Crosslinking of comb-shaped polymer anion exchange membranes via thiol-ene click chemistry

Liang Zhu, Tawanda J. Zimudzi, Nanwen Li, Jing Pan, Bencai Lin, Michael A. Hickner

Research output: Contribution to journalArticle

79 Citations (Scopus)

Abstract

To produce anion conductive and durable polymer electrolytes for alkaline fuel cell applications, a series of cross-linked quaternary ammonium functionalized poly(2,6-dimethyl-1,4-phenylene oxide)s with mass-based ion exchange capacities (IEC) ranging from 1.80 to 2.55 mmol g-1 were synthesized via thiol-ene click chemistry. 1H nuclear magnetic resonance (NMR) spectroscopy and Fourier transform infrared spectroscopy (FTIR) were used to confirm the chemical structure of the samples. From small angle X-ray scattering (SAXS), it was found that the cross-linked membranes developed microphase separation between the hydrophilic PPO backbone and the hydrophobic alkyl side chains. The ion conductivity, dimensional stability, and alkaline durability of the cross-linked membranes were evaluated. The hydroxide ion conductivity of the cross-linked samples reached 60 mS cm-1 in liquid water at room temperature. The chemical stabilities of the membranes were evaluated under severe, accelerated aging conditions and degradation was quantified by measuring the ionic conductivity changes during aging. The cross-linked membranes retained their relatively high ion conductivity and good mechanical properties in both 1 M and 4 M NaOH at 80 °C after 500 h. Attenuated total reflection (ATR) spectra were used to study the degradation pathways of the membranes, and it was determined that β-hydrogen (Hofmann) elimination was likely to be the major pathway for degradation in these membranes.

Original languageEnglish (US)
Pages (from-to)2464-2475
Number of pages12
JournalPolymer Chemistry
Volume7
Issue number14
DOIs
StatePublished - Apr 14 2016

Fingerprint

Click Chemistry
Comb and Wattles
Sulfhydryl Compounds
Crosslinking
Anions
Ion exchange
Polymers
Negative ions
Membranes
Degradation
Ions
Aging of materials
Alkaline fuel cells
Polyphenylene oxides
Microphase separation
Dimensional stability
Ion Exchange
Chemical stability
Fourier Transform Infrared Spectroscopy
Ionic conductivity

All Science Journal Classification (ASJC) codes

  • Bioengineering
  • Biochemistry
  • Polymers and Plastics
  • Organic Chemistry

Cite this

@article{7aa55c26acfe49a7bada65c12fc6e9d3,
title = "Crosslinking of comb-shaped polymer anion exchange membranes via thiol-ene click chemistry",
abstract = "To produce anion conductive and durable polymer electrolytes for alkaline fuel cell applications, a series of cross-linked quaternary ammonium functionalized poly(2,6-dimethyl-1,4-phenylene oxide)s with mass-based ion exchange capacities (IEC) ranging from 1.80 to 2.55 mmol g-1 were synthesized via thiol-ene click chemistry. 1H nuclear magnetic resonance (NMR) spectroscopy and Fourier transform infrared spectroscopy (FTIR) were used to confirm the chemical structure of the samples. From small angle X-ray scattering (SAXS), it was found that the cross-linked membranes developed microphase separation between the hydrophilic PPO backbone and the hydrophobic alkyl side chains. The ion conductivity, dimensional stability, and alkaline durability of the cross-linked membranes were evaluated. The hydroxide ion conductivity of the cross-linked samples reached 60 mS cm-1 in liquid water at room temperature. The chemical stabilities of the membranes were evaluated under severe, accelerated aging conditions and degradation was quantified by measuring the ionic conductivity changes during aging. The cross-linked membranes retained their relatively high ion conductivity and good mechanical properties in both 1 M and 4 M NaOH at 80 °C after 500 h. Attenuated total reflection (ATR) spectra were used to study the degradation pathways of the membranes, and it was determined that β-hydrogen (Hofmann) elimination was likely to be the major pathway for degradation in these membranes.",
author = "Liang Zhu and Zimudzi, {Tawanda J.} and Nanwen Li and Jing Pan and Bencai Lin and Hickner, {Michael A.}",
year = "2016",
month = "4",
day = "14",
doi = "10.1039/c5py01911g",
language = "English (US)",
volume = "7",
pages = "2464--2475",
journal = "Polymer Chemistry",
issn = "1759-9954",
publisher = "Royal Society of Chemistry",
number = "14",

}

Crosslinking of comb-shaped polymer anion exchange membranes via thiol-ene click chemistry. / Zhu, Liang; Zimudzi, Tawanda J.; Li, Nanwen; Pan, Jing; Lin, Bencai; Hickner, Michael A.

In: Polymer Chemistry, Vol. 7, No. 14, 14.04.2016, p. 2464-2475.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Crosslinking of comb-shaped polymer anion exchange membranes via thiol-ene click chemistry

AU - Zhu, Liang

AU - Zimudzi, Tawanda J.

AU - Li, Nanwen

AU - Pan, Jing

AU - Lin, Bencai

AU - Hickner, Michael A.

PY - 2016/4/14

Y1 - 2016/4/14

N2 - To produce anion conductive and durable polymer electrolytes for alkaline fuel cell applications, a series of cross-linked quaternary ammonium functionalized poly(2,6-dimethyl-1,4-phenylene oxide)s with mass-based ion exchange capacities (IEC) ranging from 1.80 to 2.55 mmol g-1 were synthesized via thiol-ene click chemistry. 1H nuclear magnetic resonance (NMR) spectroscopy and Fourier transform infrared spectroscopy (FTIR) were used to confirm the chemical structure of the samples. From small angle X-ray scattering (SAXS), it was found that the cross-linked membranes developed microphase separation between the hydrophilic PPO backbone and the hydrophobic alkyl side chains. The ion conductivity, dimensional stability, and alkaline durability of the cross-linked membranes were evaluated. The hydroxide ion conductivity of the cross-linked samples reached 60 mS cm-1 in liquid water at room temperature. The chemical stabilities of the membranes were evaluated under severe, accelerated aging conditions and degradation was quantified by measuring the ionic conductivity changes during aging. The cross-linked membranes retained their relatively high ion conductivity and good mechanical properties in both 1 M and 4 M NaOH at 80 °C after 500 h. Attenuated total reflection (ATR) spectra were used to study the degradation pathways of the membranes, and it was determined that β-hydrogen (Hofmann) elimination was likely to be the major pathway for degradation in these membranes.

AB - To produce anion conductive and durable polymer electrolytes for alkaline fuel cell applications, a series of cross-linked quaternary ammonium functionalized poly(2,6-dimethyl-1,4-phenylene oxide)s with mass-based ion exchange capacities (IEC) ranging from 1.80 to 2.55 mmol g-1 were synthesized via thiol-ene click chemistry. 1H nuclear magnetic resonance (NMR) spectroscopy and Fourier transform infrared spectroscopy (FTIR) were used to confirm the chemical structure of the samples. From small angle X-ray scattering (SAXS), it was found that the cross-linked membranes developed microphase separation between the hydrophilic PPO backbone and the hydrophobic alkyl side chains. The ion conductivity, dimensional stability, and alkaline durability of the cross-linked membranes were evaluated. The hydroxide ion conductivity of the cross-linked samples reached 60 mS cm-1 in liquid water at room temperature. The chemical stabilities of the membranes were evaluated under severe, accelerated aging conditions and degradation was quantified by measuring the ionic conductivity changes during aging. The cross-linked membranes retained their relatively high ion conductivity and good mechanical properties in both 1 M and 4 M NaOH at 80 °C after 500 h. Attenuated total reflection (ATR) spectra were used to study the degradation pathways of the membranes, and it was determined that β-hydrogen (Hofmann) elimination was likely to be the major pathway for degradation in these membranes.

UR - http://www.scopus.com/inward/record.url?scp=84962074702&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84962074702&partnerID=8YFLogxK

U2 - 10.1039/c5py01911g

DO - 10.1039/c5py01911g

M3 - Article

AN - SCOPUS:84962074702

VL - 7

SP - 2464

EP - 2475

JO - Polymer Chemistry

JF - Polymer Chemistry

SN - 1759-9954

IS - 14

ER -