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

doi:10.1002/macp.201300322

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^*

^*Corresponding author for this work

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

77 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 language	English
Pages (from-to)	2099-2107
Number of pages	9
Journal	Macromolecular Chemistry and Physics
Volume	214
Issue number	18
DOIs	https://doi.org/10.1002/macp.201300322
Publication status	Published - 2013 Sept 1
Externally published	Yes

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

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10.1002/macp.201300322

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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.",

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AU - Hemp, Sean T.

AU - Zhang, Mingqiang

AU - Allen, Michael H.

AU - Cheng, Shijing

AU - Moore, Robert B.

AU - Long, Timothy Edward

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N2 - 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.

AB - 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.

KW - ammonium

KW - ionic conductivity

KW - phosphonium

KW - polymerized ionic liquids

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

Abstract

Keywords

ASJC Scopus subject areas

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