JPH04134088A - Production of phosphoric acid ester - Google Patents

Abstract

PURPOSE:To easily obtain the subject ester useful as a surfactant on an industrial scale at a low cost by reacting a specific phosphoric acid mono-or-diester with a dialkyl sulfate. CONSTITUTION:The objective compound of formula IV (R<5> is H, l-4C alkyl or group of formula II) can be produced by reacting a phosphoric acid monoester and/or phosphoric acid diester of formula I [m is 0 or 1; when m is 0, R<1> is 6-36C alkyl (H of the alkyl may be substituted with F) or substituted phenyl; R<2> is 2-3C alkylene; n is 0-30; when m is 1, n is 0 and l is 0 or 1; when l is 0, R<1> is 6-36C straight-chain alkyl (H of the alkyl may be substituted with F) or alkenyl; when l is 1, R<1> is 6-36C alkyl or alkenyl (H of the group may be substituted with F); R<3> is H or group of formula II] with a dialkyl sulfate of formula III (R<4> is 1-4C alkyl).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an industrially advantageous method for producing phosphoric acid diesters and phosphoric acid triesters useful as surfactants.

[Prior art and problems to be solved by the invention] Alkyl phosphate esters and their alkali metal salts, alkanolamine salts, and amino acid salts can be used as detergents, emulsifiers, flame retardants, antistatic agents, textile oils, rust preventives, It is widely used as a lubricating additive. Among these, phosphoric acid diesters or phosphoric acid triesters that have ester bonds with different alkyl groups, alkenyl groups, alkyl ether groups, phenyl groups, etc. in the molecule,
It is known to have better performance as a detergent and flame retardant than phosphoric acid diesters or phosphoric triesters, which have ester bonds with alkenyl groups, alkyl ether groups, phenyl groups, etc., and is useful as a surfactant. .

A known method for producing phosphoric esters useful as such surfactants is to react phosphorus oxychloride with an organic hydroxyl compound to produce a monoester, and then react with a different organic hydroxyl compound. . However, this method has the drawbacks that hydrochloric acid is produced as a by-product, and the phosphoric acid ester produced is a mixture of mono-, di-, and triester, making it difficult to obtain a highly pure one industrially. Therefore, the reaction is carried out in a nonpolar solvent system by adding a tertiary amine or pyridine, or by changing the molar ratio of phosphorus oxychloride and organic hydroxyl compound, but the reaction is carried out by changing the molar ratio of phosphorus oxychloride and organic hydroxyl compound. This is unavoidable and is not satisfactory as a method for industrially obtaining highly pure phosphoric acid diesters and phosphoric acid triesters.

Under such circumstances, various methods for synthesizing such phosphoric acid diesters and phosphoric acid triesters have been investigated. For example, a method of obtaining an asymmetric phosphate ester by using dialkyl 2-chloromethyl-4-nitrophenyl phosphate as a substrate and reacting it with an organic hydroxy compound in an aqueous pyridine solution (Bull).

Chem, Sac, Jpn, 44.232 (I9
71)) or trichloroethyl alkyl phosphate with C
A method for reacting with organic hydroxy compounds in the presence of sF (J, Am.

Chem, Soc, 99.1277 (I977)
), or a method of reacting a monoalkyl phosphate with an alkyl halide in the presence of tetramethylammonium hydroxide (Synthesis, 870.1
974), a method of reacting a dialkyl phosphoric acid with an alkyl sulfonium salt in the presence of an alkali (Synthes
IS, 291.1982), etc. are known.

However, in these reactions dialkyl 2-
The starting materials are compounds that have problems in industrial supply, such as chloromethyl-4-nitrophenyl phosphate and trichloroethyl alkyl phosphate, and are not commercially available, such as tetramethylammonium hydroxide, CsF, alkyl halides, and alkylsulfonium salts. Since it requires an expensive product for commercial use, it is not suitable as an industrial manufacturing method.

Therefore, it has been desired to develop a method for industrially producing phosphoric acid diesters and phosphoric acid triesters useful as surfactants with high purity at low cost and easily.

[Means to solve the problem]

Under these circumstances, the present inventors conducted extensive research and found that by reacting dialkyl sulfates with phosphoric acid monoesters, phosphoric diesters, or their salts, phosphoric acid diesters or phosphoric acid esters useful as surfactants were obtained. The present invention was completed based on the discovery that triesters can be obtained with high yield, high purity, and high selectivity.

The present invention is shown by the following reaction formula.

R'-(-(OCR,), (JICH,+(OR2)
, -0-P-OHOHOR3 represents a straight-chain alkyl group having 6 to 36 carbon atoms which may be substituted with a child, and when l is 1, R1 may have one or more hydrogen atoms substituted with a fluorine atom. It represents a straight or branched alkyl group or alkenyl group having 6 to 36 carbon atoms.

R3 is a hydrogen atom or a group R'-E-(OCll, ), CHCH2-+-1-(
OR2). -〇-P-OR'C In the formula, m represents 0 or l, and when m is O, R1 is a straight chain having 6 to 36 carbon atoms in which one or more hydrogen atoms may be substituted with a fluorine atom. or a branched alkyl group or alkenyl group, or a phenyl group substituted with a linear or branched alkyl group having 6 to 15 carbon atoms, R2 is an alkylene group having 2 to 3 carbon atoms, and n is 0 to 30 Indicates the number of When m is 1, n represents 0, l represents O or 1, and when 1 is 0, R1 represents one or more hydrogen atoms as fluorine atom R'+ (OCR2), CHC
H2-+T mark R2), -0■ (Here, R', R2, j!Sm and n are the same as above)
shows. R4 represents an alkyl group having 1 to 4 carbon atoms. R5
is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a group R'-f-(OCll2), CHCH2sr(OR2
), , -0■ (where R', R2, fl-, In and n are the same as above). ] That is, the present invention involves reacting one or more selected from phosphoric acid monoesters, phosphoric diesters, and salts thereof represented by the general formula (I) with a dialkyl sulfate ester represented by Tsukuriyo (n). A phosphoric acid diester represented by the general formula (I[) and/or
Or a method for producing phosphoric acid triester.

In the present invention, a group R'+ (OCR2), c) Ic) + 2 r (OR'
).

Examples of H 2 include the following, which may be the same or different. That is, m=0. n=0 and R1 is 1
Examples of straight chain or branched chain alkyl groups or alkenyl groups having 6 to 36 carbon atoms which may be substituted with fluorine atoms include straight chain or branched octyl groups, decyl groups, Dodecyl group, octadecyl group, tetracosyl group, 2-ethylhexyl group, 2-hexyldecyl group, 2-octyldodecyl group, 2-tetradecyl octadecyl group, monomethyl branched isostearyl group, octenyl group, decenyl group, dodecenyl group, hexadecenyl group , octadecenyl group, tetracosenyl group, triacontenyl group, tridecafluorooctyl group, heptadecafluorodecyl group, heneicosafluorododecyl group, pentacosafluorotetradecyl group, nonacosafluorohexadecyl group, triacontafluorooctadecyl group ,
2-pentafluoroethylpentafluorohexyl group,
2-tridecafluorohexyltridecaf)
m=Q
Examples of the case where m=Q and R1 is a phenyl group substituted with a straight chain or branched alkyl group having 6 to 15 carbon atoms include alkylphenyl groups such as octylphenyl group and nonylphenyl group. ;m=0. R1 when Q<n=30
is a straight or branched alkyl group or alkenyl group having 6 to 36 carbon atoms, in which one or more hydrogen atoms may be substituted with a fluorine atom, as an example of polyoxyethylene (3 mol) Dodecyl ether group, polyoxypropylene (3 mol) decyl ether group, polyoxyethylene (8 mol) polyoxypropylene (3 mol) dodecyl ether group, polyoxyethylene (4 mol) octatecenyl ether group, polyoxyethylene ( 3 mol) tridecafluorooctyl ether group, polyoxyethylene (
Polyoxyalkylenes such as 5 mol) hebutadecafluorodecyl ether group, polyoxyethylene (3 mol) heneicosafluorododecyl ether group, polyoxyethylene (5 mol) 2-) ridecafluorohexyltridecafluorodecyl ether group, etc. Examples include an alkyl ether group or a polyoxyalkylene alkenyl ether group; β=0. m=1. Examples of the case where n=0 and R1 is a straight alkyl group having 6 to 36 carbon atoms in which one or more hydrogen atoms may be substituted with a fluorine atom include 2-hydroxydodecyl group, 2-hydroxyhexane Examples include 2-hydroxyalkyl groups such as decyl group, 2-hydroxytridecafluorononyl group, 2-hydroxypentadecafluorodecyl group, and 2-hydroxyhebutadecafluoroundecyl group; A=1. m=1. Examples of the case where n=o and R1 is a straight or branched alkyl or alkenyl group having 6 to 36 carbon atoms in which one or more hydrogen atoms may be substituted with a fluorine atom include 2-hydroxy- 3-dodecyloxypropyl group, 2-hydroxy-3-monomethyl branched isostearyloxypropyl group, 2-hydroxy-
3-octadecenyloxypropyl group, 2-hydroxy-3hebutadecafluorodecyloxypropyl group, 2-
2-hydroxy-3-alkyloxyl group such as hydroxy-3-(2-pentafluoroethylpentafluorohexyloxy)propyl group or 2-hydroxy-3-
Examples include alkenyloxypropyl group.

Examples of the salts of these raw material phosphate esters (I) include alkali metal salts, ammonium salts, trialkylammonium salts, and pyridinium salts.

Raw material phosphoric acid monoester or phosphoric acid diester (I)
can be obtained by reacting a corresponding organic hydroxy compound, glycidyl ether compound, or α-olefin epoxide with a suitable phosphorylating agent by a known method.

Preferred examples of the dialkyl sulfate (II) include dimethyl sulfate, diethyl sulfate, di-n-propyl sulfate, and the like. This dialkyl sulfate ester can be produced by reacting an alcohol such as methanol with sulfuric acid.

In the method of the present invention, when a salt of a phosphoric acid monoester or a phosphoric diester is used as a raw material, it is sufficient to directly react the dialkyl sulfate (II>); When using , it is desirable to carry out the reaction in the presence of an alkaline substance.

To carry out the method of the present invention, for example, the raw material phosphate ester (I) is first dissolved or dispersed in an aqueous solution of an alkaline substance. Examples of the aqueous alkaline substance solution used here include aqueous solutions of sodium hydroxide, trimethylamine, triethylamine, ammonia, pyridine, etc. Among them, aqueous solutions of sodium hydroxide and potassium hydroxide are preferred.

The amount of alkali is: ・OH of the raw material phosphate ester (I)
The amount is the amount necessary to completely neutralize the group or more, preferably 1 to 3 equivalents relative to the OH group. The concentration of the alkaline aqueous solution may be any concentration that takes into consideration the solubility and dispersibility of the raw material phosphoric acid monoester or phosphoric acid diester, and is preferably 5 to 50% by weight. Ethanol, It may contain organic solvents such as isopropanol and tetrahydrofuran.

After the phosphoric acid ester (I) is dissolved or dispersed in an aqueous alkaline solution, the temperature is raised to 30 to 100°C, and dialkyl sulfuric acid (I[) is added dropwise. The dropping method may be any method such as batch dropping, split dropping, or slow dropping over a certain period of time. The amount of dialkyl sulfate (II) is the O of the phosphate ester.
The amount may be equivalent to or in excess of the H group, preferably from an equivalent to 5 times the equivalent.

After completion of the dropwise addition, ripening is performed, and the progress of the reaction is monitored using high performance liquid chromatography equipped with a reversed phase column. After the reaction is completed, the reaction solution is made acidic with hydrochloric acid or sulfuric acid, and extracted with an organic solvent such as hexane, diethyl ether, ethyl acetate, chloroform, isopropyl ether, etc. to obtain the desired phosphoric acid diester or phosphoric acid triester (III). is obtained. After extraction, it is possible to recrystallize from an appropriate solvent or purify using a silica gel column, if necessary.

The thus obtained phosphoric acid diester and/or phosphoric acid triester represented by the above-mentioned -tsusuriyo (III) may be converted into a salt such as an alkali metal salt, an alkanolamine salt, an amino acid salt, etc. by a conventional method.

〔Effect of the invention〕

According to the present invention, by reacting dialkyl sulfuric acid with phosphoric acid monoester or phosphoric diester obtained by a known method, phosphoric acid diester or phosphoric acid triester useful as a surfactant can be produced industrially at low cost and easily. can be manufactured. The thus obtained phosphoric acid diesters and phosphoric acid triesters and their alkali metal salts, alkanolamine salts, and amino acid salts are useful as surfactants for detergents, emulsifiers, flame retardants, and the like.

〔Example〕

Next, the present invention will be further explained with reference to Examples, but the present invention is not limited to these Examples.

Example 1 100 g of monolauryl phosphoric acid (first equivalent point acid value 208
, 3, second equivalent point acid value 418.2.0.371 mol) and potassium hydroxide (reagent made by Shiboshi Kagaku Kogyo, purity 85%) 9
Mix 8.4g and 760.0g of ion-exchanged water and heat at 60°C.
The temperature was raised to 100% and dissolved. Add 140.4 dimethyl sulfate to this solution.
g was added dropwise over a period of 8 hours.

After the addition was completed, the mixture was aged at 60° C. for 4 hours. The reaction yield of the target product at this time was 97% (analyzed by high performance liquid chromatography; column Cicamerck RP-
18). The reaction mixture thus obtained was acidified with hydrochloric acid, and then extracted three times with 250 ml of ethyl ether. The residue obtained by distilling off ethyl ether under reduced pressure was recrystallized three times from ethanol to obtain lauryl methyl phosphate 88
．． 5 g was obtained.

Elemental analysis value theoretical value C: 55.70 H: 10.43 P:
11.05 Actual value C: 54.88 H: 10.
05 P: 10.79 first equivalent point acid value 198.8.
Second equivalent point acid value 202.1 Purity 97.4% Example 2 Monolauryl phosphoric acid 100g (first equivalent point acid value 208
, 3, second equivalent point acid value 41g, 2.0.371 mol) and potassium hydroxide (reagent made by Shiboshi Kagaku Kogyo, purity 85%) 9
8.4g and 760.0g of ion-exchanged water were mixed,
The temperature was raised to ℃ and dissolved. Add 171% of diethyl sulfate to this solution.
6 g was added dropwise over 8 hours.

After the addition was completed, the mixture was aged at 70°C for 4 hours. The reaction yield of the target product at this time was 95% (analyzed by high performance liquid chromatography;
18). The reaction mixture thus obtained was acidified with hydrochloric acid, and then extracted three times with 250 ml of ethyl ether. The residue obtained by distilling off ethyl ether under reduced pressure was recrystallized three times from ethanol to obtain lauryl ethyl phosphate 85
．． 4g was obtained.

Elemental analysis value theoretical value C: 57.12 H: 10.61 P:
10.53 Actual value C: 57.65 H: 10.
25 P: 10.09 first equivalent point acid value 192.6.
Second equivalent point acid value 194.3 Purity 98.1% Example 3 Mono-2-hexyldecyl phosphoric acid 100 g (first equivalent point acid value 172.8, second equivalent point acid value 342.8.0, 308
mole) and potassium hydroxide (Shibashi Kagaku Kogyo reagent, purity 8)
5%) 80.7g, 500g of ethanol, 230g of ion exchange water. Og was mixed and heated to 70°C to dissolve. 142.5 g of diethyl sulfuric acid was added dropwise to this solution over a period of 8 hours. After the addition was completed, the mixture was aged at 70°C for 4 hours. The reaction yield of the target product at this time was 90% (analyzed by high performance liquid chromatography; column cica-merc
RP-18) manufactured by K.

The reaction mixture thus obtained was acidified with hydrochloric acid, and then extracted three times with 250 ml of ethyl ether. The residue obtained by distilling off ethyl ether under reduced pressure was recrystallized three times from ethanol to obtain 86.4 g of 2-hexyldecylethyl phosphoric acid.

Elemental analysis value theoretical value C: 61.68 H: 11.22 P:
8.84 Actual value C: 60.75 H: 10.
55 P: 7.96 first equivalent point acid value 158.3.
Second equivalent point acid value 162.2 Purity 96.4% Example 4 Monotrioxyethylene lauryl phosphoric acid 100 g (first equivalent point acid value 141.8, second equivalent point acid value 283, 0.0
．． 253 moles), 66.6 g of potassium hydroxide (reagent manufactured by Shiboshi Kagaku Kogyo, purity 85%), and 157.0 g of ion-exchanged water.
were mixed and heated to 70°C to dissolve. 117.0 g of diethyl sulfuric acid was added dropwise to this solution over a period of 8 hours. After the addition was completed, the mixture was aged at 70°C for 4 hours. The reaction yield of the target product at this time was 96% (analyzed by high performance liquid chromatography; column RP-18 manufactured by Cica-Merck).
). The reaction mixture thus obtained was acidified with hydrochloric acid, and then extracted three times with 250 ml of ethyl ether. The residue obtained by distilling off ethyl ether under reduced pressure was recrystallized three times from ethanol to obtain 84.3 g of trioxyethylene laurylethyl phosphoric acid.

Elemental analysis value theoretical value C: 56J2 H: 10.16 P:
7.26 Actual value C: 55.58 H: 10.5
8 P: 7.52 first equivalent point acid value 129.5. Second equivalent point acid value 132.0 Purity 96.5% Example 5 Mono-2-hydroxylauryl phosphoric acid 100 g (first equivalent point acid value 199.5, second equivalent point acid value 395, 0.0.3
55 mol), 58.6 g of potassium hydroxide (reagent manufactured by Shiboshi Kagaku Kogyo, purity 96%), and 234.4 g of itan exchange water were mixed, and the mixture was heated to 70° C. to dissolve. 164.2 g of diethyl sulfuric acid was added dropwise to this solution over a period of 8 hours. After the addition was completed, the mixture was aged at 70°C for 4 hours. The reaction yield of the target product at this time was 88% (analyzed by high performance liquid chromatography; column RP-18 manufactured by Cica-Merck)
. The reaction mixture thus obtained was acidified with hydrochloric acid, and then extracted three times with 250 ml of ethyl ether. The residue obtained by distilling off ethyl ether under reduced pressure was recrystallized three times from ethanol to obtain 82.1 g of 2-hydroxylaurylethyl phosphoric acid.

Elemental analysis value theoretical value C: 54.17 H: 10.07 P:
9.9B actual measurement C: 54.47 H: 10.
57 P: 9.27 first equivalent point acid value 178. O,
Second equivalent point acid value 183.5 Purity 95.4% Example 6 Monolauryl phosphoric acid 100g (first equivalent point acid value 208
, 3, second equivalent point acid value 418.2.0.371 mol) and potassium hydroxide (reagent made by Shiboshi Kagaku Kogyo, purity 85%) 9
8.4g and 760.0g of ion-exchanged water were mixed,
The temperature was raised to ℃ and dissolved. 202.8 g of di-n-propyl sulfuric acid was added dropwise to this solution over a period of 8 hours. After the addition was completed, the mixture was aged at 70°C for 4 hours.

The reaction yield of the target product at this time was 89% (analyzed by high performance liquid chromatography; column cica-m
RP-18) manufactured by Erck. After acidifying the reaction mixture thus obtained with hydrochloric acid, 250 ml of ethyl ether
Extraction was performed three times with ml. The residue obtained by distilling off ethyl ether under reduced pressure was recrystallized three times from ethanol to obtain 80.9 g of laurylpropyl phosphoric acid.

Elemental analysis value theoretical value C: 5B, 42 H: 10.78 P:
10.05 Actual value C: 57.52 H: 9.
98 P: 9.92 first equivalent point acid value 17B, 6
．． Second equivalent point acid value 182.6 Purity 96.0% Example 7 Monotridecylfluorooctyl phosphoric acid 100 g (first equivalent point acid value 127.3, second equivalent point acid value 251, 5.0
．． 227 mol), potassium hydroxide (reagent manufactured by Chuyu Kagaku Kogyo, purity 85%) 59.2 g, isopropanol 300
g and 460.0 g of ion-exchanged water were mixed and heated to 60° C. to dissolve. 85.9 g of dimethyl sulfate was added dropwise to this solution over a period of 8 hours.

After the addition was completed, the mixture was aged at 60° C. for 4 hours. The reaction yield of the target product at this time was 87% (high performance liquid chromatography showed that the column Cica-Merck RP-18
). The reaction mixture thus obtained was acidified with hydrochloric acid and extracted three times with 250 ml of isopropyl ether. The residue obtained by distilling off isopropyl ether under reduced pressure was recrystallized three times from isopropanol to obtain 78.3 g of tridecylfluorooctylethyl phosphate.

Elemental analysis value theoretical value C: 23.60 H: 1.76 P:
6.76F: 6.75 Actual value C: 23.04 H: 1.58 P:
5.90F: 55.16 First equivalent point acid value 116.8. Second equivalent point acid value 119.4
Purity 95.9% Example 8 100 g of dihexadecyl phosphoric acid (equivalent point acid value 102,
2.0.182 mol), 24.0 g of potassium hydroxide (reagent manufactured by Chuyu Kagaku Kogyo, purity 85%), and 300 g of ethanol.
, 300 g of ion-exchanged water were mixed, and the mixture was heated to 70° C. to dissolve. 84.2 g of diethyl sulfuric acid was added dropwise to this solution over a period of 8 hours. After the addition was completed, the mixture was aged at 70°C for 4 hours. The reaction yield of the target product at this time was 95% (by high performance liquid chromatography, the column cica-mer
RP-18) manufactured by ck.

The reaction mixture thus obtained was acidified with hydrochloric acid and extracted three times with 250 ml of diethyl ether. The residue obtained by distilling off diethyl ether under reduced pressure was purified by applying it to a silica gel column to obtain 81.5 g of dihexadecylethyl phosphoric acid.

Elemental analysis value theoretical value C: 71.03 H: 12.45 P:
5.39 Actual measurement C: 70.86 H: 11.
75 P: 5.02 Procedural Amendment (Voluntary) October 24, 1990 1990 Patent Application No. 254741 2, Name of invention Process for producing phosphate ester 3, Relationship with the case of the person making the amendment Application Person name (091) Kao Corporation 4, agent address 1-3-6 Nihonbashi Ningyocho, Chuo-ku, Tokyo (103)
6. Column 7 of "Detailed Description of the Invention" of the specification to be amended, content of the amendment (I) In the specification, page 23, lines 13-14, "tridecylfluorooctylethyl phosphate" Corrected to "tridecylfluorooctyl methyl phosphate."

Claims (1)

[Claims] 1. The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In the formula, m represents 0 or 1, and when m is 0, R^1
is a straight chain or branched alkyl group or alkenyl group having 6 to 36 carbon atoms, or a straight chain or branched alkyl group having 6 to 15 carbon atoms, in which one or more hydrogen atoms may be substituted with a fluorine atom. The substituted phenyl group is R
^2 represents an alkylene group having 2 to 3 carbon atoms, and n represents a number from 0 to 30. When m is 1, n is 0, l is 0 or 1, and when l is 0, R^1 is a straight carbon number of 6 to 36 in which one or more hydrogen atoms may be replaced with a fluorine atom. It represents a chain alkyl group, and when 1 is 1, R^1 represents a straight or branched alkyl group or alkenyl group having 6 to 36 carbon atoms, in which one or more hydrogen atoms may be substituted with a fluorine atom. R^3 represents a hydrogen atom or a group ▲There is a mathematical formula, chemical formula, table, etc.▼ (where R^1, R^2, l, m, and n are the same as above). ] Phosphoric acid monoester, phosphoric acid diester,
and one or more selected from these salts, general formula (II) ▲ Numerical formula, chemical formula, table, etc. ▼ (II) [In the formula, R^4 represents an alkyl group having 1 to 4 carbon atoms. ] General formula (III) characterized by reacting a dialkyl sulfate ester represented by ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) Indicates an alkyl group or group ▲A mathematical formula, a chemical formula, a table, etc.▼, and R^1, R^2, R^4, l, m, and n represent the above meanings. ] A method for producing a phosphoric acid diester and/or a phosphoric triester represented by the following.