Achieving Continuous Anion Transport Domains Using Block Copolymers Containing Phosphonium Cations

Wenxu Zhang; Ye Liu; Aaron C. Jackson; Alice M. Savage; S. Piril Ertem; Tsung Han Tsai; Soenke Seifert; Frederick L. Beyer; Matthew W. Liberatore; Andrew M. Herring; E. Bryan Coughlin

doi:10.1021/acs.macromol.6b00653

Achieving Continuous Anion Transport Domains Using Block Copolymers Containing Phosphonium Cations

Wenxu Zhang, Ye Liu, Aaron C. Jackson, Alice M. Savage, S. Piril Ertem, Tsung Han Tsai, Soenke Seifert, Frederick L. Beyer, Matthew W. Liberatore, Andrew M. Herring, E. Bryan Coughlin

Chemistry (Twin Cities)

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

53 Scopus citations

Abstract

Triblock and diblock copolymers based on isoprene (IP) and chloromethylstyrene (CMS) were synthesized by sequential polymerization using reversible addition-fragmentation chain transfer radical polymerization (RAFT). The block copolymers were quaternized with tris(2,4,6-trimethoxyphenyl)phosphine (Ar₃P) to prepare soluble ionomers. The ionomers were cast from chloroform to form anion exchange membranes (AEMs) with highly ordered morphologies. At low volume fractions of ionic blocks, the ionomers formed lamellar morphologies, while at moderate volume fractions (≥30% for triblock and ≥22% for diblock copolymers) hexagonal phases with an ionic matrix were observed. Ion conductivities were higher through the hexagonal phase matrix than in the lamellar phases. Promising chloride conductivities (20 mS/cm) were achieved at elevated temperatures and humidified conditions.

Original language	English (US)
Pages (from-to)	4714-4722
Number of pages	9
Journal	Macromolecules
Volume	49
Issue number	13
DOIs	https://doi.org/10.1021/acs.macromol.6b00653
State	Published - Jul 12 2016

Bibliographical note

Funding Information:
The authors gratefully acknowledge financial support from the Army Research Office through a MURI award, W911NF-10-1-0520, and the central analytical facilities used in these investigations are supported by the NSF-Sponsored MRSEC at UMass Amherst. This research used resources 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 DEAC02-06CH11357. A.C.J. and A.M.S. were supported by the Postgraduate Research Participation Program at the US Army Research Laboratory, administered by the Oak Ridge Institute of Science and Education through an interagency agreement between the US Department of Energy and Army Research Laboratory (Contract ORISE 1120-1120-99).

Publisher Copyright:
© 2016 American Chemical Society.

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10.1021/acs.macromol.6b00653

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abstract = "Triblock and diblock copolymers based on isoprene (IP) and chloromethylstyrene (CMS) were synthesized by sequential polymerization using reversible addition-fragmentation chain transfer radical polymerization (RAFT). The block copolymers were quaternized with tris(2,4,6-trimethoxyphenyl)phosphine (Ar3P) to prepare soluble ionomers. The ionomers were cast from chloroform to form anion exchange membranes (AEMs) with highly ordered morphologies. At low volume fractions of ionic blocks, the ionomers formed lamellar morphologies, while at moderate volume fractions (≥30% for triblock and ≥22% for diblock copolymers) hexagonal phases with an ionic matrix were observed. Ion conductivities were higher through the hexagonal phase matrix than in the lamellar phases. Promising chloride conductivities (20 mS/cm) were achieved at elevated temperatures and humidified conditions.",

author = "Wenxu Zhang and Ye Liu and Jackson, {Aaron C.} and Savage, {Alice M.} and Ertem, {S. Piril} and Tsai, {Tsung Han} and Soenke Seifert and Beyer, {Frederick L.} and Liberatore, {Matthew W.} and Herring, {Andrew M.} and Coughlin, {E. Bryan}",

note = "Funding Information: The authors gratefully acknowledge financial support from the Army Research Office through a MURI award, W911NF-10-1-0520, and the central analytical facilities used in these investigations are supported by the NSF-Sponsored MRSEC at UMass Amherst. This research used resources 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 DEAC02-06CH11357. A.C.J. and A.M.S. were supported by the Postgraduate Research Participation Program at the US Army Research Laboratory, administered by the Oak Ridge Institute of Science and Education through an interagency agreement between the US Department of Energy and Army Research Laboratory (Contract ORISE 1120-1120-99). Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

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AU - Liberatore, Matthew W.

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AU - Coughlin, E. Bryan

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PY - 2016/7/12

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N2 - Triblock and diblock copolymers based on isoprene (IP) and chloromethylstyrene (CMS) were synthesized by sequential polymerization using reversible addition-fragmentation chain transfer radical polymerization (RAFT). The block copolymers were quaternized with tris(2,4,6-trimethoxyphenyl)phosphine (Ar3P) to prepare soluble ionomers. The ionomers were cast from chloroform to form anion exchange membranes (AEMs) with highly ordered morphologies. At low volume fractions of ionic blocks, the ionomers formed lamellar morphologies, while at moderate volume fractions (≥30% for triblock and ≥22% for diblock copolymers) hexagonal phases with an ionic matrix were observed. Ion conductivities were higher through the hexagonal phase matrix than in the lamellar phases. Promising chloride conductivities (20 mS/cm) were achieved at elevated temperatures and humidified conditions.

AB - Triblock and diblock copolymers based on isoprene (IP) and chloromethylstyrene (CMS) were synthesized by sequential polymerization using reversible addition-fragmentation chain transfer radical polymerization (RAFT). The block copolymers were quaternized with tris(2,4,6-trimethoxyphenyl)phosphine (Ar3P) to prepare soluble ionomers. The ionomers were cast from chloroform to form anion exchange membranes (AEMs) with highly ordered morphologies. At low volume fractions of ionic blocks, the ionomers formed lamellar morphologies, while at moderate volume fractions (≥30% for triblock and ≥22% for diblock copolymers) hexagonal phases with an ionic matrix were observed. Ion conductivities were higher through the hexagonal phase matrix than in the lamellar phases. Promising chloride conductivities (20 mS/cm) were achieved at elevated temperatures and humidified conditions.

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Achieving Continuous Anion Transport Domains Using Block Copolymers Containing Phosphonium Cations

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