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

doi:10.1021/acs.macromol.8b02295

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 journal › Article › peer-review

6 Scopus citations

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 language	English (US)
Pages (from-to)	1371-1388
Number of pages	18
Journal	Macromolecules
Volume	52
Issue number	4
DOIs	https://doi.org/10.1021/acs.macromol.8b02295
State	Published - Feb 26 2019
Externally published	Yes

ASJC Scopus subject areas

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

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10.1021/acs.macromol.8b02295

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Price, T. L., Choi, U. H., Schoonover, D. V., Arunachalam, M., Xie, R., Lyle, S., Colby, R. H., & Gibson, H. W. (2019). Ion Conducting ROMP Monomers Based on (Oxa)norbornenes with Pendant Imidazolium Salts Connected via Oligo(oxyethylene) Units and with Oligo(ethyleneoxy) Terminal Moieties. Macromolecules, 52(4), 1371-1388. https://doi.org/10.1021/acs.macromol.8b02295

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

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.",

author = "Price, {Terry L.} and Choi, {U. Hyeok} and Schoonover, {Daniel V.} and Murugan Arunachalam and Renxuan Xie and Steven Lyle and Colby, {Ralph H.} and Gibson, {Harry W.}",

note = "Funding Information: We are very appreciative of financial support from the U.S. Army Research Office under Grant W911NF-07-1-0452 Ionic Liquids in Electroactive Devices (ILEAD) MURI. We are also grateful to Prof. James McGrath (VT, deceased) and Tim Long (VT) for use of their thermal analysis equipment and Prof. James Runt (PS) for use of his dielectric spectrometer. Funding Information: We are very appreciative of financial support from the U.S. Army Research Office under Grant W911NF-07-1-0452 Ionic Liquids in Electroactive Devices (ILEAD) MURI. We are also grateful to Prof. Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

year = "2019",

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doi = "10.1021/acs.macromol.8b02295",

language = "English (US)",

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pages = "1371--1388",

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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.

N1 - Funding Information: We are very appreciative of financial support from the U.S. Army Research Office under Grant W911NF-07-1-0452 Ionic Liquids in Electroactive Devices (ILEAD) MURI. We are also grateful to Prof. James McGrath (VT, deceased) and Tim Long (VT) for use of their thermal analysis equipment and Prof. James Runt (PS) for use of his dielectric spectrometer. Funding Information: We are very appreciative of financial support from the U.S. Army Research Office under Grant W911NF-07-1-0452 Ionic Liquids in Electroactive Devices (ILEAD) MURI. We are also grateful to Prof. Publisher Copyright: © 2019 American Chemical Society.

PY - 2019/2/26

Y1 - 2019/2/26

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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ER -

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

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