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Investigation of the interactions between 1-butyl-3-methylimidazolium-based ionic liquids and isobutylene using density functional theory

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Abstract

To identify ionic liquids (ILs) that could be used as solvents in isobutylene (IB) polymerization, the interactions between IB and eight different ILs based on the 1-butyl-3-methylimidazolium cation ([Bmim]+) were investigated using density functional theory (DFT). The anions in the ILs were chloride, hexafluorophosphate, tetrafluoroborate, bis[(trifluoromethyl)sulfonyl]imide, tetrachloroaluminate ([AlCl4]−), tetrachloroferrate, acetate, and trifluoroacetate. The interaction geometries were explained by changes in the total energy, intermolecular distances, Hirshfeld charges, and the electrostatic potential surface. The IL solvents were screened by comparing their interaction intensities with IB to the interaction intensities of reference ILs ([AlCl4]−-based ILs) with IB. The microscopic mechanism for IB dissolution was rationalized by invoking a previously reported microscopic mechanism for the dissolution of gases in ILs. Computation results revealed that hydrogen (H) bonding between C2–H on the imidazolium ring and the anions plays a key role in ion pair (IP) formation. The addition of IB leads to slight changes in the dominant interactions of the IP. IB molecules occupied cavities created by small angular rearrangements of the anions, just as CO2 does when it is dissolved in an IL. The limited total free space in the ILs and the much larger size of IB than CO2 were found to be responsible for the poor solubility of IB compared with that of CO2 in the ILs.

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Acknowledgments

This work was supported by the National Science Foundation of China (nos. 51573020, 51373026, 51503019, and 51503019), the Beijing Natural Science Foundation (nos. 2172022 and 2162014), the Beijing Science and Technology Project of the Beijing Municipal Education Commission (KM201710017005), the Undergraduate Training Program (no. 2016-238), and the URT Program (no. 2016J00036).

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Authors and Affiliations

  1. College of Material Science and Engineering, Beijing University of Chemical Technology, Beijing, 100029, China

    Xiaoning Li, Wenli Guo & Xiaoqian Zhang

  2. Department of Materials Science and Engineering, Beijing Institute of Petrochemical Technology, Beijing, 102617, China

    Xiaoning Li, Wenli Guo, Yibo Wu, Wei Li, Liangfa Gong, Xiaoqian Zhang, Shuxin Li, Yuwei Shang, Dan Yang & Hao Wang

  3. Beijing Key Lab of Special Elastomeric Composite Materials, Beijing, 102617, China

    Xiaoning Li, Wenli Guo, Yibo Wu, Wei Li, Liangfa Gong, Xiaoqian Zhang, Shuxin Li, Yuwei Shang, Dan Yang & Hao Wang

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  1. Xiaoning Li
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Li, X., Guo, W., Wu, Y. et al. Investigation of the interactions between 1-butyl-3-methylimidazolium-based ionic liquids and isobutylene using density functional theory. J Mol Model 24, 83 (2018). https://doi.org/10.1007/s00894-018-3586-y

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