Imidazolium polyesters: Structure-property relationships in thermal behavior, ionic conductivity, and morphology

Minjae Lee, U. Hyeok Choi, David Salas-De La Cruz, Anuj Mittal, Karen I. Winey, Ralph H. Colby, Harry W. Gibson

Research output: Contribution to journalArticle

68 Citations (Scopus)

Abstract

New bis(ω-hydroxyalkyl)imidazolium and 1,2-bis[N-(ω- hydroxyalkyl)imidazolium]ethane salts are synthesized and characterized; most of the salts are room temperature ionic liquids. These hydroxyl end-functionalized ionic liquids are polymerized with diacid chlorides, yielding polyesters containing imidazolium cations embedded in the main chain. By X-ray scattering, four polyesters are found to be semicrystalline at room temperature: mono-imidazolium-C11-sebacate-C6 (4e), mono-imidazolium-C11-sebacate-C11 (4c), bis(imidazolium)ethane-C6-sebacate-C6 (5a), and bis(imidazolium)ethane-C11-sebacate-C11 (5c), all with hexafluorophosphate counterions. The other imidazolium polyesters, including all those with bis(trifluoromethanesulfonyl)imide (TFSI-) counterions, are amorphous at room temperature. Room temperature ionic conductivities of the mono-imidazolium polyesters (4 × 10-6 to 3 × 10 -5 S cm-1) are higher than those of the corresponding bis-imidazolium polyesters (4 × 10-9 to 8 × 10 -6 S cm-1), even though the bis-imidazolium polyesters have higher ion concentrations. Counterions affect ionic conduction significantly; all polymers with TFSI- counterions have higher ionic conductivities than the hexafluorophosphate analogs. Interestingly, the hexafluorophosphate polyester, 1,2-bis(imidazolium)ethane-C11- sebacate-C11 (5c), displays almost 400-fold higher room temperature ionic conductivity (1.6 × 10-6 S cm-1) than the 1,2-bis(imidazolium)ethane-C6-sebacate-C6 analog (5a, 4.3 × 10-9 S cm-1), attributable to the differences in the semicrystalline structure in 5c as compared to 5a. These results indicate that semicrystalline polymers may result in high ionic conductivity in a soft (low glass tranition temperature, Tg) amorphous phase and good mechanical properties of the crystalline phase. A series of di(hydroxyalkyl) imidazolium ionic liquids and main-chain imidazolium polyesters are synthesized and characterized. The structure-property relationships for thermal behavior, ionic conductivity, and X-ray scattering morphology are investigated. C 11-sebacate-C11 spacers create semicrystalline morphologies with high ionic conductivity.

Original languageEnglish (US)
Pages (from-to)708-717
Number of pages10
JournalAdvanced Functional Materials
Volume21
Issue number4
DOIs
StatePublished - Feb 22 2011

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Polyesters
polyesters
Ionic conductivity
ion currents
Ethane
ethane
Ionic Liquids
Ionic liquids
room temperature
imides
X ray scattering
Temperature
Polymers
liquids
Salts
analogs
Imides
salts
Ionic conduction
Hot Temperature

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

Cite this

Lee, Minjae ; Choi, U. Hyeok ; Salas-De La Cruz, David ; Mittal, Anuj ; Winey, Karen I. ; Colby, Ralph H. ; Gibson, Harry W. / Imidazolium polyesters : Structure-property relationships in thermal behavior, ionic conductivity, and morphology. In: Advanced Functional Materials. 2011 ; Vol. 21, No. 4. pp. 708-717.
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title = "Imidazolium polyesters: Structure-property relationships in thermal behavior, ionic conductivity, and morphology",
abstract = "New bis(ω-hydroxyalkyl)imidazolium and 1,2-bis[N-(ω- hydroxyalkyl)imidazolium]ethane salts are synthesized and characterized; most of the salts are room temperature ionic liquids. These hydroxyl end-functionalized ionic liquids are polymerized with diacid chlorides, yielding polyesters containing imidazolium cations embedded in the main chain. By X-ray scattering, four polyesters are found to be semicrystalline at room temperature: mono-imidazolium-C11-sebacate-C6 (4e), mono-imidazolium-C11-sebacate-C11 (4c), bis(imidazolium)ethane-C6-sebacate-C6 (5a), and bis(imidazolium)ethane-C11-sebacate-C11 (5c), all with hexafluorophosphate counterions. The other imidazolium polyesters, including all those with bis(trifluoromethanesulfonyl)imide (TFSI-) counterions, are amorphous at room temperature. Room temperature ionic conductivities of the mono-imidazolium polyesters (4 × 10-6 to 3 × 10 -5 S cm-1) are higher than those of the corresponding bis-imidazolium polyesters (4 × 10-9 to 8 × 10 -6 S cm-1), even though the bis-imidazolium polyesters have higher ion concentrations. Counterions affect ionic conduction significantly; all polymers with TFSI- counterions have higher ionic conductivities than the hexafluorophosphate analogs. Interestingly, the hexafluorophosphate polyester, 1,2-bis(imidazolium)ethane-C11- sebacate-C11 (5c), displays almost 400-fold higher room temperature ionic conductivity (1.6 × 10-6 S cm-1) than the 1,2-bis(imidazolium)ethane-C6-sebacate-C6 analog (5a, 4.3 × 10-9 S cm-1), attributable to the differences in the semicrystalline structure in 5c as compared to 5a. These results indicate that semicrystalline polymers may result in high ionic conductivity in a soft (low glass tranition temperature, Tg) amorphous phase and good mechanical properties of the crystalline phase. A series of di(hydroxyalkyl) imidazolium ionic liquids and main-chain imidazolium polyesters are synthesized and characterized. The structure-property relationships for thermal behavior, ionic conductivity, and X-ray scattering morphology are investigated. C 11-sebacate-C11 spacers create semicrystalline morphologies with high ionic conductivity.",
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Imidazolium polyesters : Structure-property relationships in thermal behavior, ionic conductivity, and morphology. / Lee, Minjae; Choi, U. Hyeok; Salas-De La Cruz, David; Mittal, Anuj; Winey, Karen I.; Colby, Ralph H.; Gibson, Harry W.

In: Advanced Functional Materials, Vol. 21, No. 4, 22.02.2011, p. 708-717.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Imidazolium polyesters

T2 - Structure-property relationships in thermal behavior, ionic conductivity, and morphology

AU - Lee, Minjae

AU - Choi, U. Hyeok

AU - Salas-De La Cruz, David

AU - Mittal, Anuj

AU - Winey, Karen I.

AU - Colby, Ralph H.

AU - Gibson, Harry W.

PY - 2011/2/22

Y1 - 2011/2/22

N2 - New bis(ω-hydroxyalkyl)imidazolium and 1,2-bis[N-(ω- hydroxyalkyl)imidazolium]ethane salts are synthesized and characterized; most of the salts are room temperature ionic liquids. These hydroxyl end-functionalized ionic liquids are polymerized with diacid chlorides, yielding polyesters containing imidazolium cations embedded in the main chain. By X-ray scattering, four polyesters are found to be semicrystalline at room temperature: mono-imidazolium-C11-sebacate-C6 (4e), mono-imidazolium-C11-sebacate-C11 (4c), bis(imidazolium)ethane-C6-sebacate-C6 (5a), and bis(imidazolium)ethane-C11-sebacate-C11 (5c), all with hexafluorophosphate counterions. The other imidazolium polyesters, including all those with bis(trifluoromethanesulfonyl)imide (TFSI-) counterions, are amorphous at room temperature. Room temperature ionic conductivities of the mono-imidazolium polyesters (4 × 10-6 to 3 × 10 -5 S cm-1) are higher than those of the corresponding bis-imidazolium polyesters (4 × 10-9 to 8 × 10 -6 S cm-1), even though the bis-imidazolium polyesters have higher ion concentrations. Counterions affect ionic conduction significantly; all polymers with TFSI- counterions have higher ionic conductivities than the hexafluorophosphate analogs. Interestingly, the hexafluorophosphate polyester, 1,2-bis(imidazolium)ethane-C11- sebacate-C11 (5c), displays almost 400-fold higher room temperature ionic conductivity (1.6 × 10-6 S cm-1) than the 1,2-bis(imidazolium)ethane-C6-sebacate-C6 analog (5a, 4.3 × 10-9 S cm-1), attributable to the differences in the semicrystalline structure in 5c as compared to 5a. These results indicate that semicrystalline polymers may result in high ionic conductivity in a soft (low glass tranition temperature, Tg) amorphous phase and good mechanical properties of the crystalline phase. A series of di(hydroxyalkyl) imidazolium ionic liquids and main-chain imidazolium polyesters are synthesized and characterized. The structure-property relationships for thermal behavior, ionic conductivity, and X-ray scattering morphology are investigated. C 11-sebacate-C11 spacers create semicrystalline morphologies with high ionic conductivity.

AB - New bis(ω-hydroxyalkyl)imidazolium and 1,2-bis[N-(ω- hydroxyalkyl)imidazolium]ethane salts are synthesized and characterized; most of the salts are room temperature ionic liquids. These hydroxyl end-functionalized ionic liquids are polymerized with diacid chlorides, yielding polyesters containing imidazolium cations embedded in the main chain. By X-ray scattering, four polyesters are found to be semicrystalline at room temperature: mono-imidazolium-C11-sebacate-C6 (4e), mono-imidazolium-C11-sebacate-C11 (4c), bis(imidazolium)ethane-C6-sebacate-C6 (5a), and bis(imidazolium)ethane-C11-sebacate-C11 (5c), all with hexafluorophosphate counterions. The other imidazolium polyesters, including all those with bis(trifluoromethanesulfonyl)imide (TFSI-) counterions, are amorphous at room temperature. Room temperature ionic conductivities of the mono-imidazolium polyesters (4 × 10-6 to 3 × 10 -5 S cm-1) are higher than those of the corresponding bis-imidazolium polyesters (4 × 10-9 to 8 × 10 -6 S cm-1), even though the bis-imidazolium polyesters have higher ion concentrations. Counterions affect ionic conduction significantly; all polymers with TFSI- counterions have higher ionic conductivities than the hexafluorophosphate analogs. Interestingly, the hexafluorophosphate polyester, 1,2-bis(imidazolium)ethane-C11- sebacate-C11 (5c), displays almost 400-fold higher room temperature ionic conductivity (1.6 × 10-6 S cm-1) than the 1,2-bis(imidazolium)ethane-C6-sebacate-C6 analog (5a, 4.3 × 10-9 S cm-1), attributable to the differences in the semicrystalline structure in 5c as compared to 5a. These results indicate that semicrystalline polymers may result in high ionic conductivity in a soft (low glass tranition temperature, Tg) amorphous phase and good mechanical properties of the crystalline phase. A series of di(hydroxyalkyl) imidazolium ionic liquids and main-chain imidazolium polyesters are synthesized and characterized. The structure-property relationships for thermal behavior, ionic conductivity, and X-ray scattering morphology are investigated. C 11-sebacate-C11 spacers create semicrystalline morphologies with high ionic conductivity.

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