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Title: Achieving Continuous Anion Transport Domains Using Block Copolymers Containing Phosphonium Cations

Abstract

Triblock and diblock copolymers based on isoprene (Ip) and chloromethylstyrene (CMS) were synthesized in this paper 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. Finally, promising chloride conductivities (20 mS/cm) were achieved at elevated temperatures and humidified conditions.

Authors:
 [1];  [2];  [3];  [3];  [1];  [1];  [4];  [3];  [5];  [2];  [1]
+ Show Author Affiliations
  1. Univ. of Massachusetts, Amherst, MA (United States). Dept. of Polymer Science and Engineering
  2. Colorado School of Mines, Golden, CO (United States). Dept. of Chemical and Biological Engineering
  3. US Army Research Lab., Aberdeen Proving Ground, MD (United States)
  4. Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division
  5. Univ. of Toledo, OH (United States). Dept. of Chemical and Environmental Engineering
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States); Univ. of Massachusetts, Amherst, MA (United States); US Army Research Lab., Aberdeen Proving Ground, MD (United States)
Sponsoring Org.:
USDOE Office of Science (SC); US Army Research Office (ARO)
Contributing Org.:
Colorado School of Mines, Golden, CO (United States); Univ. of Toledo, OH (United States)
OSTI Identifier:
1368557
Grant/Contract Number:  
AC02-06CH11357; W911NF-10-1-0520
Resource Type:
Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 49; Journal Issue: 13; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; ABA Triblock copolymers; butyl acrylate; chain transfer polymerization; fuel-cell applications; functionalized polyethylene; hydroxide exchange membranes; ionic liquids; phase-behavior; polymer electrolyte membranes; radical polymerization

Citation Formats

Zhang, Wenxu, Liu, Ye, Jackson, Aaron C., Savage, Alice M., Ertem, S. Piril, Tsai, Tsung-Han, Seifert, Soenke, Beyer, Frederick L., Liberatore, Matthew W., Herring, Andrew M., and Coughlin, E. Bryan. Achieving Continuous Anion Transport Domains Using Block Copolymers Containing Phosphonium Cations. United States: N. p., 2016. Web. doi:10.1021/acs.macromol.6b00653.
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Zhang, Wenxu, Liu, Ye, Jackson, Aaron C., Savage, Alice M., Ertem, S. Piril, Tsai, Tsung-Han, Seifert, Soenke, Beyer, Frederick L., Liberatore, Matthew W., Herring, Andrew M., & Coughlin, E. Bryan. Achieving Continuous Anion Transport Domains Using Block Copolymers Containing Phosphonium Cations. United States. https://doi.org/10.1021/acs.macromol.6b00653
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Zhang, Wenxu, Liu, Ye, Jackson, Aaron C., Savage, Alice M., Ertem, S. Piril, Tsai, Tsung-Han, Seifert, Soenke, Beyer, Frederick L., Liberatore, Matthew W., Herring, Andrew M., and Coughlin, E. Bryan. Wed . "Achieving Continuous Anion Transport Domains Using Block Copolymers Containing Phosphonium Cations". United States. https://doi.org/10.1021/acs.macromol.6b00653. https://www.osti.gov/servlets/purl/1368557.
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@article{osti_1368557,
title = {Achieving Continuous Anion Transport Domains Using Block Copolymers Containing Phosphonium Cations},
author = {Zhang, Wenxu and Liu, Ye and Jackson, Aaron C. and Savage, Alice M. and Ertem, S. Piril and Tsai, Tsung-Han and Seifert, Soenke and Beyer, Frederick L. and Liberatore, Matthew W. and Herring, Andrew M. and Coughlin, E. Bryan},
abstractNote = {Triblock and diblock copolymers based on isoprene (Ip) and chloromethylstyrene (CMS) were synthesized in this paper 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. Finally, promising chloride conductivities (20 mS/cm) were achieved at elevated temperatures and humidified conditions.},
doi = {10.1021/acs.macromol.6b00653},
journal = {Macromolecules},
number = 13,
volume = 49,
place = {United States},
year = {Wed Jun 22 00:00:00 EDT 2016},
month = {Wed Jun 22 00:00:00 EDT 2016}
}
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  • Nature Chemistry, Vol. 1, Issue 9
  • DOI: 10.1038/nchem.402
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