JP2000178288A - Production of phosphoric triester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a phosphoric triester through efficiently removing alkali metal halide(s) as byproduct formed during the production process. SOLUTION: This phosphoric triester is obtained by reaction of an organic hydroxy compound of the formula R1-O(AO)n-H (R1 is a 1-12C alkyl; A is a 2C or 3C alkylene; n is a number as the average addition number of moles of the alkylene oxide, being 1-10) with a phosphorylating agent followed by neutralization to produce a reaction mixture containing the aimed phosphoric triester, which is then washed with an aqueous solution of an inorganic salt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a process for producing a phosphoric acid triester for efficiently removing and purifying an alkali metal halide by-produced during the production of a phosphoric acid triester by reacting an organic hydroxy compound with a phosphorylating agent. About the law.

[0002]

BACKGROUND OF THE INVENTION Phosphoric triesters having an alkyloxyalkylene group are:
Because of its high polarity, excellent skin affinity, low viscosity, low boiling point, and excellent safety, it is known to be used for cosmetics, external preparations, and the like (JP-A-9-241119). As a method for producing such a phosphoric acid triester having an alkyloxyalkylene group, a method of reacting an organic hydroxy compound having an alkyloxyalkylene group with a phosphorylating agent such as phosphorus oxyhalide is known.

[0003] In the above reaction, hydrogen halide is by-produced in the reaction system. However, the hydrogen halide has a high solubility in the phosphoric acid triester, which is a target substance, having a high polarity, and the reaction system has a high solubility. Remains inside. Therefore, an alkali metal halide is generated in the next neutralization step.
Since the alkali metal halide is insoluble in the phosphoric acid triester, if it remains in the target product, the resulting final product is not uniform, which is not preferable. Therefore, it is necessary to remove the alkali metal halide by means such as filtration in the process of producing the phosphoric acid triester.

However, particularly when the residual ratio of hydrogen halide before neutralization exceeds 25% by weight, the content of alkali metal halide after neutralization becomes 10% by weight or more, making removal by filtration difficult. Become.

Accordingly, the present invention provides a method for producing a phosphoric acid triester which can efficiently remove alkali metal halides derived from hydrogen halide by-produced during the production of the phosphoric acid triester even when its content is high. The purpose is to provide.

[0006]

Means for Solving the Problems The present invention provides the following general formula:
(1) R ¹ -O (AO) _n -H (1) [wherein, R ¹ represents a linear or branched alkyl group having 1 to 12 carbon atoms, and A represents a linear chain having 2 or 3 carbon atoms. Or, it represents a branched alkylene group, n represents the number of 1 to 10, which is the average number of moles of alkylene oxide added, and n A's may be the same or different. After reacting an organic hydroxy compound represented by the formula (1) with a phosphorylating agent, the reaction mixture containing the phosphoric acid triester obtained by neutralization is washed with an aqueous solution of an inorganic salt. To provide.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula (1), R ¹ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group. Pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, isononyl, decyl, undecyl, dodecyl and the like. Among them, straight or branched ones having 1 to 4 carbon atoms, particularly ethyl group and n-butyl group are preferred.

A in the general formula (1) is specifically an ethylene group, a trimethylene group or a propylene group.
Of these, an ethylene group is preferred. n is 1 to 4,
Particularly, 2-3 is preferable. The n A's may be the same or different, but are preferably the same.

The phosphorylating agent to be reacted with the organic hydroxy compound (1) is, for example, phosphorus oxyhalide,
Phosphorus trihalide and the like can be mentioned, among which phosphorus oxyhalide, particularly phosphorus oxychloride is preferable.

As a method of reacting the organic hydroxy compound (1) with a phosphorylating agent, for example, GM Kosolapoff's “Organo
phosphorus Compounds "(John Wiley & Sons. Inc., N
ew York, 1950), (a) a method of reacting sodium alkoxide of an organic hydroxy compound (1) with phosphorus oxyhalide or the like, (b) a method of reacting an excess of an organic hydroxy compound (1) with (C) reacting an organic hydroxy compound (1) with a phosphorus trihalide or the like to form a phosphite;
Then, a method of oxidizing with an appropriate oxidizing agent and the like can be mentioned, and any of these methods can be used.

In the above reaction, when synthesizing a compound having the same three residues of the phosphoric acid triester as the organic hydroxy compound, one kind of the organic hydroxy compound (1) is used,
When different compounds are synthesized, two or more kinds of organic hydroxy compounds are used. The resulting phosphoric triester is 3
Even if the organic hydroxy compound residues are the same or different,
Although there is no difference in performance when blended in cosmetics and the like, it is preferable that they are the same in terms of ease of synthesis.

The reaction molar ratio between the organic hydroxy compound (1) and the phosphorylating agent is 3: 1 to 30: 1, particularly 6: 1 to 9: 1.
Is preferred. When two or more kinds of the organic hydroxy compound (1) are used, it is preferable that the total is the above molar ratio. The reaction is carried out, for example, by adding a phosphorylating agent to the organic hydroxy compound (1) in a non-polar solvent or without solvent, preferably 4 times.
0-90 ° C., particularly preferably 40-80 ° C., preferably 2-2
It is carried out for 0 hour, particularly preferably for 3 to 18 hours. Next, the acid contained in the reaction mixture is neutralized, excess organic hydroxy compound is distilled off, and if necessary, through contact with steam,
A crude phosphoric acid triester can be obtained.

The neutralizing agent used for neutralization includes sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, etc., with sodium hydroxide being particularly preferred.

In the present invention, by washing the crude phosphoric acid triester with an aqueous solution of an inorganic salt, the alkali metal halide formed in the reaction product by the neutralization can be efficiently removed. Such inorganic salts include sodium chloride, sodium sulfate, sodium hydrogen carbonate,
Alkali metal salts such as potassium chloride are preferred, and sodium chloride is particularly preferred.

The concentration of the aqueous solution of the inorganic salt is preferably 1% by weight or more, more preferably 5% by weight or more, from the viewpoint of layer separation, and from the viewpoint of the precipitation of the inorganic salt, 26% by weight or less, particularly 20% by weight or less. Is preferred. Therefore, the preferred concentration range is from 1 to 26.
%, Especially 5 to 20% by weight.

From the viewpoint of the persistence of the inorganic salt in the organic layer, the amount of the aqueous solution of the inorganic salt used in washing the crude phosphoric acid triester is at least 0.1% by weight of the crude phosphoric acid triester, especially
It is preferably at least 0.5 times by weight, and from the viewpoint of avoiding a decrease in yield due to distribution of the organic substance in the aqueous layer, is preferably at most 10 times by weight, particularly preferably at most 2 times by weight of the crude phosphoric acid triester.
Therefore, the preferable range is 0.1% of crude phosphoric acid triester.
It is 10 times by weight, especially 0.5 to 2 times by weight.

After washing with an aqueous solution of an inorganic salt, dehydration and filtration are further carried out, if necessary, to obtain a phosphoric acid triester substantially containing no alkali metal halide.

[0018]

EXAMPLE 1 Diethylene glycol monoethyl ether was placed in a flask.
600 g (4.47 mol) was added, and the mixture was stirred under reduced pressure (20 kPa) while blowing nitrogen at 50 ml / min. While maintaining the reaction solution at room temperature, 114 g (0.745 mol) of phosphorus oxychloride was added dropwise thereto, and the mixture was aged at 40 to 60 ° C for 5 hours. Next, 149.0 g of a 16% by weight aqueous sodium hydroxide solution (0.596
mol) was added to neutralize the mixture, excess diethylene glycol monoethyl ether was distilled off, and the residue was brought into contact with steam to obtain 366.9 g of a crude phosphoric acid triester. This crude phosphoric acid triester was a heterogeneous liquid containing 10% by weight of sodium chloride. Then, 16 to this crude phosphoric acid triester
Washing was performed by adding 300 g of an aqueous solution of sodium chloride by weight.
Thereafter, through dehydration and filtration, 266.1 g of the desired tris (ethoxyethoxyethyl) phosphate was obtained (80% yield). It is a colorless, transparent and homogeneous liquid.As a result of chlorion analysis, the chlorion content is
It was less than 10 mg / kg and contained substantially no sodium chloride.

Example 2 The reaction and purification were carried out in the same manner as in Example 1 except that diethylene glycol monobutyl ether was used instead of diethylene glycol monoethyl ether, to obtain the desired tris (n-butoxyethoxyethyl) phosphate in a yield.
82% obtained. This is a colorless, transparent and homogeneous liquid,
In addition, as a result of chlorion analysis, the chlorion content was 10 mg / kg or less, and it was substantially free of sodium chloride.

Comparative Example 1 300 g of water was added to the crude phosphoric acid ester obtained in Example 1.
, But the system became homogeneous and the sodium chloride could not be removed.

COMPARATIVE EXAMPLE 2 The crude phosphate ester obtained in Example 1 was subjected to filtration as it was. As a result, clogging occurred and a considerable time was required, and 173.0 g of the desired product was obtained (yield: 52%). ), And the yield decreased.

[0022]

According to the present invention, the alkali metal halide by-produced during the production of the phosphoric triester can be efficiently removed.

Claims (1)

[Claims] A compound represented by the following general formula (1): R ¹ -O (AO) _n -H (1) wherein R ¹ represents a linear or branched alkyl group having 1 to 12 carbon atoms; Represents a linear or branched alkylene group having 2 or 3 carbon atoms, n represents a number of 1 to 10 which is an average addition mole number of the alkylene oxide, and n A's may be the same or different. A reaction mixture containing a phosphoric acid triester obtained by reacting an organic hydroxy compound represented by the formula (1) with a phosphorylating agent, and then washing the resulting mixture with an aqueous solution of an inorganic salt.