Comparing ammonium and phosphonium polymerized ionic liquids: Thermal analysis, conductivity, and morphology

Sean T. Hemp, Mingqiang Zhang, Michael H. Allen, Shijing Cheng, Robert B. Moore, Timothy Edward Long

Research output: Contribution to journalArticle

52 Citations (Scopus)

Abstract

Conventional free radical polymerization and anion metathesis of ammonium and phosphonium styrenics successfully generates high-molecular-weight polymerized ionic liquids (PILs). Phosphonium polyelectrolytes containing Cl- counterions display significantly higher thermal stabilities (>370 °C) compared with ammonium analogs (<220 °C). Anion exchange to BF4 -, TfO-, and Tf2N- improves the thermal stability of all the PILs and depresses their T g. Impedance-spectroscopy-probed ionic conductivities of PILs containing Tf2N-, and phosphonium PILs exhibit higher values than ammonium analogs. Phosphonium PILs displayed many advantages over ammonium PILs for emerging applications that demand higher thermal stabilities and ionic conductivities. A large library of ammonium- and phosphonium- containing polymerized ionic liquids (PILs) enables a thorough structure-property analysis. The alkyl substituent length and counterion directly impact the thermal properties, wherein longer alkyl substituent lengths and bulkier counterions depress the glass transition temperature. Ultimately, phosphonium PILs exhibit superior thermal properties and ionic conductivities compared with ammonium analogs.

Original languageEnglish
Pages (from-to)2099-2107
Number of pages9
JournalMacromolecular Chemistry and Physics
Volume214
Issue number18
DOIs
Publication statusPublished - 2013 Sep 1
Externally publishedYes

Fingerprint

Ionic Liquids
Ammonium Compounds
Ionic liquids
Thermoanalysis
thermal analysis
conductivity
liquids
Ionic conductivity
ion currents
Thermodynamic stability
thermal stability
analogs
Anions
Negative ions
Thermodynamic properties
thermodynamic properties
anions
metathesis
Free radical polymerization
Polyelectrolytes

Keywords

  • ammonium
  • ionic conductivity
  • phosphonium
  • polymerized ionic liquids

ASJC Scopus subject areas

  • Materials Chemistry
  • Polymers and Plastics
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Condensed Matter Physics

Cite this

Comparing ammonium and phosphonium polymerized ionic liquids : Thermal analysis, conductivity, and morphology. / Hemp, Sean T.; Zhang, Mingqiang; Allen, Michael H.; Cheng, Shijing; Moore, Robert B.; Long, Timothy Edward.

In: Macromolecular Chemistry and Physics, Vol. 214, No. 18, 01.09.2013, p. 2099-2107.

Research output: Contribution to journalArticle

Hemp, Sean T. ; Zhang, Mingqiang ; Allen, Michael H. ; Cheng, Shijing ; Moore, Robert B. ; Long, Timothy Edward. / Comparing ammonium and phosphonium polymerized ionic liquids : Thermal analysis, conductivity, and morphology. In: Macromolecular Chemistry and Physics. 2013 ; Vol. 214, No. 18. pp. 2099-2107.
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