JPS6399082A - Synthesis of metal salts - Google Patents

Abstract

PURPOSE:To obtain metal salts useful for a cosmetic additive, perfume carrier, anti-sunburn agent, etc., without containing a strong electrolytic ion as an impurity, by reacting a specific organophosphoric acid ester with a metal salt of an organic lower fatty acid in an alcohol based solvent. CONSTITUTION:(A) An organophosphoric acid ester expressed by formula I and/or formula II (R represents 1-18C alkyl) is reacted with (B) a preferably equivalent or less amount of a metal salt of an organic lower fatty acid (preferably Mg, Ca, Sr, Br, Cu, Zn, Cd, Al, Sn, Pb, Sb, Bi, Mn, Fe, Co or Ni salt of formic acid, acetic acid, propionic acid or butyric acid) in an alcohol based solvent (example; 1-4C alkanol, etc.) to afford the aimed metal salts of the organophosphoric acid esters.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for synthesizing organophosphate metal salts. Conventional methods for synthesizing this type of compound include (I) neutralizing an organic phosphate ester with an alkali metal hydroxide, such as sodium hydroxide, in an aqueous solution to form a sodium salt;
A method of obtaining the desired product by subsequently adding an aqueous solution of metal sulfate or chloride.

(II) A method of obtaining the desired product by reacting an organic phosphoric acid ester and a metal acetate at high temperature and under reduced pressure for a long period of time without using a solvent, as described in Japanese Patent Publication No. 42-12646. was the typical method. However, each of the above methods had drawbacks. For example, in the method (I), since the lower alkyl phosphate metal salt is water-soluble, it is extremely difficult to separate the pure product after the reaction using the above method. That is, by-produced Na2804. Since Na1 is also water-soluble, it is impossible to separate it from these, and in the synthesis of higher alkyl phosphate metal salts, Na1l is a by-product.
Neutral inorganic salts such as 2804 or NaCl are not completely removed. Many of the higher alkyl phosphate metal salts produced are extremely poorly soluble in solvents, and therefore cannot be purified by recrystallization, extraction, etc., so it is necessary to remove inorganic salts by washing the crystals with water. In this method, inorganic ions remain in the crystal. In addition, since the metal salt produced is extremely poorly soluble in water, the alkali metal salt of the organophosphoric acid ester is incorporated into the metal salt produced, and the exchange method performed in an aqueous solution does not result in complete exchange. Unexchanged alkali metal salts of organic phosphates remain in the higher alkyl phosphate metal salts.

In addition, in the method (II), since the reaction is carried out at high temperature for a long time without using a solvent, the organic phosphate ester as the raw material and the organic phosphate metal salt as the target substance are deteriorated.
Deterioration and decomposition were unavoidable, resulting in a poor yield and a brown coloration of the product, making it impossible to obtain a highly pure target product.

On the other hand, although the claimed substance is used for various purposes and has many possibilities, there is currently no way to obtain a pure product, and it is susceptible to contamination with strong electrolytic ions such as alkali metal ions, halogen ions, and sulfate ions, and coloration. Its performance could not be evaluated in fields where sexuality is feared. Therefore, the present inventors conducted extensive research to synthesize a highly pure organic phosphate metal salt that does not contain strong electrolytic ions as impurities, and as a result, the present invention was achieved.

1B represents a saturated or unsaturated alkyl group. ) is a method for synthesizing organic phosphate ester metal salts, which is characterized by reacting an organic phosphate ester shown in , barium, copper, zinc.

Cadmium, aluminum, tin, lead, antimony.

These are bismuth, manganese, iron, cobalt, and nickel.

Organic lower fatty acid components include formic acid, acetic acid, propionic acid, and butyric acid.

The metal salts obtained according to the present invention can be used as cosmetic additives, fragrance carriers, sunburn inhibitors, antiperspirants, humectants, 4I1 fat additives, ultraviolet absorbers, and weather resistance improvers.

It is an extremely useful substance as a polymer polymerization catalyst, lubricating oil additive, fuel additive, fire extinguishing agent, flame retardant, lubricant, mold release agent, etc.

Next, an outline of the implementation of the present invention will be described.

That is, the corresponding organic phosphoric acid ester and organic lower fatty acid metal salt are reacted in a solvent at room temperature to 150°C for 80 minutes to 5 hours, and then filtered, purified, concentrated, dried, etc. to obtain the desired product. get.

The reaction rate between organic phosphate ester and organic lower fatty acid metal salt is determined by calculating the total acid value for organic phosphate ester,
Based on this, the amount of the starting material metal salt to be added can be determined. In order to complete the reaction, it is preferable that the raw metal salt be used in an amount equivalent to or less than the amount of the organic phosphoric acid ester. Desirably, 1.0 equivalent to 0.5 equivalent of the raw metal salt is added to the total acid value of the organic phosphate ester.

It is essential that the reaction be carried out in an alcoholic solvent, and examples of the solvent include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, and n-butyl alcohol. Ketones such as acetone and methyl ethyl ketone, n-hexane, petroleum ether, benzene, and toluene.

A mixed solvent of a hydrocarbon such as xylene or another halogenated hydrocarbon and the above-mentioned alcohol solvent may also be used. When selecting a solvent for the reaction, at least one of the organic phosphate ester and lower fatty acid metal salt which are the reaction raw materials, and the organic phosphate ester metal salt which is the reaction product is used. It is desirable to dissolve it in a solvent at room temperature or when heated.

The reason why an alcoholic solvent was used as the solvent is that the lower fatty acids that are liberated as the reaction progresses react with the alcohol of the solvent to produce esters, thereby accelerating the reaction.

The organic phosphate esterified metal used as the raw material of this application is a mixture of monoester and diester obtained by a known method, that is, the reaction of phosphoric anhydride and alcohol, or the ester reaction of phosphorus oxychloride and alcohol, followed by a purification process. High purity monoester or diester. On the other hand, the organic lower fatty acid metal salts which are another raw material of the present application include magnesium, calcium, strontium, barium, copper, zinc, cadmium, and aluminum.

i, lead, antimony, bismuth, manganese, iron.

Cobalt, nickel formate or acetate, propionate or butyrate.

As these salts, not only anhydrous salts but also commonly industrially obtained aqueous salts may be used.

Further, the case where the raw material metal salt of the present application is generated during the reaction is also included. That is, organic lower fatty acids are added to the oxides, hydroxides, carbonates, etc. of the above metals to produce fatty acid metal salts, which are not isolated, but the organic phosphoric acid ester is added thereto to form an alcohol-based A method of synthesizing an organic phosphate metal salt in a solvent is also included in the synthesis method of the present application. Table 1 shows the physical properties of typical products obtained by the method of the present invention.

However, in the table n represents the valence of the metal, and M represents the metal.

(The following is a blank space) For reference, the physical properties of n-dodecyl phosphate zinc salts synthesized by the method of the present invention and the conventional method described above are described in Table 2.

(The following is a blank space) However, (1) The raw material n-dodecyl phosphate used was diethyl:monoester=1.0:1.1 (mole ratio) and a total acid value of 241. Zn (%) of the zinc salt obtained using this = 12.4 (calculated value) ② Synthesis method The raw fatty acid metal salt was synthesized using zinc acetate and ethanol was used as a solvent.

(1): Organic phosphoric acid ester was neutralized with an aqueous sodium hydroxide solution, and an aqueous zinc sulfate solution was added thereto for synthesis.

(■): 150 by adding zinc acetate to organic phosphate ester
The reaction was carried out at ~200°C under reduced pressure for 6 hours.

Next, embodiments of the synthesis method will be explained using examples.

Example 1 Methyl phosphate ester [diester nimonoester=
1.0 : 1.0 (mole ratio) Total acid value 677] 19.
7gr in 100ml of ethanol! Mg
(CHg C00) 2 ・4H2025,5gr
was added and heated under reflux at 70 to 80°C for 2 hours.

After the reaction, the reaction mixture was concentrated under reduced pressure and dried to obtain 22.1 gr (yield: 98.7%) of white crystalline methyl phosphate magnesium salt. Furthermore, ethyl acetate, which is an ester component, was confirmed in the distillate concentrated under reduced pressure by gas chromatography.

Example 2 24.5 g of methyl phosphate used in Example 1
r Dissolve in t o o mz in wometa/-le and add 0 to this.
219.2 gr of a(HOOO) was added and heated under reflux at 60 to 70°C for 8 hours. After the reaction, the reaction mixture was concentrated under reduced pressure and dried to obtain 29.9 gr (yield: 99.0%) of white crystalline methyl phosphate calcium salt.

Example 8 Methyl phosphate ester [diester: monoester=
1.0 : 1.0 (Sol ratio) Total acid value 677] 15.
6gr isopropyl alcohol, coal 100ml! Dissolve in and add cd(CzHsOOO)2.2H2027 to this.
, 7 gr was added thereto and heated at 90 to 100°C for 8 hours.

After the reaction, the reaction mixture was concentrated under reduced pressure and dried to obtain 25.8 gr (yield: 97.8%) of pale yellow crystalline methyl phosphoric acid ester cadmium salt.

Example 4 Ethyl phosphate ester [diester: monoester=
1.0: 1.2 (mole ratio) total acid value 599] 9.2
gr was dissolved in 50ml of ethanol, and Zn(C!
Add HsCOO)g2H2010,8gr and make 25
After stirring at ~80°C for 8 hours, water was distilled off by vacuum concentration and drying was performed.12. A white crystalline ethyl phosphate zinc salt of tgr (yield 98.4%) was obtained.

Example 5 n-butyl phosphate ester [diester: monoester = 1.0: 1.0 (mole ratio) total acid value 442] 1
1.5gr to 25ml of n-propyl alcohol! Mn(CIIsOOOO) 2.4% go 11
．． After adding TGR and heating under reflux at 70 to 80°C for 1 hour, it was cooled to room temperature and dried separately to give 12.9 g.
A white crystalline n-butyl phosphate manganese salt of r (yield 92.8%) was obtained.

Example 6 n-dodecyl phosphate ester [diester: monoester = 1.0 = 1.1 (mole ratio), total acid value 241] 11.
5gr was dissolved in 50ml of isopropyl alcohol, 0u(OHaCoo)s+ .H2O4, 9gr was added thereto, and the mixture was heated and stirred at 100 to 110°C for 8 hours. After the reaction is complete, cool to room temperature, filter and dry.
1.5 gr (yield: 88.5%) of pale blue crystalline n-dodecyl phosphate copper salt was obtained.

Example 7 n-dodecyl phosphate ester used in Example 15.
Dissolve 6gr in ethanol 501M and add N'xCH to this.
COO)25. The mixture was heated under reflux at 70 to 80° C. for 5 hours with 7 J+ of Ogr added. After the reaction is completed, cool to room temperature, filter and dry.17. A pale blue crystalline n-dodecyl phosphate nickel salt of tgr (yield 96.1%) was obtained.

Example 8 N-octadecyl phosphate ester [diester j: monoester = i, o: 1.8 (mole ratio), total acid value 220': 180.5gr was heated and dissolved in 100ml of ethanol) Zn(CHs(300)22Hz01B
, 17 g gr were added thereto, and the mixture was heated under reflux at 0 to 40°C for 8 hours. After the reaction is completed, filter and dry the crystals separated from each other.
, 5g (yield 91.8%) of white crystalline n-octadecyl phosphate zinc salt was obtained.

The presence of ethyl acetate in the solution was also confirmed by gas chromatography.

Example 9 n-octadecyl phosphate ester [diester: monoester = 1.0: 1.8 (mole ratio), total acid value 2
20) Dissolve 26.8gr in 100ml 1Vc of ethanol and add 19.7g of Pb(Call I7000)2 to this.
r was added and heated under reflux at 70 to 80°C for 8 hours.

After the reaction was completed, it was cooled to room temperature, filtered, and the separated crystals were thoroughly washed with ethanol and then dried to obtain 84, tgr.
A white crystalline n-octadecyl phosphate lead salt was obtained (yield 92.4%).

Patent applicant: Osaka Fragrance Co., Ltd. Continuation of the book from the Showa era.

2 years! February 2nd

Claims (1)

[Claims] 1. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or /
and ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, in the formula, R represents a saturated or unsaturated alkyl group having 1 to 18 carbon atoms.) An organic phosphoric acid ester represented by the formula and an organic lower fatty acid metal salt are combined with alcohol. A method for synthesizing organic phosphate ester metal salts, which is characterized by reaction in a system solvent. 2. The metals of the organic phosphate metal salts are magnesium, calcium, strontium, barium, copper, zinc,
A method for synthesizing metal salts according to claim 1, which are cadmium, aluminum, tin, lead, antimony, bismuth, manganese, iron, cobalt, and nickel. 3. The method for synthesizing metal salts according to claim 1, wherein the organic lower fatty acid component of the organic lower fatty acid metal salt is formic acid, acetic acid, propionic acid, or butyric acid.