Ion Conducting ROMP Monomers Based on (Oxa)norbornenes with Pendant Imidazolium Salts Connected via Oligo(oxyethylene) Units and with Oligo(ethyleneoxy) Terminal Moieties

Terry L. Price, U. Hyeok Choi, Daniel V. Schoonover, Murugan Arunachalam, Renxuan Xie, Steven Lyle, Ralph H. Colby, Harry W. Gibson

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

A matrix of 22 two-armed norbornene-based imidazolium TFSI monomers (8) was synthesized to determine the optimal structure in terms of single ion conductivity. For the chain tethering the imidazolium ring to the norbornene ring three or four oxyethylene units are optimal. A terminal group of two ethyleneoxy units was optimal. NMR studies indicated that both the tether oxyethylene units and the terminal ethyleneoxy units interact with the imidazolium cation via hydrogen bonding. 8r (X = 4, Y = 2) exhibited a conductivity of 9.57 × 10 -5 S/cm at 25 °C and a T g of -46 °C. Low T g values do not correlate with higher conductivity as a result of the H-bonding interactions. Stability toward autopolymerization and reasonable conductivities provide an acceptable platform for ion conducting ROMP polymers. Four one-armed norbornene-based imidazolium TFSI monomers (15) were prepared with tetra(ethyleneoxy) linkers/spacers and variable terminal groups. All of these exhibited low T g s (<-55 °C) and room temperature conductivities >10 -4 S/cm, the highest being 4.39 × 10 -4 S/cm for 15c (T g = -69 °C), the analogue of 8r, providing hope for outstanding polymers. Three oxanorbornene-based two-armed imidazolium TFSI monomers (18) were prepared with varied linkers and terminal groups. 18b possesses a room temperature conductivity of 1.2 × 10 -4 S/cm, again augering well for polymers derived therefrom by ROMP.

Original languageEnglish (US)
Pages (from-to)1371-1388
Number of pages18
JournalMacromolecules
Volume52
Issue number4
DOIs
StatePublished - Feb 26 2019

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Salts
Monomers
Ions
Polymers
Conducting polymers
Cations
Hydrogen bonds
Positive ions
Nuclear magnetic resonance
2-norbornene
Temperature

All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Price, Terry L. ; Choi, U. Hyeok ; Schoonover, Daniel V. ; Arunachalam, Murugan ; Xie, Renxuan ; Lyle, Steven ; Colby, Ralph H. ; Gibson, Harry W. / Ion Conducting ROMP Monomers Based on (Oxa)norbornenes with Pendant Imidazolium Salts Connected via Oligo(oxyethylene) Units and with Oligo(ethyleneoxy) Terminal Moieties. In: Macromolecules. 2019 ; Vol. 52, No. 4. pp. 1371-1388.
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abstract = "A matrix of 22 two-armed norbornene-based imidazolium TFSI monomers (8) was synthesized to determine the optimal structure in terms of single ion conductivity. For the chain tethering the imidazolium ring to the norbornene ring three or four oxyethylene units are optimal. A terminal group of two ethyleneoxy units was optimal. NMR studies indicated that both the tether oxyethylene units and the terminal ethyleneoxy units interact with the imidazolium cation via hydrogen bonding. 8r (X = 4, Y = 2) exhibited a conductivity of 9.57 × 10 -5 S/cm at 25 °C and a T g of -46 °C. Low T g values do not correlate with higher conductivity as a result of the H-bonding interactions. Stability toward autopolymerization and reasonable conductivities provide an acceptable platform for ion conducting ROMP polymers. Four one-armed norbornene-based imidazolium TFSI monomers (15) were prepared with tetra(ethyleneoxy) linkers/spacers and variable terminal groups. All of these exhibited low T g s (<-55 °C) and room temperature conductivities >10 -4 S/cm, the highest being 4.39 × 10 -4 S/cm for 15c (T g = -69 °C), the analogue of 8r, providing hope for outstanding polymers. Three oxanorbornene-based two-armed imidazolium TFSI monomers (18) were prepared with varied linkers and terminal groups. 18b possesses a room temperature conductivity of 1.2 × 10 -4 S/cm, again augering well for polymers derived therefrom by ROMP.",
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Ion Conducting ROMP Monomers Based on (Oxa)norbornenes with Pendant Imidazolium Salts Connected via Oligo(oxyethylene) Units and with Oligo(ethyleneoxy) Terminal Moieties. / Price, Terry L.; Choi, U. Hyeok; Schoonover, Daniel V.; Arunachalam, Murugan; Xie, Renxuan; Lyle, Steven; Colby, Ralph H.; Gibson, Harry W.

In: Macromolecules, Vol. 52, No. 4, 26.02.2019, p. 1371-1388.

Research output: Contribution to journalArticle

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T1 - Ion Conducting ROMP Monomers Based on (Oxa)norbornenes with Pendant Imidazolium Salts Connected via Oligo(oxyethylene) Units and with Oligo(ethyleneoxy) Terminal Moieties

AU - Price, Terry L.

AU - Choi, U. Hyeok

AU - Schoonover, Daniel V.

AU - Arunachalam, Murugan

AU - Xie, Renxuan

AU - Lyle, Steven

AU - Colby, Ralph H.

AU - Gibson, Harry W.

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N2 - A matrix of 22 two-armed norbornene-based imidazolium TFSI monomers (8) was synthesized to determine the optimal structure in terms of single ion conductivity. For the chain tethering the imidazolium ring to the norbornene ring three or four oxyethylene units are optimal. A terminal group of two ethyleneoxy units was optimal. NMR studies indicated that both the tether oxyethylene units and the terminal ethyleneoxy units interact with the imidazolium cation via hydrogen bonding. 8r (X = 4, Y = 2) exhibited a conductivity of 9.57 × 10 -5 S/cm at 25 °C and a T g of -46 °C. Low T g values do not correlate with higher conductivity as a result of the H-bonding interactions. Stability toward autopolymerization and reasonable conductivities provide an acceptable platform for ion conducting ROMP polymers. Four one-armed norbornene-based imidazolium TFSI monomers (15) were prepared with tetra(ethyleneoxy) linkers/spacers and variable terminal groups. All of these exhibited low T g s (<-55 °C) and room temperature conductivities >10 -4 S/cm, the highest being 4.39 × 10 -4 S/cm for 15c (T g = -69 °C), the analogue of 8r, providing hope for outstanding polymers. Three oxanorbornene-based two-armed imidazolium TFSI monomers (18) were prepared with varied linkers and terminal groups. 18b possesses a room temperature conductivity of 1.2 × 10 -4 S/cm, again augering well for polymers derived therefrom by ROMP.

AB - A matrix of 22 two-armed norbornene-based imidazolium TFSI monomers (8) was synthesized to determine the optimal structure in terms of single ion conductivity. For the chain tethering the imidazolium ring to the norbornene ring three or four oxyethylene units are optimal. A terminal group of two ethyleneoxy units was optimal. NMR studies indicated that both the tether oxyethylene units and the terminal ethyleneoxy units interact with the imidazolium cation via hydrogen bonding. 8r (X = 4, Y = 2) exhibited a conductivity of 9.57 × 10 -5 S/cm at 25 °C and a T g of -46 °C. Low T g values do not correlate with higher conductivity as a result of the H-bonding interactions. Stability toward autopolymerization and reasonable conductivities provide an acceptable platform for ion conducting ROMP polymers. Four one-armed norbornene-based imidazolium TFSI monomers (15) were prepared with tetra(ethyleneoxy) linkers/spacers and variable terminal groups. All of these exhibited low T g s (<-55 °C) and room temperature conductivities >10 -4 S/cm, the highest being 4.39 × 10 -4 S/cm for 15c (T g = -69 °C), the analogue of 8r, providing hope for outstanding polymers. Three oxanorbornene-based two-armed imidazolium TFSI monomers (18) were prepared with varied linkers and terminal groups. 18b possesses a room temperature conductivity of 1.2 × 10 -4 S/cm, again augering well for polymers derived therefrom by ROMP.

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