Dispersity and architecture driven self-assembly and confined crystallization of symmetric branched block copolymers

Louis M. Pitet, Bradley M. Chamberlain, Adam W. Hauser, Marc A. Hillmyer

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4 Scopus citations

Abstract

The effect of macromolecular architecture on the morphology and thermal characteristics of triblock copolymers was evaluated for linear, H-shaped, and arachnearm architectures with poly(cis-cyclooctene) (PCOE) midblocks flanked with arms of poly(d,l-lactide) (PLA). Chain topology was found to significantly influence the interfacial curvature of the microphase separated domains, as implicated by morphological differences observed by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS). The branched molecular architectures and molar mass dispersities of the triblock polymers examined here resulted in a significant shift in the phase boundaries between conventional equilibrium microphase separated structures to higher volume fractions of the end blocks (i.e., PLA) as compared to conventional low dispersity linear triblocks. Macromolecular topology was also found to strongly influence the extent of homo-vs. heterogeneous nucleation in the semi-crystalline PCOE block. The culmination of the bulk phase behavior analysis demonstrates the ability to fine-tune the properties of the block polymers by exploiting different architectures through a synthetically straightforward route.

Original languageEnglish (US)
Pages (from-to)5385-5395
Number of pages11
JournalPolymer Chemistry
Volume10
Issue number39
DOIs
StatePublished - Oct 21 2019

Bibliographical note

Funding Information:
This work was funded by the National Science Foundation (DMR-0605880 and DMR-1006370 and DMR-1609459). L. M. P. acknowledges support from a fellowship awarded by the UMN Graduate School. B. M. C. gratefully acknowledges the Office of the Dean at Luther College for financial support of a sabbatical leave of absence. Parts of this work were carried out at the University of Minnesota Characterization Facility, a member of the NSF-funded Materials Research Facilities Network (http://www.mrfn.org). Synchrotron SAXS analyses were conducted at the DuPontNorthwesternDow Collaborative Access Team (DND-CAT) located at Sector 5 of the Advanced Photon Source (APS), supported by E. I. DuPont de Nemours & Co., the Dow Chemical Company, and Northwestern University. Use of the APS, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the U.S. DOE under Contract DE-AC02-06CH11357. We are grateful for careful reviewing of the manuscript by Nicholas Hampu and Claire Dingwell.

Funding Information:
This work was funded by the National Science Foundation (DMR-0605880 and DMR-1006370 and DMR-1609459). L. M. P. acknowledges support from a fellowship awarded by the UMN Graduate School. B. M. C. gratefully acknowledges the Office of the Dean at Luther College for financial support of a sabbatical leave of absence. Parts of this work were carried out at the University of Minnesota Characterization Facility, a member of the NSF-funded Materials Research Facilities Network (http://www.mrfn.org). Synchrotron SAXS analyses were conducted at the DuPont– Northwestern–Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the Advanced Photon Source (APS), supported by E. I. DuPont de Nemours & Co., the Dow Chemical Company, and Northwestern University. Use of the APS, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the U.S. DOE under Contract DE-AC02-06CH11357. We are grateful for careful reviewing of the manuscript by Nicholas Hampu and Claire Dingwell.

Publisher Copyright:
© The Royal Society of Chemistry.

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