JPH04221390A - Production of phosphoric acid diester - Google Patents

Abstract

PURPOSE:To obtain the subject compound useful as a surfactant, etc., in 100% conversion in an easily purifiable state by reacting an aqueous slurry of a specific phosphoric acid monoester salt with an epoxy compound in the presence of an alkaline substance. CONSTITUTION:The objective phosphoric acid diester of formula III (M<2> is cationic group or negative charge) (e.g. sodium lauryl 2,3- dihydroxypropylphosphate) can be produced by reacting an aqueous slurry of a phosphoric acid monoester salt of formula I [M<1> is cationic group; m is 0 or 1; R<1> is (fluorine-substituted) 1-36C alkyl, alkenyl, (substituted) phenyl, etc.; R<2> is 2-3C alkylene; n is 0-30; l is 0 or 1] (e.g. monosodium monolauryl phosphate) with an epoxy compound of formula II (R<3> to R<6> are H or organic group; R<3> and R<5> may together form a ring) (e.g. glycidol) in the presence of an alkaline substance (e.g. triethylamine).

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention provides the following general formula (3) useful as a surfactant:

[Image Omitted] (In the formula, M2 represents a cationic group, or when a quaternary ammonium group is present in R5 or R6, represents a negative charge itself, and m represents 0 or 1. m is 0 In the case of , R1 is a straight chain or branched alkyl group or alkenyl group having 1 to 36 carbon atoms, or a straight chain or branched chain having 1 to 15 carbon atoms, in which one or more hydrogen atoms may be substituted with a fluorine atom. a phenyl group substituted with an alkyl group or an alkylene group, R2 is an alkylene group having 2 to 3 carbon atoms, n is a number from 0 to 30; when m is 1,
n is 0, l indicates 0 or 1, and when l is 0, R1
represents a straight-chain or branched alkyl group having 1 to 36 carbon atoms, in which one or more hydrogen atoms may be substituted with a fluorine atom, and when l is 1, R1 represents one or more hydrogen atoms with a fluorine atom. R2 represents an optionally substituted linear or branched alkyl group or alkenyl group having 1 to 36 carbon atoms, and R2 represents an alkylene group having 2 to 3 carbon atoms. R3, R4, R5
and R6 represent a hydrogen atom or an organic group, and R3 and R
5 may form a ring together with adjacent carbon atoms. ) The present invention relates to a method for easily and efficiently producing a phosphoric acid diester represented by

0002

[Prior Art and Problems to be Solved by the Invention] The above-mentioned phosphoric acid diester (3) is known to be an excellent surfactant that can be widely used in the fields of various detergents, cosmetics, and cosmetics. There is. As a method for producing this phosphoric acid diester, a method was proposed in which a phosphoric acid monoester salt was reacted with an epoxy compound in water (for example, JP-A-62
-51691, 63-208593).

However, since this method involves a reaction in an aqueous solution, a ring-opening reaction of the epoxy compound occurs simultaneously, and a diol compound is produced as a by-product. Therefore, the reaction rate is 100
% level requires a large excess of epoxy compound relative to the phosphoric acid monoester salt.
It is uneconomical, and furthermore, since a compound in which an epoxy compound is further added to the target phosphoric acid ester is obtained as a side reaction, it takes time and effort to separate and purify the target product.

0004

[Means for Solving the Problems] Under these circumstances, the present inventors have conducted extensive research in order to solve the above problems, and as a result, the present inventors have developed an alkali substance to reduce the reaction between an aqueous slurry of phosphoric acid monoester salt and an epoxy compound. If carried out in the presence of , the reaction between the phosphoric acid monoester salt and the epoxy compound will be accelerated,
The present invention was completed by discovering that the reaction rate can be achieved at a level of 100% by using 1 to 2 times as much epoxy compound as the phosphoric acid monoester salt.

That is, the present invention is based on the general formula (1)

[Formula 5] (wherein, M1 represents a cationic group, l, m, n, R1
and R2 have the same meanings as above), and an aqueous slurry of a phosphoric acid monoester salt represented by the general formula (2)

[
Formula 6 (wherein R3, R4, R5 and R6 have the same meanings as above) is reacted in the presence of an alkaline substance.
3)

embedded image (where l, m, n, R1 , R2 , R3 , R4
, R5, R6 and M2 have the same meanings as above)
The present invention provides a method for producing a phosphoric acid diester represented by:

In the general formula (1) showing the phosphoric acid monoester salt as a raw material, one or more hydrogen atoms represented by R1 may be substituted with a fluorine atom and have a carbon number of 1 to 36.
Examples of the straight chain or branched alkyl group or alkenyl group include straight chain or branched octyl group, decyl group,
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-tridecafluorohexyltridecafluorodecyl group, 2-heptadecafluorooctylheptadecafluorododecyl group, 2-heneicosafluorodecylheneicosafluorotetradecyl group, etc. can be mentioned.

[0007] The phenyl group optionally substituted with a straight or branched alkyl group having 1 to 15 carbon atoms includes:
Examples include octylphenyl group and nonylphenyl group. In addition, in general formula (1), m=0, n=1 to 36
Examples of the group represented by the substituent R1 -(OR2)n- in the case of Oxypropylene (3 moles) dodecyl ether group, polyoxyethylene (4 moles) octadecenyl ether group, polyoxyethylene (3 moles) tridecafluorooctyl ether group, polyoxyethylene (5 moles) heptadecafluorodecyl ether group , polyoxyalkylene alkyl ether groups such as polyoxyethylene (3 mol) heneicosafluorododecyl ether group, polyoxyethylene (5 mol) 2-tridecafluorohexyltridecafluorodecyl ether group, polyoxyalkylene alkenyl ether group etc. In addition, the substituent when l=n=0 and m=1, R1 -CH(OH)CH2
Examples of the group represented by - include 2-hydroxydodecyl group, 2-hydroxyhexadecyl group, 2-hydroxytridecafluorononyl group, 2-hydroxypentadecafluorodecyl group, 2-hydroxyheptadecafluoroundecyl group, etc. can be mentioned. In addition, the substituent in the case of l=m=1 and n=0, R1 -OCH2 CH(OH
) Examples of the group represented by CH2- include 2-hydroxy-3-dodecyloxypropyl group, 2-hydroxy-3-monomethyl branched isostearyloxypropyl group, 2-hydroxy-3-octadecenyloxypropyl group, 2-hydroxy-3-alkyloxyl group such as 2-hydroxy-3-heptadecafluorodecyloxypropyl group, 2-hydroxy-3-(2-pentafluoroethylpentafluorohexyloxy)propyl group, or 2-hydroxy-3 -alkenyloxypropyl group and the like.

In the general formula (1), M1 is not particularly limited as long as it is a cationic group, but an alkali metal ion, ammonium ion or alkanol ammonium ion is preferable from the viewpoint of water solubility. Further, as the epoxy compound represented by the general formula (2), for example, glycidyl (
Compounds containing glycidyl groups such as meth)acrylates, allyl glycidyl ethers, alkyl glycidyl ethers, glycidyl trialkylammonium halides, and diglycidyl ethers such as bisphenol A; epoxy groups at the terminals of molecules such as epichlorohydrin, glycidol, and α-olefin epoxides. and compounds having an epoxy group in the molecule such as bis-(3,4-epoxy-6-methylcyclohexylmethyl)adipate.

In the method of the present invention, the phosphoric acid monoester salt (1) is used as an aqueous slurry. Such a water slurry has, for example, 0% of the phosphoric ester (1).
．． It can be prepared by adding 1 to 5 parts by weight, preferably 0.2 to 2 parts by weight of water, and mixing and stirring. The reactor used for mixing and stirring is not particularly limited as long as the phosphoric acid monoester salt (1) and water can be mixed in the reactor, and examples include a kneader reactor, draft tube, spiral blade, etc. A reactor capable of high viscosity stirring or a reactor equipped with a conventional stirring device can be used. In such a reactor, a mixture of phosphoric acid monoester salt and water is heated to 30 to 100°C, preferably 40 to 90°C, and stirred sufficiently to obtain a water slurry. Next, before or after raising the temperature of the water slurry, an alkaline substance is added in an amount of 0.01 to 1 equivalent, preferably 0.01 to 1 equivalent relative to the phosphoric acid monoester salt (1).
．． Add 0.05 to 0.5 equivalent and stir. Examples of the alkaline substances used include hydroxides such as sodium hydroxide and potassium hydroxide; organic amine compounds such as trimethylamine and triethylamine; nitrogen-containing heterocyclic compounds such as pyridine and lutidine; basic ion exchange resins, etc. For example, organic amines such as trimethylamine and triethylamine are particularly preferred.

[0010] During the reaction, the epoxy compound (2) is used in an amount of 1 to 3 times the mole of the phosphoric acid monoester salt (1),
In particular, it is preferable to use 1 to 2 times the mole. The above amount of epoxy compound (2) may be added as is or dissolved in an appropriate solvent. The addition method is not particularly limited either, and it may be added dropwise gradually from a dropping funnel or the like, or it may be added all at once.

After adding the epoxy compound (2) to the system containing the water slurry and the alkaline substance, the reactant was
The reaction is completed by aging at 00°C, preferably 40-90°C. Aging time is 1 to 20 hours, preferably 3 to 10 hours.
About an hour is preferable. After distilling off the solvent, the desired phosphoric acid diester (3) can be obtained by washing with a solvent such as ethanol, isopropanol, or acetone. In addition, the general formula (
In 3), when obtaining a compound in which M2 exhibits a negative charge itself, an inorganic salt is produced as a by-product, which may be desalted by electrodialysis, ion exchange chromatography, etc., if necessary.

0012

EXAMPLES Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto.

Example 1 100 g (0.35 mol) of monosodium monolaurate and 100 g of ion-exchanged water were placed in a reactor equipped with a stirring device.
Add triethylamine 3.g and add triethylamine while stirring thoroughly.
9 g (0.035 mol) were mixed and the temperature was raised to 80°C. 39 g (0.52 mol) of glycidol was added to this slurry and reacted at 80° C. for 8 hours. The reaction product was poured into 200g of ethanol to obtain the target product, sodium lauryl 2,3-dihydroxypropyl phosphate.
22g was obtained (yield 98%). In addition, the conversion rate of monosodium monolauryl phosphate is 1 according to potentiometric titration.
It was 00%. 1H-NMR (D2O. Internal standard; Sodium 3-trimethylsilylpropanesulfonate δ:
ppm) 0.8 (t,3H,-P-OCH2 (CH
2 ) 10 CH3 ) 1.3 (broad.s, 2
0H, -P-OCH2 (CH2)10 CH3)
3.4 to 4.0 (m, 7H, -CH2 CHCH2
O-P-OCH2)

Example 2 In a reactor equipped with a stirring device, 100 g (0.35 mol) of monosodium monolauryl phosphate and 1 mol of ion-exchanged water were added.
00g of triethylamine was added thereto, and 3.9g (0.035 mol) of triethylamine was mixed with sufficient stirring, and the temperature was raised to 80°C. This slurry was added to 58 g of epichlorohydrin (0.
52 mol) was added thereto and reacted at 80°C for 8 hours. The reaction product was poured into 200 g of ethanol to obtain 123 g of sodium lauryl 2-hydroxy-3-chloropropyl phosphate (yield: 92%). The conversion rate of monosodium monolauryl phosphate was 100% according to potentiometric titration. 1H-NMR (D2
O. Internal standard; Sodium 3-trimethylsilylpropanesulfonate δ: ppm) 0.8 (t,3H,-P-OC
H2 (CH2)10 CH3)1.3 (bro
ad. s, 20H, -P-OCH2 (CH2)10
CH3 ) 3.4 ~ 4.1 (m, 7H, -CH2
CHCH2 O-P-CH2 )

Example 3 100 g (0.35 mol) of monosodium monolauryl phosphate and 10 mol of ion-exchanged water were placed in a reactor equipped with a stirring device.
Add 0g of triethylamine and add triethylamine 3 while stirring thoroughly.
．． 9 g (0.035 mol) were mixed and the temperature was raised to 80°C. To this slurry was added 212 g (0.42 mol) of a 30% aqueous solution of glycidyltrimethylammonium chloride, and the mixture was reacted at 80° C. for 8 hours. 200% of the reaction product
When added to acetone g, the target product lauryl 2
-Hydroxy-3-trimethylammonium phosphate 13
0 g (yield 97%). The conversion rate of monosodium monolauryl phosphate is 10% by potentiometric titration.
It was 0%. 1H-NMR (D2 O. internal standard;
Sodium 3-trimethylsilylpropanesulfonate δ: p
pm)0.8 (t,3H,-P-OCH2 (CH2
)10 CH3 )1.3 (broad.s,20
H, -P-OCH2 (CH2)10 CH3)3
．． 2 (s, 9H, -P-O-CH2 CHCH2 -
N(CH3)3 )3.4 ~4.1 (m,7H,-
CH2 CHCH2 OP-OCH2 )

Example 4 100 g (0.35 mol) of monosodium monolauryl phosphate and 100 g of ion-exchanged water were placed in a reactor equipped with a stirring device, and while stirring thoroughly, 3.9 g (0.035 mol) of triethylamine was added. mol) were mixed and the temperature was raised to 80°C. Glycidyl methacrylate 74.6 was added to this slurry.
g (0.52 mol) and reacted at 80° C. for 8 hours. When the reaction product is poured into 200g of ethanol,
146 g of sodium lauryl 2-hydroxy-3-methacryloyloxyphosphate, which is the target product, was obtained (yield: 97
%). The conversion rate of monosodium monolauryl phosphate was 100% according to potentiometric titration. 1H-
NMR (D2O. Internal standard; Sodium 3-trimethylsilylpropanesulfonate δ: ppm) 0.8 (t, 3
H, -P-OCH2 (CH2)10 CH3)1
．． 2 (broad.s, 20H, -P-OCH2 (
CH2)10CH3)2.0 (s, 3H, -P-
O-CH2 CHCH2 OCH2 =CH3)3.7
~4.3 (m, 7H, -CH2CHCH2O-
P-OCH2)5.5, 6.1(broad,-P
-OCH2 CHCH2 OCH2 =CH3)

0
Example 5 100 g (0.35 mol) of monosodium monolauryl phosphate and 100 g of ion-exchanged water were placed in a reactor equipped with a stirring device, and while stirring thoroughly, 3.9 g (0.035 mol) of triethylamine was added. ) and raise the temperature to 80°C. Add 37g of glycidyl methyl ether to this slurry.
(0.42 mol) was added and reacted at 80°C for 8 hours. The reaction product was poured into 200 g of acetone to obtain 127 g of lauryl 2-hydroxy-3-methoxypropyl phosphoric acid (yield: 97%). The conversion rate of monosodium monolauryl phosphate was 100% according to potentiometric titration. 1H-NMR (D2O
．． Internal standard; Sodium 3-trimethylsilylpropanesulfonate δ: ppm) 0.9 (t,3H,-P-OCH
2 (CH2)10 CH3)1.3 (broa
d. s, 20H, -P-OCH2 (CH2)10C
H3)3.4 (s,3H,-P-O-CH2CH
CH2 OCH3 ) 3.5 ~ 4.0 (m, 7H,
-CH2 CHCH2 OP-OCH2 )

Example 6 Into a reactor equipped with a stirring device, 100 g of monosodium monotrioxylauryl phosphate (
0.24 mol) and 100 g of ion-exchanged water, and while stirring thoroughly, add 2.4 g (0.024 mol) of triethylamine.
mol) and heated to 80°C. 27 g (0.36 mol) of glycidol was added to this slurry and heated to 80°C.
Allowed time to react. When the reaction product was added to 200g of ethanol, the target product, trioxylauryl 2,3
-112 g of sodium dihydroxypropyl phosphate was obtained. The conversion rate of monosodium monotrioxylauryl phosphate was 100% according to potentiometric titration. Elemental analysis value

Example 7 In a reactor equipped with a stirring device, 100 g (0.35 mol) of monolauryl phosphate sodium salt and 100 g of ion-exchanged water were added.
Add 1.g of sodium hydroxide and add 1.g of sodium hydroxide while stirring thoroughly.
4 g (0.035 mol) were mixed and the temperature was raised to 80°C. 39 g (0.52 mol) of glycidol was added to this slurry.
was added and reacted at 80°C for 8 hours. 20% of the reaction product
When added to 0 g of ethanol, the target product, sodium lauryl 2,3-dihydroxypropyl phosphate 12
2g was obtained (yield 96%). In addition, the conversion rate of monolauryl phosphate sodium salt was 100% as determined by potentiometric titration.

Example 8 100 g (0.33 mol) of monosodium mono-2-hydroxylauryl phosphate and 100 g of ion-exchanged water were placed in a reactor equipped with a stirring device, and 3.3 g of triethylamine was added while thoroughly stirring. The mixture was mixed and heated to 80°C. 34 g (0.46 mol) of glycidol was added to this slurry and reacted at 80° C. for 8 hours. 200% of the reaction product
119 g of the target product, sodium 2-hydroxylauryl 2,3-dihydroxypropyl phosphate, was obtained (yield: 95%). In addition, the conversion rate of monolauryl phosphate sodium salt was 100% as determined by potentiometric titration.

Example 9 100 g (0.21 mol) of monosodium monotridecylfluorooctyl phosphate and 100 g of ion-exchanged water were placed in a reactor equipped with a stirring device, and while stirring thoroughly, 2.1 g of triethylamine ( 0.021 mol) were mixed and the temperature was raised to 80°C. Glycidol 2 in this slurry
3g (0.32 mol) was added and reacted at 80°C for 8 hours. The reaction product was poured into 200 g of acetone to obtain 110 g of sodium monotridecylfluorooctyl 2,3-dihydroxypropyl phosphate (yield: 97%). The conversion rate of monodecylfluorooctyl phosphate monosodium salt was determined by potentiometric titration to be 100%.
%Met.

Comparative Example 1 In the same manner as in Example 1, 100 g (0.35 mol) of monolauryl phosphate monosodium salt and 100 g of ion-exchanged water were used.
was added to the slurry, and the temperature was raised to 80° C. with sufficient stirring, but no alkaline substance was added at that time, and 39 g (0.52 mol) of glycidol was added to the slurry, followed by reaction at 80° C. for 8 hours. When the reaction product was poured into 200 g of ethanol, 95 g of a mixture of sodium lauryl 2,3-dihydroxypropyl phosphate, the target product, and monosodium monolauryl phosphate, the raw material, was obtained. The conversion rate of monosodium monolauryl phosphate was 64% as determined by potentiometric titration.

Comparative Example 2 When glycidol was added to the same slurry as in Comparative Example 1 and reacted at 80°C for 8 hours, the conversion rate of monosodium monolauryl phosphate was 100% by potentiometric titration. When the amount of glycidol needed to be added was measured, it was found that 65 g (0.88 mol) of glycidol was required. Furthermore, in addition to the target substance, sodium 2,3-dihydroxypropyl phosphate, ring-opened products of glycidol and glycidol added to the target substance were produced as by-products, and 500 g of these by-products were removed.
required washing with acetone.

[0024]

Effects of the Invention: According to the method of the present invention, in the reaction between a phosphoric acid monoester salt and an epoxy compound, a conversion rate of the phosphoric acid monoester salt is achieved at a level of 100% with a smaller amount of epoxy compound than before. It is possible to purify the phosphoric acid diester more easily than in the past, making it possible to produce the desired phosphoric acid diester industrially very advantageously.

Claims (1)

[Claims] Claim 1: General formula (1) [Formula 1] (wherein, M1 represents a cationic group, and m represents 0 or 1. When m is 0, R1 represents a hydrogen atom in which at least one hydrogen atom is a fluorine atom. A straight chain or branched alkyl group or alkenyl group having 1 to 36 carbon atoms which may be substituted with , or a phenyl group which may be substituted by a straight chain or branched alkyl group having 1 to 15 carbon atoms. , R2 represents an alkylene group having 2 to 3 carbon atoms, n represents a number from 0 to 30; when m is 1, n represents 0, l represents 0 or 1, and when l is 0, R1
represents a straight-chain or branched alkyl group having 1 to 36 carbon atoms, in which one or more hydrogen atoms may be substituted with a fluorine atom, and when l is 1, R1 represents one or more hydrogen atoms with a fluorine atom. R2 represents an optionally substituted linear or branched alkyl group or alkenyl group having 1 to 36 carbon atoms, and R2 represents an alkylene group having 2 to 3 carbon atoms. ) and the aqueous slurry of the phosphoric acid monoester salt represented by the general formula (2) [Chemical formula 2] General formula (3) [Chemical formula 3] (where l, m, n, R1, R2, R3, R4
, R5 and R6 have the same meanings as above, M2 represents a cationic group, or a fourth group is present in R5 or R6.
A method for producing phosphoric acid diesters represented by the following formula (indicates a negative charge itself if an ammonium group is present).