JP3348964B2 - Method for producing rare earth metal alkoxy alcoholate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a rare earth metal alkoxy alcoholate, and more particularly to a rare earth metal which is a useful precursor for producing a fine powder, a thin film, a fiber, a coating material, etc. of a rare earth metal oxide. The present invention relates to a method for producing a metal alkoxy alcoholate. The fine powder, thin film, fiber, coating material and the like of the rare earth metal oxide are used in a wide range of fields as phosphors, catalysts, ceramics, optical glass, abrasives, magnets or functional electronic materials.

[0002]

BACKGROUND OF THE INVENTION Heretofore, there have been known several types of alkoxy alcoholates of rare earth metals, Cu and the like, and methods for producing these metal alkoxy alcoholates as shown below. (1) JP-A-62-281835 describes a metal alkoxyalkoxide represented by the following general formula.

[0003]

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(Wherein M ³ represents a metal selected from scandium, yttrium and lanthanum, and n, m and p may be the same or different, each being a positive integer of 1 to 12 Selected, Z represents (R ¹⁰ ) — or (R ¹ ) —, and R ¹ and R ² represent the same or different alkyl groups containing 1 to 20 carbon atoms.) Describes that such metal alkoxyalkoxides are synthesized by a direct reaction between an alkoxy alcohol containing an alcohol reactant and a metal. (2) JP-A-3-285827 discloses that La (OC ₂ H ₄ OCH ₃ ) ₃ is obtained by the same reaction as described above. (3) Chemical Abtostract, Vol. 117, 102829
In d, it is described that Nd (OC ₂ H ₄ OCH ₃ ) ₃ is obtained by using Nd and alcohol as raw materials and performing an electrolytic reaction. (4) The chemical Abutosurakuto 12th Collective Index formula's, as compounds corresponding to C ₁₂ H ₂₇ ErO _6,

[0005]

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Further, Eu (OCH ₂ CH ₂ CH ₂ OCH ₃ ) ₃ is described as a compound corresponding to C ₁₂ H ₂₇ EuO ₆ . (5) JP-A-63-270688 discloses a method for synthesizing a copper (II) alkoxy alcoholate in which a copper organic carboxylate and an alkoxy alcohol are reacted in the presence of an alkali metal A as shown in the following reaction formula. Has been described.

[0007]

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Wherein R ¹ and R ^{3 each} represent a hydrogen atom or a lower alkyl group; R ² represents a lower alkyl group;
Or, it represents an integer of 2, and A represents an alkali metal. On the other hand, the following methods are known as methods for producing rare earth metal alkoxides. (6) reacting anhydrous scandium chloride with methanol,
Method for synthesizing methoxyscandium [Zeitschrift phil anoganiche und algemeine
Chemie, 67-71, 325 (1-2) 1963
Year]:

[0009]

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(7) A method of synthesizing a rare earth metal alkoxy compound by reacting a rare earth metal chloride anhydride with an alkali metal alkoxide [Proceedin Nuclear Radiation Chemical Symposium (Proceedin)
g Nuclear Radiation Chemical Symposium) No. 15-1
9 pages (1964)]:

[0011]

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(Wherein M ″ represents Pr, Nd, La). (8) The rare earth metal yttrium (Y) is reacted with an alcohol in the presence of a mercuric chloride catalyst to form propoxyyttrium. Synthesis Method [Inorganic Chemistry, Vol. 5 (3), No. 34]
2-346 (1966)]:

[0013]

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(9) A method of reacting a rare earth metal carboxylate with an alkali metal alkoxide to synthesize a rare earth metal alkoxide [Japanese Patent Publication No. 62-6694]:

[0015]

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(In the formula, M represents a rare earth metal, X represents a carboxylic acid residue, R represents an alkyl group, and A represents an alkali metal.) (10) A lanthanum halide is mixed with an alkali metal alkoxide. A method of synthesizing alkoxy lanthanum by using toluene as a reaction solvent and reacting while performing polishing and stirring [Japanese Patent Laid-Open No. 6-1737]:

[0017]

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However, the method for producing a rare earth metal alkoxy alcoholate which can be industrially mass-produced in a high yield and a high purity, and the above-mentioned La, Sc, Nd, Er, Eu and The alkoxy alcoholates of rare earth metals other than Y are not yet known.

Among the above-mentioned known techniques, the method for synthesizing the rare earth metal alkoxy alcoholate is as follows.
In (1), a method is described in which lanthanum is reacted with methoxyethanol to obtain La (OC ₂ H ₄ OCH ₃ ) _3. However, this starting material, lanthanum, is very expensive like other rare earth metals. In order to complete the reaction, it is necessary to heat and reflux for as long as 24 hours, and the yield is as low as 62%. Therefore, there is a problem in cost as a method for industrially producing a large amount of a rare earth metal alkoxy alcoholate.

[0020]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems associated with the prior art described above, and to easily and industrially mass-produce various rare earth metal alkoxy alcoholates in high yield and high purity. It is an object of the present invention to provide a method for producing a rare earth metal alkoxy alcoholate.

An object of the present invention is to provide a novel rare earth metal alkoxy alcoholate which is a useful precursor for producing fine powders, thin films, fibers, coating materials and the like of rare earth metal oxides. The rare earth metal oxide fine powder, thin film, fiber, coating material and the like can be expected to be used in a wide range of fields as a phosphor, a catalyst, a ceramic, an optical glass, an abrasive, a magnet or a functional electronic material.

[0022]

SUMMARY OF THE INVENTION A first method for producing a rare earth metal alkoxy alcoholate according to the present invention is represented by the following general formula (II): M ¹ _b X ₃ (II) wherein M ¹ represents a rare earth metal and X represents A carboxylic acid residue; b represents 1 or 2; However, when b is 1,
X represents a monovalent carboxylic acid residue, and when b is 2, X represents a divalent carboxylic acid residue. And a rare earth metal carboxylate represented by the general formula (III):

[0023]

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Wherein A represents an alkali metal, R ¹ represents a hydrogen atom or a lower alkyl group, R ² represents a lower alkyl group, and a represents an integer of 1-3. And an alkali metal alkoxy alcoholate represented by the following general formula (Ia):

[0025]

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Wherein M ¹ and R ¹ , R ² and a are the same as above. ] Is manufactured. The second method for producing a rare earth metal alkoxy alcoholate according to the present invention is represented by the following general formula (II): M ¹ _b X ₃ ... (II) wherein M ¹ , X and b are the same as above. And a rare earth metal carboxylate represented by the general formula (IV):

[0027]

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Wherein R ¹ , R ² and a are the same as above. With an alkoxy alcohol represented by the general formula (Ia):

[0029]

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Wherein M ¹ , R ¹ , R ² and a are the same as above. ] Is manufactured. According to the present invention , a rare earth metal alkoxy alcoholate represented by the following general formula (I)
can get.

General formula (I):

[0032]

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[Where M is Ce, Pr, Sm, Dy , H
R represents a hydrogen atom or a lower alkyl group, R ² represents a lower alkyl group, and a represents an integer of 1 to 3. According to the present invention as described above, various rare earth metal alkoxy alcoholates are
A method for producing a rare earth metal alkoxy alcoholate that can be easily mass-produced industrially with high yield and high purity is provided.

The rare earth metal alkoxy alcoholate more obtained in the present invention as described above, fine powder of rare earth metal oxides, thin films, fibers, used as a precursor in the production of coating materials and the like. The fine powder, thin film, fiber, coating material and the like of the rare earth metal oxide are expected to be used in a wide range of fields as phosphors, catalysts, ceramics, optical glasses, abrasives, magnets, functional electronic materials, and the like.

[0035]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the method for producing a rare earth metal alkoxy alcoholate according to the present invention and the novel rare earth metal alkoxy alcoholate will be described in detail.

In the following description, for example, the compound represented by the formula (A) may be represented as “compound (A)”. [First production method of rare earth metal alkoxy alcoholate]
In the present invention, by reacting a rare earth metal carboxylate represented by the following general formula (II) with an alkali metal alkoxy alcoholate represented by the following general formula (III), the following general formula (Ia) Manufacture of the rare earth metal alkoxy alcoholate represented.

General formula (II): M ¹ _b X ₃ (II) wherein M ¹ represents a rare earth metal, X represents a carboxylic acid residue, and b represents 1 or 2. However, when b is 1,
X represents a monovalent carboxylic acid residue, and when b is 2, X represents a divalent carboxylic acid residue. General formula (III):

[0038]

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[In the formula, A represents an alkali metal, R ¹ represents a hydrogen atom or a lower alkyl group, R ² represents a lower alkyl group, and a represents an integer of 1-3. General formula (Ia):

[0040]

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[Wherein, M ¹ represents a rare earth metal, R ¹ represents a hydrogen atom or a lower alkyl group, R ² represents a lower alkyl group, and a represents an integer of 1-3. More specifically, it is as follows.

[0042]

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(Where M ¹ , X, A, R ¹ , R ² , a, b
Is the same as above. That is, a mixed solution comprising a rare earth metal carboxylate represented by the above formula (II) and an organic solvent as described below,
An alkali metal alkoxy alcoholate solution represented by the formula (III) is gradually dropped, for example, over about 10 minutes. Next, the obtained rare earth metal carboxylate (I
I) and alkali metal alkoxy alcoholates (III)
From 80 to 180 ° C., preferably 100 to 140 ° C., which is the reflux temperature of the organic solvent used from room temperature.
And the mixture is usually stirred at the reflux temperature of the solvent for about 2 to 4 hours. Thus, rare earth metal carboxylate (II)
And a mixture containing the alkali metal alkoxyalcoholate (III) and the alkali metal alkoxyalcoholate (III) is stirred at the reflux temperature of the solvent for the above-mentioned time to obtain a rare earth metal alkoxyalcoholate represented by the above formula (Ia) and the alkali metal carboxylate An organic solvent solution (reaction solution) containing (XA _b ) is obtained.

By filtering the obtained reaction solution to remove the by-product alkali metal carboxylate (XA _b ), a uniform transparent organic solvent solution of the rare earth metal alkoxy alcoholate (Ia) is obtained. Next, by evaporating the organic solvent from the organic solvent solution of the rare earth metal alkoxy alcoholate (Ia) to dry and solidify the rare earth metal alkoxy alcoholate (Ia), a desired rare earth metal alkoxy alcoholate (Ia) is obtained.

In the organic solvent solution of the rare earth metal alkoxy alcoholate (Ia) thus obtained,
When an alkali metal carboxylate (XA _b ) is contained, it may be removed as follows. That is, by evaporating the organic solvent from the organic solvent solution of the rare earth metal alkoxy alcoholate, a dried product of the rare earth metal alkoxy alcoholate is obtained. Then
An organic solvent such as toluene or xylene as described below is added to the precipitated dried product to dissolve the precipitated dried product of the rare earth metal alkoxy alcoholate (Ia) again, and the insoluble matter in the organic solvent is again filtered off. , By-product (XA
It is possible to obtain an organic solvent solution (filtrate) of a rare and transparent rare earth metal alkoxy alcoholate (Ia) containing almost no impurities such as _b ).

As the rare earth metal carboxylate represented by the above formula (II), conventionally known carboxylate salts are used. For example, in "Chemical Encyclopedia" published on August 15, 1989, Kyoritsu Shuppan, Vol. 3, pp. 819B, describes anhydrous acetate of scandium, and is disclosed in JP-A-59-186935. Also describes various rare earth metal carboxylate salts,
Such a rare earth metal carboxylate (II) can be obtained by a conventionally known synthesis method.

As the rare earth metal carboxylate, a hydrate having several molecules of water of crystallization is known in addition to an anhydrous salt. The rare earth metal carboxylate used in the present invention is an anhydrous salt, and this anhydrous salt can be easily obtained by heat-treating a hydrate of a rare earth metal carboxylic acid to remove crystallization water, if necessary.

In producing the carboxylate of a rare earth metal represented by the formula (II), a method of reacting a rare earth metal oxide with a carboxylic acid is used. As the rare earth metal element (M ¹ ), a specific method is used. Scandium (S
c), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (N
d), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (E)
r), thulium (Tm), ytterbium (Yb), and lutetium (Lu).

As the carboxylic acid, a monovalent or divalent carboxylic acid is used. Specifically, for example, monovalent carboxylic acids such as formic acid, acetic acid, propionic acid and benzoic acid, and divalent acids such as oxalic acid are used. Carboxylic acid, formic acid, acetic acid,
Propionic acid is preferably used.

Such a rare earth metal carboxylate (II)
Specifically, for example, Sc (OCOC)
_{H 3) 3, Y (OCOCH} 3) 3, La (OCOCH 3) 3,
La (OCOH) ₃ , La (OCOC ₂ H ₅ ) ₃ , La (O
COC ₆ H ₅ ) ₃ , Ce (OCOCH ₃ ) ₃ , Pr (OCO
CH ₃ ) ₃ , Nd (OCOCH ₃ ) ₃ , Sm (OCOC)
H ₃ ) ₃ , Eu (OCOCH ₃ ) ₃ , Gd (OCOC)
H ₃ ) ₃ , Tb (OCOCH ₃ ) ₃ , Dy (OCOC
H ₃ ) ₃ , Ho (OCOCH ₃ ) ₃ , Er (OCOC)
H ₃ ) ₃ , Tm (OCOCH ₃ ) ₃ , Yb (OCOC
Compounds of formula (II) wherein X is a monovalent carboxylic acid residue, such as H ₃ ) ₃ , Lu (OCOCH ₃ ) ₃ , La
Compounds in which X in the formula (II) is a divalent carboxylic acid residue, such as ₂ (C ₂ O ₄ ) ₃ , are mentioned.

The alkali metal alkoxy alcoholate represented by the above formula (III) is disclosed in JP-A-63-270688.
And can be obtained by a conventionally known synthesis method. The compound represented by the formula (III):

[0052]

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In the above, A represents an alkali metal, and specifically includes, for example, lithium, sodium, potassium and the like, but sodium is most preferably used in consideration of availability, economy and the like. R ¹ represents a hydrogen atom or a lower alkyl group, and specific examples of such a lower alkyl group include those having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. About 1-4 carbon atoms such as a linear alkyl group and an i-propyl group.
Branched alkyl groups, and the like. Of these, a methyl group and an ethyl group are particularly preferred. R ² represents a lower alkyl group, which may be the same as R ^1, and a represents an integer of 1 to 3.

Specific examples of such an alkali metal alkoxy alcoholate (III) include, for example, lithium ethoxyethyl, sodium ethoxyethylate, sodium methoxyethylate, sodium 1-methoxy-2-propylate, sodium 4-methoxy 1-butyrate, sodium n-butoxy-2-ethylate, sodium 3-ethoxy-1-propylate, sodium 2-i
And propoxyethylate, potassium ethoxyethylate, etc., sodium ethoxyethylate, sodium methoxyethylate, sodium 1-methoxy-2-propylate, sodium 4-methoxy-1-butyrate, sodium n-butoxy-2-ethylate, sodium 3-ethylate Sodium alkoxy alcoholates such as ethoxy 1-propylate and sodium 2-ipropoxyethylate are preferably used.

The alkoxy alcohol (IV) used for forming such an alkali metal alkoxy alcoholate (III) is described in "Solvent Handbook" (No. 12).
2, p. 2, May 1967, published by Sangyo Tosho), and specifically include, for example, monoethers of ethylene glycol (eg, methoxyethanol, ethoxyethanol, butoxyethanol, etc.), Secondary alkoxy alcohol (eg, 1-methoxy-2-propanol) and the like can be mentioned. Among such alkoxy alcohols, those having a boiling point of 180 ° C. or less are preferable. When an alkoxy alcohol having such a boiling point is used, an organic solvent is easily and efficiently recovered from a reaction solution obtained by reacting a rare earth metal carboxylate (II) with an alkali metal alkoxy alcoholate (III) and reused. can do.

In the present invention, the rare earth metal carboxylate (II) is reacted with the alkali metal alkoxy alcoholate (III) to produce the rare earth metal alkoxy alcoholate (Ia). The alkali metal alkoxy alcoholate (III) is usually used in a stoichiometric amount with respect to 1 mol of the metal carboxylate (II). That is, the alkali metal alkoxyalcoholate (III) is used in an amount of 3.0 mol per mol of the monovalent rare earth metal carboxylate (II), and is added with 6.0 mol per mol of the divalent rare earth metal carboxylate (II). The organic solvent is used in an amount of about 0.6 to 7 liters.

As the organic solvent, an inert organic solvent which does not react with the starting material rare earth metal carboxylate (II) and alkali metal alkoxy alcoholate (III) is used. Among such organic solvents, aromatic hydrocarbons such as benzene, toluene and xylene, which can dissolve the above-mentioned raw materials (II, III) particularly well and have excellent operability such as reflux and distillation, are used. It is preferably used.

The above rare earth metal alkoxy alcohols
According to a first process for the production of the acrylates, the compounds of the formula (Ia)
Rare earth metal alkoxy alcoholates such as La
(OC_TwoH_FourOC_TwoH_Five)_Three, La (OC_TwoH_FourOCH_Three)_Three,
La [OCH (CH_Three) CH_TwoOC _TwoH_Five]_Three, La (OC_Four
H₈OCH_Three)_Three, La (OC_TwoH_FourOn-C_FourH₉)_Three, Sc
(OC_TwoH_FourOC_TwoH_Five)_Three, Nd (OC_TwoH_FourOC_TwoH_Five)_Three,
Er (OC_TwoH_FourOC_TwoH_Five) _Three, Eu (OC_TwoH_FourOC
_TwoH_Five)_Three, Y (OC_TwoH_FourOC_TwoH_Five)_ThreeEtc., of course, below
A novel rare earth according to the present invention represented by the general formula (I)
High yield and high purity of metal alkoxy alcoholate (I)
Is obtained.

The rare earth metal alkoxy alcoholates represented by the general formulas (I) and (Ia) are suitable as precursors for producing fine powders, thin films, fibers, coating materials and the like of rare earth metal oxides. Rare earth metal oxide fine powders, thin films, fibers, coating materials, and the like are expected to be used in a wide range of fields as phosphors, catalysts, ceramics, optical glasses, abrasives, magnets, functional electronic materials, and the like. [New Rare Earth Metal Alkoxy Alcoholate] This new rare earth metal alkoxy alcoholate is represented by the following general formula (I).

Formula (I):

[0061]

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[Wherein M is Ce, Pr, Sm, Gd,
Tb, Dy, Ho, Tm, Yb or Lu are shown. R ¹ represents a hydrogen atom or a lower alkyl group, R ² represents a lower alkyl group, and a represents an integer of 1 to 3. As the rare earth metal alkoxy alcoholate represented by the general formula (I), for example, M is Ce,
R ¹ is a hydrogen atom or a lower alkyl group; R ² is a linear or branched lower alkyl group having about 1 to 4 carbon atoms; and a is a compound wherein a is an integer of 1 to 3. Specifically, Ce [OCH ₂ CH ₂ —OC ₂ H ₅ ] ₃ ,
Ce [OCHCH ₃ CH ₂ OCH ₃ ] _{3 and the} like.

As the rare earth metal alkoxy alcoholate wherein M is Pr, specifically, for example, Pr [O
Etc. _{CH 2 CH 2 OC 2 H 5} ] 3 and the like. Specific examples of the rare earth metal alkoxy alcoholate in which M is Sm include, for example, Sm [OCH ₂ CH ₂ OC ₂ H ₅ ] ₃ , Sm
[OCH ₂ CH ₂ OiC ₃ H ₇ ] _{3 and the} like.

As the rare earth metal alkoxy alcoholate wherein M is Gd, specifically, for example, Gd [OCH
₂ CH ₂ OC ₂ H ₅ ] _{3 and the} like. Specific examples of the rare earth metal alkoxy alcoholate wherein M is Tb include, for example, Tb [OCH ₂ CH ₂ OC ₂ H ₅ ] ₃ .

As the rare earth metal alkoxy alcoholate wherein M is Dy, specifically, for example, Dy [OCH
₂ CH ₂ OC ₂ H ₅ ] _{3 and the} like. Specific examples of the rare earth metal alkoxy alcoholate wherein M is Ho include, for example, Ho [OCH ₂ CH ₂ OC ₂ H ₅ ] _{3 and the} like.

As the rare earth metal alkoxy alcoholate wherein M is Tm, specifically, for example, Tm [OCH
₂ CH ₂ OC ₂ H ₅ ] _{3 and the} like. Specific examples of the rare earth metal alkoxy alcoholate wherein M is Yb include, for example, Yb [OCH ₂ CH ₂ OC ₂ H ₅ ] _{3 and the} like.

As the rare earth metal alkoxy alcoholate wherein M is Lu, specifically, for example, Lu [OCH
₂ CH ₂ OC ₂ H ₅ ] _{3 and the} like. The structure of such a new rare earth metal alkoxy alcoholate is based on elemental analysis,
It is determined by IR, NMR, mass spectrum and the like. [Second production method of rare earth metal alkoxy alcoholate]
The rare earth metal alkoxy alcoholate (Ia) containing the novel rare earth metal alkoxy alcoholate (I) as described above of the present invention is represented by the above rare earth metal carboxylate (II) and the following general formula (IV) With the above-mentioned alkoxy alcohol in the presence of the above-mentioned alkali metal (A).

Formula (IV):

[0069]

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Wherein R ¹ represents a hydrogen atom or a lower alkyl group; R ² represents a lower alkyl group;
Indicates an integer. The second of this rare earth metal alkoxy alcoholate (Ia)
The production method of is more specifically described as follows.

[0071]

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(Wherein, M ¹ , X, A, R ¹ , R ² , a, b
Is the same as above. That is, the rare earth metal carboxylate represented by the formula (II), the alkoxy alcohol represented by the formula (IV), and the same organic solvent as described above are charged into the reactor. While stirring the obtained reactor contents [organic solvent solution of rare earth metal carboxylate (II) and alkoxy alcohol (IV)], add alkali metal (A) to the contents over 30 minutes to 2 hours. Add slowly.

The mixed solution containing the alkali metal (A) thus obtained is heated from room temperature to 80 to 180 ° C., preferably 100 to 140 ° C., which is the reflux temperature of the organic solvent. Stir for ~ 6 hours.

As described above, the rare earth metal carboxylate (I
When the organic solvent solution containing I), the alkoxy alcohol (IV), and the alkali metal (A) is stirred at the reflux temperature of the solvent for the above-mentioned time, hydrogen is generated as the reaction proceeds, and the above-mentioned formula (Ia) ) An organic solvent solution (reaction solution) containing the rare earth metal alkoxy alcoholate represented by the formula (1) and a by-product alkali metal carboxylate (XA _b )
Is obtained.

The reaction solution thus obtained is filtered in the same manner as in the first production method to remove the alkali metal carboxylate (XA _b ), thereby obtaining a uniform and transparent rare earth metal alkoxy alcoholate (XA _b ). An organic solvent solution of Ia) is obtained. Then, the organic solvent solution is evaporated to dryness to obtain a desired rare earth metal alkoxy alcoholate (I-
a) is obtained. When the alkali metal carboxylate (XA _b ) is dissolved in the organic solvent solution of the rare earth metal alkoxy alcoholate (Ia) thus obtained, the above-mentioned first production method is used. What is necessary is just to remove similarly.

The rare earth metal carboxylate (II), alkoxy alcohol (IV), alkali metal (A), organic solvent and alkoxy alcohol (IV) are the same as those used in the first production method. Is used.

In the second production method, the rare earth metal carboxylate (II), the alkoxy alcohol (IV) and the alkali metal (A) are reacted to form the rare earth metal alkoxy alcoholate (Ia). In the production, the alkoxy alcohol (IV) is usually used in an amount of 0.1 to 2 liters [about 3.6 to 14 mol] per 1 mol of the rare earth metal carboxylate (II), (A) is usually about 3.0 to 6.0 moles (eg, 3.0 moles).
Mol), and the organic solvent is used in an amount of about 0.5 to 5 liters.

According to the second production method of such a rare earth metal alkoxy alcoholate (Ia), the same rare earth metal alkoxy alcoholate as in the first production method can be obtained with high yield and high purity.

[0079]

According to the present invention as described above, there is provided a process for producing a rare earth metal alkoxy alcoholate which can easily and industrially mass-produce various rare earth metal alkoxy alcoholates in high yield and high purity. You.

Further, according to the present invention, a novel rare earth metal alkoxy alcoholate is provided. The novel rare earth metal alkoxy alcoholate is suitably used as a precursor for producing fine powders, thin films, fibers, coating materials and the like of rare earth metal oxides. The rare earth metal oxide fine powder, thin film, fiber, coating material and the like are used in a wide range of fields as phosphors, catalysts, ceramics, optical glasses, abrasives, magnets, functional electronic materials, and the like.

[0081]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

[0082]

Embodiment 1Production of yttrium ethoxyethylate [First production
Law] Yttrium acetate anhydride in a 100 ml round bottom flask
8.0 g (0.03 mol) and 50 ml of toluene were added.
While stirring the contents of the flask, the
Ethoxyethanol solution of thorium ethoxyethylate
50 g [equivalent to 0.09 mol as sodium]
The solution was gradually dropped over 0 minutes. Then the contents of the flask
Is heated to 110 ° C with a mantle heater and heated for 4 hours
Refluxed. Then, the obtained reaction solution was cooled to room temperature.
After that, salts produced as by-products in the reaction solution were removed by filtration. Next
Then, the solvent is distilled off from the obtained filtrate and evaporated to dryness.
Was. To the obtained dried product, 30 ml of toluene was added and dissolved.
After that, it was filtered again to make it uniform and transparent.
A toluene solution of muethoxyethylate was obtained. this
The toluene solution is evaporated to dryness and the yttrium ethoxyethyl
Got the rate. Yttrium ethoxyethylate yield is
10.30 g, and the yield was 96.4%. element
The analytical values are shown in Table 1.

[0083]

[Table 1]

[0084]

Examples 2 to 28 Various rare earth metal alkoxy alcoholates as shown in Table 1 were produced in the same manner as in Example 1. The used rare earth metal carboxylate, solvent, alkali metal alkoxy alcoholate, reaction conditions, products and elemental analysis results are shown in Tables 2 to 5.

[0085]

[Table 2]

[0086]

[Table 3]

[0087]

[Table 4]

[0088]

[Table 5]

[0089]

Embodiment 29Production of yttrium methoxyethylate [Second production
Law] Yttrium formate anhydrous in a 100 ml round bottom flask
6.7 g (0.03 mol) and 40 ml of toluene,
20 g (0.29 mol) of ethanol was added and the flask was
While stirring the contents, 2.1 g of metallic sodium (0.1 g) was added.
(0.9 mol) over about 30 minutes.
Added. In this way, add sodium metal to the flask
Then, heat was generated and hydrogen gas was generated. Metal nutri
After completion of the addition of
After heating and refluxing for 4 hours, the same treatment as in Example 1 was performed.
Thus, yttrium methoxyethylate was obtained. Itliu
The yield of mumethoxyethylate was 9.1 g, and the yield was
96.2%.

Table 6 shows the elemental analysis values.

[0091]

[Table 6]

Various products shown in Tables 2 to 5 can be obtained according to the method described in Example 29.

[0093]

Comparative Example 1 La (O) was prepared by directly reacting lanthanum with ethoxyethanol in accordance with the method for synthesizing rare earth metal alkoxyalcoholates described in JP-A-62-281835.
C ₂ H ₄ OC ₂ H ₅ ) ₃ was produced as follows.

That is, a metal La: 1.28 g (equivalent to 0.0092 mol, manufactured by Kanto Chemical Reagent, about 1 mm in diameter × 1 cm in length) and 50 ml of ethoxyethanol [50 g (0.05 mol) in a 200 ml round bottom flask. And heated with a mantle heater to reflux at a temperature of 130 to 135 ° C. for a total of 14 hours. When heated and refluxed in this manner, most of the metal La in the flask disappeared, and the reaction solution became a brown and turbid solution. Then, after cooling the reaction solution, the insoluble matter was separated by filtration and washed with about 20 ml of toluene to obtain a solution of La (OC ₂ H ₄ OC ₂ H ₅ ) ₃ in ethoxyethanol / toluene. The solvent was distilled off from this solution to obtain lanthanum ethoxyethylate. The yield of lanthanum ethoxyethylate was 2.32 g, and the yield was 62.0%.

Table 7 shows the elemental analysis values.

[0096]

[Table 7]

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Akiyoshi Nagai 4-29-2 Okada, Atsugi-shi, Kanagawa 105 Orion Heights 105 (56) References JP-A-2-36137 (JP, A) JP-A-6-136 25036 (JP, A) JP-A-59-186935 (JP, A) JP-A-59-186936 (JP, A) Canadian Patent Application Publication No. 2002606 Publication (1990) (58) .Cl. ⁷ , DB name) C07F 5/00 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A general formula (II): M ¹ _b X ₃ (II) wherein M ¹ represents a rare earth metal, X represents a carboxylic acid residue, and b represents 1 or 2. However, when b is 1,
X represents a monovalent carboxylic acid residue, and when b is 2, X represents a divalent carboxylic acid residue. And a rare earth metal carboxylate represented by the general formula (III): [In the formula, A represents an alkali metal, R ¹ represents a hydrogen atom or a lower alkyl group, R ² represents a lower alkyl group, and a represents an integer of 1 to 3. And reacting with an alkali metal alkoxy alcoholate represented by the general formula (Ia): [Wherein M ¹ , R ¹ , R ² and a are the same as above. ] The method for producing a rare earth metal alkoxy alcoholate represented by the formula: 2. A general formula (II): M ¹ _b X ₃ ... (II) wherein M ¹ , X and b are the same as above. And a rare earth metal carboxylate represented by the general formula (IV): Wherein R ¹ , R ² and a are the same as above. With an alkoxy alcohol represented by the general formula (Ia): [Wherein, M ¹ , R ¹ , R ² and a are the same as above. ] The method for producing a rare earth metal alkoxy alcoholate represented by the formula: