JP3859889B2 - Method for producing phosphoric triester - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a phosphoric acid triester having no off-flavor and excellent stability.
[0002]
[Prior art and problems to be solved by the invention]
The phosphoric acid triester having an alkyloxyalkylene group is highly polar and excellent in skin affinity, and has low viscosity, low boiling point and excellent safety. Therefore, it is known for uses such as cosmetics and external preparations ( 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]
However, the phosphoric acid triesters having an alkyloxyalkylene group obtained as described above contain peroxides, carbonyl compounds, etc. that are by-produced during the reaction, and this causes a bad odor. Since it adversely affects the surface, it has been a problem when used as a base component for cosmetics and the like.
[0004]
Accordingly, an object of the present invention is to produce a high-quality phosphate triester that is substantially free of peroxides and carbonyl compounds that cause off-flavors and that is excellent in stability and can be used in cosmetics and cosmetics. It is to provide a method.
[0005]
[Means for Solving the Problems]
The present inventors have found that the alkyloxyalkylene group in the phosphoric acid triester molecule is susceptible to alteration by oxidation, and that alteration can be prevented by adding an antioxidant to the reaction system.
[0006]
That is, 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, A represents a linear or branched alkylene group having 2 or 3 carbon atoms, and n represents an average addition of alkylene oxide. The number of moles is 1 to 10, and n A's may be the same or different. ]
A method for producing a phosphoric acid triester in which an antioxidant is added at any stage of the process for producing a phosphoric acid triester by a reaction between an organic hydroxy compound represented by formula (1) and a phosphorylating agent.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
In general formula (1), as R ¹ , for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group , Heptyl group, octyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group, undecyl group, dodecyl group and the like. Of these, linear or branched ones having 1 to 4 carbon atoms, particularly ethyl and n-butyl groups are preferred.
[0008]
Further, A in the general formula (1) is specifically an ethylene group, trimethylene group or propylene group, and among them, an ethylene group is preferable. As n, 1-4 are preferable, especially 2-3. The n A's may be the same or different, but are preferably the same.
[0009]
Examples of the phosphorylating agent to be reacted with the organic hydroxy compound (1) include phosphorus oxyhalide and phosphorus trihalide. Among these, phosphorus oxyhalide, particularly phosphorus oxychloride is preferable.
[0010]
As a reaction method of the organic hydroxy compound (1) and the phosphorylating agent, for example, as described in “Organophosphorus Compounds” (John Wiley & Sons. Inc., New York, 1950) of GM Kosolapoff, A method of reacting an organic hydroxy compound (1) with phosphorus oxyhalide or the like in the presence of a secondary amine, (b) a method of reacting a sodium alkoxide of the organic hydroxy compound (1) with phosphorus oxyhalide or the like, (c) A method of reacting excess organic hydroxy compound (1) with phosphorus oxyhalide, etc., (d) reacting organic hydroxy compound (1) with phosphorus trihalide or the like to form phosphite, and then using a suitable oxidizing agent. Examples of the method include oxidation, and any of these methods can be used.
[0011]
In the above reaction, one organic hydroxy compound (1) is used when three organic hydroxy compound residues of the phosphoric acid triester are synthesized, and two or more different ones are synthesized when different ones are synthesized. An organic hydroxy compound is used. The obtained phosphoric acid triester has the same or different three organic hydroxy compound residues, but there is no difference in performance when blended in cosmetics, etc., but it is the same in terms of ease of synthesis. preferable.
[0012]
The reaction molar ratio of the organic hydroxy compound (1) to the phosphorylating agent is preferably 3: 1 to 30: 1, particularly 6: 1 to 9: 1. When using 2 or more types of organic hydroxy compounds (1), it is preferable that the sum total becomes the said molar ratio. The reaction is carried out by adding a phosphorylating agent to the organic hydroxy compound (1), for example, in a nonpolar solvent or without a solvent, preferably at 40 to 90 ° C, particularly preferably at 40 to 80 ° C, preferably 2 to 20 hours, Particularly preferably, it is performed for 3 to 18 hours. Next, the acid contained in the reaction mixture is neutralized, and the excess organic hydroxy compound is distilled off to obtain a phosphoric acid triester.
[0013]
In the present invention, an antioxidant is added to the reaction system or to the obtained phosphoric acid triester at any stage of the production process (from charging of raw materials to final product) including the above reaction process. Thus, a phosphoric acid triester that substantially does not contain a peroxide or carbonyl compound that causes odor can be obtained.
[0014]
Antioxidants include 2,6-di-tert-butyl-4-methylphenol (butylated hydroxytoluene; BHT), 2 (3) -tert-butyl-4-methoxyphenol (butylated hydroxyanisole; BHA), α-tocopherol , Γ-tocopherol, δ-tocopherol, nordihydroguaiaretic acid (NDGA), propellate gallate, guaiac fat and the like, among which BHT is preferable. These antioxidants can be used alone or in combination of two or more. In addition to the antioxidant, a synergist such as citric acid, malic acid, ascorbic acid or the like can also be used.
[0015]
The addition amount of the antioxidant is preferably 1 to 1000 ppm, particularly preferably 10 to 300 ppm, based on the weight of the raw material organic hydroxy compound (1). The addition timing and number of additions of the antioxidant are not particularly limited, but are preferably added before the reaction between the organic hydroxy compound (1) and the phosphorylating agent.
[0016]
In order to further improve the effect of the present invention, the crude phosphoric acid triester obtained by the above reaction (here, a phosphoric acid triester that has not been brought into contact with water vapor after synthesis) is brought into contact with water vapor. Is preferable, and the quality and stability of the resulting phosphate triester are further improved. The contact with water vapor can be performed by using, for example, a distiller, but the form thereof is not particularly limited, and may be any of batch type, thin film type, and the like.
[0017]
The amount of water vapor brought into contact with 100 parts by weight of the crude phosphoric acid triester is preferably 20 to 500 parts by weight, particularly 20 to 100 parts by weight. The flow rate of water vapor relative to 100 g of the crude phosphoric acid triester is preferably 10 to 200 g / hr, more preferably 10 to 100 g / hr. The pressure when bringing the water vapor into contact is preferably 0.0267 to 26.7 kPa, particularly preferably 0.133 to 13.3 kPa. The temperature is preferably 80 to 150 ° C, particularly 80 to 120 ° C. Under such pressure and temperature conditions, peroxides and carbonyl compounds can be efficiently distilled off, and decomposition of the phosphoric acid triester can be suppressed.
[0018]
Peroxide value of the desired phosphate triester obtained in this way [In accordance with the Japan Oil Chemistry Association's “Standard Oil Analysis Test” (1986) Peroxide Value Measurement Method (code number 2.4.12-86) ] Is preferably 0.5 meq / kg or less, more preferably 0.2 meq / kg or less. In addition, the carbonyl value of the target phosphoric acid triester (according to the above-mentioned carbonyl value measurement method (code number 2.4.22-73)) is preferably 0.5 μmol / g or less, particularly preferably 0.2 μmol / g or less. When the peroxide value and the carbonyl value are within the above ranges, a high-quality phosphate triester having almost no problems in terms of odor and stability is obtained. The peroxide value of 0.5 meq / kg or less and the carbonyl value of 0.5 μmol / g or less are preferably maintained even after one month after production.
[0019]
The phosphoric acid triester thus obtained is excellent in quality such as odor and stability, and can be suitably used for various uses such as cosmetics and external preparations.
[0020]
【Example】
Example 1
The flask was charged with 600 g (4.47 mol) of diethylene glycol monoethyl ether and 24 mg of BHT (40 ppm of diethylene glycol monoethyl ether) and stirred under reduced pressure (8.0 kPa) while blowing nitrogen at 50 ml / min. Thereto, 114 g (0.745 mol) of phosphorus oxychloride was dropped while keeping the reaction solution at room temperature, and aged at 60 ° C. for 5 hours. Next, 15.1 g (0.061 mol) of a 16 wt% aqueous sodium hydroxide solution was added to the reaction product to neutralize it, and excess diethylene glycol monoethyl ether was distilled off to obtain a crude phosphoric acid triester. 100 g of this crude phosphoric acid triester was placed in a reaction vessel and contacted at 120 ° C. and 6.67 kPa with 50 g of steam and a steam flow rate of 10 g / hr.
The resulting tris (ethoxyethoxyethyl) phosphate has a peroxide value of 0.1 meq / kg and a carbonyl value of 0.1 μmol / g. Even after storage at 50 ° C. for one month, the peroxide value is 0.1 meq. / kg, carbonyl value was 0.1 μmol / g. The sensory evaluation of the odor of this product was good both immediately after production and after storage.
[0021]
Example 2
The reaction and purification were conducted in the same manner as in Example 1 except that diethylene glycol monobutyl ether was used instead of diethylene glycol monoethyl ether. The obtained tris (n-butoxyethoxyethyl) phosphate has a peroxide value of 0.1 meq / kg and a carbonyl value of 0.1 μmol / g. Even after being stored at 50 ° C. for 1 month, the peroxide value is 0.1 The milliequivalent / kg and the carbonyl value were 0.1 μmol / g. The sensory evaluation of the odor of this product was good both immediately after production and after storage.
[0022]
Example 3
The reaction and purification were conducted in the same manner as in Example 1 except that the amount of BHT added was 120 mg (200 ppm of diethylene glycol monoethyl ether). The resulting tris (ethoxyethoxyethyl) phosphate has a peroxide value of 0.1 meq / kg and a carbonyl value of 0.1 μmol / g. Even after storage at 50 ° C. for one month, the peroxide value is 0.1 meq. / kg, carbonyl value was 0.1 μmol / g. The sensory evaluation of the odor of this product was good both immediately after production and after storage.
[0023]
Example 4
The reaction and purification were performed in the same manner as in Example 1 except that contact with water vapor was not performed. The resulting tris (ethoxyethoxyethyl) phosphate has a peroxide value of 0.2 meq / kg and a carbonyl value of 0.3 μmol / g. Even after storage at 50 ° C. for one month, the peroxide value is 0.2 meq. / kg, carbonyl value was 0.3 μmol / g. The sensory evaluation of the odor of this product was good both immediately after production and after storage.
[0024]
Example 5
The reaction and purification were performed in the same manner as in Example 1 except that BHT was not added. The obtained tris (ethoxyethoxyethyl) phosphate had a peroxide value of 0.1 meq / kg and a carbonyl value of 0.1 μmol / g.
To 50 g of this tris (ethoxyethoxyethyl) phosphate, 2 mg of BHT was added. The peroxide value of tris (ethoxyethoxyethyl) phosphate immediately after addition of BHT is 0.1 meq / kg and the carbonyl value is 0.1 μmol / g. Even after being stored at 50 ° C. for 1 month, the peroxide value is 0.1 mm. Equivalent / kg, carbonyl value was 0.3 μmol / g. Also, the sensory evaluation of the odor of this product was good immediately after production and after storage.
Comparative Example 1
Into the flask, 600 g (4.47 mol) of diethylene glycol monoethyl ether was added, and stirred under reduced pressure (8.0 kPa) while blowing nitrogen at 50 ml / min. Thereto, 114 g (0.745 mol) of phosphorus oxychloride was dropped while keeping the reaction solution at room temperature, and aged at 60 ° C. for 5 hours. Next, 15.1 g (0.061 mol) of a 16% by weight aqueous sodium hydroxide solution was added to the reaction product to neutralize it, and excess diethylene glycol monoethyl ether was distilled off.
The resulting tris (ethoxyethoxyethyl) phosphate has a peroxide value of 0.67 meq / kg and a carbonyl value of 1.0 μmol / g. After storage at 50 ° C. for 1 month, the peroxide value is 3.10 meq / kg. kg and carbonyl value were 2.6 μmol / g. Further, in the sensory evaluation of the odor of this product, there was a strange odor immediately after production, and a stronger odor was observed after storage.
[0026]
【The invention's effect】
According to the present invention, high-quality phosphorous having excellent stability that is substantially free of peroxides and carbonyl compounds that cause malodors and can be suitably used for cosmetics, cosmetics, and the like. Acid triesters can be produced.

Claims (2)

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 4 carbon atoms, A represents a linear or branched alkylene group having 2 or 3 carbon atoms, and n represents an average addition of alkylene oxide. The number of moles is 1 to 4 , and n A's may be the same or different. ]
A method for producing a phosphoric acid triester, wherein an antioxidant is added at any stage of the process for producing a phosphoric acid triester by a reaction between an organic hydroxy compound represented by formula (1) and a phosphorylating agent. The method for producing a phosphoric acid triester according to claim 1, wherein the addition of the antioxidant is carried out to the reaction system.