JP2007191661A - Aromatic compound gelling agent having perfluoroalkyl group - Google Patents

Abstract

（ｍは６〜１２、ｐは１〜４；Ａｒは核原子数５〜３０の２価の芳香族基；αは水素又は水酸基；Ｒは炭素数１〜２０の１価の炭化水素基。）このゲル化剤は、有機電解液に適した高誘電率溶媒をゲル化できる。このゲル化剤で有機電解液をゲル化したものは、有機電解液を高含有量にすることができ、ゲル電解質として好ましい。
【選択図】なしThe present invention provides an organic low-molecular gelling agent that can be gelled by many kinds of organic liquids and that can be gelled by adding a small amount.
The gelling agent comprises an aromatic compound having a perfluoroalkyl-hydroxyethylene (oligomethylene) oxy group and a hydrocarbon oxy group.

(M is 6 to 12, p is 1 to 4; Ar is a divalent aromatic group having 5 to 30 nuclear atoms; α is hydrogen or a hydroxyl group; R is a monovalent hydrocarbon group having 1 to 20 carbon atoms. ) This gelling agent can gel high dielectric constant solvents suitable for organic electrolytes. What gelatinized organic electrolyte solution with this gelatinizer can make organic electrolyte solution high content, and is preferable as gel electrolyte.
[Selection figure] None

Description

  The present invention relates to an organic liquid gelling agent containing a novel perfluoroalkyl derivative as an active ingredient, and an organic liquid gel gelled using the gelling agent. The organic liquid gel of the present invention can be used as a gel electrolyte.

Lithium Ion Battery Electrolyte The electrolyte of a lithium ion battery is generally a liquid, but a gel or solid is also used as a polymer electrolyte. In any electrolyte, the following characteristics are required.
1) High conductivity (high mobility of lithium ions)
2) Large chemical and electrochemical stability for electrode materials 3) Wide usable temperature range 4) High safety 5) Low price Electrolyte solvent High concentration of lithium salt and high conductivity As the solvent, an aprotic organic solvent having a large relative dielectric constant and a small viscosity is suitable. However, since the relative permittivity is large and the viscosity of the solvent having a strong polarity is increased, the practical electrolytic solution is a mixture of a plurality of solvents. For example, propylene carbonate (PC) having a dielectric constant of 64.4 and a viscosity of 2.3 cp, or a mixture of ethylene carbonate (EC) having a dielectric constant of 95.3 and a viscosity of 1.9 cp and dimethyl carbonate (DMC) having a viscosity of 0.59 cp. Solvents are known. These mixed solvents have compositions exhibiting maximum conductivity, and the compositions have been studied in detail along with the types of electrolyte salts to be added.

As the electrolyte salt electrolyte salt, other lithium perchlorate (LiClO _4), LiPF ₆ containing _{fluorine, LiAsF 6, Li (CF 3} SO 2) 2 N, such as LiBF _3, LiCF 3 SO 3 is used . The ionic conductivity of the organic solvent electrolyte in which these are dissolved is about 10 ⁻² S / cm.

Gel Electrolyte Gel electrolyte, which is a mixture of an organic polymer and a liquid electrolyte, has a high ionic conductivity and has a history of commercialization earlier than solid electrolytes. The gel electrolyte uses a carbon-based negative electrode material and is applied as a lithium ion secondary battery, particularly a thin film battery.

Gelling agents in various technical fields Conventionally, organic liquids (animal and vegetable oils and fats) in various industrial fields such as paints, inks, lubricants, agriculture, fisheries, cosmetics, pharmaceuticals, fibers, resins, polymers, rubbers, metals, etc. , Esters, polyols, ethers, alcohols, hydrocarbons, etc.) have been used to solidify low-molecular gelling agents or high-molecular gelling agents. Polymer gelling agents are often used in the technical field of batteries as gelling agents for gel electrolytes.

Low molecular weight organic gelling agent Although development of a low molecular weight gelling agent is slower than this, 12-hydroxystearic acid, dialkylurea derivatives, dibenzylidene sorbitol, and the like are known.

  Among them, 12-hydroxystearic acid is inexpensive, but there are few kinds of organic liquids that can be gelled, and the temperature at which the obtained gel softens is also low. There are few types of organic liquids that can be gelled with dialkylurea derivatives. On the other hand, although dibenzylidene sorbitol forms a strong gel with a small amount of addition, it has the disadvantage of liberating benzaldehyde, and it is unsuitable for solidifying low-boiling short-chain alcohols, etc. due to its high melting point. is there. Alkali metal salts and alkaline earth metal salts of fatty acids require a large amount of addition for gelation or solidification, and have limitations such as limited usable conditions.

Perfluoroalkylalkanes Perfluoroalkylalkanes: F (CF ₂ ) n (CH ₂ ) mH has n = 12, m = 8-20, gelling decane, n = 10, m = 12. It has been reported that a hydrocarbon solvent is gelled (Non-patent Document 1).

It has been reported that perfluoroalkylalkane: F (CF ₂ ) ₈ (CH ₂ ) ₈ H gels methyl alcohol, ethyl alcohol, and propyl alcohol (Non-patent Document 2).

Disadvantages of the prior art However, there are many types of organic liquids that can be gelled, and no organic low-molecular gelling agent that can be gelled with a small amount of addition has been known so far. And the organic low molecular weight gelatinizer which gelatinizes the high dielectric constant solvent suitable for organic electrolyte solution was not known.
Robert J. et al. Twang, et al, "Observations of a" Gel "Phase in Binary Mixture of Semifluorinated n-Alkanes with Hydrocarbon Liquids, 1985, 1836, 1836. Massimo Napoli, et al, "Synthesis of F (Ch2) 8 (Ch2) 8H and gel phase formation from solutions in homologous alcohols.

  An object of the present invention is to provide an organic low-molecular gelling agent that has many kinds of organic liquids that can be gelled and that can be gelled with a small amount of addition. An object of this invention is to provide the organic low molecular weight gelatinizer which can gelatinize the high dielectric constant solvent suitable for organic electrolyte solution. An object of this invention is to provide the gel formed by gelatinizing an organic liquid with this organic low molecular weight compound.

  The present inventors newly synthesized an aromatic compound having a perfluoroalkyl group, and surprisingly, it was found that this compound can be gelled with a small amount of addition of most organic liquids. The gelling agent comprising this compound can be gelled by adding a small amount of most organic liquids.

Gelling agent of the present invention The gelling agent of the present invention gels an organic liquid. The gelling agent of the present invention comprises an aromatic compound having a perfluoroalkyl-hydroxyethylene (oligomethylene) oxy group and a hydrocarbon oxy group represented by the following chemical formula (1).

（式中、
基Ｃ_ｍＦ_２ｍ＋１は、ペルフルオロアルキル基、ｍは、６〜１２の自然数；
基（ＣＨ_２）は、メチレン基、ｐはメチレン基の数で、１〜４の自然数；
基Ａｒは、置換もしくは無置換の核原子数５〜３０の２価の芳香族基；
基Ｏは、酸素原子；
基αは、水素もしくは水酸基；
基Ｒは、飽和もしくは不飽和の炭素数１〜２０の１価の炭化水素基である）。

(Where
The group C _m F _{2m + 1} is a perfluoroalkyl group, m is a natural number from 6 to 12;
The group (CH ₂ ) is a methylene group, p is the number of methylene groups, and a natural number of 1 to 4;
The group Ar is a substituted or unsubstituted divalent aromatic group having 5 to 30 nuclear atoms;
The group O is an oxygen atom;
The group α is hydrogen or hydroxyl;
The group R is a saturated or unsaturated monovalent hydrocarbon group having 1 to 20 carbon atoms).

The manufacturing method of the gelatinizer of this invention The manufacturing method of the gelatinizer of this invention is a halogenated alkene of the following Chemical formula (3), the aromatic compound which has the hydroxyl group and hydrocarbon oxy group of following Chemical formula (2), The reaction consists of reacting the product with perfluoroalkyl iodide of the following chemical formula (4) and substituting iodine of this product (chemical formula (5)) with hydrogen or a hydroxyl group.

（式中の記号の意味は、化学式1の場合と同じ。基Ｘはチオール基に反応性のハロゲン原子；基Ｉはヨウ素原子）。

(The meaning of the symbols in the formula is the same as in Chemical Formula 1. The group X is a halogen atom reactive with a thiol group; the group I is an iodine atom).

Gel of the present invention The gelling agent or gel of the present invention is an industry including processing fields such as battery electrolytes, paints, inks, lubricants, agriculture, fisheries, cosmetics, pharmaceuticals, fibers, resins, polymers, rubbers, metals, etc. Used in the field. Especially, the gel which consists of an organic ionic liquid and the gel containing the ionic substance melt | dissolved in an organic solvent can be utilized suitably as electrolytes of batteries, such as a lithium ion battery and a dye-sensitized solar cell.

  The gelling agent of the present invention has many kinds of organic liquids that can be gelled, and can gel the organic liquid with a small addition. The gelling agent of the present invention can gel a high dielectric constant solvent suitable for an organic electrolyte. Since the gel produced by gelling a high dielectric constant solvent with the gelling agent of the present invention has a low concentration of the gelling agent, it can advantageously increase the content of the organic electrolyte when used as an electrolyte gel. .

Compound used as gelling agent of the present invention The compound used as the gelling agent of the present invention is an aromatic compound having a perfluoroalkyl-hydroxyethylene (oligomethylene) oxy group and a hydrocarbon oxy group. The compound used as the gelling agent of the present invention is represented by the following chemical formula 1.

（式中、
基Ｃ_ｍＦ_２ｍ＋１は、ペルフルオロアルキル基、ｍは、６〜１２の自然数；
基（ＣＨ_２）は、メチレン基、ｐはメチレン基の数で、１〜４の自然数；
基Ａｒは、置換もしくは無置換の核原子数５〜３０の２価の芳香族基；
基Ｏは、酸素原子；
基αは、水素もしくは水酸基；
基Ｒは、飽和もしくは不飽和の炭素数１〜２０の１価の炭化水素基である）。

(Where
The group C _m F _{2m + 1} is a perfluoroalkyl group, m is a natural number from 6 to 12;
The group (CH ₂ ) is a methylene group, p is the number of methylene groups, and a natural number of 1 to 4;
The group Ar is a substituted or unsubstituted divalent aromatic group having 5 to 30 nuclear atoms;
The group O is an oxygen atom;
The group α is hydrogen or hydroxyl;
The group R is a saturated or unsaturated monovalent hydrocarbon group having 1 to 20 carbon atoms).

Method for Producing Aromatic Compound of the Present Invention The method for producing an aromatic compound of the present invention comprises reacting an aromatic compound having a hydroxyl group of the following chemical formula 2 and a hydrocarbon oxy group with a halogenated alkene of the following chemical formula 3, The product is reacted with a perfluoroalkyl iodide of the following chemical formula 4 to produce a compound of the reaction formula (5).

（式中の記号の意味は、化学式1の場合と同じ。基Ｘはチオール基に反応性のハロゲン原子；基Ｉはヨウ素原子）。

(The meaning of the symbols in the formula is the same as in Chemical Formula 1. The group X is a halogen atom reactive with a thiol group; the group I is an iodine atom).

  Next, this is dissolved in an organic solvent such as diethyl ether or THF, and treated at room temperature in the presence of a basic reagent such as lithium aluminum hydride to obtain a compound of the following chemical formula (7).

（式中、
基Ｃ_ｍＦ_２ｍ＋１は、ペルフルオロアルキル基、ｍは、６〜１２の自然数；
基（ＣＨ_２）は、メチレン基、ｐはメチレン基の数で、１〜２の自然数；
基Ａｒは、置換もしくは無置換の核原子数５〜３０の２価の芳香族基；
基Ｏは、酸素原子；
基Ｒは、飽和もしくは不飽和の炭素数１〜２０の１価の炭化水素基である）。

(Where
The group C _m F _{2m + 1} is a perfluoroalkyl group, m is a natural number from 6 to 12;
The group (CH ₂ ) is a methylene group, p is the number of methylene groups, and is a natural number of 1 to 2;
The group Ar is a substituted or unsubstituted divalent aromatic group having 5 to 30 nuclear atoms;
The group O is an oxygen atom;
The group R is a saturated or unsaturated monovalent hydrocarbon group having 1 to 20 carbon atoms).

  Further, by treating the product of the chemical formula (5) with a basic reagent in the presence of an extremely small amount of water, preferably about equimolar amount to about 10 times molar amount of water with respect to the compound of the chemical formula (5). A compound of the following chemical formula (8) is obtained.

（式中、
基Ｃ_ｍＦ_２ｍ＋１は、ペルフルオロアルキル基、ｍは６〜１２の自然数；
基（ＣＨ_２）は、メチレン基、ｐは１〜２の自然数
基Ａｒは、置換もしくは無置換の核原子数５〜３０の２価の芳香族基；
基Ｏは、酸素原子；
基ＯＨは、水酸基；
基Ｒは、飽和もしくは不飽和の炭素数１〜２０の１価の炭化水素基である。）
である。）
上記２通りの反応においては、たとえ化学式（７）の化合物を目的とする場合であっても、反応系に全く水分を存在させないことは極めて困難であるため、多くの場合、化学式（８）の化合物が副生する。

(Where
The group C _m F _{2m + 1} is a perfluoroalkyl group, m is a natural number of 6-12;
The group (CH ₂ ) is a methylene group, p is a natural number group of 1-2, Ar is a substituted or unsubstituted divalent aromatic group having 5-30 nuclear atoms;
The group O is an oxygen atom;
The group OH is a hydroxyl group;
The group R is a saturated or unsaturated monovalent hydrocarbon group having 1 to 20 carbon atoms. )
It is. )
In the above two reactions, even if the compound of the chemical formula (7) is intended, it is extremely difficult to make no water present in the reaction system. Therefore, in many cases, the chemical formula (8) Compound is by-produced.

  On the contrary, when the compound of the chemical formula (8) is intended, if a large amount of water is present, hydrolysis occurs and the desired product cannot be obtained. Moreover, when there is too little quantity of water, the compound of Chemical formula (7) will be by-produced.

  Usually, by using a solvent containing water to such an extent that moisture in the air is naturally absorbed, a mixture gelling agent in which the compounds of chemical formula (7) and chemical formula (8) are co-produced can be obtained. .

  Of course, the method for producing the aromatic compound of the present invention is not limited to the above method.

Aromatic group Ar
In the present specification, the aromatic group Ar is a divalent group of a cyclic compound exhibiting so-called “aromaticity”. The cyclic compound may be a carbocyclic compound or a heterocyclic compound. These cyclic compounds may be substituted with a substituent or may not be substituted. Substituents unfavorable for (1) introduction of a perfluoroalkyl (oligomethylene) thio group and (2) introduction of a hydrocarbon oxy group are substitution of an aromatic compound having a hydroxyl group and a thiol group (chemical formula (2)). Not preferred as a group.

  In the case of an aromatic carbocyclic compound group, the number of nuclear atoms is 6 to 30, and it may be substituted with a substituent or may not be substituted. For example, compounds having a nucleus such as a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, an anthranylene group, a phenanthrylene group, a pyrenylene group, a chrysenylene group, and a fluoranthenylene group can be given.

In the case of an aromatic heterocyclic compound, the number of nuclear atoms is 5 to 30, for example, a pyrrolene group, a furylene group, a thiophenylene group, a triazolen group, an oxadiazolene group, a pyridylene group, a pyrimidylene group, etc. Examples include compounds having a nucleus.

Among these, as the aromatic group Ar, a phenylene group, a biphenylene group, or a naphthylene group is preferable.

  Examples of the substituent of the aromatic nucleus include an alkyl group such as a methyl group and an ethyl group, and a halogen atom.

Perfluoroalkyl group CmF _{2m + 1}
In this specification, the perfluoroalkyl group CmF _{2m + 1} is a perfluoroalkyl group having 6 to 12 carbon atoms. When the carbon number m is 5 or less, the compound of the chemical formula (1) has a low gelling ability. When the carbon number m is 13 or more, the compound of the chemical formula (1) does not dissolve even when heated depending on the type of the organic solvent.

Oligomethylene Group In the compound of the present invention, the oligomethylene group (CH ₂ ) _p has 1 to 4 carbon atoms. When the number of carbon atoms of the oligomethylene group (CH ₂ ) _p is 5 or more, the compound of the chemical formula (1) has a low gelling ability.

Hydrocarbon group R
In the present specification, the hydrocarbon group R is a saturated or unsaturated monovalent hydrocarbon group having 1 to 20 carbon atoms. In the case of an aliphatic hydrocarbon, the hydrocarbon group R may be branched or may not be branched. Further, when an aromatic hydrocarbon is contained, a substituent may be present in the aromatic nucleus. Of course, it may be an arylalkyl group such as a benzyl group.

  Without the hydrocarbon group R, the compound of the chemical formula (1) does not dissolve in the organic liquid, and the organic liquid cannot be gelled. When the number of carbon atoms is 21 or more, it is difficult to obtain raw materials.

Halogen atom In the present specification, the halogen atom X of the halogenated alkene CH═CH— (CH ₂ ) _p —X may be reactive to the hydroxyl group OH of the chemical formula (2) (HO—Ar—OR), Chlorine, bromine, iodine and fluorine can be used.

Gelling of organic liquid The gelling agent of the present invention gels almost all organic liquids by adding a small amount of about 5% or less. The gelling agent of the present invention is added to an organic solvent, dissolved by heating, and the resulting solution is gelled by returning it to room temperature. The gelling agent of the present invention can gel a high dielectric constant solvent suitable for an organic electrolyte, for example, propylene carbonate. The gel produced by gelling a high dielectric constant solvent with the gelling agent of the present invention can be used as an electrolyte gel. This electrolyte gel can be used for a lithium ion battery. And it can utilize also for gel electrolytes, such as a dye-sensitized solar cell. The gelling agent of the present invention or the gel produced thereby is used in industrial fields including processing fields such as paints, inks, lubricants, agriculture, fisheries, cosmetics, pharmaceuticals, fibers, resins, polymers, rubbers, metals, etc. Can also be used.

In the case of an electrolyte gel, generally an ionic substance soluble in an organic liquid, for example, in the case of a lithium ion battery, LiClO ₄ , LiPF ₆ , LiAsF ₆ , Li (CF ₃ SO ₂ ) ₂ N, LiBF ₃ , LiCF _It is preferable that an ionic substance such as ₃ SO ₃ is dissolved in an organic solvent and the gelling agent of the present invention is added thereto to form a gel. Of course, organic ionic liquids such as N, N, N-trialkyl (alkoxyalkyl) ammonium bis (trifluoromethanesulfonyl) imide or a mixture obtained by dissolving them in a nonionic organic solvent can also be suitably used.

Production of Compound (C) According to the following chemical reaction formula (6), first, compound (A) is produced, then compound (B) is produced, and then compound (C) and compound (D) are produced. .

化合物（Ａ）の合成
４−ペンチルオキシフェノール３ｇの３‐ペンタノン溶液に１．０当量の４‐ブロモブテンと１．５当量の炭酸カリウムを加え、２日間環流した。反応溶液に析出する沈殿を濾別し、濾液の溶媒を留去した後、残渣をシリカゲルカラムクロマトグラフィーにより精製し、化合物（Ａ）を得た。（２ｇ，４０％）
油状物質
ＩＲ＝８２３．５，１０３９．４，１２３０．４，１５０８．１，２９３１．３
^１ＨＮＭＲ（２７０ＭＨｚ，ＣＤＣｌ_３）δ＝０．９２（３Ｈ，ｔ，Ｊ＝６．９Ｈｚ），１．３３−１．４６（４Ｈ，ｍ），１．７５（２Ｈ，ｑｕｉｎ，Ｊ＝６．９Ｈｚ），２．５１（２Ｈ，ｑ，Ｊ＝６．９Ｈｚ），３．８９（２Ｈ，ｔ，Ｊ＝６．４Ｈｚ），３．９６（２Ｈ，ｔ，Ｊ＝６．６Ｈｚ），５．０７−５，１９（２Ｈ，ｍ），５．８２−５．９７（１Ｈ，ｍ），６．８２（４Ｈ，ｓ）ｐｐｍ．

化合物（Ｂ）の合成
化合物Ａ（２．０ｇ，８．７７ｍｍｏｌ）のアセトニトリル（８．５ｍｌ）、水（５．５ｍｌ）溶液に，ペルフルオロオクチルアイオダイド（４．８ｇ，８．７９ｍｍｏｌ），炭酸水素ナトリウム（０．７ｇ，８．６９ｍｍｏｌ），ハイドロサルファイトナトリウム（１．５ｇ，８．７９ｍｍｏｌ）を加え，遮光し一晩撹拌した。反応終了後，酢酸エチルで薄め，水で二回，食塩水で洗浄した。有機層を硫酸ナトリウムで乾燥した後，溶媒を減圧除去した。残渣をクロロホルム溶媒によるカラムクロマトグラフィーにより精製した。２．８ｇ（４１％）
ＩＲ（ＫＢｒ）１１４９．４， １２０３．４， １２３４．２ｃｍ^−１（Ｃ−Ｆ）， １５１１．９ｃｍ^−１， ２９３３．２， ２９５８．３ｃｍ^−１（Ｃ−Ｈ）
^１ＨＮＭＲ（２７０ＭＨｚ，ＣＤＣＬ_３）δ＝０．９３（３Ｈ，ｔ，Ｊ＝６．９Ｈｚ）， １．２６−１．４８（４Ｈ，ｍ），１．７６（２Ｈ，ｑｕｉｎ，Ｊ＝６．９Ｈｚ）， ２．１４−２．３６（２Ｈ，ｍ），２．８４−３．０６（２Ｈ，ｍ），３．９１（２Ｈ，ｔ，Ｊ＝６．６Ｈｚ）， ４．００−４．１６（２Ｈ，ｍ）， ４．５６−４．６６（１Ｈ，ｍ）， ６．８４（４Ｈ，ｓ）ｐｐｍ

化合物（Ｃ）の合成
化合物Ｂ（２．８ｇ，３．５８ｍｍｏｌ）を大気に触れないように蒸留したＴＨＦ（２５ｍｌ）に溶解し、溶液にＬｉＡｌＨ_４（０．２８ｇ，７．３７ｍｍｏｌ）を加え，一晩撹拌した。反応終了後，塩化アンモニウム水溶液を加え，抽出した後，水で二回と食塩水で洗浄した。有機層を硫酸マグネシウムで乾燥した後、溶媒を減圧除去した。残渣をクロロホルム溶媒によるカラムクロマトグラフィーにより精製し，無色の固体（Ｃ）を得た。１．３９ｇ（６０％）
ｍｐ＝５７℃
ＩＲ（ＫＢｒ） １１４９．４， １２０９．１， １２３８．１ｃｍ^−１（Ｃ−Ｆ）， １５０８．１ｃｍ^−１， ２８７３．４， ２９１３．９， ２９５２．５ｃｍ^−１（Ｃ−Ｈ）
^１ＨＮＭＲ（ＣＤＣｌ_３） δ＝０．９３（３Ｈ，ｔ，Ｊ＝７．０Ｈｚ）， １．３０−１．４５（４Ｈ，ｍ）， １．７０−１．９０（６Ｈ，ｍ）， ２．１５（２Ｈ， ｍ）， ３．９０（２Ｈ，ｔ，Ｊ＝７．０Ｈｚ）， ３．９２（２Ｈ，ｔ，Ｊ＝７．０Ｈｚ）， ６．８２（４Ｈ，ｓ）ｐｐｍ．

化合物（Ｄ）の合成）
化合物Ｂ（１．１０ｇ）を蒸留後数時間後のジエチルエーテル（２０ｍｌ）溶液にＬｉＡｌＨ_４（０．１ｇ）を加え、一晩撹拌した。反応終了後，１Ｎ ＨＣｌを加え，抽出した後，水で二回，食塩水で洗浄した。有機層を硫酸マグネシウムで乾燥した後，溶媒を減圧除去し，クロロホルム溶媒によるカラムクロマトグラフィーにより，無色の固体（Ｄ）を得た。０．３２ｇ，ｍｐ＝９２℃
ＩＲ（ＫＢｒ） １１４７．４， １２０３．４， １２３８．１， １５１１．９， ２９３７．１， ３４１５．３， ３４３８．５， ３４６９．３， ３４９８．２ ｃｍ^−１
１ＨＮＭＲ （ＣＤＣＬ_３） δ＝０．９３（３Ｈ，ｔ，Ｊ＝７．１Ｈｚ）， １．３４−１．４６（４Ｈ， ｍ）， １．７６（２Ｈ，ｑｕｉｎ，Ｊ＝６．９Ｈｚ）， ２．０２（２Ｈ，ｍ）， ２．２０−２．４６（２Ｈ，ｍ）， ２．７０（１Ｈ，ｄ， Ｊ＝３．３Ｈｚ）， ３．９０（２Ｈ，ｔ，Ｊ＝６．６Ｈｚ）， ４．０７−４．２０（２Ｈ，ｍ）， ４．４６（１Ｈ，ｍ）， ６．８３（４Ｈ，ｓ）ｐｐｍ

上記化合物（Ｃ）のゲル化能
上記化合物（Ｃ）を、有機溶媒に添加し、昇温して溶解し、生成した溶液を常温に戻すことによりゲル化するかどうか観察することにより、ゲル化能を測定した。本実施例で試みた有機溶媒は、プロピレンカーボネート、メタノール、ＤＭＦ、１−オクタノール、アセトニトリル、である。上記化合物（１）は、これらの有機溶媒を、ゲル化することができた。

Synthesis of Compound (A) 1.0 equivalent of 4-bromobutene and 1.5 equivalent of potassium carbonate were added to a 3-pentanone solution of 3 g of 4-pentyloxyphenol and refluxed for 2 days. The precipitate precipitated in the reaction solution was filtered off, the solvent in the filtrate was distilled off, and the residue was purified by silica gel column chromatography to obtain compound (A). (2g, 40%)
Oily substance IR = 823.5, 1039.4, 1230.4, 1508.1, 2931.3
¹ HNMR (270 MHz, CDCl ₃ ) δ = 0.92 (3H, t, J = 6.9 Hz), 1.33-1.46 (4H, m), 1.75 (2H, quin, J = 6. 9 Hz), 2.51 (2H, q, J = 6.9 Hz), 3.89 (2H, t, J = 6.4 Hz), 3.96 (2H, t, J = 6.6 Hz), 5. 07-5, 19 (2H, m), 5.82-5.97 (1H, m), 6.82 (4H, s) ppm.

Synthesis of Compound (B) Compound A (2.0 g, 8.77 mmol) in acetonitrile (8.5 ml) and water (5.5 ml) was dissolved in perfluorooctyl iodide (4.8 g, 8.79 mmol), hydrogen carbonate. Sodium (0.7 g, 8.69 mmol) and sodium hydrosulfite (1.5 g, 8.79 mmol) were added, and the mixture was stirred overnight while protected from light. After completion of the reaction, the reaction mixture was diluted with ethyl acetate, washed twice with water and washed with brine. After the organic layer was dried over sodium sulfate, the solvent was removed under reduced pressure. The residue was purified by column chromatography with chloroform solvent. 2.8 g (41%)
IR (KBr) 1149.4, 1203.4, 1234.2 cm ⁻¹ (C—F), 1511.9 cm ⁻¹ , 2933.2, 2958.3 cm ⁻¹ (C—H)
¹ HNMR (270 MHz, CDCL ₃ ) δ = 0.93 (3H, t, J = 6.9 Hz), 1.26-1.48 (4H, m), 1.76 (2H, quin, J = 6. 9 Hz), 2.14-2.36 (2H, m), 2.84-3.06 (2H, m), 3.91 (2H, t, J = 6.6 Hz), 4.00-4. 16 (2H, m), 4.56-4.66 (1H, m), 6.84 (4H, s) ppm

Synthesis of Compound (C) Compound B (2.8 g, 3.58 mmol) was dissolved in THF (25 ml) distilled so as not to be exposed to the atmosphere, and LiAlH ₄ (0.28 g, 7.37 mmol) was added to the solution. Stir overnight. After completion of the reaction, an aqueous ammonium chloride solution was added and extracted, and then washed twice with water and with brine. After the organic layer was dried over magnesium sulfate, the solvent was removed under reduced pressure. The residue was purified by column chromatography using a chloroform solvent to obtain a colorless solid (C). 1.39 g (60%)
mp = 57 ° C
IR (KBr) 1149.4, 1209.1, 1238.1 cm ⁻¹ (C−F), 1508.1 cm ⁻¹ , 2873.4, 2913.9, 2952.5 cm ⁻¹ (C−H)
¹ HNMR (CDCl ₃ ) δ = 0.93 (3H, t, J = 7.0 Hz), 1.30-1.45 (4H, m), 1.70-1.90 (6H, m), 2 .15 (2H, m), 3.90 (2H, t, J = 7.0 Hz), 3.92 (2H, t, J = 7.0 Hz), 6.82 (4H, s) ppm.

Synthesis of compound (D))
LiAlH ₄ (0.1 g) was added to a diethyl ether (20 ml) solution several hours after distillation of Compound B (1.10 g), and the mixture was stirred overnight. After completion of the reaction, 1N HCl was added and extracted, and then washed twice with water and with brine. The organic layer was dried over magnesium sulfate, the solvent was removed under reduced pressure, and a colorless solid (D) was obtained by column chromatography using a chloroform solvent. 0.32g, mp = 92 ° C
IR (KBr) 1147.4, 1203.4, 1238.1, 1511.9, 2937.1, 3415.3, 3438.5, 3469.3, 3498.2 cm ^-1
1 HNMR (CDCL ₃ ) δ = 0.93 (3H, t, J = 7.1 Hz), 1.34-1.46 (4H, m), 1.76 (2H, quin, J = 6.9 Hz) , 2.02 (2H, m), 2.20-2.46 (2H, m), 2.70 (1H, d, J = 3.3 Hz), 3.90 (2H, t, J = 6. 6Hz), 4.07-4.20 (2H, m), 4.46 (1H, m), 6.83 (4H, s) ppm

Gelation ability of the above compound (C) The above compound (C) is added to an organic solvent, dissolved by raising the temperature, and by observing whether the resulting solution is returned to room temperature or not, it is gelled. Performance was measured. The organic solvents tried in this example are propylene carbonate, methanol, DMF, 1-octanol, and acetonitrile. The compound (1) was able to gel these organic solvents.

Minimum Gelation Concentration of Compound (D) The minimum gelation concentration (wt%) of the compound (1) at room temperature is as follows.
Propylene carbonate (2.3), methanol (3.6), DMF (4.6), 1-octanol (14.0), acetonitrile (20.1)
Gelation ability of the above compound (D) The above compound (D) is added to an organic solvent, dissolved by heating, and the resulting solution is returned to room temperature to observe whether it gels or not. Performance was measured. The organic solvents tried in this example are propylene carbonate, methanol, DMF, 1-octanol, acetonitrile, cyclohexane, and octane. The compound (D) was able to gel these organic solvents.

Minimum Gelation Concentration of Compound (D) The minimum gelation concentration (wt%) of the compound (D) at room temperature is as follows.

  Propylene carbonate (1.1), cyclohexane (2.1), octane (2.5), methanol (5.2), 1-octanol (5.6), acetonitrile (5.9), N, N-diethyl -N-methyl-N- (2methoxyethyl) ammonium bis (trifluoromethanesulfonyl) imide (4.7)

Claims (7)

An organic liquid gelling agent comprising an aromatic compound having a perfluoroalkyl group represented by the following chemical formula (1)

(Where
The group C _m F _{2m + 1} is a perfluoroalkyl group, m is a natural number from 6 to 12;
The group (CH ₂ ) is a methylene group, p is the number of methylene groups, and a natural number of 1 to 4;
The group Ar is a substituted or unsubstituted divalent aromatic group having 5 to 30 nuclear atoms;
The group O is an oxygen atom;
The group α is hydrogen or hydroxyl;
The group R is a saturated or unsaturated monovalent hydrocarbon group having 1 to 20 carbon atoms. ) The gelling agent according to claim 1, wherein the aromatic group Ar is a phenylene group, a biphenylene group or a naphthylene group. An organic liquid gelling agent comprising a perfluoroalkyl group derivative represented by the following chemical formula (7)

(Where
The group C _m F _{2m + 1} is a perfluoroalkyl group, m is a natural number from 6 to 12;
The group (CH ₂ ) is a methylene group, p is the number of methylene groups, and is a natural number of 1 to 2;
The group Ar is a substituted or unsubstituted divalent aromatic group having 5 to 30 nuclear atoms;
The group O is an oxygen atom;
The group R is a saturated or unsaturated monovalent hydrocarbon group having 1 to 20 carbon atoms. ) An organic liquid gelling agent comprising an aromatic compound having a perfluoroalkyl group represented by the following chemical formula (8)

(Where
The group C _m F _{2m + 1} is a perfluoroalkyl group, m is a natural number of 6-12;
The group (CH ₂ ) is a methylene group, p is a natural number group of 1-2, Ar is a substituted or unsubstituted divalent aromatic group having 5-30 nuclear atoms;
The group O is an oxygen atom;
The group R is a saturated or unsaturated monovalent hydrocarbon group having 1 to 20 carbon atoms;
The group OH is a hydroxyl group. ) An aromatic compound having a hydroxyl group and a hydrocarbon oxy group of the following chemical formula (2) is reacted with a halogenated alkene of the following chemical formula (3), and the product is reacted with an iodinated perfluoroalkyl of the following chemical formula (4), The manufacturing method of the gelatinizer of any one of Claims 1-4 which consists of substituting the iodine of this product (Chemical formula (5)) with a hydroxyl group.

(The meaning of the symbols in the formula is the same as in the chemical formula (1). The group X is a halogen atom reactive with a hydroxyl group; the group I is an iodine atom)   The gel formed by gelatinizing an organic liquid with the gelatinizer of any one of Claims 1-4.   The gel of claim 4, wherein the gel is an electrolyte gel.