Specific Solvation of Benzyl Methacrylate in 1-Ethyl-3-methylimidazolium Bis(trifluoromethanesulfonyl)amide Ionic Liquid

Matsugami, Masaru; Fujii, Kenta; Ueki, Takeshi; Kitazawa, Yuzo; Umebayashi, Yasuhiro; Watanabe, Masayoshi; Shibayama, Mitsuhiro

doi:10.2116/analsci.29.311

Cited by 27 publications

(39 citation statements)

References 22 publications

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“…This opposite tendency suggests that the solvation mechanism is different between ILs and aqueous systems. Here, the former is ascribed to the sidechain ''philic'' interaction between the phenyl group of PPhEtMA and the C 2 mIm cation, 28 while the latter in the side-chain ''phobic'' interaction is stabilized by the solvent-solvent interaction. 44,45,49 When the cohesive interaction between solvent molecules is enhanced by deuterium substitution, 46 the side-chain ''philic'' interaction should become unfavorable whereas the sidechain ''phobic'' interaction favorable.…”

Section: Resultsmentioning

confidence: 99%

“…2 Furthermore, our investigations of the microscopic solvation structure of PBnMA in [C 2 mIm + ][TFSA À ] by high-energy X-ray total scattering (HEXTS) modeled with the aid of MD simulations demonstrated that the C 2 mIm + cations are localized above and below the benzyl groups of PBnMA. 28 This partially ordered microscopic solvation structure of PBnMA in [C 2 mIm + ][TFSA À ] solution decreases the mixing entropy, resulting in the observed LCSTtype phase behavior. From a thermodynamic aspect, it was reported that the mixing enthalpy and entropy values of PBnMA in [C 2 mIm + ][TFSA À ] are significantly smaller than those of PNIPAm in H 2 O, indicating that T c of the system can be easily modified by a slight change in the free energy of mixing.…”

Section: Introductionmentioning

confidence: 99%

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SANS study on the solvated structure and molecular interactions of a thermo-responsive polymer in a room temperature ionic liquid

Hirosawa

Fujii

Ueki

et al. 2016

Phys. Chem. Chem. Phys.

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We have utilized small-angle neutron scattering (SANS) to quantitatively characterize the LCST-type phase behavior of the poly(benzyl methacrylate) (PBnMA) derivative poly(2-phenylethyl methacrylate) (PPhEtMA) in the deuterated ionic liquid (IL) d8-1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide (d8-[C2mIm(+)][TFSA(-)]). The SANS curves showed a discontinuous change from those characteristics of dispersed polymer chains to those of large aggregates of PPhEtMA chains suspended in the IL solution, indicating that phase separation occurs discontinuously at Tc. Furthermore, we evaluated the enthalpic and entropic contributions to the effective interaction parameter χeff of PPhEtMA in [C2mIm(+)][TFSA(-)] and compared them with those of PBnMA. The absolute value of the enthalpic contribution observed for PPhEtMA was smaller than that for PBnMA. This difference in the enthalpic term can be attributed to the unfavorable interaction between the IL and the alkyl group in the side chain of PPhEtMA. In addition, the temperature dependence of χeff was smaller than the previously reported value for a thermo-responsive polymer in an aqueous system. It was found out that the strong dependence of Tc on the chemical structure in IL systems originated from the relatively smaller temperature dependence of χeff.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

SANS study on the solvated structure and molecular interactions of a thermo-responsive polymer in a room temperature ionic liquid

Hirosawa

Fujii

Ueki

et al. 2016

Phys. Chem. Chem. Phys.

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“…33,126 We reported for the first time the upper critical solution temperature (UCST) phase behavior (low-temperature-insoluble and high-temperaturesoluble behavior) 127 and lower critical solution temperature (LCST) phase behavior (low-temperature-soluble and high-temperatureinsoluble behavior) [128][129][130][131][132][133][134] for certain polymers in ILs (Fig. 11).…”

Section: Phase Behavior Of Polymers In Ils and Materializationmentioning

confidence: 97%

Design and Materialization of Ionic Liquids Based on an Understanding of Their Fundamental Properties

Watanabe

2016

Electrochemistry

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Ionic liquids (ILs) are defined as salts that have melting points lower than 100°C. Most are organic salts, and these may be designed and tailored to have suitable properties. ILs are recognized as a third group of solvents (and electrolytes), after water and organic solvents. They are characterized by their unique properties such as nonvolatilities, high thermal stabilities, and high ionic conductivities. In this article, our work on the design and preparation of ILs is briefly reviewed. The concept of ionicity is proposed as a metric to characterize the basic nature (dissociativity) of ILs, which is affected by the Lewis acidity/basicity of cations/anions (i.e., coulombic interactions), the directionality of interactions between cations and anions, and van der Waals interactions between ions. The ionicity of ILs is dominated by a subtle balance between coulombic and van der Waals interactions, which clearly discriminates ILs from conventional high-temperature inorganic molten salts. Here, the design of protic ILs for fuel cell electrolytes, electron-transporting ILs for dye-sensitized solar cell electrolytes, and Li + -conducting solvate ILs for lithium battery electrolytes are discussed based on an understanding of the fundamental properties of ILs. Furthermore, the combination of ILs with polymers and colloidal particles affords intriguing quasi-solid materials (ion gels), and the ion transport in these gels is decoupled from the mechanical relaxation time of these materials, yielding new solid electrolytes. The possibility of temperature and photo-sensitive solubility dependence of polymers in ILs allows the creation of stimuli-responsive materials. Finally, protic ILs/protic salts are demonstrated to be good precursors for N-doped carbon materials.

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“…This phenomenon has been investigated using X-ray scattering and molecular dynamics (MD) simulations, which revealed that structureforming solvation between the aromatic ring of PBnMA and the imidazolium cation ([C n mim]) leads to a negative entropic mixing term, resulting in LCST-type phase separation. 59,60 PEO also exhibits LCST-type phase separation in [C n mim]BF 4 . 61 Moreover, we reported that the mixture of poly(ethyl glycidyl ether) (PEGE) and [ 62,63 In that study, we evaluated the effect of IL structure on phase behavior and reported that the presence of a methyl substituent at the C-2 position of the imidazolium cation (i.e., 1-alkyl-2,3-dimethylimidazolium) significantly decreases the LCST.…”

Section: Ionic Liquids As Solvents For Polymersmentioning

confidence: 99%

Block copolymer self-assembly in ionic liquids

Tamate

Hashimoto

Ueki

et al. 2018

Phys. Chem. Chem. Phys.

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Ionic liquids (ILs), solely composed of cations and anions, are regarded as a novel class of promising liquids, potentially applicable to energy devices, reaction media, separation materials, etc. ILs have also attracted great attention as new media for molecular self-assembly, capable of producing novel soft materials with unique features never observed for conventional soft materials containing organic and aqueous solvents. In this review, we focus on recent developments in block copolymer (BCP) self-assembly in ILs. Self-assembled structures formed by dilute and concentrated BCP solutions in ILs are discussed in detail. Ion gels formed by BCP self-assembly have received special interest because they exhibit excellent physical properties of tunable viscoelasticity and solution processability without impairing the intrinsic properties of ILs, such as nonvolatility, nonflammability, and high ionic conductivity. Applications of ion gels based on BCP self-assembly for electric double layer capacitors, lithium-ion batteries, and electroactive soft actuators are also addressed.

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Specific Solvation of Benzyl Methacrylate in 1-Ethyl-3-methylimidazolium Bis(trifluoromethanesulfonyl)amide Ionic Liquid

Cited by 27 publications

References 22 publications

SANS study on the solvated structure and molecular interactions of a thermo-responsive polymer in a room temperature ionic liquid

SANS study on the solvated structure and molecular interactions of a thermo-responsive polymer in a room temperature ionic liquid

Design and Materialization of Ionic Liquids Based on an Understanding of Their Fundamental Properties

Block copolymer self-assembly in ionic liquids

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