JPS6399034A - Production of metal-containing composition soluble in organic solvent - Google Patents

Abstract

PURPOSE:To produce an organic solvent-soluble metal-containing composition simply and industrially advantageously, by reacting a metallic carboxylate with an ethanolamine or an aliphatic amine and a carboxylic acid in an alcohol. CONSTITUTION:A carboxylate of a metal selected from a group consisting of Mg, Ca, Sr, Ba, Zn and Cd of group II, Al, In and Y of group III and lanthanum type elements, n molds based on 1mol metallic salt of n numbers of oxidation of an ethanolamine or aliphatic amine (e.g. diethylenediamine, etc.) and 1-n mols based on 1mol metallic salt of 1-4C carboxylic acid (e.g. acetic acid, etc.) are suspended in an alcohol or a mixed solution of an alcohol and an aromatic hydrocarbon and heated until a uniform solution is obtained to give an organic solvent-soluble metal-containing composition. A crosslinking agent for resins, a reaction catalyst, a very small amount additive for new glass, etc., and an additive of sintering auxiliary for new ceramics.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention involves reacting a metal carboxylate with ethanolamines or aliphatic amines in alcohol to produce a metal-containing composition soluble in organic solvents. It is related to the method.

[Prior Art] Metal complex compounds having eta/-rumisos or aliphatic amines as ligands are metal halides, sulfates,
It can be produced by dissolving nitrate or perchlorate in water or alcohol and then adding the above-mentioned amines.

Also known is a method of producing a metal complex compound by reacting a metal alkoxide with the above-mentioned amines. These metal complex compounds are useful as crosslinking agent 1 reaction catalysts for resins, trace additives to new glasses, etc., or additives such as sintering aids in the field of new ceramics.

[Problem that the development is intended to solve] However, metal halides, sulfates, nitrates or a! When using leached salts, the resulting metal complex compounds are often crystalline and have low solubility in organic solvents, which often limits practical use.Moreover, the production process is limited to the production of halide ions.

Contamination with F& acid ions, nitrate ions, or perchlorate ions is unavoidable, and it may be necessary to remove these anions before use. In addition, the reaction rate between the metal alkoxide and the above-mentioned amines is slow, and this method is not suitable for industrial production.

The present invention was made in view of the above situation, and its purpose is to improve fP! of metal complex compounds soluble in organic solvents. The purpose is to provide a method that can be manufactured in a wide and industrially efficient manner.

[Means for solving the problems] The composition of the method of the present invention that can achieve the above object is as follows: (A) metal carboxylate, (B) ethanolamines or aliphatic amines, and (C) Contains carboxylic acid. The gist of this method is to heat an organic solvent suspension containing at least alcohol to form a uniform solution.

[Effect] Non-occurrence [When implementing the 91 method,
g, Ca, Sr, Ba, Zn, Cd, Group 1 Al, I
A metal carboxylate selected from the group consisting of n, Y, and lanthanum-based elements; and ■ ethanolamines or aliphatic amines per mole of metal salt with oxidation number n, and @C.
1-C4 charcoal 3: It! A carboxylic acid having [ is used in the range of 1 to n mole per mole of metal salt, and these are suspended in an alcohol or a mixture of an alcohol and an aromatic hydrocarbon and heated until a homogeneous solution is obtained. . The resulting homogeneous solution can be used as is, but if necessary, wood, alcohols, or aromatic hydrocarbons produced as by-products in the reaction step may be removed by distillation to make it soluble in organic solvents. It will be put into practical use as a metal-containing composition. ■When using ethanolamines as a component, the metal-containing composition obtained is 1700 to 1500 cr.
The infrared absorption band of acyclic amide in the spectral region of I and 1800-1700c-1 and 1300-100100
It has an ester infrared absorption band in the O1 spectral region,
In addition, when using aliphatic amines, 1700 to 15
F5I is defined as a metal-containing composition that is soluble in organic solvents and has an infrared absorption band of acyclic 7mide in the spectral region of 00c layer-1.

The metal carboxylate used in the present invention is carbon a.
Examples include salts of carboxylic acids having C+ to C4, but since acetate is industrially most preferred, the following explanation will be made with acetate as a representative example.

In carrying out the method of the present invention, Mg of group Ⅰ, Ca,
An acetate selected from the group consisting of Sr, Ba, Zn, Cd, Group 1 AI, In, Y, and lanthanum-based elements, and ethanolamines or aliphatic amines are added to 1 mole of a metal salt of In oxide. A carboxylic acid having a carbon number of 01 to C4 is blended in a range of 1 to n moles, preferably in a range of 1-n/2 moles, to 1 mole of metal/salt, and these are added to alcohols or alcohols. and an aromatic hydrocarbon. The most common alcohols used are C1-Ca i6 Z f3t alcohols, and the aromatic hydrocarbons typically used are benzene, toluene, or xylene. These organic solvents may be either alcohol alone or a mixture of alcohol and aromatic hydrocarbon; in the case of a mixture, no matter what the mixing ratio is, it will not affect the reaction itself. It has no effect.

The difference between using alcohol alone and using a mixture with an aromatic hydrocarbon appears when the by-product water is removed in one reaction step, and when an azeotrope is formed, water-alcohol or water-aromatic Rather than removing hydrocarbon water as a secondary fractional azeotropic mixture, it is better to remove it as a tertiary fractional co-clean mixture of water-alcohol-aromatic hydrocarbon because the azeotropic temperature is 10 to 20.
Since the temperature is lowered, the water removal operation becomes easier.

For example, in water-ethyl alcohol system, the boiling point is 78.2
If the water composition is 4% by weight at ℃, the boiling point of the water-ethyl alcohol-benzene system is 64.9℃, which is approximately 7ffr.
The water composition is ffi%, and in the water-benzene system, the boiling point is 63.3°C and the water composition is 9% by weight.

Group Ⅰ Mg, Ca, Sr, Ba, Zn.

The acetate of a metal selected from the group consisting of Cd, Group II AI, In, Y, and lanthanum-based elements can be prepared by a conventionally known method.
For example, an acetate hydrate obtained by suspending the corresponding oxide or carbonate in an acetic acid aqueous solution and then heating is dissolved or suspended in N,N-dimethylformamide, and dried benzene is added to this. After that, the benzene-Kyodo mixture is removed by distillation. By distilling off the N,N-dimethylformamide from the product thus obtained, an anhydrate of the 1% i salt of vinegar is obtained.

When using praseodymium oxide or terbium oxide as a starting material among rank-made elements, the acetate can be obtained by first converting it into sesquioxide by hydrogen reduction or the like, and then applying the above-mentioned method. Further, cerium (IV) oxide can be converted into cerium (III) carbonate and then converted into acetate by the method described above.

In the case of zinc acetate, the 6-eternal product of zinc nitrate is reacted with acetic anhydride by heating, and after cooling, the white crystals formed are separated by filtration, washed with acetic anhydride and ether, and then dried with sodium hydroxide and concentrated sulfuric acid in a vacuum. An anhydrate of acetate is obtained.

Magnesium acetate can be prepared by dissolving magnesium carbonate in acetic acid aqueous solution, filtering it, and adding a mixture of equal amounts of ethyl alcohol and ether to the filtrate. Upon heating, it is obtained as an anhydrate.

The feature of the present invention is that
Group Mg, Ca, Ba, Sr, Za.

Anhydrous metal acetate selected from the group consisting of Cd, Group Ⅰ Al, In, Y, and lanthanum-based elements, a specific amine, and a carboxylic acid having a carbon number of Cl-C4, 01
The solution is suspended in an alcohol having a carbon number of ~C4 or a mixed solution of an alcohol-aromatic hydrocarbon and heated until a homogeneous solution is obtained. The heating temperature may be any temperature higher than room temperature, but industrially it is preferably from 50° C. or higher to reflux temperature.

The ethanolamines used in the present invention are heptanoethanolamine, jetanolamine or triethanolamine, and the aliphatic amines include ethylenediamine, diethylenetriamine or triethylenetetramine.

Further, the carboxylic acid used may be any carboxylic acid having a carbon number of Cl-C4, and gold FJ
Although it is most common to use an acid having the same number of carbon atoms as the carboxylic acid constituting the 4-salt, it is of course also possible to use a combination of metal carboxylates and carboxylic acids that have different numbers of carbon atoms. be. The amount added is 1 metal salt with oxidation number n
moles, in the range l-n moles, preferably l-n/2
The mixture of alcohol and aromatic hydrocarbon, which is preferably in the molar range, has no effect on the properties of the reaction product in any combination.

The homogeneous solution obtained in this way can be used as it is, but if necessary, it can be further distilled to remove the water and alcohol or aromatic hydrocarbons produced by the amidation or esterification reaction into a co-liquid mixture. If it can be removed as an azeotrope, it is removed as an azeotropic mixture, and if it cannot be an azeotrope, it is removed individually to obtain a metal-containing composition. The composition obtained in this way has an
Infrared absorption bands of acyclic amides in the spectral region of CIm-1 and 1800-1700 cm-1 and 1300-1O0
The ester has an infrared absorption band in the 0 cit-' spectral region, and when aliphatic amines are used, it has an infrared absorption band of 1700-150
The composition has an infrared absorption band of the acyclic amide in the spectral region of the 0c layer-X, and this composition also contains aromatic hydrocarbons, e.g.
It is insoluble in paraffinic and olefinic hydrocarbons, acetic acid ester, inpropyl ether, petroleum ether, chloroform, and trichloride tetrachloride, and sparingly soluble in alcohols and acetone, but diethyl ether, N,N-dimethylformamide, It is easily soluble in pyridine, dimethyl sulfoxide, terpineol, and butylcarpitol,
It can be used as an easy-to-handle organic solvent solution.

[Examples] The present invention will be specifically explained with reference to Examples below, but the present invention is not limited by the Examples below.

Example 1 Yttrium oxide (Y2O:l) 113 g (0,
5 mol) (manufactured by Nippon Yztrium Co., Ltd.) is dissolved in 4 volumes of 50% acetic acid aqueous solution, and if there is any undissolved material, it is filtered out. The resulting aqueous solution is heated to a temperature of 70 to 80°C to evaporate water to obtain yttrium acetate crystals.

The yttrium acetate hydrate thus obtained is heated in vacuo at 150 to 180°C to obtain an anhydrate of yttrium acetate. This anhydrate and triethanolamine 4so
In one reaction, suspend g (3 moles) and acetic acid 90 g (1.5 moles) in a mixture of 11 methyl alcohol and 1 mixture of benzene and heat in the range of 55 to 60 ° C until a homogeneous solution is obtained. A reflux device is attached to prevent the solvent from volatilizing.The suspension before heating is a slurry-like dispersion of white crystalline solids, but by heating, it becomes a white gel-like substance in about 10-15 hours. After 25 hours, the gel-like solid begins to gradually dissolve, and about 3
0ff! ? A homogeneous solution will form between the two. This reaction product can be used as a solution, but by further removing water, methyl alcohol and benzene as by-products by distillation, a yttrium-containing composition soluble in organic solvents is obtained. This composition has an infrared absorption of the acyclic amide at 1630 cm-1 and 1730 cm-1 and 1250 crl,
It has an ester infrared absorption at 108108O', and is insoluble in aromatic hydrocarbons, paraffinic and olefinic hydrocarbons, ethyl acetate, isopropyl ether, petroleum ether, chloroform, and carbon tetrachloride, and insoluble in alcohols and acetone. Diethyl ether, which is sparingly soluble,
It is readily soluble in N,N-dimethylformamide, pyridine, dimethyl sulfoxide, terpineol, and butylcarpitol.

Example 2 Gadolinium acetate tetrahydrate [Gd(CH3COO)x
・4ToO] 406g (1 mol) (manufactured by Kishida Chemical Co., Ltd.),
Dissolve dry 4-grams in N,N-dimethylformamide. Then, after adding 5 parts of dry benzene, the benzene-water co-liquid mixture was removed by distillation, and the mother liquor was distilled to dryness to form the product [Gd(CHxCOO)3.DMFI (however, DMF
: N,N-dimethylformamide) is obtained.

When this material is heated to 200-210°C to remove DMF, gadolinium acetate anhydrate [Gd(C:)13
COO)3] is obtained.

This anhydrate, 183 g (3 mol) of monoethanolamine, and 90 g (1.5 mol) of acetic acid were added to 1 mol of ethyl alcohol.
Suspend the mixture in a mixture of 1 part of toluene and 1 part of toluene, and heat under reflux for approximately 25 hours until the white crystalline solid in the liquid is uniformly dissolved. After 10-15 hours, the reaction solution becomes a white gel-like solid, and after 25 hours it becomes a homogeneous solution. This solution can be used as it is, but by distilling it to remove by-product water, ethyl alcohol, and toluene, a viscous liquid trinium-containing composition is obtained.

Conogadolinium-containing Ml compositions exhibit amide infrared absorption at 1830 cm-' and 1580 CS-+, and 1720
It has ester infrared absorption in Hokan, 1240C layer-1 and 108108O1.

Aromatic hydrocarbons, paraffinic and olefinic hydrocarbons, ethyl acetate, isopropyl ether, petroleum ether, chloroform, alcohols that are insoluble in carbon tetrachloride, and slightly soluble in acetone, but diethyl ether and N,N-dimethyl. It is easily soluble in formamide, pyridine, dimethyl sulfoxide, terpineol, and butylcarpitol.

FIG. 1 shows the infrared absorption spectrum of the gadolinium-containing composition obtained above.

Comparative Example 1 Yttrium formate dihydrate [Y(HCOOh・2H2
0] 260 g (1 mol) (manufactured by Kishida Chemical Co., Ltd.) in Example 2
Used in place of gadolinium acetate tetrahydrate.

An anhydrate was obtained in the same manner as in Example 2. This anhydrate and 315 g (3 moles) of jetanolamine were suspended in a mixture of 1 M ethyl alcohol and 1 part benzene, and heated to reflux without adding carboxylic acid. However, although the crystalline precipitate changed into a gel-like precipitate, as the reflux time became longer, the gel-like precipitate increased, and after 20 hours, almost all of the gel-like precipitate had gelled. This gel was also insoluble in diethyl ether, dimethylformamide, pyridine, dimethyl sulfoxide, terpineol, and butylcarpitol.

Comparative Example 2 Yttrium formate made with W in the same manner as Comparative Example 1, jetanolamine 315 g (3 mol), and formic acid 69 g
(1.5 mol) with ethyl alcohol 11 and benzene 1n
Ethyl alcohol and benzene were removed by suspending the solution in water and distilling it without heating until it became a homogeneous solution.

The product obtained is a gel-like material, with a temperature of 1730 cm
Although 108O and 108O had some visible infrared absorption of the ester, no infrared absorption of the amide could be confirmed. Moreover, it is poorly soluble in organic solvents such as alcohols, aromatic hydrocarbons, and N,N-dimethylformamide.

Example 3 Zinc nitrate hexahydrate [Z! 1(N03)2・8H20]2
After reacting 97 g (1 mol) (manufactured by Kishida Chemical Co., Ltd.) with 1200 ml of acetic anhydride, it is further boiled for 10 to 20 minutes. After standing for a while, the crystals precipitated are filtered through cold absorption, washed with a small amount of acetic anhydride, further washed with ether, and then dried in a desiccator with potassium hydroxide and concentrated sulfuric acid to obtain anhydrous zinc acetate.

This anhydrous zinc acetate and monoethanolamine tz2g (2
mol) and propionic acid (74 g (1 mol)) were suspended in a mixture of 1M isopropyl alcohol and toluene In.
The reaction vessel is heated in the range of 5 to 60°C and equipped with a reflux tIL device to prevent the solvent from volatilizing. As the heating continues, the white crystalline solid present in the liquid gradually becomes gel-like, After 20 hours, it becomes a homogeneous solution with a pale yellow color.

This product can be used as a solution, but also '/
When water, isopropyl alcohol and toluene produced as by-products are removed by distillation, a viscous liquid zinc-containing composition is obtained. The resulting zinc-containing compositions were 1840 cm-1 and 15
Infrared absorption of amide in 70c intestine-1. 1710c
It had ester infrared absorption at rl, 1280 cm -1 and 1090 c = 1, and showed the same results as Example 1 in terms of solubility in organic solvents.

Example 4 Magnesium carbonate (MgC (h
) 84 g (1 mol) (manufactured by Kishida Chemical Co., Ltd.) was dissolved, filtered, and the filtrate was evaporated and concentrated in a concentrated sulfuric acid desiccator to precipitate magnesium acetate tetrahydrate. When this tetrahydrate is heated at 130-135°C until the weight becomes constant, it becomes an anhydrate.

The thus obtained magnesium acetate anhydrate, 210 g (2 mol) of jetanolamine, and 88 g (1 mol) of acetic acid are suspended in a mixture of secondary butyl alcohol 11 and xylene IJ1, and heated at 60 to 65°C. The container is equipped with a reflux device to prevent the solvent from volatilizing.6 As the reaction continues, the white crystalline solid present in the liquid gradually becomes gel-like, and becomes a pale reddish-brown homogeneous solution in 20 to 25 hours. This solution can be used as it is, but if it is further distilled to remove by-products such as wood, secondary butyl alcohol and xylene, a viscous liquid magnesium-containing composition can be obtained. This composition has amide infrared absorptions at 1850 cm-1 and 1573C11', and 1735 cm-1 and 1258 cm-1.
It had ester infrared absorption at Cr 1 and 1100 crl, and showed the same results as Example 1 in terms of solubility in organic solvents.

Example 5 Indium nitrate 113 hydrate [I! +(803)3・3
1,355 g (1 mol) of H20 (manufactured by Yaku Kagaku Co., Ltd.) was reacted with 10,100 O of acetic anhydride, and after the completion of the reaction, an additional 10 to 2
Boil for 0 minutes. The precipitated crystals are filtered under suction when cold, washed with Shozhu acetic anhydride, washed with ether, and then dried with potassium hydroxide and concentrated sulfuric acid in a vacuum desiccator to obtain indium acetate anhydride.

This indium acetate, 120 g (2 mol) of ethylenediamine, and 60 g (1 mol) of acetic acid are suspended in a mixture of 1 part isopropyl alcohol and 1 part benzene, and heated to reflux. As the reaction progresses, 3 white crystalline solids are formed. It reaches its maximum level after ~5 hours, but gradually dissolves after that, and reaches its maximum level after ~5 hours.
After some time, it becomes a homogeneous solution. This solution can be used as it is, but by further removing water, isopropyl alcohol and benzene produced by distillation, a viscous liquid indium-containing composition is obtained. This composition is 1
It has amide infrared absorption bands in B10c layer-1 and 1540c layer-1, and is insoluble in aromatic hydrocarbons, paraffinic and olefinic hydrocarbons, ethyl acetate, isopropyl ether, petroleum ether, chloroform, and carbon tetrachloride. It was poorly soluble in alcohols and acetone, but easily soluble in diethyl ether, N,N-dimethylformamide, pyridine, dimethyl sulfoxide, terpineol, and butyl carpitol.

Example 6 Aluminum ethoxide [AI(0(zHs)xl
162g (1 mol) (r? Ta Kagakusha 51) of acetic anhydride 8
After adding 50 pieces of aluminum dropwise, the reaction is accelerated by heating.The reaction mixture is cooled to obtain white aluminum acetate. This was dried at 100° C. for 5 hours under reduced pressure to obtain aluminum acetate. This aluminum acetate and diethylenetriamine 7309g (3 mol) and M+acid 90g
g (1.5 mol) was suspended in a mixture of 1 mole of ethyl alcohol and 1M toluene and heated under reflux until a homogeneous solution was obtained. This solution can be used as it is, but if it is further distilled to remove the by-product water, ethyl alcohol, and toluene, it becomes a viscous liquid containing aluminum.
A T composition is obtained. This composition is 1B45c [l and 1
It has an infrared absorption of amide at 570c-1, is insoluble in aromatic hydrocarbons, paraffinic and olefinic hydrocarbons, ethyl acetate, isopropyl ether, petroleum ether, chloroform, tetrachloride), and is insoluble in alcohols. , slightly soluble in acetone, but diethyl ether and N
, N-dimethylformamide, pyridine, dimethyl sulfoxide, terpineol, and butylcarpitol.

In addition, an aluminum-containing composition obtained by carrying out the same operation as in Example 6 except that 438 g (3 mol) of triethylenetetramine was used in place of diethylenetriamine also had infrared absorption of amide at IEi 50 cm-1 and 1585 cm-1. and the solubility in organic solvents is also that of Example 6.
It was the same.

[Effects of the Invention] The present invention is configured as described above, and its effects can be summarized as follows.

(1) Many ordinary metal complex compounds are crystalline and have low solubility in organic solvents, which limits their applications.
According to the present invention, group Ⅰ Mg, Ca, Sr, Ba, Z
n.

A metal-containing composition soluble in an organic solvent is prepared from a metal carboxylate selected from Cd, Group 1 Al, In, Y, and lanthanum-based elements, ethanolamines or aliphatic amines, and carboxylic acids. can be done.

(2) Group Ⅰ c7) Mg, Ca, Sr, Ba, Zn.

A metal-containing composition soluble in an organic solvent obtained from a metal carboxyl lv salt selected from Cd, Group Ⅰ AI, In, Y, and lanthanum-based elements, ethanolamines or aliphatic amines, and a carboxylic acid is , diethyl ether or N,N-dimethylformamide, pyridine, dimethyl sulfoxide, terpineol, butyl carpitol.
It can be extremely effectively used as a crosslinking agent for resins, a reaction catalyst, a trace additive for new glasses, etc., and as a sintering aid in the field of new ceramics.

[Brief explanation of the drawing]

FIG. 1 shows an infrared absorption spectrum of the gadolinium-containing composition obtained in Example 2.

Claims (5)

[Claims] (1) An organic solvent suspension containing at least an alcohol containing (A) a metal carboxylate, (B) ethanolamines or aliphatic amines, and (C) a carboxylic acid is heated to form a uniform A method for producing a metal-containing composition soluble in an organic solvent, the method comprising forming a composition into a solution. (2) The metal carboxylate is Group II Mg, Ca, Sr,
A method for producing a metal-containing composition soluble in an organic solvent according to claim 1, which is Ba, Zn, Cd, Group III Al, In, Y, and lanthanum-based elements. (3) Soluble in the organic solvent according to claims 1 and 2, wherein the metal carboxylate and carboxylic acid are the same or different and have carbon numbers of C_1 to C_4. A method for producing a metal-containing composition. (4) Claims 1 to 3, wherein the ethanolamine is monoethanolamine, diethanolamine, or triethanolamine, and the aliphatic amine is ethylenediamine, diethylenetriamine, or triethylenetetramine. A method for producing a metal-containing composition soluble in an organic solvent. (5) The method for producing a metal-containing composition soluble in an organic solvent according to any one of claims 1 to 4, wherein the alcohol is an alcohol having a carbon number of C_1 to C_4.