JP3356388B2 - Solid catalyst used for etherification reaction and method for producing ether compound using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a solid catalyst for an etherification reaction and a method for producing an ether compound using the same.

[0002]

2. Description of the Related Art

[0003]

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Carboxymethoxysuccinic acid (C)
Biodegradable salts (especially sodium salts) of MOS) are useful as phosphorus-free detergent builders and are known to be obtained by reacting maleic anhydride with glycolic acid (Chemical Abstract, 75). , 894
58 (1971)). This reaction is a homogeneous reaction using water-soluble calcium hydroxide (Ca (OH) ₂ ) as a catalyst in an aqueous medium. Since the product is a calcium salt, sodium carbonate (Na ₂ C
O ₃ ) to add CM
After replacing with the sodium salt of OS, a step of separating precipitated calcium carbonate (CaCO ₃ ) by filtration is essential. In addition, the above-mentioned literature describes that a hydroxide of zinc, strontium, barium and magnesium can be used instead of calcium hydroxide, but in these cases, a separation step is required.

In the same homogeneous reaction as described above, it has been reported that a lanthanoid-based ion can be used as a catalyst instead of calcium ion (J. Che).
m. Soc. Dalton Trans. , 2723-
2728 (1988)). That is, by reacting sodium glycolate and disodium maleate in an aqueous medium in the presence of water-soluble lanthanum trichloride (LaCl ₃ ), a lanthanum salt of CMOS can be obtained. In this case, it is necessary to separate lanthanum ions from the reaction product by using an ion exchange resin or the like in order to obtain a target CMOS sodium salt.

[0006]

As described above, since the conventional method is a homogeneous reaction, a step of separating calcium ions, lanthanum ions and the like after the reaction is essential. However, such a separation operation increases the number of production steps and increases the production cost. Therefore, it is desirable to omit such a step relating to the separation of the used catalyst in industrial practice.

Accordingly, the present invention solves the inevitable drawbacks of the homogeneous reaction as described above, and it is possible to produce an ether compound such as CMOS by a simple method without a step relating to catalyst separation. An object of the present invention is to provide a solid catalyst that can be used, and a method for producing an ether compound using the solid catalyst, specifically, a method for producing a corresponding ether compound from an organic compound having a hydroxyl group and an unsaturated carboxylic acid compound or an epoxy compound. Is what you do.

[0008]

According to the study of the present inventors, the borate of a rare earth element is insoluble in water, and
Knowing that the above-mentioned object can be achieved by using this rare earth element borate instead of calcium ions or lanthanum ions used as catalysts, that is, by making it a heterogeneous reaction because it has a catalytic action, Based on this finding, the present invention has been completed.

That is, the present invention is a solid catalyst for an etherification reaction in an aqueous medium, comprising a borate of a rare earth element. The present invention also provides an ether compound comprising reacting an organic compound having a hydroxyl group with an unsaturated carboxylic acid compound or an epoxy compound in the presence of a solid catalyst containing a borate of the rare earth element in an aqueous medium. It is a manufacturing method.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The rare earth element of the present invention means a lanthanoid element, scandium and yttrium. Representative examples of the lanthanoid-based elements include lanthanum, cerium, praseodymium, neodymium, and the like. Of these, lanthanum is particularly preferably used.

The rare earth element borate is, for example, Ze
sz. Nauk. Politech. Slsk. , C
hem. (1979), (88), 178-9, or Chemical Abstractr
t, 99 , 98109. That is, borate of rare earth element is
It is obtained as a precipitate formed by mixing a solution containing a salt of a rare earth element with boric acid, or by firing a mixture of a rare earth oxide and boric acid at 800 to 1200 ° C. In the present invention, for example,
When borate is obtained in aqueous solution from chloride of rare earth element and boric acid, the obtained solid can be used as a catalyst in any state from dry to wet after filtration and washing. It is. Examples of the salts of rare earth elements include lanthanum chloride, lanthanum nitrate, cerium chloride, cerium nitrate, and hydrates thereof. Examples of the boric acid source include orthoboric acid, metaboric acid, tetraboric acid, and organic boric acid represented by RB (OH) ₂ (R: alkyl group, phenyl group, and substituted phenyl group) (a typical example is dihydroxy boric acid). Methylborane, dihydroxyethylborane, dihydroxyphenylborane, etc.) and their salts (ammonium salt, sodium salt)
Etc. can be used.

In the case where lanthanum chloride and boric acid or a salt thereof are used as raw materials,
It is preferable to use boric acid or a salt thereof in a range of 0.05 to 5 mol, preferably 0.1 to 2 mol. Depending on the preparation conditions, several types of borates (ortho borates, meta borates, tetra borates, etc.) can be obtained, but compounds of any composition or mixtures thereof are effective in the present invention. The rare earth element borate used has a purity of 100
%, And the solid obtained as a precipitate in the above reaction can be used as it is without going through a purification step.

Specific examples of the organic compound having a hydroxyl group used in the method of the present invention include a hydroxycarboxylic acid compound, a polyhydric alcohol compound, a higher alcohol compound having 6 to 22 carbon atoms, and a saccharide.
The details of these organic compounds are as follows. (1) Hydroxycarboxylic acid compound (a) Compound represented by the following general formula (1)

[0014]

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Wherein R ¹ and R ² are each independently
X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom,
Represents an ammonium group, an alkyl ammonium group or an alkanol ammonium group, and m represents an integer of 1 to 10. Representative examples include glycolic acid, β-hydroxypropionic acid, lactic acid, and the like.

(B) a compound represented by the following general formula (2)

[0017]

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In the formula, R ³ is a hydrogen atom or a group having 1 to 3 carbon atoms.
Wherein n represents an integer of 1 to 10, and X has the same meaning as in formula (1). Typical examples thereof include glyceric acid and gluconic acid. (C) a compound represented by the following general formula (3) HO—CH ₂ — (CH ₂ —O—CH ₂ ) _P —COOX (3) In the formula, p represents an integer of 1 to 10, X has the same meaning as in general formula (1). Typical examples thereof include diethylene glycol monocarboxylic acid.

(D) a compound represented by the following general formula (4)

[0020]

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Wherein R ⁴ and R ⁵ are each independently
It represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁶
Represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a hydroxyl group, and X has the same meaning as in formula (1). Typical examples thereof include malic acid and tartaric acid. (E) a compound represented by the following general formula (5)

[0022]

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In the formula, R ⁷ is a hydrogen atom or a group having 1 to 3 carbon atoms.
Wherein X is as defined in general formula (1). A typical example thereof is tartronic acid. (F) a compound represented by the following general formula (6)

[0024]

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In the formula, R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X has the same meaning as in the general formula (1). is there. A typical example is citric acid. (2) Polyhydric alcohol compound (a) Compound represented by the following general formula (7)

[0026]

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In the formula, R ^{12 to} R ¹⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Typical examples thereof include ethylene glycol and isopropylene glycol. (B) Condensate of 2 to 10 of the compound of the general formula (7) As a typical example thereof, diethylene glycol and the like can be mentioned.

(C) Glycerin and its derivatives Representative examples thereof include glycerin, diglycerin, polyglycerin and the like. (D) sorbitol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, etc. (3) higher alcohol compounds having 6 to 22 carbon atoms (RO
H) As typical examples, R is hexyl, heptyl, octyl, nonyl, decyl, undecyl, lauryl, myristyl, palmityl, stearyl, arachidyl, behenyl,
Alcohols such as oleyl, linole, linolenyl, 2-ethylhexyl and the like can be mentioned. (4) Sugars Representative examples thereof include glucose, mannose, galactose, fructose, lactose, and sucrose.

Specific examples of the unsaturated carboxylic acid compound used in the method of the present invention include unsaturated monocarboxylic acids and unsaturated dicarboxylic acids. These will be described more specifically below. (1) Unsaturated monocarboxylic acid compound (a) Compound represented by the following general formula (8)

[0030]

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In the formula, R ^{16 to} R ¹⁸ each independently represent
X represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms;
Has the same meaning as in formula (1). Typical examples thereof include acrylic acid and methacrylic acid. (2) Unsaturated dicarboxylic acid compound (a) Compound represented by the following general formula (9)

[0032]

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In the formula, R ¹⁹ and R ²⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X has the same meaning as in formula (1). A typical example is maleic acid.
The unsaturated dicarboxylic acid may be an anhydride. Specific examples of the epoxy compound used in the method of the present invention include the following compounds. (1) Compound represented by the following general formula (10)

[0034]

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In the formula, R ^{21 to} R ²⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or — (C
H ₂ ) _n -COOX (where n is an integer of 0 to 10 and X is as defined in general formula (1)), at least one of which is-(CH ₂ ) _n -COOX It is. Typical examples thereof include glycidic acid and epoxy succinic acid.

In a preferred embodiment of the present invention, glycolic acid, in the presence of a borate of a rare earth element in an aqueous medium,
hydroxycarboxylic acids such as β-hydroxypropionic acid, lactic acid, glyceric acid, gluconic acid, diethylene glycol monocarboxylic acid, malic acid, tartaric acid, tartronic acid and citric acid; ethylene glycol, isopropylene glycol, diethylene glycol, glycerin, diglycerin, poly Polyhydric alcohols such as glycerin, sorbitol, 1,4-sorbitan, pentaerythritol, dipentaerythritol; higher alcohols having 6 to 22 carbon atoms; and glucose, mannose, galactose,
At least one compound (A) selected from sugars such as fructose, lactose and sucrose and an unsaturated monocarboxylic acid such as acrylic acid and methacrylic acid; and (anhydrous)
The compound (B) is reacted with at least one compound selected from unsaturated dicarboxylic acids such as maleic acid, or the compound (A) is reacted with an epoxy compound (C) such as glycidic acid or epoxy succinic acid. To produce the corresponding ether compound. In a particularly preferred embodiment,
Among the above compounds (A), glycolic acid, malic acid,
The corresponding ether compound is produced by reacting tartaric acid or tartronic acid with (anhydride) maleic acid of the above compound (B) or with epoxysuccinic acid of the above compound (C).

In the present invention, the reaction formula between the organic compound (A) having a hydroxyl group and the unsaturated carboxylic acid (B) or the epoxy compound (C) is defined as glycolic acid as the compound (A) and maleic acid as the compound (B). The case where epoxy succinic acid is used as compound (C) is shown below as an example. Reaction of glycolic acid with maleic acid

[0038]

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Reaction of glycolic acid with epoxy succinic acid

[0040]

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The production method of the present invention usually comprises 40 to 150
C., and preferably at a temperature in the range of 70 to 120.degree. The reaction pressure may be normal pressure or pressurization, but the reaction is usually performed under normal pressure. About the ratio of the organic compound (A) having a hydroxyl group to the unsaturated carboxylic acid (B) or the epoxy compound (C), the ratio is usually (A)
The molar ratio of / (B) or (A) / (C) should be in the range of 0.5 to 2, preferably 0.8 to 1.2. The amount of the solid catalyst containing a borate of a rare earth element is usually 0.0001 to 5 mol, preferably 0.005 to 5 mol per mol of the organic compound (A) having a hydroxyl group.
It can be appropriately selected in the range of 2 mol.

When the organic compound (A) having a hydroxyl group is reacted with the unsaturated carboxylic acid (B) according to the production method of the present invention, a part or all, preferably all of each carboxyl group is converted to an alkali metal salt. , Especially as a sodium salt. Specifically, when manufacturing CMOS by reacting glycolic acid and maleic anhydride, it is preferable to react as sodium glycolate and disodium maleate, respectively. As a product, trisodium salt of CMOS (CMOS-3N
An aqueous solution of a) is obtained, and depending on the use, may be an aqueous solution or a solid obtained by distilling off water.

In the reaction between compound (A) and compound (B),
The reaction solution is neutralized or alkaline, and specifically, the pH of the reaction solution is usually 6 or more, preferably 6 to 13,
More preferably, the reaction is performed after adjusting to 7.5 to 12.5. Even when the pH of the reaction solution is 6 to 9, the etherification reaction can be performed more stably and with a high yield. For adjusting the pH, sodium hydroxide is particularly preferably used.

Similarly to the above reaction, when the organic compound (A) having a hydroxyl group is reacted with the epoxy compound (C), a part or all, preferably all, of each carboxyl group is preferably an alkali metal salt, especially The reaction is preferably performed as a sodium salt. Specifically, when producing carboxymethoxymalic acid (CMOM) by reacting glycolic acid and epoxy succinic acid, it is preferable to react as sodium glycolate and disodium epoxy succinate, respectively. The product is CMOM
An aqueous solution of trisodium salt (CMOM-3Na) is obtained. Depending on the use, an aqueous solution or a solid obtained by distilling off water may be used. Similar to the above reaction,
The reaction solution is neutralized or alkaline, and specifically, the pH of the reaction solution is usually 6 or more, preferably 6 to 13,
More preferably, the reaction is performed after adjusting to 7.5 to 10.5. Even when the pH of the reaction solution is 6 to 9, the etherification reaction can be performed more stably and with a high yield. For adjusting the pH, sodium hydroxide is particularly preferably used.

The production method of the present invention may be either a continuous method or a batch method, but by conducting the reaction in a continuous manner, the desired ether compound can be produced with high productivity. The ether compound, which is a reaction product, is separated from the solid catalyst contained in the reaction solution after the reaction using ordinary solid-liquid separation means such as filtration and centrifugation, and is easily isolated from the obtained separation solution. it can. As a method for isolating the ether compound from the separated liquid, for example, a method in which an aqueous medium contained in the separated liquid is distilled off under normal pressure or reduced pressure and the mixture is evaporated to dryness, or the separated liquid is kept under normal pressure or reduced pressure And the ether compound is precipitated as a precipitate.

Among the ether compounds obtained by the production method of the present invention, CMOS, CMOM, and the like, and alkali metal salts thereof, particularly sodium salts, have biodegradability and have excellent metal ion trapping performance. Therefore, it is useful as a detergent builder.

[0047]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. Example 1 (Preparation of lanthanum borate) Lanthanum chloride heptahydrate
2 g are dissolved in 200 g of water and 12.4 orthoboric acid is dissolved.
g, and the pH was adjusted to 11 with a 48% aqueous sodium hydroxide solution.
After being adjusted to the vicinity, stirring was performed at a temperature of 50 ° C. for 1 hour. The resulting precipitate was filtered, washed with water several times, and dried under reduced pressure to obtain 42.5 g of a white solid. From the result of the X-ray diffraction analysis, it was confirmed that the solid product (LB-1) contained a lanthanum borate structure. Example 1-1 (Etherification reaction) After dissolving 9.8 g of maleic anhydride and 7.6 g of glycolic acid in 200 g of water, 12.0 g of sodium hydroxide was added. Example 1 was added to this solution.
After adding 21.25 g of LB-1 obtained in the above, and further adjusting the pH at the start of the reaction to 8, the reaction was carried out at 95 ° C. with stirring for 6 hours. After the completion of the reaction, the solid catalyst LB-1
The reaction solution was filtered in order to separate the product, and the filtrate was evaporated to dryness. The obtained white crystals were analyzed by ¹ H-NMR and ¹³ C-NMR.
And confirmed that the product was carboxymethoxysuccinic acid trisodium salt (CMOS-3Na). Further, when the filtrate was analyzed by high performance liquid chromatography, the yield of CMOS-3Na was 54.3 mol% (based on maleic anhydride).

When the filtrate was analyzed by ICP, the concentration of rare earth metal ions in the filtrate was 15 ppm or less. Examples 1-2 to 1-5 (Etherification reaction) The same procedures as in Example 1-1 were carried out except that the amount of LB-1 added and the pH at the start of the reaction were changed to the values shown in Table 1. Similarly, the reaction is performed, and CMOS-3
Na was obtained. The yield of the obtained CMOS-3Na and the rare earth metal ion concentration in the filtrate were as shown in Table 1. Example 2 (Preparation of lanthanum borate) A lanthanum borate was prepared in the same manner as in Example 1 except that the amount of orthoboric acid was changed to 6.2 g. The resulting precipitate was filtered, washed with water several times, and dried under reduced pressure to obtain 40.2 g of a white solid. From the result of the X-ray diffraction analysis, it was confirmed that the solid product (LB-2) contained a lanthanum borate structure. Example 2-1 (Etherification reaction) In Example 1-1, LB-1 was added to 21.
Instead of adding 25 g, LB-2 obtained in Example 2 was used.
Was performed in the same manner as in Example 1-1, except that 2.01 g of was added and the pH was changed to 12 at the start of the reaction.
-3Na was obtained. The yield of the obtained CMOS-3Na and the rare earth metal ion concentration in the filtrate were as shown in Table 1. Example 3 (Preparation of cerium borate)
Cerium borate was prepared in the same manner as in Example 1 except that 74.2 g of the hydrate was changed to 74.5 g of cerium chloride heptahydrate. The resulting precipitate was filtered, washed with water several times, and dried under reduced pressure to obtain 43.2 g of a white solid. This solid product (CB-1) was obtained from the result of its X-ray diffraction analysis.
It was confirmed that it contained the structure of cerium borate. Examples 3-1 to 3-2 (Etherification reaction) In Example 1-1, LB-1 was converted to 21.
Instead of adding 25 g, the CB-1 obtained in Example 3 was used.
, And the reaction was carried out in the same manner as in Example 1-1, except that the pH at the start of the reaction was changed to the value shown in Table 1.
CMOS-3Na was obtained. The yield of the obtained CMOS-3Na and the concentration of rare earth metal ions in the filtrate were as shown in Table 1.

[0049]

[Table 1]

[0050]

By using the solid catalyst of the present invention, a heterogeneous reaction can be carried out instead of the conventional homogeneous reaction. Therefore, the catalyst can be easily separated after the reaction, and the reaction process can be simplified. Further, since the solid catalyst can be used even in a neutral region (pH 6 to 9) of the reaction solution in the etherification reaction, the etherification reaction can be performed more stably with a high yield.

According to the method of the present invention, in an aqueous medium, in the presence of a solid catalyst containing a borate of the rare earth element,
By reacting an organic compound having a hydroxyl group with an unsaturated carboxylic acid compound or an epoxy compound, the corresponding ether compound can be efficiently produced without requiring a further step such as separation of a catalyst after the reaction.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI // C07B 61/00 300 C07B 61/00 300 (72) Inventor Kazuo Sagi 5-8 Nishiminaburicho, Suita-shi, Osaka, Japan (72) Inventor Yoshiyuki Takahashi 5-8, Nishimitabi-cho, Suita-shi, Osaka Japan Co., Ltd. (56) References JP-A-5-186217 (JP, A) US Patent 5130435 (US, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) B01J 21/00-38/74 C07C 41/00-43/32

Claims (3)

(57) [Claims] 1. A solid catalyst for use in an etherification reaction in an aqueous medium, comprising a borate of a rare earth element. 2. A method for producing an ether compound, comprising reacting an organic compound having a hydroxyl group with an unsaturated carboxylic acid compound or an epoxy compound in an aqueous medium in the presence of the solid catalyst according to claim 1. 3. The method for producing an ether compound according to claim 2, wherein the solid catalyst is separated from the reaction solution after the reaction, and an ether compound is obtained from the separated solution.