Anomalous Thermal Characteristics of Poly(ionic liquids) Derived from 1-Butyl-2,3-dimethyl-4-vinylimidazolium Salts
The synthesis of 1-butyl-2,3-dimethyl-4-vinylimidazolium triflate, its polymerization, and ion exchange to yield a trio of 1-butyl-2,3-dimethyl-4-vinylimidazolium polymers is described. Irrespective of the nature of the anion, substitution at the 2-position of the imidazolium moiety substantially in...
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| Format: | Article |
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MDPI AG
2022-01-01
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| Series: | Polymers |
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| Online Access: | https://www.mdpi.com/2073-4360/14/2/254 |
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| author | Fan Yang Meng Zhao Darren Smith Peggy Cebe Sam Lucisano Thomas Allston Thomas W. Smith |
| author_facet | Fan Yang Meng Zhao Darren Smith Peggy Cebe Sam Lucisano Thomas Allston Thomas W. Smith |
| author_sort | Fan Yang |
| collection | DOAJ |
| description | The synthesis of 1-butyl-2,3-dimethyl-4-vinylimidazolium triflate, its polymerization, and ion exchange to yield a trio of 1-butyl-2,3-dimethyl-4-vinylimidazolium polymers is described. Irrespective of the nature of the anion, substitution at the 2-position of the imidazolium moiety substantially increases the distance between the anion and cation. The methyl substituent at the 2-position also served to expose the importance of H-bonding for the attractive potential between imidazolium moiety and anions in polymers without a methyl group at the 2-position. The thermal characteristics of poly(1-butyl-2,3-dimethyl-4-vinylimidazolium) salts and corresponding poly(1-ethyl-3-methyl-4-vinylimidazolium) salts were evaluated. While the mid-point glass transition temperatures, T<sub>g</sub>-mid, for 1-ethyl-3-methyl-4-vinylimidazolium polymers with CF<sub>3</sub>SO<sub>3</sub><sup>−</sup>, (CF<sub>3</sub>SO<sub>2</sub>)<sub>2</sub>N<sup>−</sup> and PF<sub>6</sub><sup>−</sup> counterions, were 153 °C, 88 °C and 200 °C, respectively, the T<sub>g</sub>-mid values for 1-butyl-2,3-dimethyl-4vinylimidazolium polymers with corresponding counter-ions were tightly clustered at 98 °C, 99 °C and 84 °C, respectively. This dramatically reduced influence of the anion type on the glass transition temperature was attributed to the increased distance between the center of the anions and cations in the 1-butyl-2,3-dimethyl-4-vinylimidazolium polymer set, and minimal H-bonding interactions between the respective anions and the 1-butyl-2,3-dimethyl-4-vinylimidazolium moiety. It is believed that this is the first observation of substantial independence of the glass transition of an ionic polymer on the nature of its counterion. |
| first_indexed | 2024-03-10T00:40:11Z |
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| id | doaj.art-4e42d0147fc84bb5bef6a01a99d7f9ff |
| institution | Directory Open Access Journal |
| issn | 2073-4360 |
| language | English |
| last_indexed | 2024-03-10T00:40:11Z |
| publishDate | 2022-01-01 |
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| spelling | doaj.art-4e42d0147fc84bb5bef6a01a99d7f9ff2023-11-23T15:08:33ZengMDPI AGPolymers2073-43602022-01-0114225410.3390/polym14020254Anomalous Thermal Characteristics of Poly(ionic liquids) Derived from 1-Butyl-2,3-dimethyl-4-vinylimidazolium SaltsFan Yang0Meng Zhao1Darren Smith2Peggy Cebe3Sam Lucisano4Thomas Allston5Thomas W. Smith6Versick Analytics, Jersey City, NJ 07310, USABOE Technology Group, Beijing 100176, ChinaWalter Reed Army Institute of Research, Silver Spring, MD 20910, USAPhysics and Astronomy Department, Tufts University, Medford, MA 02155, USAXerox Corporation, Webster, NY 14580, USASchool of Chemistry & Materials Science, Rochester Institute of Technology, Rochester, NY 14623, USASchool of Chemistry & Materials Science, Rochester Institute of Technology, Rochester, NY 14623, USAThe synthesis of 1-butyl-2,3-dimethyl-4-vinylimidazolium triflate, its polymerization, and ion exchange to yield a trio of 1-butyl-2,3-dimethyl-4-vinylimidazolium polymers is described. Irrespective of the nature of the anion, substitution at the 2-position of the imidazolium moiety substantially increases the distance between the anion and cation. The methyl substituent at the 2-position also served to expose the importance of H-bonding for the attractive potential between imidazolium moiety and anions in polymers without a methyl group at the 2-position. The thermal characteristics of poly(1-butyl-2,3-dimethyl-4-vinylimidazolium) salts and corresponding poly(1-ethyl-3-methyl-4-vinylimidazolium) salts were evaluated. While the mid-point glass transition temperatures, T<sub>g</sub>-mid, for 1-ethyl-3-methyl-4-vinylimidazolium polymers with CF<sub>3</sub>SO<sub>3</sub><sup>−</sup>, (CF<sub>3</sub>SO<sub>2</sub>)<sub>2</sub>N<sup>−</sup> and PF<sub>6</sub><sup>−</sup> counterions, were 153 °C, 88 °C and 200 °C, respectively, the T<sub>g</sub>-mid values for 1-butyl-2,3-dimethyl-4vinylimidazolium polymers with corresponding counter-ions were tightly clustered at 98 °C, 99 °C and 84 °C, respectively. This dramatically reduced influence of the anion type on the glass transition temperature was attributed to the increased distance between the center of the anions and cations in the 1-butyl-2,3-dimethyl-4-vinylimidazolium polymer set, and minimal H-bonding interactions between the respective anions and the 1-butyl-2,3-dimethyl-4-vinylimidazolium moiety. It is believed that this is the first observation of substantial independence of the glass transition of an ionic polymer on the nature of its counterion.https://www.mdpi.com/2073-4360/14/2/254poly(ionic liquids)ionic liquid polymerthermal analysision-conductive polymervinylimidazolium monomersionic liquids |
| spellingShingle | Fan Yang Meng Zhao Darren Smith Peggy Cebe Sam Lucisano Thomas Allston Thomas W. Smith Anomalous Thermal Characteristics of Poly(ionic liquids) Derived from 1-Butyl-2,3-dimethyl-4-vinylimidazolium Salts Polymers poly(ionic liquids) ionic liquid polymer thermal analysis ion-conductive polymer vinylimidazolium monomers ionic liquids |
| title | Anomalous Thermal Characteristics of Poly(ionic liquids) Derived from 1-Butyl-2,3-dimethyl-4-vinylimidazolium Salts |
| title_full | Anomalous Thermal Characteristics of Poly(ionic liquids) Derived from 1-Butyl-2,3-dimethyl-4-vinylimidazolium Salts |
| title_fullStr | Anomalous Thermal Characteristics of Poly(ionic liquids) Derived from 1-Butyl-2,3-dimethyl-4-vinylimidazolium Salts |
| title_full_unstemmed | Anomalous Thermal Characteristics of Poly(ionic liquids) Derived from 1-Butyl-2,3-dimethyl-4-vinylimidazolium Salts |
| title_short | Anomalous Thermal Characteristics of Poly(ionic liquids) Derived from 1-Butyl-2,3-dimethyl-4-vinylimidazolium Salts |
| title_sort | anomalous thermal characteristics of poly ionic liquids derived from 1 butyl 2 3 dimethyl 4 vinylimidazolium salts |
| topic | poly(ionic liquids) ionic liquid polymer thermal analysis ion-conductive polymer vinylimidazolium monomers ionic liquids |
| url | https://www.mdpi.com/2073-4360/14/2/254 |
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