JP2013151628A - Gelatinizer comprising alkyl hydrazide compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new gelatinizer.SOLUTION: A new gelatinizer includes an alkyl hydrazide compound represented by formula [I] or a dialkyl hydrazide compound represented by formula [II] (wherein Rand Rare each independently a 1-30C aliphatic group which may have substituents).

Description

  The present invention relates to a novel gelling agent containing an alkyl hydrazide derivative.

  A structure in which a fluid is contained in a three-dimensional network structure formed by a substance having gel-forming ability (gelling agent) is called a gel. Generally, when the fluid is water, hydrogel (hydrogel), other than water The organic liquid (organic solvent, oil, etc.) is called an organogel or an oil gel. Oil gels (organogels) are used to adjust the fluidity of cosmetics and paints in the fields of cosmetics, pharmaceuticals, agricultural chemicals, foods, adhesives, paints, resins, and the like. Further, for example, it is widely used in the field of environmental conservation, such as gelling waste oil to prevent water contamination as a solid substance.

  Research on gelling agents has been conducted mainly on high molecular compounds, but in recent years, research and development on low molecular weight compounds that are easier to introduce various functions than on high molecular compounds are underway. . As described above, oil gels (organogels) have been used in a wide range of fields, and future expansion of the fields of use is expected. For this reason, gelling agents for low-molecular compounds (hereinafter sometimes referred to as low-molecular gelling agents) are required to have gel-forming ability for a wide variety of organic solvents in order to expand the use of oil gels. In response to these problems, urea compounds have been disclosed as low molecular gelling agents that can form gels with excellent stability with a small amount of addition to various organic solvents (for example, Patent Document 1). 2). In addition, it is disclosed that α-aminolactam derivatives have gelling ability with respect to squalane, liquid paraffin, and the like (for example, Patent Document 3).

  On the other hand, it has been reported that an alkoxy-substituted benzohydrazide derived from a benzoic acid ester has a gelling ability of an organic solvent (Non-patent Document 1).

JP 2000-256303 A JP 2004-359543 A Japanese Patent Application Laid-Open No. 10-256571

C. Tan et al. , Journal of Molecular Liquids, 124 (2006) 32-36.

So far, oil gelling agents composed of low molecular weight compounds for non-aqueous media such as organic solvents have been proposed, but new oil gels with new applications and functionality, such as limited media that can be gelled, have been proposed. In the creation, new low-molecular oil gelling agents capable of gelling various media are being sought. However, although a new skeleton molecule has been studied as a low molecular weight organogelator, no examples have been reported so far in which alkylhydrazide derivatives not containing an aromatic ring have been studied as oil gelators.
The present invention has been made based on the above circumstances, and a problem to be solved is to provide a novel gelling agent having a structure that has not been proposed so far.

  As a result of intensive studies to solve the above problems, the present inventors were surprised when an alkyl hydrazide derivative, which had not been studied so far, was applied as a gelling agent for non-aqueous solvents such as organic solvents. It was found that a gel can be formed, and the present invention has been completed.

That is, the present invention relates to the following novel gelling agent and a gelled solid electrolyte containing the gelling agent.
[1] A gelling agent comprising an alkyl hydrazide compound represented by the general formula [I].
(In the formula, R ₁ represents an aliphatic group having 1 to 30 carbon atoms which may have a substituent.)
[2] A gelling agent comprising a dialkyl hydrazide compound represented by the general formula [II].
(In the formula, R ₁ and R ₂ each independently represents an aliphatic group having 1 to 30 carbon atoms which may have a substituent.)
[3] The gelling agent according to [1], comprising two or more alkyl hydrazide compounds represented by the general formula [I] and exhibiting thixotropic properties in the formed gel.
[4] The gelling agent according to [2], which contains two or more dialkyl hydrazide compounds represented by the general formula [II] and exhibits thixotropic properties in the formed gel.
[5] A gel-like solid electrolyte comprising a solid electrolyte salt, a solvent, and the gelling agent according to any one of [1] to [4].
[6] the solid electrolyte _{salt, LiPF6, LiBF 4, LiClO 4} , LiAsF 6, LiCF 3 SO 3, LiN (SO 2 CF 3) 2, LiN (SO 2 C 2 F 5) 2, LiN (SO 2 CF ₃ ) (
The gelled solid electrolyte according to [5], which is selected from the group consisting of SO ₂ C ₄ F ₉ ) and a mixture thereof.
[7] A gel comprising an alkyl hydrazide compound represented by the general formula [I].
(In the formula, R ₁ represents an aliphatic group having 1 to 30 carbon atoms which may have a substituent.)
[8] A gel comprising a dialkyl hydrazide compound represented by the general formula [II].
(In the formula, R ₁ and R ₂ each independently represents an aliphatic group having 1 to 30 carbon atoms which may have a substituent.)
[9] The gel according to [7], comprising two or more alkyl hydrazide compounds represented by the general formula [I] and exhibiting thixotropic properties.
[10] The gel according to [8], comprising two or more dialkyl hydrazide compounds represented by the general formula [II] and exhibiting thixotropic properties.

The gelling agent of the present invention can form a gel by gelling an organic solvent.
In particular, the gelling agent of the present invention is capable of gel formation with various organic solvents having various dielectric constants, and can also form an electrolyte solution that is a host material of an ionic conductor, and the obtained gel is an electrolyte solution. It is possible to obtain good ionic conduction at the same level as or comparable to that of ionic conduction.

FIG. 1 is a photograph showing the gelation behavior of a toluene solution mixed with an alkyl hydrazide derivative in Examples 1 to 3 (Example 1: (a) stearic acid hydrazide (2 wt%), Example 2: (b ) Palmitic acid hydrazide (2 wt%), Example 3: (c) n-octanohydrazide (4 wt%)). FIG. 2 is a photograph showing the gelation behavior of various solutions mixed with stearic acid hydrazide (5 wt%) in Example 4 ((1) propylene carbonate, (2) DMSO, (3) DMF, (4) methanol, (5) acetonitrile, (6) acetone, (7) dichloroethane, (8) tetrahydrofuran, (9) ethyl acetate, (10) toluene, (11) n-hexane). FIG. 3 is a view showing a photograph of a scanning electron microscope (SEM) image of toluene xerogel of stearic acid hydrazide (stearic acid hydrazide concentration: 10 wt%) in Example 8 ((a) to (c) show the magnification. This is an image taken with a change.) FIG. 4 is a photograph showing a scanning electron microscope (SEM) image of toluene xerogel of palmitic acid hydrazide (palmitic acid hydrazide concentration: 10 wt%) in Example 9 ((a) to (c) are magnifications. This is an image taken with a change.) FIG. 5 is a photograph showing a scanning electron microscope (SEM) image of toluene xerogel of n-octanohydrazide (concentration of n-octanohydrazide: 10 wt%) in Example 10 ((a) to (c). ) Is an image taken at different magnifications). FIG. 6 is a photograph showing a scanning electron microscope (SEM) image of methanol xerogel of stearic acid hydrazide (stearic acid hydrazide concentration: 10 wt%) in Example 11 ((a) to (c) show the magnification. This is an image taken with a change.) FIG. 7 shows photographs of scanning electron microscope (SEM) images of n-hexane xerogel of stearic acid hydrazide (stearic acid hydrazide concentration: 10 wt%) in Example 12 ((a) to (c)). This is an image taken at a different magnification.) FIG. 9 is a photograph showing a scanning electron microscope (SEM) image of DMF xerogel of stearic acid hydrazide (stearic acid hydrazide concentration: 10 wt%) in Example 13 ((a) to (c) show the magnification. This is an image taken with a change.) FIG. 9 is a diagram showing photographs of scanning electron microscope (SEM) images of methanol xerogel of palmitic acid hydrazide (concentration of palmitic acid hydrazide: 10 wt%) in Example 14 ((a) to (c) are magnifications. This is an image taken with a change.) FIG. 10 shows photographs of scanning electron microscope (SEM) images of stearic acid hydrazide in Example 15 ((a) to (c) are images taken at different magnifications). FIG. 11 is a photograph showing a scanning electron microscope (SEM) image of the crystalline state of palmitic acid hydrazide in Example 16 ((a) to (c) are images taken at different magnifications). FIG. 12 is a diagram showing photographs of a scanning electron microscope (SEM) image of the crystalline state of n-octanohydrazide in Example 17 ((a) to (c) are images taken at different magnifications. ). FIG. 13 is a photograph showing the gelation behavior of a toluene solution (FIG. 13 (1)) and a THF solution (FIG. 13 (2)) mixed with Compound 1 (dialkylhydrazide derivative) (2 wt%) in Example 22. FIG. 14 shows photographs of scanning electron microscope (SEM) images of toluene gel (compound 1 concentration: 10 wt%) of compound 1 (dialkylhydrazide derivative) in Example 23 ((a) to (c)). Is an image taken at different magnifications). FIG. 15 is a photograph showing the gelation behavior of a toluene solution (mixture concentration: 1 wt%) of an alkyl hydrazide derivative two-component system in Example 24 ((1) Mass mixing ratio of stearic hydrazide / palmitic acid hydrazide 2 / 1, (2) Same as 1/1, (3) Same as 1/2, (4) Mass mixing ratio of stearic acid hydrazide / n-octanohydrazide 2/1, (5) Same as 1/1, (6) 1/2). FIG. 16 is a photograph showing the gelation behavior of a toluene solution (mixture concentration: 1 wt%) of an alkyl hydrazide derivative ternary mixture system in Example 25 ((1) stearic acid hydrazide / palmitic acid hydrazide / n-octano. Hydrazide mass mixing ratio 1/1/1, (2) 2/1/1, (3) 1/2/1, (4) 1/1/2, (5) 2/2/1, (6) 2/1/2, (7) 1/2/2). 17 is a photograph showing gelation behavior and thixotropic behavior of various alkyl hydrazide derivatives (single system) in Example 26 ((1) stearic acid hydrazide 2 wt% chlorobenzene gel, (2) palmitic acid hydrazide 2 wt. % Chlorobenzene gel, (3) n-octanohydrazide 6 wt% chlorobenzene gel, (4) stearic acid hydrazide 2 wt% chlorobenzene gel after 12 hours of grinding, (5) palmitic acid hydrazide 2 wt% chlorobenzene gel after 12 hours of grinding, ( 6) n-octanohydrazide 6 wt% chlorobenzene gel after pulverization 12 hours). 18 is a photograph showing the gelation behavior and thixotropic behavior of a chlorobenzene solution of an alkyl hydrazide derivative ternary mixed system in Example 27 (1 wt% chlorobenzene gel of (1), 2 wt% chlorobenzene gel of (2), (3) 1 wt% chlorobenzene gel after 1 minute of grinding, (4) 2 wt% chlorobenzene gel after 1 minute of grinding, (5) 1 wt% chlorobenzene gel after 1 hour of grinding, (6) 2 wt% chlorobenzene after 1 hour of grinding. gel).

The present invention relates to a gelling agent comprising the alkyl hydrazide compound represented by the general formula [I] or the dialkyl hydrazide compound represented by [II].
Hereinafter, the present invention will be described in detail. Hereinafter, the “compound represented by the general formula [I]” is also referred to as “compound [I]”. The same applies to compounds with other formula numbers.

In the definitions of R ₁ in the above general formula [I] and R ₁ and R ₂ in [II], the aliphatic group preferably represents an alkyl group having 1 to 30 carbon atoms. Examples thereof include a branched alkyl group having 1 to 30 carbon atoms or a cyclic alkyl group having 3 to 30 carbon atoms, preferably a linear, branched or cyclic alkyl group having 7 to 20 carbon atoms. Is mentioned.
Specifically, linear, branched or cyclic heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group (lauryl group), tridecyl group, tetradecyl group (myristyl group) shown below Pentadecyl group, hexadecyl group (cetyl group, palmityl group), heptadecyl group (margaryl group), octadecyl group (stearyl group), nonadecyl group, icosyl group and the like. Among these, n-heptyl group, n-pentadecyl group, and n-heptadecyl group are preferable.

The alkyl groups may be the same or different and have 1 to 3 substituents. Examples of the substituent include a hydroxy group, a carboxyl group, a halogen atom, an alkoxy group, an alkoxyalkoxy group, and a fluorine-substituted alkoxy group.
Examples of the alkyl portion of the alkoxy group include linear or branched alkyl groups having 1 to 8 carbon atoms or cyclic alkyl groups having 3 to 8 carbon atoms. Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, 2-methylbutyl group, tert-pentyl group, hexyl Group, octyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like. Examples of the fluorine-substituted alkoxy group include groups in which at least one alkyl portion of the alkoxy group is substituted with a fluorine atom.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The alkyl part of the alkoxyalkoxy group (—O-alkylene-O-alkyl group) has the same meaning as described above, and the alkylene part of the alkoxyalkoxy group has the same meaning as that obtained by removing one hydrogen atom from the alkyl group.

  The alkyl group may contain one or more unsaturated double bonds and unsaturated triple bonds, and the alkyl group may be interrupted by an oxygen atom or a nitrogen atom.

Examples of the organic solvent to be gelled according to the present invention include aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and tetralin; aliphatics such as n-hexane, n-heptane, mineral spirit, and cyclohexane; Alicyclic hydrocarbon solvents; halogen solvents such as methyl chloride, methyl bromide, methyl iodide, methylene dichloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethylene, perchloroethylene, orthodichlorobenzene; ethyl acetate, butyl acetate , Ester solvents such as methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, γ-butyrolactone, γ-valerolactone, propylene glycol monomethyl ether acetate, diethyl ether, Ether solvents such as tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, 1,2-dimethoxyethane; acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone, etc. Ketone solvents; alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, 2-ethylhexyl alcohol, benzyl alcohol, ethylene glycol; dimethyl carbonate (dimethyl carbonate, DMC), Diethyl carbonate (diethyl carbonate, DEC), ethyl methyl carbonate, ethylene carbonate (ethylene carbonate), propylene carbonate (propylene -Bonate), linear or cyclic carbonates such as vinylene carbonate (vinylene carbonate); amide solvents such as N, N-dimethylformamide (DMF) and N, N-dimethylacetamide; sulfoxides such as dimethyl sulfoxide (DMSO) Solvents; heterocyclic compound solvents such as N-methyl-2-pyrrolidone; nitrile solvents such as acetonitrile; and a mixture of two or more of these.

In the gelling agent of the present invention, the total amount of the alkyl hydrazide compound or dialkyl hydrazide compound is 1 to 30% by mass, preferably 3 to 20% by mass, more preferably 5 to 15% by mass with respect to the organic solvent as a medium. It is preferable to use in such an amount.
A gelled product can be obtained by adding the gelling agent of the present invention to an organic solvent as a medium, heating and stirring as necessary, and then allowing it to stand at room temperature. The gel strength can be adjusted by the concentration of the gelling agent.

Moreover, the gelling agent of this invention can also use what mixed said compound [I] or compound [II] individually by 1 type or in mixture of 2 or more types.
For example, in compound [I], n-octanohydrazide [C wherein R ₁ represents a heptyl group
8HD], palmitic acid hydrazide [C16HD] wherein R ₁ represents a pentadecyl group
And stearic acid hydrazide [referred to as C18HD] wherein R ₁ represents a heptadecyl group, for example, C8HD: C18HD at a mass ratio of 1 to 10: 1 to 10 and C16HD: C18HD. It can be mixed and used in the ratio of 1-10: 1-10. Moreover, these can also be used as a mixture of 3 types, for example, C8HD: C16HD: C18HD in the ratio of 1-10: 1-10: 1-30.
A gelling agent composed of a mixture of two or more compounds can gel an organic solvent as a medium with a smaller amount of use than a gelling agent composed of one kind of compound. Even in an amount that cannot be gelled by a gelling agent comprising the above compound, it may be possible to gel the organic solvent.
Moreover, the gelling agent which consists of a mixture of these 2 or more types of compounds can express thixotropic property in the formed gel.

  In addition, the gel formed by the gelling agent of the present invention has various additives (surfactant, ultraviolet absorber, moisturizing agent) as needed, such as its application, within a range that does not inhibit the gelling ability of the gelling agent. Organic compounds such as agents, preservatives, antioxidants, fragrances, and physiologically active substances (medicinal ingredients), and inorganic compounds such as titanium oxide, talc, mica, and water) can be mixed.

In the gel, an electrolyte (salt) is a lithium salt, specifically, an inorganic lithium salt selected from LiPF ₆ , LiBF ₄ , LiClO ₄ and LiAsF ₆ , derivatives of these inorganic lithium salts, LiSO ₃ CF ₃ , LiN ( SO ₂ CF ₃ ) ₂ , LiN (SO ₂ C ₂ F ₅ ) ₂ and Li
An organic lithium salt selected from N (SO ₂ CF ₃ ) (SO ₂ C ₄ F ₉ ), a derivative of the organic lithium salt, and the like can also be mixed. These lithium salts are also solid electrolyte salts that can be used in lithium ion secondary batteries.
That is, the gel formed by the gelling agent of the present invention is useful as a gel-like solid electrolyte, and the solid electrolyte is also an object of the present invention.
The gel electrolyte is configured to include the above-described gelling agent of the present invention, the above-described electrolyte (solid electrolyte salt), and a solvent, and the above-mentioned solvent is cited as <organic solvent to be gelled>. A solvent generally used as an electrolytic solution can be preferably used. Examples thereof include dimethyl carbonate (dimethyl carbonate, DMC), diethyl carbonate (diethyl carbonate, DEC), ethyl methyl carbonate, ethylene carbonate (ethylene carbonate), propylene carbonate (propylene carbonate), vinylene carbonate (vinylene carbonate), and the like. Or cyclic carbonates.

  The gel containing the compound [I] or compound [II], which is the gelling agent of the present invention, and a mixture of two or more of these compounds [I] or compound [II], and having thixotropic properties A gel that expresses is also an object of the present invention.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to the following Example.
The reagents described in the following examples were obtained from Tokyo Chemical Industry Co., Ltd., and the solvents were obtained from Wako Pure Chemical Industries, Ltd. and used as they were. The apparatus and conditions used for various measurements and analyzes are shown below.
(1) Differential scanning calorimetry / apparatus: PerkinElmer Diamond DSC Co., Ltd. Perkin Elmer Japan Co., Ltd./ Container: Ag-made sealed sample container / Temperature raising / lowering rate: 10 ° C./min (2) Scanning electron microscope Photo / Equipment: JSM-7400, JEOL Ltd.
・ Acceleration voltage: 1.0 kV
・ Sample treatment: Sample treatment with a conductive substance is not performed. (3) Transmission electron micrograph ・ Device: H-8000, Hitachi High-Technologies Corporation ・ Operation voltage: 200 kV
・ Sample treatment: Sample treatment with conductive material is not performed. (4) Ion conductivity measurement ・ Device: precision LCR Meter E4980A, manufactured by Agilent Technologies ・ Test lead: HP16089B KELVIN CLIP LEADS, Agilent Technologies ) Made and measured impedance: 20 Hz to 2 MHz, impedance measured when an alternating electric field is applied. Measurement cell: Silicon spacer (0.92 mm thick) with a 5.4 mm diameter hole between aluminum plate electrodes. Put the prepared gel in this hole and measure it.
(5) ¹ H-NMR spectrum / apparatus: AVANCE 500 (500 MHz), manufactured by Bruker BioSpin Co., Ltd. (6) MALDI-TOF MS spectrum / apparatus: autoflex III, manufactured by Bruker Daltonics Co./matrix: dithranol ( 1,8-dihydroxy-9 (10H) -anthracenone)
(7) Elemental analysis / equipment: Yanaco CHN coder MT-5 type, manufactured by Yanaco Technical Science Co., Ltd. (8) Thixotropy test (gel grinding)
・ Equipment: Vortex mixer (Jenny 2), manufactured by ASONE

[Examples 1 to 3: Gelation test of alkyl hydrazide derivative]
Various organic solvents (propylene carbonate) so that the addition amount of the alkyl hydrazide derivative (stearic hydrazide, palmitic hydrazide, or n-octanohydrazide) and the alkyl hydrazide derivative is a predetermined mass percent (wt%) in a 2 cc sample tube. Glycerin, ethylene glycol, acetonitoyl, N, N-dimethylformamide (DMF), methanol, N-methyl-2-pyrrolidone (NMP), ethanol, acetone, 1-butanol, dichloroethane, tetrahydrofuran, ethyl acetate, chlorobenzene, chloroform, Diisopropyl ether, SH245 (cyclic silicone manufactured by Toray Dow Corning Co., Ltd.), toluene, n-hexane) are put, covered, and the organic solvent having a boiling point exceeding 100 ° C. is 1 At 0 ° C., then heated to 5 ° C. under boiling in the case of other organic solvents, to produce an alkyl hydrazide derivative solution. Thereafter, these solutions were allowed to cool at room temperature (approximately 23 ° C.) to confirm gelation. In addition, after standing to cool, the fluidity of the solution was lost, and the state in which the solution did not flow down even when the sample tube was inverted was judged as “gelation”. This gelation test was performed on solutions having various alkyl hydrazide derivative concentrations, and the minimum concentration (wt%) of the alkyl hydrazide derivative required for gelation was defined as the minimum gelation concentration. About n-octanohydrazide, the result examined to the density | concentration of 10 wt% was described.
The obtained results are shown in Table 1. A photograph of each sample tube after cooling in a test conducted using toluene is shown in FIG. 1 ((1) 2 wt% solution of stearic acid hydrazide, (2) 2 wt% solution of palmitic hydrazide, (3) 4 wt% of n-octanohydrazide. % Solution).

  As shown in Table 1, the result that the alkyl hydrazide derivative has the gel formation ability with respect to various organic solvents was obtained.

[Example 4: Gelation test of stearic acid hydrazide]
In the above test, a gelation test was conducted in the same manner as in Example 1 for stearic acid hydrazide having a low minimum gelation concentration and showing good results.
Stearic acid hydrazide and organic solvent (propylene carbonate, dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF), methanol so that the addition amount of stearic acid hydrazide is 5 mass percent (wt%) in a 2 cc sample tube , Acetonitrile, acetone, dichloroethane, tetrahydrofuran, ethyl acetate, toluene, n-hexane), capped, and heated to a temperature of 5 ° C. below the boiling point of each organic solvent to prepare a stearic acid hydrazide solution. Thereafter, these solutions were allowed to cool at room temperature (approximately 23 ° C.), and gelation was confirmed in any organic solvent. When water was added instead of the organic solvent, stearic acid hydrazide was not dissolved in water.
The obtained results are shown in Table 2. In addition, photographs of each sample tube after being allowed to cool are shown in FIG. 2 ((1) propylene carbonate, (2) DMSO, (3) DMF, (4) methanol, (5) acetonitrile, (6) acetone, (7) dichloroethane. , (8) tetrahydrofuran, (9) ethyl acetate, (10) toluene, (11) n-hexane).

  As shown in Table 2 and FIG. 2, the result was obtained that stearic acid hydrazide has gel forming ability with respect to various organic solvents having various relative dielectric constants.

[Examples 5 to 7: Thermal behavior of gels obtained using alkyl hydrazide derivatives]
Toluene is selected as the organic solvent, and the alkyl hydrazide derivative is prepared by the same procedure as in Examples 1 to 3 with the concentration of the alkyl hydrazide derivative (stearic hydrazide, palmitic hydrazide, or n-octanohydrazide) being 10 wt%. A solution was prepared and then allowed to cool at room temperature to form a gel.
Next, for each gel obtained, the sol-gel transition temperature and the gel-sol transition temperature were measured with a differential scanning calorimeter. The obtained results are shown in Table 3.

  As shown in Table 3, it was quantitatively confirmed that a gel using an alkyl hydrazide derivative as a gelling agent undergoes a sol-gel transition.

[Examples 8 to 10: Observation of microstructure of gel formed using alkyl hydrazide derivative (1)]
In the same procedure as in Example 1 described above, the gel was formed using toluene as the organic solvent with the alkyl hydrazide derivative concentration of 10 wt%. The gel thus obtained was vacuum-dried at room temperature to obtain a xerogel, and the state of the obtained xerogel was observed with a scanning electron microscope (SEM). The obtained results are shown in FIGS.
Here, FIGS. 3A to 3C are SEM images of the toluene xerogel of stearic acid hydrazide of Example 8, and FIGS. 4A to 4C are SEMs of the toluene xerogel consisting of palmitic acid hydrazide of Example 9. FIGS. 5A to 5C show SEM images of toluene xerogel composed of n-octanohydrazide of Example 10, respectively.
As shown in FIGS. 3 to 5, it was confirmed that the toluene xerogel of the alkyl hydrazide derivative is composed of a multilayer sheet having a thickness of several hundreds of nm and a width of several tens of μm.

By the way, plate-like crystals with a thickness of nm and several tens of μm of clay minerals and plate-like wax crystals with a thickness of several hundreds of nm and width of several tens of μm are composed of these sheet-like substances (plate-like crystals) as a framework. It is known to produce a solvent-containing solid by holding water or an organic solvent in the voids of the card house structure (reference: (1) “Clay Handbook”, Gihodo Publishing Co., Ltd. (2009), ( 2) “Gel Control—How to Make a Gel Well and Suppression of Gelation”, Information Organization (2009), pages 15-17, (3) Colloids and Surfaces, 51 (1990), pages 219-238 Page, etc.).
That is, in the gel formed using an alkyl hydrazide derivative as a gelling agent and a medium: toluene, a multilayer sheet structure was observed in a dry gel (xerogel) state. It can be considered that the toluene gel formed by using has a card house structure, held the solvent in the voids of the structure, and led to gel formation. In addition, it is estimated that the multilayer sheet structure was produced by aggregation of sheet-like substances forming the card house structure during the drying process.

[Examples 11 to 14: Observation of microstructure of gel formed using alkyl hydrazide derivative (2)]
In the same procedure as in Example 1 above, the concentration of the alkyl hydrazide derivative was set to 10 wt%, and a gel was formed using methanol, n-hexane and DMF as organic solvents, and then these were vacuum dried at room temperature. The state of the xerogel obtained by this was observed with SEM. The obtained results are shown in FIGS.
Here, FIGS. 6A to 6C are SEM images of methanol xerogel comprising stearic acid hydrazide of Example 11, and FIGS. 7A to 7C are n-hexane comprising stearic acid hydrazide of Example 12. SEM images of xerogel, FIGS. 8A to 8C are SEM images of DMF xerogel composed of stearic acid hydrazide of Example 13, and FIGS. 9A to 9C are methanol composed of palmitic hydrazide of Example 14. SEM images of xerogel are shown respectively.
As shown in FIGS. 6 to 9, stearic acid hydrazide methanol, n-hexane and DMF xerogels have different polarities of solvents and dielectric constants as shown in Table 2, respectively. It was confirmed to be composed of a multilayer sheet having a thickness of 100 nm and a width of several tens of μm. Similar results were obtained with palmitic hydrazide methanol xerogels with different alkyl chain lengths.

  As described above, in the xerogel obtained with the various solvents of the alkyl hydrazide derivative, the multilayer sheet structure was found in all cases. It is presumed that the solvent was retained and gel formation was achieved.

[Example 15 to Example 17: Observation of microstructure of alkyl hydrazide]
Furthermore, the state of the crystal (reagent state) of the alkyl hydrazide derivative was observed by SEM.
The obtained results are shown in FIG. 10, FIG. 11, and FIG. Here, FIGS. 10A to 10C are SEM images of the stearic acid hydrazide crystal of Example 15, FIGS. 11A to 11C are SEM images of the palmitic acid hydrazide crystal of Example 16, and FIG. a) to (c) show SEM images of the n-octanohydrazide crystal of Example 17, respectively.
From these results, it was found that the crystal of the alkyl hydrazide derivative itself has a multilayer sheet structure in which sheet-like crystals are folded.

  Considering the above results, when an alkyl hydrazide derivative is added to an organic solvent at a high concentration above the minimum gelation concentration and cooled after heating and dissolution, a larger number of crystal nuclei are formed than in the case of normal recrystallization, It is presumed that the sheet-like crystals are in contact with each other in various directions, thereby making it easy to form a card house structure and leading to gel formation.

[Examples 18 to 20: Evaluation of ionic conductivity of electrolyte-containing organogel formed using alkyl hydrazide derivative]
Next, the gel ion conductor obtained by using an alkyl hydrazide derivative as a gelling agent was evaluated as a host material.
Results of evaluation of ionic conductivity of organogel obtained by the same procedure as in Example 1 above using 15 wt% LiClO ₄ propylene carbonate (PC) solution (salt concentration of 0.1 molm ⁻³ ) of the above-mentioned three kinds of alkyl hydrazide derivatives Is shown in Table 4. As a reference substance, only LiClO ₄ PC solution (salt concentration of 0.1 molm ⁻³ ) was also evaluated.

  As shown in Table 4, the result that the alkyl hydrazide derivative showed good ionic conductivity at the same level as the electrolyte solution was obtained. In addition, these results indicate that the alkyl hydrazide derivative is expected to be applied as a gel electrolyte.

[Example 21: Synthesis of compound 1 (dialkyl hydrazide derivative)]
Compound 1 (dialkyl hydrazide derivative) was synthesized by the following procedure. In addition, the reagent described in the following examples was obtained from Tokyo Chemical Industry Co., Ltd., the solvent was obtained from Wako Pure Chemical Industries, Ltd., and used as it was (sodium carbonate was obtained from Wako Pure Chemical Industries, Ltd.).

1.28 g of palmitoyl chloride was added dropwise at room temperature to a tetrahydrofuran (THF) mixed solution of 1.00 g of palmitic acid hydrazide and 1.51 g of sodium carbonate. After stirring at room temperature for 6 hours (precipitate was observed), 100 mL of water was added, and the mixture was further stirred for 1 hour. The precipitate was collected by filtration and washed with THF to obtain Compound 1 (1.74 g, white crystals, yield 92.6%).
MALDI-TOF MS: calcd for C ₃₂ H ₆₄ N ₂ O ₂ (MW = 508.50): m / z = 506.98 ([M−H] ⁺ ).
Elemental analysis: Compound 1 C ₃₂ H ₆₄ N ₂ O ₂
Calculated: C, 75.53%; H, 12.68%; N, 5.51
Analytical value: C, 75.36%; H, 12.68%; N, 5.66.

[Example 22: Gelation test of dialkyl hydrazide derivative (Compound 1)]
The gelation test of Compound 1 was conducted using various solvents (toluene, tetrahydrofuran (THF), DMF, DMSO, n-hexane, methanol, propylene carbonate, dichloroethane, ethyl acetate) in the same procedure as in Example 1. It was. Table 5 shows the presence or absence of gelation and the minimum gelation concentration of Compound 1. Moreover, the photograph of each sample tube after standing_to_cool of the test implemented using toluene and THF is shown in FIG. 13 ((1) Toluene gel (dialkyl hydrazide 2 wt% solution), (2) THF gel (dialkyl hydrazide 2 wt% solution)) Shown in

  As shown in Table 5, Compound 1 gelled at a minimum gelation concentration of 2 wt% when both toluene and THF were used as organic solvents. Compound 1 formed a partial gel at 3 wt% in DMF and a partial gel at 5 wt% in DMSO. However, n-hexane, methanol, propylene carbonate, dichloroethane, and ethyl acetate were slightly soluble and did not form a gel.

As described above, compound 1 which is a dialkyl hydrazide derivative can be gelled with toluene or THF, and can form a partial gel with DMF or DMSO, but various solvents compared with stearic acid hydrazide which is an alkyl hydrazide derivative. As a result, it was found that the gelling ability with respect to was limited. Moreover, the result that the gelatinization ability with the solvent which melt | dissolves the supporting electrolyte in an ionic conductor, such as propylene carbonate and dichloroethane, is low was obtained.
Thus, compared to the dialkyl hydrazide derivative of Compound 1, alkyl hydrazide derivatives such as stearic acid hydrazide, palmitic acid hydrazide, or n-octanohydrazide are preferred gelling agents in terms of application development as a gel electrolyte. It became the result.

[Example 23: Observation of microstructure of gel formed using dialkylhydrazide derivative]
A xerogel obtained by forming a gel using toluene as an organic solvent in the same procedure as in Example 1 described above, with the concentration of compound 1 being 10 wt% and using toluene as the organic solvent, and then vacuum drying the gel at room temperature. The state of was observed with SEM. The obtained result is shown in FIG.
Here, FIGS. 14A to 14C show SEM images of toluene xerogel of Compound 1. FIG.
As shown in FIG. 14, it was confirmed that the toluene xerogel of Compound 1 was composed of a multilayer sheet having a thickness of several hundred nm and a width of several tens of μm.
From this, it is considered that the toluene gel retained the solvent by the card house structure and formed the gel in the dialkyl hydrazide derivative as well as the alkyl hydrazide derivative.

[Example 24: Gelation test 1 of alkylhydrazide derivative mixed system]
In the same procedure as in Example 1, using toluene, stearic acid hydrazide having a relatively good gelling ability was used as the main gelling agent, and two-component mixed system with palmitic acid hydrazide or n-octanohydrazide The gelation test was conducted.
First, palmitic acid hydrazide or n-octanohydrazide was mixed with stearic acid hydrazide at various ratios, and an alkyl hydrazide derivative solution was prepared so that the concentration of the mixture was 1 wt%, and a gelation test was performed.
The obtained results (gelation behavior) are shown in FIG. 15 ((1) Stearic acid hydrazide / palmitic acid hydrazide mass mixing ratio 2/1, (2) 1/1, (3) 1/2, (4) The mass mixing ratio of stearic acid hydrazide / n-octanohydrazide is 2/1, (5) 1/1, (6) 1/2).
From these results, it is possible to gel in a mixture of two kinds of alkyl hydrazide derivatives in which a part of stearic acid hydrazide is replaced with another alkyl hydrazide derivative, and further to make a mixture system at a concentration that does not form a gel by itself. It was confirmed that a gel was formed. In any of the mixed systems, some liquid separation was observed although gelation occurred when the concentration was 0.5 wt%.

[Example 25: Gelation test 2 of alkylhydrazide derivative mixed system]
In the same procedure as in Example 1, a gelation test of a three-component mixed system of stearic acid hydrazide, palmitic acid hydrazide and n-octanohydrazide, which had relatively good gelling ability, was performed using toluene. went.
First, stearic acid hydrazide, palmitic acid hydrazide, and n-octanohydrazide were mixed, an alkyl hydrazide derivative solution was prepared so that the concentration of the mixture was 1 wt%, and a gelation test was performed.
The obtained results are shown in FIG. 16 ((1) mass mixing ratio of stearic acid hydrazide / palmitic acid hydrazide / n-octanohydrazide 1/1/1, (2) 2/1/1, (3) 1 / 2/1, (4) 1/1/2, (5) 2/2/1, (6) 2/1/2, and (7) 1/2/2).
From these results, it is possible to gel in a mixture of three kinds of alkyl hydrazide derivatives in which a part of stearic acid hydrazide is replaced with another alkyl hydrazide derivative, and further to make a mixture system at a concentration that does not form a gel by itself. It was confirmed that a gel was formed.

[Example 26: Thixotropic test of single system and mixed system (two-component mixed system) of alkyl hydrazide derivative]
The behavior of the alkyl hydrazide derivative single gel and mixed gel (two-component mixed system) after gel grinding was evaluated.

<Single gel of alkyl hydrazide derivative>
In the same procedure as in Example 1, various alkyl hydrazides (stearic hydrazide, palmitic hydrazide or n-octanohydrazide) were used as gelling agents, and organic solvents (19 types, used in Examples 1 to 3) were used. However, in the case of n-octanohydrazide, only 12 gelled gels (separated ones, including partial gelation) are used, and a gel is prepared at the minimum gelation concentration and the minimum gelation concentration + 1 wt%. did.
Next, the sample tube is applied to a vortex mixer, the internal gel is pulverized for 10 seconds, and allowed to stand for a predetermined time (1 minute, 10 minutes, 1 hour or 12 hours), then the sample tube is inverted and the gel flows. Confirmed whether or not.
In various types of single gels of alkyl hydrazide derivatives, the sample gelled at the minimum gelation concentration and the minimum gelation concentration + 1 wt% in any organic solvent and any alkyl hydrazide derivative is any predetermined time when inverted after grinding. Even after standing, the gel sagged down, and thixotropic properties were not expressed in this test example.
FIG. 17 shows the thixotropic behavior of gels gelled at the lowest gelation concentration using various alkyl hydrazide derivative chlorobenzenes. FIG. 17 shows chlorobenzene gels before grinding (1) to (3) [(1) stearic acid hydrazide 2 wt% gel, (2) palmitic acid hydrazide 2 wt% gel, (3) n-octanohydrazide 6 wt% gel] (4) to (6) [(4) stearic acid hydrazide 2 wt% gel after grinding, (5) palmitic acid hydrazide 2 wt% gel after grinding, (6) ) N-octanohydrazide 6 wt% gel after grinding].

<Two-component gel of alkyl hydrazide derivative>
In the same procedure as in Example 1, as a two-component mixed system, stearic acid hydrazide / n-octanohydrazide mixed system 2 wt% toluene gel, stearic acid hydrazide as various mixing ratios (see Tables 6 to 8). / Palmitic acid hydrazide mixed system 2 wt% toluene gel, stearic acid hydrazide / n-octanohydrazide mixed system 1 wt% or 2 wt% chlorobenzene gel was prepared (concentration is the concentration as a mixture).
Next, the sample tube was applied to a vortex mixer, the internal gel was pulverized by mechanical vibration for 10 seconds to form a sol, and allowed to stand for a predetermined time (1 minute, 10 minutes, 1 hour or 12 hours), and then the sample The tube was inverted and it was checked whether the gel was flowing. The obtained results are shown in Tables 6 to 8.

  As shown in Tables 6 to 8 above, toluene gel of alkyl hydrazide derivative does not exhibit thixotropic properties in a single system gel using one derivative, but is mixed like stearic acid hydrazide / n-octanohydrazide By using the system, it was confirmed that thixotropic properties may be expressed even when the concentration is below the minimum gelation concentration of each individual derivative. It was also confirmed that thixotropic properties were not exhibited depending on the combination of the mixed systems, such as a combination of stearic acid hydrazide / palmitic acid hydrazide. Furthermore, it was confirmed that the chlorobenzene gel also exhibits thixotropic properties.

  The study of two-component mixed gels is described in K.A. Hanabusa et al. , J .; Chem. Soc. , Chem. Commun. (1993) pages 1382 to 1383, and the like. Suzuki et al. Langmuir. 25 (2009) pp. 8579-8585, recent research is summarized, but a new result obtained only by mixing low molecular weight gelling agents having different alkyl chains as in the present invention. There have been few reports on the effect (thixotropic properties) so far, and the results show the unique effects of the gelling agent of the present invention.

[Example 27: Thixotropic test of mixed system of alkyl hydrazide derivative (3-component mixed system)]
The behavior of an alkyl hydrazide derivative mixed gel (three-component mixed system) after gel grinding was evaluated.
In the same procedure as in Example 1, as a three-component mixed system, 1 wt% of stearic acid hydrazide / palmitic acid hydrazide / n-octanohydrazide mixed system at various mixing ratios (Table 9 to Table 15 three layers) 2 wt% toluene gel, 1 wt% or 2 wt% chlorobenzene gel, 2 wt% octane gel, 2 wt% SH245 (cyclic silicone manufactured by Toray Dow Corning Co., Ltd.) gel, 6 wt% propylene carbonate gel were prepared (concentration is the concentration as a mixture) ).
Next, the sample tube is applied to a vortex mixer, the internal gel is pulverized by mechanical vibration for 10 seconds to form a sol, and then statically left for a predetermined time (1 minute, 10 minutes, 1 hour (or 30 minutes) or 12 hours). After placement, the sample tube was inverted and it was checked whether the gel would flow. The obtained results are shown in Tables 9 to 14.

As an example, FIG. 18 shows the thixotropic test results of a chlorobenzene gel in a three-component mixed system (composition (mass ratio) = 1/1/10 of stearic acid hydrazide / palmitic acid hydrazide / n-octanohydrazide). FIG. 18 shows (1) to (2) [(1) 1 wt% gel, (2) 2 wt% gel] crushed chlorobenzene gel before pulverization for 10 seconds, left standing for 1 minute, and then inverted behavior (3) to (4) [(3) 1 wt% gel after 1 minute of pulverization, (4) 2 wt% gel after 1 minute of pulverization], and behavior of inversion after standing for 1 hour after standing for 1 hour (5) to (6) [(5) 1 wt% gel after 1 hour of pulverization, (6) 2 wt% gel after 1 hour of pulverization]

As shown in Tables 9 to 13, toluene gel and chlorobenzene gel (concentration: 1 wt%, 2 wt%) of alkyl hydrazide derivatives are mixed in three components such as stearic acid hydrazide / palmitic acid hydrazide / n-octanohydrazide. It was confirmed that thixotropic properties were expressed by using the system. It was also confirmed that thixotropic properties can be easily obtained when the concentration of the alkyl hydrazide derivative mixture is 2 wt%. In particular, there was a tendency that thixotropic properties were easily obtained for gels obtained using a mixture in which the mixing ratio of n-octanohydrazide was higher than that of the other two hydrazides (Tables 12 and 13).
However, as shown in Table 13, in the mixture of alkyl hydrazide derivatives, the mixture with a very high ratio of n-octanohydrazide (1/1/30) does not exhibit good thixotropy, and n-octahydride When the mixing ratio of alkyl hydrazide (stearic acid hydrazide) other than nohydrazide is increased (10/1/1), thixotropic properties do not appear, and the results suggesting the existence of the optimal composition range for thixotropic properties are obtained. It was.
Moreover, as shown in Table 14, it was confirmed that the thixotropic property was expressed also in the gel produced using octane, SH245, and propylene carbonate.
As described above, it was confirmed that the alkyl hydrazide derivative expresses thixotropy in toluene gel, chlorobenzene gel, octane gel, SH245 gel, and propylene carbonate gel when a three-component mixed system is used.
As described above, there has been almost no report on the new effect (thixotropic property) obtained only by mixing low molecular weight gelling agents having different alkyl chains as in the present invention, and the gelling agent of the present invention. It became the result which shows the peculiar effect which has.

Claims (10)

A gelling agent comprising an alkyl hydrazide compound represented by the general formula [I].
(In the formula, R ₁ represents an aliphatic group having 1 to 30 carbon atoms which may have a substituent.) A gelling agent comprising a dialkyl hydrazide compound represented by the general formula [II].
(In the formula, R ₁ and R ₂ each independently represents an aliphatic group having 1 to 30 carbon atoms which may have a substituent.) 2. The gelling agent according to claim 1, comprising two or more alkyl hydrazide compounds represented by the general formula [I] and exhibiting thixotropic properties in the formed gel. The gelling agent according to claim 2, comprising two or more dialkyl hydrazide compounds represented by the general formula [II] and exhibiting thixotropic properties in the formed gel. A gelled solid electrolyte comprising a solid electrolyte salt, a solvent, and the gelling agent according to any one of claims 1 to 4. The solid electrolyte salt is LiPF ₆ , LiBF ₄ , LiClO ₄ , LiAsF ₆ , LiCF ₃ S.
O ₃ , LiN (SO ₂ CF ₃ ) ₂ , LiN (SO ₂ C ₂ F ₅ ) ₂ , LiN (SO ₂ CF ₃ ) (SO ₂
C ₄ F ₉₎ and is selected from the group consisting of mixtures, gelled solid electrolyte according to claim 5. A gel comprising an alkyl hydrazide compound represented by the general formula [I].
(In the formula, R ₁ represents an aliphatic group having 1 to 30 carbon atoms which may have a substituent.) A gel comprising a dialkyl hydrazide compound represented by the general formula [II].
(In the formula, R ₁ and R ₂ each independently represents an aliphatic group having 1 to 30 carbon atoms which may have a substituent.) The gel according to claim 7, comprising two or more alkyl hydrazide compounds represented by the general formula [I] and exhibiting thixotropic properties. The gel according to claim 8, comprising two or more dialkyl hydrazide compounds represented by the general formula [II] and exhibiting thixotropic properties.