JPS63270688A - Copper (ii) alkoxyalcolate and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R1 represents H or lower alkyl; R2 represents lower alkyl; n is 1 or 2). EXAMPLE:Copper (II) ethoxyethylate. USE:A precursor for producing copper (II) oxide, which can be afforded as uniform ultrafine particles of <=0.1mum and usable as a raw material for ceramics and one component constituting ceramic based high temperature superconducting materials. PREPARATION:A copper salt of an organic carboxylic acid expressed by formula II (R3 represents H or lower alkyl) (preferably anhydrous copper acetate) is reacted with an alkoxyalcohol expressed by formula III in the presence of an alkali metal element (preferably Li or Na).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to copper(n) alkoxyalcoholate and a method for producing the same.

This copper (n) alkoxy alcoholate is an important component of ceramic raw materials and ceramic-based high-temperature superconducting materials, and is also used as a coloring agent for pigments, catalysts, glassware, etc.
It is useful as a precursor for cupric oxide fine powder, which has uses such as light electrical parts.

[Prior Art] In recent years, demand for metal oxides has been increasing as raw materials for producing ceramics and as important constituents of ceramic-based high-temperature superconducting materials. Metal oxides can be produced with extremely high purity and 0.1μm by hydrolyzing metal alkoxides.
In this reaction, the metal alkoxide is converted into benzene, toluene, xylene,
It is required to be soluble in various organic solvents such as hexane and methanol. Most metals form metal alkoxides, most of which are soluble in 9 solvents.

As m (II) alkoxide produced from copper (n
) methoxide and copper(II) ethoxide (rJour
nal of Inorganic Nucle
ar Chemistry J27 (1), 59~
62 (1965) and 27 (2) 281-285° (1965)), both of which were found to be insoluble in organic solvents.

Therefore, it has been impossible to produce ultrafine cupric oxide powder from conventional copper (n) alkoxide.

[Problems to be solved by the invention] When cupric oxide fine powder is used as various new materials, cupric oxide is sometimes used alone, but in many cases, cupric oxide is used alone.
For example, barium is a high-temperature superconducting material that has attracted attention in recent years.
It is used as a substrate for one of several components, as in the oxides of yttrium or rare earth metals. A metal alkoxide hydrolysis method is widely used as a method for advantageously producing homogeneous fine powder of such composite oxides. According to this method, if the metal alkoxides obtained from each metal are easily soluble in an organic solvent, a homogeneous multi-component system can be obtained by mixing predetermined amounts of them to form a solution. By hydrolyzing this homogeneous solution, a fine oxide powder having the same degree of homogeneity as that in the solution can be easily obtained. Therefore, metal alkoxides that are soluble in organic solvents are essential.

Therefore, an object of the present invention is to provide a compound that is soluble in an organic solvent,
An object of the present invention is to provide a copper (n) alkoxy alcoholate that can be used as a precursor for cupric oxide fine powder and a method for producing the same.

[Means for Solving the Problems] The present invention first provides the following: General formula (I) [wherein R1 represents a hydrogen atom or a lower alkyl group,
R2 represents a lower alkyl group, and n represents an integer of 1 or 2).

In the formula, R1 represents a hydrogen atom or a lower alkyl group. Examples of lower alkyl groups include methyl group, ethyl group, n-
Examples include, but are not limited to, propyl group, isopropyl group, n-butyl group, and the like. Particularly preferred are methyl and ethyl groups.

R2 represents a lower alkyl group, preferably a methyl group or an ethyl group.

Specific compounds of the I(II) alkoxyalcolate of formula (1) include copper(II) methoxyethylate C
u(OCH2cH2ocH3)2, copper(II) ethoxyethylate Cu (OCRCHQCH) copper(II)22252ゝmethoxyisopropylate n-butoxyethylate Cu(OCH2CH20o-C4H9)2, and the like.

The copper (n) alkoxy alcoholate obtained in the present invention is
Although there are some differences depending on the type of compound, it mainly has a practically sufficient solubility in aromatic hydrocarbons such as benzene, toluene, and xylene. That is, it dissolves in these organic solvents at a rate of 0°4 moΩ/g or more. Therefore, copper(n) oxide can be easily obtained by hydrolyzing this compound. Copper (II) methoxide and copper (n) ethoxide, which are conventional copper (II) alkoxides, do not have practically sufficient solubility in organic solventsC0,05moD/
(less than or equal to 1).

Second, the present invention provides general formula (II) Cu (OCOR3)2 (■) [in the formula R3
represents a hydrogen atom or a lower alkyl group] and an alkoxy alcohol represented by the general formula (m) [where Rt , R and n are as defined above] are combined into an alkali metal element. Copper of formula (I) characterized in that it is reacted in the presence of
If) a method for producing an alkoxyalcoholate.

The reaction in the method of the present invention is shown as follows.

Cu (OCORa ) 2 + (n) (m) In the above general formula (n), R3 is a hydrogen atom or a lower alkyl group, such as methyl, ethyl, propyl, butyl, etc., and these are linear or branched. It may be in any form. Specific examples of the organic copper carboxylate represented by general formula (II) include copper formate, copper acetate, copper propionate, and the like.

R and R2 in general formula (m) are as defined for formula (I). Examples of compound (2) include monoethers of ethylene glycol, such as methyl cellosolve (methoxyethanol), ethyl cellosolve (ethoxyethanol), butyl cellosolve (butoxethanol), and 1-methoxy-2-propatol. Secondary alkoxy alcohols such as these can also be used. It is desirable that these have a boiling point of about 180° C. or lower in consideration of recovery, reuse, etc. of the solvent after the reaction.

M represents an alkali metal, and lithium, sodium, potassium, etc. are usually used as the alkali metal, but sodium is the most desirable in terms of availability and cost.

In this case, the type of organic solvent used is not particularly limited as long as it dissolves the copper(II) alkoxyalcoholate, but examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene, hexane, and octane. Examples include aliphatic hydrocarbons, alcohols such as methanol, ethanol, and n-butanol, ketones such as acetone, ethers such as ethyl ether, butyl ether, and tetrahydrofuran, and esters such as ethyl acetate, but especially benzene, Hydrocarbons such as toluene and xylene are preferred.

The alkali metal (IV) is reacted with the alkoxy alcohol of the general formula (Iff) to produce a metal salt of the alkoxy alcohol, and then subjected to a substitution reaction with the organic copper carboxylic acid of the general formula (II) to form the metal salt of the alkoxy alcohol of the present invention. Copper (1)
II) Generates an alkoxyalcoholate, which itself becomes a metal salt of an organic carboxylic acid.

The method for producing copper (■) alkoxy alcoholate of the present invention will be explained in more detail.

First, in a flask equipped with a stirrer, an organic carboxylic acid copper of the general formula (II), an alkoxy alcohol of the general formula (I), and an aromatic hydrocarbon such as benzene, toluene, or xylene as a solvent are poured into a flask. Stir. In this case, the amount of alkoxy alcohol (m) is the organic copper carboxylate (
(2) 2 to 10 times the molar amount, preferably 4 to 6 times the molar amount. In addition, the amount of the solvent used is as follows: organic copper carboxylate (H
)] about 0.5 to 5 g per mole, preferably about 1 to 3j11.

Furthermore, there is no restriction on the order in which the organic carboxylic acid copper (If), the alkoxy alcohol (III), and the organic solvent used here are added.

Next, an alkali metal is cut into appropriate sizes and added thereto at room temperature. The size of the alkali metal is from 0.2 to 1.0, depending on the scale of the reaction. Ocm angle is preferable, and the amount used is 2.0 to 2
, double the mole. When an alkali metal is added in this way, the alkali metal generates hydrogen gas accompanied by an exothermic reaction, which gradually disappears, and at the same time, the reaction between the organic copper carboxylate (n) and the alkoxy alcohol (III) proceeds. In order to complete the reaction even after the alkali metal has disappeared, the solvent is kept at a temperature near the boiling point of the solvent and refluxed using an antle heater or the like.

Alternatively, in this reaction, first alkoxy alcohol (I
After reacting II) with an alkali metal, it is also possible to add organic carboxylic acid copper (n) and heat the reaction.

The resulting reaction mixture gradually becomes viscous and takes on a green to blue color. After the reaction mixture is cooled to room temperature, the organic carboxylate of the alkali metal produced as a by-product is removed by filtration or the like, and then thoroughly washed with an aromatic hydrocarbon.

When the solvent is distilled off from the aromatic hydrocarbon solution of copper(n) alkoxyalcoholate thus obtained, a crude product of copper(II) alkoxyalcoholate, which is the target compound, is obtained as blue-green crystals.

This crystal is dissolved again in a suitable organic solvent such as an aromatic hydrocarbon, cooled and recrystallized to obtain pure copper (n
) Crystals of alkoxyalcoholate are obtained.

In order to obtain a fine powder of copper(II) oxide from the obtained copper(II) alkoxyalcoholate of general formula (I), it may be hydrolyzed by the following method.

Hydrolysis is carried out either by dropping a solution of the (If) alkoxy alcoholate in an organic solvent into deionized water or by dropping deionized water into a solution of the copper(II) alkoxy alcohol. In either case, it is preferable to stir so that both are sufficiently mixed. In this case steel (I
T) A crude product of the alkoxide may be used.

Fine powder of oxidized steel can be produced in this way.

Further, by mixing it with another metal alkoxide and then hydrolyzing it as described above, a fine powder of a composite oxide containing copper oxide can be produced.

Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 Preparation of copper (II) ethoxychetylate Anhydrous copper acetate (97% purity) was added in a round bottom flask equipped with a stirrer.
) 18.1g (0.1 mol), Tolue > 200ml
100 ml of s-technoxyethanol was added and stirred vigorously. At room temperature, 4.7 g (0,204 mol) of metallic sodium cut into 0.5 cm square pieces was added over about 30 minutes. The reaction progressed gradually with an exothermic reaction, and hydrogen gas was observed to be generated. After the exothermic reaction was completed in about 1 hour from the start of the reaction, it was further heated with a mantle heater.
The reaction was completed by heating under reflux for an hour. The reaction mixture initially appeared green and gradually turned blue. After cooling to room temperature, yellow crystals of sodium acetate produced by-product were removed by suction filtration, and washed with about 50 ml of toluene. Chelate titration of 1 ml of the obtained solution (380 ml) was performed to determine the copper content, which was 0.203 mo#/Ω and the copper yield was 91.496.

Next, the solvent toluene is distilled off, and the precipitated crystals are again dissolved in toluene and then recrystallized. The obtained crystals were then taken out and dried under vacuum. The yield was 4.8 g, the total yield from the starting material was 74.1%, and the recrystallization yield was 81.1% based on the acetic acid steel used.

The elemental analysis values were as follows.

Elemental analysis value Cu% C% H% O20 Calculated value: 2B, 3 39.8 7.5 2
0.5 Actual Δpj value: 25.8 40.2 7
．． 7 213.3 (blank below) Example 2 Production of copper (n) methoxyethanol Cu (OCHOCHs) 2 In a round bottom flask equipped with a stirrer, copper formate anhydride (purity 95
%) 16.2g (0.1 mol), xylene 200m
1 and 80 ml of methoxyethanol were added and stirred vigorously. 1.4 g of granular metallic lithium is added to this mixture over a period of about 1 hour at room temperature. The reaction progressed gradually with an exothermic reaction, and hydrogen gas was generated. After the exothermic reaction was completed in about 1 hour from the start of the reaction, the mixture was further heated with a mantle heater and heated under reflux for 2 hours to complete the reaction. The reaction mixture initially appeared green and gradually turned black-rimmed. After cooling to room temperature, by-product lithium formate crystals were removed by suction and washed with about 50 ml of xylene. When 1 ml of the obtained Nippon solution (360 ml) was taken and subjected to chelate titration for copper content, it was found to be 0.233 moN/Ω, and the copper plate ratio was 83.9%.

Next, recrystallization was performed by the method of Example 1.

The yield was 4.2 g, the recrystallization yield was 84.5%, and the total yield from the starting material was 70.9%.

The elemental analysis values were as follows.

Cu% C% H% O% Calculated value: 29.7 33.7 G, 8
30.0 Actual aFI value: 29.3 34.0
G, 2 30.5 Example 3 m (n) Preparation of Methoxyisopropylate Anhydrous copper acetate (97% purity) in a round bottom flask with a stirrer 18.
7 g (0.1 mol), 300 ml of benzene and 80 ml of methoxyisopropanol were added and stirred vigorously. At room temperature, 4.8 g (0.21 mol) of metallic sodium cut into approximately 0.5 cm squares was added over approximately 30 minutes. The reaction progressed gradually with an exothermic reaction, and hydrogen gas was observed to be generated. After the exothermic reaction was completed in about 1 hour from the start of the reaction, the mixture was further heated with a mantle heater and heated under reflux for 3 hours to complete the reaction. The reaction mixture initially appeared green and gradually turned to a black border. After cooling to room temperature,
The by-product sodium acetate crystals were removed by suction filtration and washed with about 50 ml of benzene. The obtained quenching liquid (
When 1 ml of 450 ml) was taken and the copper content was chelate titrated, it was 0.203 mojll/i) and the copper plate rate was 91.
．． It was 4%.

Then, recrystallization was performed according to Example 1, and the yield was 4.0 g, the recrystallization yield was 81.6%, and the total yield from the starting materials was 81.6%.

The elemental analysis values were as follows.

Cu% C% H% 0% Calculated value: 2B, 3 39.8 7.5 2
6.5 Actual alll value: 2B, 0 39.3
7.7 27.0 Example 4 Production Example 1 of copper(II) n-butoxyethylate
Copper (II) n-butoxyethylate was produced according to the method. The copper plate rate is 86.496, and the yield after recrystallization is 82.
At 8%, the total yield from starting material was 71.5%.

The elemental analysis values were as follows.

Cu% C% H% 0% Calculated value: 21.3 48.4 g, 7
21.5 actual 71111 value: 21.1 48.8
8.2 21.9 Reference Example 1 Production of fine copper oxide powder from copper(II) ethoxyethylate Solution of copper(II) ethoxyethylate obtained in Example 1 in a mixed solvent of toluene and ethoxyethanol (concentration 0.245 moΩ/Ω) was dropped into 300 ml of vigorously stirred deionized water for hydrolysis.

The organic solvent was then recovered by distillation under reduced pressure to obtain 1
It was concentrated to about 50ml. The produced black precipitate was collected, thoroughly washed, dried with ventilation at 60°C for 24 hours, and then heat-treated in an electric furnace at 600°C for 1 hour.

The yield of the obtained black crystals was 1.8 g, and the yield was 92.3%.
Met. Furthermore, as shown in the figure, the X-ray diffraction pattern of this crystal completely matched that of copper oxide. Also, the specific surface area is 2
rrr/g.

Reference Example 2 Production of fine copper oxide powder from copper(II) methoxyethylate A solution of copper(II) methoxyethylate obtained in Example 2 in a mixed solvent of xylene and methoxynitinol (concentration 0.233n+oΩ/ g) Add 250 ml of deionized water into the 100 ml while stirring vigorously.
1 was added dropwise for hydrolysis.

The organic solvent was then recovered by distillation under reduced pressure and concentrated to about 100ml. The produced black precipitate was collected by centrifugation, dried with ventilation at 60°C for 24 hours, and then concentrated in an electric furnace at 600°C for 1 hour.

The yield of the obtained black crystals was 1.8 g, the yield was 97.3%.
Met. The X-ray diffraction pattern of this crystal is Reference Example 1
It is the same as that obtained in , indicating that copper oxide was obtained. Further, the specific surface area was 2 rrr/g.

[Effects of the Invention] According to the present invention, there is obtained a novel compound steel (II) alkoxyalcoholate and a method for producing the same, which consists of reacting an organic copper carboxylic acid with an alkoxyalcohol.

The copper (n) alkoxy alcoholates of the present invention are soluble in organic solvents, whereas known copper (II) alkoxides are insoluble in organic solvents.

This solubility is comparable to or greater than that required for conversion to a homogeneous copper oxide fine powder.

Therefore, by using the copper (n) alkoxy alcoholate of the present invention as a precursor, it becomes possible for the first time to obtain homogeneous and ultrafine copper (II) oxide powder of 0.1 μm or less.

As a result, it has become possible to obtain a fine powder in which a plurality of oxide components including copper oxide are homogeneously mixed and dispersed.

This fine copper oxide powder is used as a raw material for ceramics and as one of the components of ceramic-based high-temperature superconducting materials.

[Brief explanation of drawings]

The figure shows the X-ray diffraction pattern of the crystal obtained in Reference Example 1. Patent applicant: Hokuko Chemical Industry Co., Ltd.

Claims (1)

[Claims] 1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R_1 represents a hydrogen atom or a lower alkyl group, R_2 represents a lower alkyl group, and n represents an integer of 1 or 2] A copper (II) alkoxy alcoholate represented by: 2) The copper(II) alkoxy alcoholate according to claim 1, wherein R_2 represents a hydrogen atom, R_3 represents a methyl group or an ethyl group, and n represents 1. 3) General formula (II) Cu(OCOR_3)_2(II) [In the formula, R_3 represents a hydrogen atom or a lower alkyl group] Organic carboxylic acid copper and general formula (III) ▲ Numerical formula, chemical formula, table, etc. ▼ (III) [In the formula, R_1 represents a hydrogen atom or a lower alkyl group, R_2 represents a lower alkyl group, and n represents an integer of 1 or 2] and an alkoxy alcohol of an alkali metal element. General formula (I) characterized by reaction in the presence of
A method for producing copper(II)-alkoxyalcoholate represented by 4) The organic copper carboxylate of general formula (II) is anhydrous copper acetate (
4. The manufacturing method according to claim 3, wherein R_3 is a methyl group. 5) The manufacturing method according to claim 3, wherein the alkali metal element is lithium or sodium.