JP3374359B2 - Method for producing ether compound using solid catalyst - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to a process for the preparation of ether compound using solid bodies catalysts. More particularly, the present invention is a rare earth element in an aqueous medium in the presence of including solid bodies catalysts, corresponding ether by reacting an organic compound having a hydroxyl group and an unsaturated carboxylic oxide <br/> compound A method of making a compound.

[0002]

[Prior art]

The following formula

[0003]

[Chemical 1]

Carboxymethoxysuccinic acid (C
It is known that biodegradable salts (especially sodium salts) of MOS) are useful as phosphorus-free detergent builders, and that these compounds are obtained by reacting maleic anhydride with glycolic acid (chemicals). -Abstract, 75 , 89458 (1971)). This reaction is carried out by using water-soluble calcium hydroxide (Ca (O
H) ₂ ) is a homogeneous reaction, and since the product is a calcium salt, sodium carbonate (Na ₂ CO ₃ ) is added after the reaction to precipitate calcium carbonate (CaCO ₃ ). The step of separating the intended sodium salt of CMOS by filtration is essential. In addition, it is described in the above literature that hydroxides of zinc, strontium, barium and magnesium can be used instead of calcium hydroxide.

Further, it has been reported that in the same homogeneous reaction as described above, ions of lanthanoid elements can be used as catalysts instead of calcium ions (J.C.
hem. Soc. Dalton Trans. 272
3-2728 (1988)). That is, by reacting sodium glycolate and disodium maleate in an aqueous medium in the presence of lanthanum trichloride (LaCl ₃ ),
It is said that a lanthanum salt of CMOS can be obtained. Therefore, in order to obtain the intended sodium salt of CMOS, it is necessary to separate the lanthanum ion from the reaction product using an ion exchange resin or the like.

[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, if such a separation operation is performed, the number of manufacturing steps increases, which in turn increases the manufacturing cost.
In industrial practice, it is desirable to omit the step related to the separation of the catalyst used.

The present invention solves the above-mentioned unavoidable drawbacks in the conventional homogeneous reaction, and produces an ether compound such as CMOS by a simple method without a special step relating to catalyst separation. mETHOD fOR pRODUCING be ether compound using solid catalysts capable of, specifically intended to provide a method for producing a corresponding ether compound and an organic compound and an unsaturated carboxylic acid compound having a hydroxyl group.

Accordingly, purpose is the present invention, the presence of a solid catalyst containing a rare earth in an aqueous medium, an organic compound and an unsaturated carboxylic acid compound having a hydroxyl group is reacted, the corresponding ether compounds, It is to provide a simple and efficient manufacturing method.

[0009]

According to the research conducted by the present inventors, a rare earth element oxide or a rare earth element phosphate is used in place of calcium ion or lanthanum ion used as a catalyst in a conventional homogeneous reaction. (However, lanthanum phosphate is excluded), phosphonate of rare earth element, or using a solid catalyst in which a rare earth element is supported on a resin substrate having a phosphate group, that is, by a heterogeneous reaction,
Knowing that the above object can be achieved, the present invention has been completed based on this finding.

That is, the present invention provides a dilute solution in an aqueous medium.
Oxides of earth elements, phosphates of rare earth elements (however,
Phosphonic acid of rare earth elements)
Rare earth elements are added to resin bases that have salts and phosphate groups.
In the presence of a solid catalytic including at least one selected from the group consisting of those carrying a process for the preparation of an organic compound and an unsaturated carboxylic acid compound and an ether compound which comprises reacting a having a hydroxyl group.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention , the rare earth element is
Means the lanthanide series elements scandium and yttrium. Typical examples of the lanthanoid element include lanthanum, cerium, praseodymium, and neodymium. Among them, lanthanum is particularly preferably used.

In the present inventionRuTouchMedium, Rare earth element
Oxide of Rare earth element phosphate (provided that lanthanum
(Excluding phosphate), Rare earth phosphonate,And
And Rare earth element supported on resin substrate with phosphate group
thingContains at least one selected from the group consisting of.Since
Below, the solid catalyst in the present invention is simply referred to as "rare earth element
It may be referred to as a "comprising solid catalyst".Rare earth oxides
Are commercially available, and in the present invention, these commercially available rare compounds are used.
Earth element oxides can be used.

Typical examples of the oxides of the rare earth elements are Y ₂ O ₃ , La ₂ O ₃ , Nd ₂ O ₃ , Pm ₂ O ₃ , Sm ₂ O ₃ , Eu ₂ O ₃ ,
Ga ₂ O ₃ , Dy ₂ O ₃ , Ho ₂ O ₃ , Er ₂ O ₃ , Tm ₂ O ₃ , Yb ₂ O ₃ , Lu
₂ O _{3 and the} like can be mentioned. Phosphates of rare earth elements are, for example, Bulletin of Chemica
l Society of Japan, Vol. 51
(12), 3645-3646 (1978). Specifically, in the case of cerium phosphate (CePO ₄ ), it can be easily obtained by reacting cerium trichloride with orthophosphoric acid or a salt thereof (such as sodium dihydrogen phosphate) in an aqueous medium. This phosphate is usually obtained as a hydrate, but any hydrate can be used in the present invention. The reaction temperature for carrying out the above reaction is not particularly limited and can be appropriately selected usually from the range of 20 to 90 ° C. The ratio of the rare earth element chloride to orthophosphoric acid or its salt is 0.1 to 3 moles, preferably 0.2 to 1 mole, relative to 1 mole of the rare earth element chloride.
It is preferable to use orthophosphoric acid or a salt thereof in the range of 1.5 mol. The solid phosphate of rare earth element is obtained by reacting with stirring for a predetermined time and then filtering the precipitate. The phosphate thus obtained can be used in any state from wet ones after filtration and washing to dried ones. The rare earth element phosphate used in the present invention does not have to have a purity of 100%, and the rare earth element phosphate obtained as a precipitate in the above reaction is used as it is without undergoing a particular purification step. be able to.

Typical examples of the above-mentioned phosphates of rare earth elements include YPO ₄ , CePO ₄ , PrPO ₄ , NdPO ₄ , PmPO ₄ , SmPO ₄ , and E.
uPO ₄ , GdPO ₄ , TbPO ₄ , DyPO ₄ , HoPO ₄ , ErPO ₄ , TmP
O ₄ , YbPO ₄ , LuPO _{4 and the} like can be mentioned. Rare earth phosphonates, such as lanthanum phosphonates, can be prepared in the same manner as the cerium phosphates described above, except that lanthanum and phosphonic acid are used instead of cerium and phosphoric acid, respectively. The ratio of rare earth element chloride and phosphonic acid used is 0.5 to 2.5 mol, preferably 1 to 1 mol of phosphonic acid.
It is preferred to use rare earth chlorides in the range of up to 2 moles.
Further, similarly to the phosphate, the usage state of the phosphonate is not particularly limited and may be any from wet to dried.

A resin having a phosphoric acid group, more specifically, a resin having a phosphon group (-PO ₃ H ₂ ) and / or a phosphine group (-PH ₂ O ₂ ) (in the present invention, these are collectively referred to as a phosphoric acid group). A solid catalyst in which a rare earth element is supported on a substrate (called a resin) is
For example, Journal of Applied Po
Lymer Science, Vol. 52,1153
It can be prepared by the method described in -1164 (1994). As a typical example of the resin substrate having a phosphate group, the following repeating unit:

[0016]

[Chemical 2]

A resin (A) having the following repeating units:

[0018]

[Chemical 3]

A resin (B) having the following repeating units:

[0020]

[Chemical 4]

A resin (C) having the following repeating units:

[0022]

[Chemical 5]

Examples thereof include a resin (D) having All of these resins are known ones described in the above-mentioned documents and the like. Styrene and divinylbenzene are used as starting materials, and these are subjected to suspension polymerization in an organic solvent to produce a resin (I). I) and ether chloride are reacted in the presence of aluminum trichloride to produce a resin (II), which is subsequently reacted with phosphorus trichloride in the presence of aluminum trichloride and then hydrolyzed. Then, the resin (C), and further, the resin (C) is oxidized with nitric acid to obtain the resin (D). Alternatively, the resin (I) is reacted with phosphorus trichloride in the presence of aluminum trichloride, then hydrolyzed to give the resin (A), and further the resin (A) is oxidized with nitric acid to obtain the resin (B). Is obtained.

The degree of crosslinking can be adjusted by changing the amount of divinylbenzene used with respect to styrene. The porosity can be adjusted by appropriately adding, for example, 2,2,4-trimethylpentane as a foaming agent in the suspension polymerization of styrene and divinylbenzene. In order to support the rare earth element on the resins (A) to (D), it is sufficient to bring the rare earth element ion into contact with the resin. Specifically, the rare earth element chloride is added to an aqueous solution of lanthanum trichloride. Each resin may be thoroughly dried, added, and sufficiently contacted, and then separated. The conditions such as the concentration of the rare earth element chloride and the contact temperature at this time can be appropriately determined according to the desired amount of the rare earth element supported.

The amount of the rare earth element supported on each of the above resins varies depending on the degree of crosslinking, but is usually 0.5 mm per 1 g of the resin.
It is preferable to support rare earth elements of ol or more. The amount of the rare earth element supported can be easily obtained by measuring the difference in the rare earth element ion concentration in the aqueous solution before and after the contact with the resin. The above-mentioned rare earth oxides, rare earth phosphates (excluding lanthanum phosphates), rare earth phosphonates, and solid catalysts having a rare earth element supported on a resin substrate having a phosphate group may be used alone. Well, or two or more kinds may be appropriately combined and used.

According to the method of the present invention, in an aqueous medium in the presence of a solid catalyst containing the above rare earth elements, by reacting an organic compound having a hydroxyl group and an unsaturated carboxylic acid compound, the corresponding ether The compound can be efficiently produced without requiring an additional step such as separation of the catalyst after the reaction. Specific examples of the organic compound having a hydroxyl group include a hydroxycarboxylic acid compound, a polyhydric alcohol compound, a higher alcohol compound having 6 to 22 carbon atoms, and a saccharide. The organic compounds will be described in more detail below. (1) Hydroxycarboxylic acid compound (a) A compound represented by the following general formula (1).

[0027]

[Chemical 6]

In the formula, R ¹ and R ² are each independently
Represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom,
It represents an ammonium group, an alkylammonium group or an alkanolammonium group, and m represents an integer of 1 to 10. Typical examples thereof include glycolic acid, β-hydroxypropionic acid and lactic acid.

(B) A compound represented by the following general formula (2).

[0030]

[Chemical 7]

In the formula, R ³ is a hydrogen atom or has 1 to 3 carbon atoms.
In the formula, 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 - in _{(CH 2 -O-CH 2)} P -COOX ··· (3) formula, p represents an integer of 1 to 10, X is the same as that in general formula (1). A typical example thereof is diethylene glycol monocarboxylic acid.

(D) A compound represented by the following general formula (4).

[0033]

[Chemical 8]

In the formula, R ⁴ and R ⁵ are each independently
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).

[0035]

[Chemical 9]

In the formula, R ⁷ is a hydrogen atom or has 1 to 3 carbon atoms.
Represents an alkyl group, and X has the same meaning as in formula (1). A typical example thereof is tartronic acid. (F) A compound represented by the following general formula (6).

[0037]

[Chemical 10]

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 formula (1). is there. Typical examples thereof include citric acid and the like. (2) Polyhydric alcohol compound (a) A compound represented by the following general formula (7).

[0039]

[Chemical 11]

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) 2 to 10 condensates of the compound of the general formula (7). Typical examples thereof include diethylene glycol.

(C) Glycerin and its derivatives. Typical examples thereof include glycerin, diglycerin, polyglycerin and the like. (D) Sorbitol, 1,4-sorbitan, pentaerythritol, dipentaerythritol and the like. (3) Higher alcohol compound having 6 to 22 carbon atoms (RO
H).

As typical examples thereof, R is hexyl, heptyl, octyl, nonyl, decyl, undecyl, lauryl, myristyl, palmityl, stearyl, arachidyl, behenyl, oleyl, linole, linolenyl, 2-
Alcohols such as ethylhexyl can be mentioned. (4) Sugar.

[0043] Typical examples thereof may be mentioned glucose, mannose, galactose, full Kutosu, lactose, sucrose and the like. Specific examples of the unsaturated carboxylic acid compound include unsaturated monocarboxylic acid and unsaturated dicarboxylic acid. The following is a more detailed description of these. (1) Unsaturated monocarboxylic acid compound (a) A compound represented by the following general formula (8).

[0044]

[Chemical 12]

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

[0046]

[Chemical 13]

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 thereof is maleic acid.
The unsaturated dicarboxylic acid may be an anhydride .

[0048]

[0049]

Therefore, in a preferred embodiment of the present invention, a rare earth element oxide, a rare earth element phosphate (excluding lanthanum phosphate), a rare earth element phosphonate or phosphorus is used in an aqueous medium. (A) glycolic acid, β-hydroxypropionic acid, lactic acid, glyceric acid, gluconic acid, diethylene glycol monocarboxylic acid, malic acid, tartaric acid, tartron in the presence of a solid catalyst in which a resin substrate having an acid group supports a rare earth element. Hydroxycarboxylic acids such as acid and citric acid; ethylene glycol, isopropylene glycol, diethylene glycol, glycerin, diglycerin, polyglycerin, sorbitol,
Polyhydric alcohols such as 1,4-sorbitan, pentaerythritol and dipentaerythritol; carbon number 6 to 22
Higher alcohols; and at least one compound selected from sugars such as glucose, mannose, galactose, fructose, lactose, and sucrose; and (B) unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid; and (anhydrous) maleic acid. It is reacted with at least one compound selected from unsaturated dicarboxylic acids such as acid producing pairs <br/> response to ether compound. In a particularly preferred embodiment, glycolic acid among the compounds of (A) above,
Malic acid, to produce a tartaric acid or the corresponding ether compound and maleic acid (anhydride) by reaction of the compound of tartronic acid and the (B).

The reaction formula of the organic compound having a hydroxyl group (A) and the unsaturated carboxylic acid (B) in the present invention is as follows:
An example of using glycolic acid as (A) and maleic acid as (B) is as follows. Reaction of glycolic acid with maleic acid

[0052]

[Chemical 15]

[0053]

[0054]

The production method of the present invention is usually 40 to 150.
It is good to carry out at a temperature in the range of ℃, preferably in the range of 70 to 120 ℃. The reaction pressure may be either normal pressure or increased pressure, but the reaction is usually carried out under normal pressure. Regarding the ratio of (A) the organic compound having a hydroxyl group to (B) the unsaturated carboxylic acid, the molar ratio of (A) / (B ) is usually 0.5 to
It is preferable to set it in the range of 2, preferably 0.8 to 1.2. The amount of the solid catalyst containing a rare earth element to be used can be appropriately selected usually in the range of 0.1 to 5 mol, preferably 0.5 to 2 mol, per 1 mol of the (A) hydroxyl group-containing organic compound.

When the organic compound having a hydroxyl group (A) 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 an alkali metal salt. , Especially as the sodium salt. Specifically, when a CMOS is manufactured by reacting glycolic acid and maleic anhydride, it is preferable to react them as sodium glycolate and disodium maleate, respectively. Trisodium salt of CMOS as a product (CMOS-3N
Although the aqueous solution of a) is obtained, it may be either an aqueous solution or a solid obtained by distilling off water depending on its use. Further, the reaction solution is made alkaline, and specifically, the pH of the reaction solution is adjusted to 7.5 or more, preferably 7.5 to 13, and the reaction is performed. Sodium hydroxide is particularly preferably used for adjusting the pH.

[0057]

The method of the present invention may be a continuous system or a batch system, but particularly by carrying out the reaction in a continuous system, the desired ether compound can be produced with high productivity. Among the ether compounds obtained by the method of the present invention, CMOS, CMOM and the like, and their alkali metal salts, especially sodium salts, are biodegradable and have excellent metal ion scavenging performance, and therefore, they are used as detergent builders. It is useful.

[0059]

EXAMPLES The present invention will be described in more detail below with reference to examples. Example 1 (Preparation of cerium phosphate) Cerium chloride heptahydrate 14
After dissolving 9.06 g in 200 g of water, 143.2 g of disodium hydrogen phosphate dodecahydrate was added, and the pH was adjusted to around 9 with a 48% sodium hydroxide aqueous solution, and then 50
The reaction was carried out at a temperature of ° C for 1 hour. After the reaction was completed, the formed precipitate was filtered, washed with water several times and dried under reduced pressure to obtain 110.2 g of a white solid. From the result of the X-ray diffraction analysis, it was confirmed that this solid product contained the structure of cerium phosphate. (Etherification reaction) Maleic anhydride 9.8 g was added to water 200
After dissolving in g, 7.6 g of glycolic acid was added, and further 12.0 g of sodium hydroxide was added. 27.6 g of the above cerium phosphate was added to this solution, and the pH was adjusted to 1
After adjusting to around 0, the reaction was carried out at 90 ° C. under stirring for 24 hours. After completion of the reaction, the reaction solution was filtered, and the filtrate was analyzed by high performance liquid chromatography to find that carboxymethoxysuccinic acid trisodium salt (CMOS-3Na)
Was obtained in a yield of 34.5 mol% (based on maleic anhydride). The white crystal obtained by evaporating the filtrate to dryness was analyzed by ¹ H-NMR and ¹³ C-NMR, and as a result, it was confirmed that the main component was CMOS-3Na.

When the filtrate was analyzed by ICP, the concentration of cerium ions in the filtrate was 0.5 ppm or less. Example 2 (Preparation of Yttrium Phosphate) In the preparation of cerium phosphate of Example 1, the reaction was carried out in the same manner except that yttrium chloride hexahydrate was used instead of cerium chloride heptahydrate to prepare phosphoric acid. 92.8 g of yttrium was obtained. (Etherification reaction) In the same manner as in Example 1, except that 23.2 g of yttrium phosphate was used in place of 27.6 g of cerium phosphate and the reaction time was 12 hours in the etherification reaction of Example 1. Then, an etherification reaction was carried out to obtain CMOS-3Na in a yield of 12 mol%.

When the filtrate was analyzed in the same manner as in Example 1, the yttrium ion concentration in the filtrate was 0.1.
It was below ppm. Example 3 An etherification reaction was carried out using commercially available lanthanum oxide, neodymium oxide and yttrium oxide as oxides of rare earth elements.

In the etherification reaction of Example 1, the etherification reaction was carried out in the same manner as in Example 1 except that lanthanum oxide, neodymium oxide and yttrium oxide were used instead of cerium phosphate and the reaction time was 12 hours. It was Table 1 shows the amounts of lanthanum oxide, neodymium oxide and yttrium oxide added and the yields in each case.
When the filtrate was analyzed in the same manner as in Example 1, the metal ion concentration in the filtrate was 5 ppm or less in all cases.

[0063]

[Table 1]

Example 4 9.8 g of maleic anhydride was dissolved in 200 g of water, 15.0 g of tartaric acid was added, and sodium hydroxide 16.
0 g was added. 27.6 g of the cerium phosphate obtained in Example 1 was added to this solution, the pH was further adjusted to around 10, and the reaction was carried out at 90 ° C. for 24 hours with stirring. After the reaction was completed, the reaction solution was filtered, and the filtrate was analyzed by high performance liquid chromatography to obtain tartaric acid monosuccinic acid tetrasodium salt (TMS-4Na) at a yield of 16.4 mol% (based on maleic anhydride). I found out that In addition,
The white crystals obtained by evaporating the filtrate to dryness were converted into ¹ H-NM.
As a result of analysis by R and ¹³ C-NMR, it was confirmed that the crystal contained TMS-4Na.

When the filtrate was analyzed in the same manner as in Example 1, the cerium ion concentration was 1 ppm or less. Example 5 In Example 4, instead of cerium phosphate, Example 2 was used.
The etherification reaction was carried out in the same manner as in Example 4 except that the yttrium phosphate obtained in 1 above and the commercially available lanthanum oxide and neodymium oxide were used. Table 2 shows the amounts of yttrium phosphate, lanthanum oxide and neodymium oxide added and the yields in each case.

[0066]

[Table 2]

[0067]

INDUSTRIAL APPLICABILITY In the present invention , by using a solid catalyst containing a rare earth element , a heterogeneous reaction can be carried out instead of the conventional homogeneous reaction. Therefore, the catalyst after the reaction can be easily separated, and the reaction process can be simplified.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ identification code FI C07C 59/305 C07C 59/305 (56) Reference JP-A-6-228038 (JP, A) JP-A-7-223987 (JP , A) JP 54-14910 (JP, A) JP 63-72640 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) B01J 21/00 -38/74 C07C 51/367 C07C 59/305 JISST file (JOIS)

Claims (2)

(57) [Claims] 1. An oxide of a rare earth element in an aqueous medium ,
Rare earth element phosphate (excluding lanthanum phosphate
), Phosphonates of rare earth elements, and phosphate groups
Consist of a rare earth element supported on a resin base having
At least one in the presence of a solid catalytic including, process for producing an organic compound with an unsaturated carboxylic acid compound and an ether compound which comprises reacting a having a hydroxyl group selected from the group. 2. The amount of the solid catalyst used contains the hydroxyl group.
0.1 to 5 mol per mol of the organic compound
Item 2. A method for producing an ether compound according to Item 1 .