired by the paintings of Piet Mondrian and Jackson Pollock, respectively. This work was funded by the NSF through the Center for Sustainable Polymer (CHE-1413862). Parts of this work were carried out in the Characterization Facility, University of Minnesota, which receives partial support from NSF through the MRSEC program. This research used resources of the Advanced Photon Source (APS), 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. Part of this work was performed at the DuPont− Northwestern−Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the APS. DND-CAT is supported by E.I. DuPont de Nemours & Co., The Dow Chemical Company, and Northwestern University. Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

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doi = "10.1021/acs.macromol.7b02262",

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AU - Schibur, Haley J.

AU - Bates, Frank S.

N1 - Funding Information: The authors thank Debbie Schneiderman for generously providing TOC artwork. The background of the TOC image is an original piece of artwork by Debbie Schneiderman. The images on the left and right were inspired by the paintings of Piet Mondrian and Jackson Pollock, respectively. This work was funded by the NSF through the Center for Sustainable Polymer (CHE-1413862). Parts of this work were carried out in the Characterization Facility, University of Minnesota, which receives partial support from NSF through the MRSEC program. This research used resources of the Advanced Photon Source (APS), 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. Part of this work was performed at the DuPont− Northwestern−Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the APS. DND-CAT is supported by E.I. DuPont de Nemours & Co., The Dow Chemical Company, and Northwestern University. Publisher Copyright: © 2017 American Chemical Society.

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N2 - The order-disorder transitions of diblock copolymers grafted to a common backbone were examined by oscillatory shear rheology and small-angle X-ray scattering. The effect of grafting density, graft molecular weight, number of grafts, and backbone dispersity were studied using poly[(styrene-alt-N-hydroxyethylmaleimide)-random-(styrene-alt-N-ethylmaleimide)]-graft-poly(4-methylcaprolactone-block-d,l-lactide) [PSHE-g-(P4MCL-PLA)] as a model graft block copolymer. At high grafting densities (25-50%), the order-disorder temperature (T ODT) of the graft polymers was nearly identical to the analogous linear diblock. At lower grafting densities (<25%), the T ODT was found to systematically decrease. The number of grafts did not significantly change the value of the T ODT; however, increasing the number of grafts resulted in broad, ill-defined transitions. Backbone dispersity was found to have little impact on the T ODT. Ordered morphologies were imaged by transmission electron microscopy. Long-range order was observed in polymers with at least 10 grafts/chain.

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The Order–Disorder Transition in Graft Block Copolymers

Abstract

Bibliographical note

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MRSEC IRG-3: Hierarchical Multifunctional Macromolecular Materials

MRSEC Program DMR-1420013

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The Order–Disorder Transition in Graft Block Copolymers

Abstract

Bibliographical note

Publisher link

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Projects

MRSEC IRG-3: Hierarchical Multifunctional Macromolecular Materials

MRSEC Program DMR-1420013

Cite this