JPH0529357B2 - - Google Patents

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 () neutralizing an organic phosphate ester with an alkali metal hydroxide, such as sodium hydroxide, in an aqueous solution to form a sodium salt, and then preparing an aqueous solution of the metal sulfate or chloride; How to obtain the desired object by adding .
() 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. 12646/1973. was the typical method. However, each of the above methods had drawbacks. For example, in the method (), it was extremely difficult to separate the pure product after the reaction in the above method because the lower alyl phosphate metal salt is water-soluble. That is, the by-produced Na ₂ So ₄ or NaCl is also water-soluble, so it is impossible to separate them, and in the synthesis of higher alkyl phosphate metal salts, the by-produced Na 2 So 4 or NaCl is also water-soluble.
Neutral inorganic salts such as Na ₂ SO ₄ or NaCl are not completely removed. The resulting higher alkyl phosphorus residual ester metal salts are often extremely poorly soluble in solvents and cannot be purified by recrystallization, extraction, etc., so methods such as washing the crystals with water to remove inorganic salts have to be used. 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 organic phosphate ester is incorporated into the metal salt produced, and the exchange method performed in an aqueous solution does not completely exchange the salt. Unexchanged alkali metal salts of organic phosphates remain in the higher alkyl phosphate metal salts. In addition, in method (), since the reaction is carried out at high temperature for a long time without using a solvent, alteration, deterioration, and decomposition of the organic phosphate ester, which is the raw material, and the organic phosphate ester metal salt, which is the target substance, are unavoidable. The yield was poor, the product was colored brown, and a highly pure target product could not be obtained. 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. The present invention is based on the general formula

[expression] or/o call

[Formula] (where R represents a saturated or unsaturated alkyl group having 1 to 18 carbon atoms) is characterized by reacting an organic phosphoric acid ester represented by the formula with an organic lower fatty acid metal salt in an alcoholic solvent. A method for synthesizing organophosphate metal salts, the metals being magnesium, calcium, strontium, 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 by the present invention can be used as cosmetic additives, fragrance carriers, sunscreen agents, antiperspirants, humectants, resin additives, ultraviolet absorbers, 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 were mixed in a solvent at room temperature to 150°C for 30 minutes.
After carrying out the reaction for 5 to 5 hours, operations such as filtration, washing, concentration, and drying are performed to obtain the desired product. Note that the reaction ratio between the organic phosphoric acid ester and the organic lower fatty acid metal salt may be determined by determining the total acid value of the organic phosphoric acid ester, and based on this, the amount of the raw material metal salt to be added may 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, 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 metal salt, which is the reaction product, should be dissolved in the solvent used at room temperature or when heated. This is desirable. 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 promoting the reaction. The organic phosphoric acid ester compound used as the raw material of this application is a mixture of a monoester and a diester obtained by a known method, that is, a reaction between phosphoric anhydride and an alcohol, or a purification step after an ester reaction between phosphorus oxychloride and an alcohol. It is a highly purified monoester or diester. On the other hand, as the organic lower fatty acid metal salt which is another raw material of the present application,
Magnesium, calcium, strontium, barium, copper, zinc, cadmium, aluminum,
tin, lead, antimony, bismuth, manganese, iron,
cobalt, nickel formate or acetate or propionate or butyrate. Not only these anhydrous salts but also hydrated salts which are usually obtained industrially 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 above-mentioned metal oxides, hydroxides, carbonates, etc. 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, di-type in the front

【formula】 mono body

【formula】 n represents the valence of the metal, and M represents the metal.

【table】

Table 2 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 listed in Table 2.

[Table] However, raw material n-dodecyl phosphate ester is diester:monoester=1.0:1.1 (mole ratio), total acid value
241 was used. Zn (%) of zinc salt obtained using this = 12.4 (calculated value) Synthesis method This invention: A raw fatty acid metal salt was synthesized using zinc acetate using ethanol as a solvent. (): Synthesized by neutralizing an organic phosphate ester with an aqueous sodium hydroxide solution and adding an aqueous zinc sulfate solution thereto. ( ): Zinc acetate was added to the organic phosphoric acid ester and reacted at 150 to 200°C under reduced pressure for 6 hours. Next, embodiments of the synthesis method will be explained using examples. Example 1 19.7 gr of methyl phosphoric acid ester [diester: monoester = 1.0:1.0 (molar ratio) total acid value 677] was dissolved in 100 ml of ethanol, and Mg (CH ₈ COO) ₂ .
25.5 gr of 4H ₂ O 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, the presence of ethyl acetate, an ester component, in the distillate concentrated under reduced pressure was confirmed by gas chromatography. Example 2 Methyl phosphate ester used in Example 1
Dissolve 24.5gr in 100ml of methanol and add Ca to this.
19.2 gr of (HCOO) ₂ was added and heated under reflux at 60 to 70°C for 3 hours. After the reaction, the reaction mixture was concentrated under reduced pressure and dried to obtain 29.9gr (yield: 99.0%) of white crystalline methyl phosphate calcium salt. Example 3 15.6gr of methyl phosphoric acid ester [diester:monoester = 1.0:1.0 (molar ratio) total acid value 677] was dissolved in 100ml of isopropyl alcohol, and Cd
( _C2H5COO ) _27.7gr of _2.2H2O was added and heated at 90-100°C _for 3 hours. After the reaction, the reaction mixture was concentrated under reduced pressure and dried to obtain 25.3g (yield: 97.3%) of pale yellow crystalline methyl phosphoric acid ester cadmium salt. Example 4 Ethyl phosphate ester [diester:monoester = 1.0:1.2 (molar ratio) total acid value 599] 9.2gr was dissolved in 50ml of ethanol, and Zn(CH ₃ COO) ₂ .
Add 10.8gr of _2H2O and stir at 25-80℃ for 3 hours, then remove water by vacuum concentration and dry.
12.1gr (yield 98.4%) of white crystalline ethyl phosphate zinc salt was obtained. Example 5 n-butyl phosphate ester [diester: monoester = 1.0:1.0 (mole ratio) total acid value 442] 11.5 gr
Dissolve in 25ml of n-propyl alcohol and add to this
Add Mn( _CH3COO ) ₂・_4H2O11.1gr and heat to 70~80℃
After heating under reflux for 1 hour, the mixture was cooled to room temperature and dried separately to obtain 12.9 gr (yield 92.8%) of white crystalline n-butyl phosphate manganese salt. Example 6 n-dodecyl phosphate ester [diester: monoester = 1.0:1.1 (mole ratio), total acid value 241]
Dissolve 11.5gr in 50ml of isopropyl alcohol and add 4.9gr of Cu(CH ₃ COO) ₂ H ₂ O to 100~
The mixture was heated and stirred at 110°C for 3 hours. After the reaction is complete, cool to room temperature and overdry to yield 11.5gr.
A pale blue crystalline n-dodecyl phosphate copper salt was obtained (yield: 88.5%). Example 7 15.6 g of n-dodecyl phosphate used in Example 6 was dissolved in 50 ml of ethanol, and Ni was added to it.
5.0 gr of (HCOO) ₂ was added and heated under reflux at 70 to 80°C for 5 hours. After the reaction was completed, the mixture was cooled to room temperature and overdried to obtain 17.1 gr (yield: 96.1%) of pale blue crystalline n-dodecyl phosphoric acid ester nickel salt. Example 8 n-octadecyl phosphate ester [diester: monoester = 1.0:1.3 (mole ratio), total acid value
220〕Dissolve 30.5gr in 100ml of ethanol by heating, add _13.1gr of Zn(CH ₃ COO) 2.2H ₂ O, and heat to 70-80℃.
The mixture was heated under reflux for 3 hours. After the reaction was completed, the separated crystals were dried to yield 31.5gr (yield 91.8%).
A white crystalline n-octadecyl phosphate zinc salt was obtained. The presence of ethyl acetate in the liquid was also confirmed by gum chromatography. Example 9 n-octadecyl phosphate ester [diester: monoester = 1.0:1.3 (mole ratio), total acid value
220〕Dissolve 26.3gr in 100ml of ethanol and add Pb to this.
(C ₃ H ₇ COO) ₂ 19.7 gr was added and heated under reflux at 70 to 80°C for 3 hours. After the reaction was completed, it was cooled to room temperature and filtered. The separated crystals were thoroughly washed with ethanol and then dried to obtain 34.1 g (yield 92.4%) of white crystalline n-octadecyl phosphate lead salt.

[Claims]

1. A method for producing bis(diphenylphosphino)amine, which comprises reacting chlorodiphenylphosphine and hexamethyldisilazane, and then adding an organic tertiary amine to the resulting reaction mixture.