JP2003212879A - Method for synthesizing ion metal complex - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for synergistic an ionic metal complex useful as a supporting electrolyte for an electrochemical device such as a lithium battery, a lithium ion battery, an electric double layer capacitor, a polymerization catalyst for a polyolefin or a catalyst for organic synthesis, etc. <P>SOLUTION: In this method for synthesizing an ionic metal complex composed of a chemical structural formula represented by general formula (1), a compound represented by general formula (2) is reacted with a halogen-containing compound represented by general formula (3) or general formula (4) in an organic solvent in the presence of a reaction auxiliary containing an element of the group I, the group II or group IV of the periodic table. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a supporting electrolyte for electrochemical devices such as lithium batteries, lithium-ion batteries and electric double layer capacitors, polymerization catalysts such as polyolefins, and ionic metals used as catalysts for organic synthesis. A method for synthesizing a complex.

[0002]

2. Description of the Related Art Conventionally, ionic complexes such as PF ₆ ⁻ , BF ₄ ⁻ , and AsF ₆ ⁻ in which a Lewis acid and F ion are bonded are characterized by their solubility, ionic dissociation property, and high activity for reaction. It has been used as a supporting electrolyte for chemical devices, a polymerization catalyst for polyolefins, and a catalyst for organic synthesis.

While the range of application is diversifying, the optimum ionic complex for each use is being searched for, and its properties such as heat resistance, hydrolysis resistance, low toxicity and recyclability are required. There is. Under such circumstances, not only conventional complexes in which fluorine, oxygen, etc. are simply bonded to the central element, but many complexes in which organic ligands are bonded to the central element have also been found. . There are various synthetic methods. For example, a neutralization reaction between a hydroxide of an element corresponding to the central element and a ligand having active hydrogen with high acidity, a halide of an element corresponding to the central element and an alkali metal having a high dissociation property. Examples include a desalting reaction of the ligand, but the reactivity may be low depending on the combination of the ligand and the central element, and it is often difficult to freely obtain a complex as designed.

[0004]

[Means for Solving the Problems] As a result of intensive studies in view of the problems of the prior art, the present inventors have found that the ligand of the periodic table I The present invention has arrived at the present invention by finding a novel method for synthesizing a complex by reacting in the presence of a reaction aid containing a group, group II, group III or group IV element.

That is, in the present invention, in synthesizing an ionic metal complex having a chemical structural formula represented by the general formula (1), the compound represented by the general formula (2) and the general formula (3) or the general formula (4) ) Is reacted with a halogen-containing compound represented by the formula (1) in an organic solvent in the presence of a reaction aid containing an element of group I, group II, group III or group IV of the periodic table. The present invention provides a method for synthesizing an ionic metal complex represented by (1).

[0006]

[Chemical 2]

However, M is a transition metal, III of the periodic table.
Group IV, IV, or V element, A^{a +}Is a metal ion, hydrogen
Ion, or onium ion, a is 1 to 3, b is
1-3, p is b / a, m is 1-4, n is 0-8,
q represents 0 or 1, respectively, and X¹Is O, S, N
R^Five, Or NR^FiveR⁶, R¹, R²Are independent of each other,
H, halogen, C₁~ C_TenAlkyl of, or C₁~ C_Ten
Alkyl halide of R ³Is C₁~ C_TenArche of
N, C₁~ C_TenAn alkylene halide of C,_Four~ C₂₀A
Lee Ren or C_Four~ C₂₀Halogenated arylene
(These alkylene and arylene groups are
It may have a substituent or a hetero atom, and there are m R's.
³May be combined with each other. ), R^FourIs halogen,
C₁~ C_TenAlkyl, C₁~ C_TenThe halogenated alky
Le, C_Four~ C₂₀Aryl, C_Four~ C₂₀The halogenated ants
Or X²R⁷(These alkyl and aryl are
The structure may have a substituent or a hetero atom, and
R existing n^FourAre linked together to form a ring
Good. ), X²Is O, S, NR^Five, Or NR^FiveR⁶, R
^Five, R⁶Is H or C₁~ C_TenAlkyl of R⁷Is C
₁~ C_TenAlkyl, C₁~ C_TenAn alkyl halide of
C_Four~ C₂₀Aryl or C_Four~ C₂₀Halogenated
Reel (these alkyls and aryls are
It may have a substituent or a hetero atom, and there are n atoms.
R⁷May be combined with each other. ) Respectively,
E¹, E²Are each independently hydrogen or alkali gold
Genus, R⁸Each represent halogen.

The present invention will be described in more detail below.

Here, the ionic metal complex synthesized for the purpose of the present invention may have any structure as long as it has a structure in which an inorganic or organic ligand is bound to the central element, and preferably the general formula (1) ) Has a structure represented by.

[0010]

[Chemical 3]

M in the formula is a transition metal, III in the periodic table.
Selected from Group III, IV or V elements, preferred
Ku, Al, B, V, Ti, Si, Zr, Ge, Sn, C
u, Y, Zn, Ga, Nb, Ta, Bi, P, As, S
c, Hf, and Sb. A ^{a +}Is a metal ion, hydrogen
Ion or onium ion, preferably Li ion,
Quaternary alkyl ammonium ion or hydrogen ion
It Concrete A^{a +}As lithium ion, sodium
Ion, potassium ion, magnesium ion, calci
Umium ion, barium ion, cesium ion, silver ion
Ion, zinc ion, copper ion, cobalt ion, iron ion
Ion, nickel ion, manganese ion, titanium ion,
Lead ion, chromium ion, vanadium ion, ruthenium
Muion, yttrium ion, lanthanoid ion,
Actinide ion, tetrabutylammonium ion
Ion, tetraethyl ammonium ion, tetramethyl ammonium ion
Ammonium ion, triethylmethylammonium ion
Ion, triethylammonium ion, pyridinium ion
Ion, imidazolium ion, hydrogen ion, tetraethyl
Phosphonium ion, tetramethylphosphonium ion
Ion, tetraphenylphosphonium ion, triphenyl
Sulfonium ion, triethylsulfonium ion,
Examples thereof include triphenylmethyl ion.

The valence number a of the cation of A ^{a +} is preferably from 1 to 3, and when it is larger than 3, the crystal lattice energy becomes large, which causes a problem that it becomes difficult to dissolve it in a solvent. Therefore, 1 is more preferable when solubility is required. Similarly, the valence b of the anion is preferably 1 to 3, and more preferably 1. The constant p representing the ratio of the cation and the anion is inevitably determined by the valence ratio b / a of the two.

R ¹ and R ² are each independently selected from H, halogen, C ₁ -C ₁₀ alkyl, or C ₁ -C ₁₀ halogenated alkyl, preferably R 1.
^At least one of ¹ and R ² is a fluorinated alkyl, and more preferably at least one of R ¹ and R ² is a trifluoromethyl group. The presence of an electron-withdrawing halogen or alkyl halide in R ¹ and R ² disperses the negative charge of M at the center and increases the electrical stability of the anion.
It becomes very easy to dissociate into ions, and solubility in a solvent, ionic conductivity, catalytic activity, etc. increase. Further, other heat resistance, chemical stability and hydrolysis resistance are also improved. In particular, the effect is greater when the halogen is fluorine, and the effect is greatest when the halogen is a trifluoromethyl group.

R³Is C₁~ C_TenAlkylene, C₁~ C
_TenAn alkylene halide of C,_Four~ C ₂₀Arylene of the
Or C_Four~ C₂₀Selected from halogenated arylene
Chelate ring with M at the center
It is preferable to form a 5- to 10-membered ring when forming. 10
If it is larger than the member ring, the chelating effect becomes smaller.
Therefore, it is not preferable. Also, R³Is hydroxyl or carboxyl
If the group has a group in the structure, the central
It is also possible to make a bond to M. These alkylenes
And arylene have a substituent or a hetero atom in the structure.
You may. Specifically, on alkylene and arylene
In place of hydrogen, halogen, chain or cyclic alkyl
Group, aryl group, alkenyl group, alkoxy group, aryl
Roxy group, sulfonyl group, amino group, cyano group, carbo
Nyl group, acyl group, amide group, hydroxyl group, oxo group (=
O), and instead of carbon on alkylene and arylene
Other examples include structures with nitrogen, sulfur, and oxygen introduced.
be able to. Furthermore, there are multiple Rs³Are each
May be combined.

R ⁴ is halogen, C ₁ -C ₁₀ alkyl,
It is selected from the group consisting of C _{1 to} C ₁₀ alkyl halides, C _{4 to} C ₂₀ aryls, C _{4 to} C ₂₀ aryl halides, and X ² R ⁷ , with fluorine being preferred.

X ¹ and X ² are each independently O, S or NR ⁵ R ⁶ and are bonded to M through these heteroatoms. Here, coupling other than O, S and N means
It is not impossible, but it is very complicated in terms of synthesis.

R ⁵ and R ⁶ are selected from H or C ₁ -C ₁₀ alkyl. This moiety does not require an electron withdrawing group, unlike other moieties. When an electron-withdrawing group is introduced here, the electron density on N decreases and the central M
Can no longer be coordinated with.

R ⁷ is C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀
Alkyl halides, aryl C ₄ -C _20, or C ₄ is formed of one selected from an aryl halide of -C _20, preferably fluorinated alkyl C ₁ -C _10. The presence of an electron-withdrawing alkyl halide in R ⁷ disperses the negative charge of M at the center and increases the electrical stability of the anion, which makes it very easy to dissociate into ions, resulting in solubility in a solvent or ionicity. Conductivity, catalytic activity, etc. increase. Further, other heat resistance, chemical stability and hydrolysis resistance are also improved. In particular, when the alkyl halide is a fluorinated alkyl, the effect becomes larger. Also,
These alkyls and aryls have substituents in their structure,
It may have a hetero atom. Specifically, instead of hydrogen on alkyl and aryl, halogen, chain or cyclic alkyl group, aryl group, alkenyl group, alkoxy group, aryloxy group, sulfonyl group, amino group, cyano group, carbonyl group, acyl group. , An amide group, a hydroxyl group, an oxo group (═O), and a structure in which nitrogen, sulfur, or oxygen is introduced instead of carbon on the alkyl and the aryl. Furthermore, a plurality of R ^7's may be bonded to each other.

The constants m and n related to the number of ligands described so far are determined by the type of central M, but m is preferably 1 to 3 and n is preferably 0 to 4. .

Next, specific examples of this complex are shown below.

[0021]

[Chemical 4]

The method of the present invention for synthesizing the above complex will be described. This method is characterized by reacting a ligand and a halogen-containing compound serving as a supply source of the central element of the complex as a raw material in an organic solvent in the presence of a reaction aid.

The ligand is preferably one having hydrogen, an alkali metal, or an alkaline earth metal active to bond with the halogen contained in the halogen-containing compound serving as a supply source of the central element and further eliminate the halogen. Examples thereof include alcohols, metal alkoxides, carboxylic acids, carboxylic acid salts, sulfonic acids, sulfonic acid salts thereof, sulfinic acids, and sulfinic acid salts thereof. More preferably, this compound is a compound having a structure represented by formula (2).

[0024]

[Chemical 5]

E in the formula¹, E²Symbols other than are general formulas
It is the same as that of (1). Where E ¹, E²Is it
Each independently represents hydrogen or an alkali metal.

Next, the halogen-containing compound serving as a source of the central element has a transition metal, a group III, IV, or V group of the periodic table as a central element, and at least one halogen is contained in the central element. May be bonded, and only halogen may be bonded, or other substituents may be bonded. This halogen-containing compound is preferably a compound having a structure represented by the general formula (3) or the general formula (4).

[0027]

[Chemical 6]

The symbols other than R ^{8 in the} formula are the same as those in formula (1). Here, R ⁸ represents halogen,
Preferred is fluorine. As a specific example, LiP
F ₆ , LiBF ₄ , LiAlCl ₄ , LiPF ₃ (C
_{F 3) 3, LiBF 3 (} Ph), BF 3, PF 5, and the like (provided that, Ph is. Representing a phenyl group).

The reaction aids are groups I, II and III of the periodic table.
Group IV or Group IV element-containing element, preferably Al,
It contains B, Si, an alkali metal, and an alkaline earth metal. The strong bond between these elements and halogen helps the reaction proceed in the present invention.
Further, these reaction aids are selected from chlorides, bromides, iodides, alkoxy compounds and carboxy compounds of the above elements, and preferably these reaction aids are selected from AlCl ₃ , BCl ₃ and SiCl _4. Consisting of what is chosen. E slightly generated when the compounds of the general formula (2) and the general formula (3) or the general formula (4) are mixed.
By removing ¹ R ⁸ and E ² R ⁸ using this reaction aid by utilizing the reaction, the equilibrium shifts toward the target complex and the desired reaction proceeds. At this time, by-products precipitate,
Alternatively, it is desirable to select a ligand, a halogen-containing compound serving as a supply source of the central element, and a reaction aid so that they can be easily removed from the system as components having a high vapor pressure.

The amount ratio of the reaction is not particularly limited, but the ligand is reacted 1 to 8 times by mole with respect to the halogen-containing compound serving as the supply source of the central element. The reaction auxiliary is reacted in a 0.1 to 10-fold molar quantity with respect to the halogen-containing compound serving as a source of the central element.

The solvent used in the above-mentioned synthetic method is a solvent which dissolves the starting material compound even in an extremely small amount, depending on the structure of the compound, and it is preferable that the solvent does not react with the compound in the system, preferably the ratio. A material having a dielectric constant of 2 or more is preferable. If a solvent that has no solubility is used, the reaction becomes extremely slow, which is not preferable. If the solubility is slight, the solubility of the target ionic metal complex is very large, and the reaction proceeds rapidly. For example, carbonates, esters, ethers, lactones, nitriles, amides, sulfones, alcohols, aromatics and the like can be used, and not only a single solvent but also a mixed solvent of two or more kinds may be used. . Specific examples include propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, dimethoxyethane, acetonitrile, propionitrile, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, nitromethane, N, N-dimethylformamide, dimethyl sulfoxide. , Sulfolane, γ-butyrolactone, toluene, ethanol, methanol and the like.

The reaction temperature is from -80 ° C to 100.
C., preferably 0 to 80.degree. C. are used. This is-
The reaction does not proceed sufficiently at a temperature lower than 80 ° C,
At temperatures above ℃, decomposition of solvent and raw materials may occur. Further, in order to obtain a sufficient reaction rate and to cause no decomposition at all, the range of 0 ° C to 80 ° C is optimum.

Since many of the raw materials used in the present invention are hydrolyzable, it is desirable to carry out the synthesis in an atmosphere of low moisture such as air, nitrogen or argon.

The ionic metal complex obtained by the above method is a recrystallization method in which the solution is concentrated to precipitate crystals, a reprecipitation method in which a large amount of a poor solvent is added to the solution for precipitation, and the obtained solid It is also possible to purify it by a method such as washing.

[0035]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to the examples.

Example 1 Hexafluoro-in a glove box with a dew point of -50.degree.
2-hydroxyisobutyric acid (HOC (C
F _{3) 2} COOH) 3.09g, lithium tetrafluoroborate (LiBF ₄₎ were mixed 1.37 g, dimethyl carbonate 20 ml, and stirred sufficiently to dissolve. Next, 1.38 g of silicon tetrachloride as a reaction aid was slowly added to this mixed solution at room temperature with stirring. Simultaneously with the start of addition, gas was vigorously generated and the reaction proceeded. After completion of the addition, stirring was continued for 3 hours, and it was confirmed that the generation of gas was completely stopped, and the reaction was terminated. 60 from the obtained reaction solution
Dimethyl carbonate was removed under reduced pressure at 133 ° C. at 133 ° C. to obtain 3.87 g of a white solid as a product.
This white product is the following lithium borate derivative.

[0037]

[Chemical 7]

Example 2 Hexafluoro-in a glove box with a dew point of -50 ° C.
2-hydroxyisobutyric acid (HOC (C
F _{3) 2} COOH) 3.09g, lithium tetrafluoroborate (LiBF ₄₎ 1.37 g, were mixed diethyl carbonate 20 ml, and stirred sufficiently to dissolve. Next, 1.30 g of aluminum trichloride, which is a reaction aid, was slowly added to this mixed solution at room temperature with stirring. A milky white precipitate was generated at the same time when the addition was started. After the addition is complete
Stirring was continued for 3 hours. The precipitate was filtered off from the obtained reaction liquid, and diethyl carbonate was removed from the filtrate under a reduced pressure condition of 80 ° C. and 133 Pa to obtain 3.79 g of the same lithium borate derivative as in Example 1.

Example 3 Hexafluoro-in a glove box with a dew point of -50.degree.
2-hydroxyisobutyric acid (HOC (C
F _{3) 2} COOH) 3.08g, lithium hexafluorophosphate (LiPF ₆₎ 2.21g, mixed dimethyl carbonate 20 ml, was sufficiently agitated to dissolve. next,
A reaction aid, 1.38 g of silicon tetrachloride, was slowly added to this mixture at room temperature with stirring. Simultaneously with the start of addition, gas was vigorously generated and the reaction proceeded. After completion of the addition, stirring was continued for 5 hours, it was confirmed that the gas generation was completely stopped, and disappearance of the raw materials was confirmed by NMR, and the reaction was terminated. After filtering the obtained reaction solution, the filtrate is washed with 60
By drying under a reduced pressure condition of 133 ° C. and 133 Pa, 2.93 g of a lithium phosphate derivative shown below was obtained.

[0040]

[Chemical 8]

Example 4 Hexafluoro-in a glove box with a dew point of -50 ° C
2-hydroxyisobutyric acid (HOC (C
F _{3) 2} COOH) 6.18g, lithium tetrafluoroborate (LiBF ₄₎ 1.37g, acetonitrile 50
ml was mixed and thoroughly stirred to dissolve. Next, 2.75 g of silicon tetrachloride as a reaction aid was slowly added to this mixed solution at room temperature with stirring. Simultaneously with the start of addition, gas was vigorously generated and the reaction proceeded. After completion of the addition, stirring was continued for 3 hours, and it was confirmed that the generation of gas was completely stopped, and the reaction was terminated. 60 ° C, 133P from the obtained reaction solution
Acetonitrile was removed under the reduced pressure condition of a to obtain the lithium borate derivative shown below.

[0042]

[Chemical 9]

[0043]

INDUSTRIAL APPLICABILITY The present invention provides a support electrolyte for electrochemical devices such as lithium batteries, lithium ion batteries and electric double layer capacitors, a polymerization catalyst such as polyolefin, or a complex used as a catalyst for organic synthesis easily and easily. This enables efficient synthesis.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Mikihiro Takahashi             2805 Imafuku Nakadai Centra, Kawagoe City, Saitama Prefecture             Le Glass Co., Ltd. (72) Inventor Yoshimi Isono             2805 Imafuku Nakadai Centra, Kawagoe City, Saitama Prefecture             Le Glass Co., Ltd. F-term (reference) 4H048 AA01 AA02 AB40 AB78 AC41                       BE90 VA11 VA75                 4H050 AA02 AB40 AB78 AB91 BE90                       WA13 WB13 WB17 WB21

Claims (7)

[Claims] 1. When synthesizing an ionic metal complex having a chemical structural formula represented by the general formula (1), the general formula (2) is used.
Reaction of a compound represented by the formula (3) or a halogen-containing compound represented by the general formula (3) or (4) in an organic solvent containing a group I, II, III or IV element of the periodic table A method for synthesizing an ionic metal complex represented by the general formula (1), which comprises reacting in the presence of an auxiliary agent. [Chemical 1] However, M is a transition metal, a group III, IV, or V element of the periodic table, A ^{a +} is a metal ion, hydrogen ion, or onium ion, a is 1 to 3, b is 1 to 3 , P
Is b / a, m is 1 to 4, n is 0 to 8, q is 0 or 1, and X ¹ is O, S, NR ⁵ , or NR ⁵ R ⁶ , R ¹ , R ^{2 s} are each independently H, halogen, C ₁ -C ₁₀ alkyl, or C ₁ -C ₁₀ alkyl halide, R ³ is C ₁ -C ₁₀ alkylene, C ₁ -C
₁₀ halogenated alkylene, C _{4 to} C ₂₀ arylene,
Or a C _{4 to} C ₂₀ halogenated arylene (these alkylenes and arylenes may have a substituent or a hetero atom in the structure, and m ³ R ^{3 s} may be bonded to each). R ⁴ is halogen, C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ alkyl halide, C ₄ -C ₂₀
Aryl, C ₄ -C ₂₀ aryl halide, or X ² R ⁷ (these alkyl and aryl may have a substituent or a hetero atom in the structure, and n ⁴ R ⁴ are each May combine with each other to form a ring), X ²
Is O, S, NR ⁵ , or NR ⁵ R ⁶ , R ⁵ , R ⁶ is
H, or C ₁ -C ₁₀ alkyl, R ⁷ is C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ halogenated alkyl, C ₄ -C ₂₀
Or an aryl halide of C _{4 to} C ₂₀ (these alkyl and aryl may have a substituent or a hetero atom in the structure thereof, and there are n R ⁷
May be combined with each other. ) Respectively,
E ¹ and E ² are each independently hydrogen or an alkali metal, and R ⁸ is halogen. 2. The method for synthesizing an ionic metal complex according to claim 1, wherein the reaction aid is a compound of Al, B, Si, an alkali metal, or an alkaline earth metal. 3. The reaction aid is a chloride, bromide, iodide, alkoxy compound, or carboxy compound of Al, B, Si, an alkali metal, or an alkaline earth metal. Method for the Synthesis of Ionic Metal Complexes. 4. The method for synthesizing an ionic metal complex according to claim 1, wherein the reaction aid is AlCl ₃ , BCl ₃ , or SiCl ₄ . 5. M is Al, B, V, Ti, Si, Z
r, Ge, Sn, Cu, Y, Zn, Ga, Nb, Ta,
The method for synthesizing an ionic metal complex according to claim 1, wherein the ionic metal complex is Bi, P, As, Sc, Hf, or Sb. 6. The method for synthesizing an ionic metal complex according to claim 1, wherein A ^{a +} is any one of Li ion, quaternary alkylammonium, and hydrogen ion. 7. The method for synthesizing an ionic metal complex according to claim 1, wherein R ⁸ is fluorine.