JPS61229888A - Production of phosphoric acid ester - Google Patents

Abstract

PURPOSE:To obtain the titled compound having surface-activity and polymerizability, etc., and high safety and useful as an artificial polymer membrane, etc., economically on an industrial scale, by reacting a specific phosphoric acid monoester alkali metal salt with glycidyl (meth)acrylate. CONSTITUTION:The objective compound is produced by reacting the compound of formula I (R1 is 1-36C alkyl or phenyl substituted with 1-15C alkyl; R2 is 2-3C alkylene; n is 0-30; M is alkali metal) (e.g. monolauryl phosphate sodium salt) with preferably 3-5 times mol of the compound of formula II (R3 is H or CH3) (e.g. glycidyl methacrylate) in an inert polar solvent (preferably water) preferably at 50-90 deg.C. The reaction system may be incorporated with preferably 50-10,000ppm (based on the compound of formula II) of a polymerization inhibitor (e.g. hydroguinone monomethyl ether).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a phosphoric ester, and more particularly to a method for producing a polymerizable phosphoric ester.

[Conventional technology]

Phosphate esters are used in a wide range of fields, including detergents, textile treatment agents, emulsifiers, rust preventives, liquid ion exchangers, and medicines.

Among phosphoric acid esters, alkali metal salts of phosphoric acid monoesters are significantly superior to other phosphoric acid esters, such as alkali metal salts of phosphoric diesters, in terms of surface activity and other functions. .

For example, alkali metal salts or alkanolamine salts of phosphoric monoesters of long-chain alkyl alcohols are water-soluble, and their aqueous solutions have extremely good foaming and detergent properties, whereas phosphoric diester salts are water-soluble. It hardly dissolves in water, has almost no foaming power, and on the contrary exhibits foam-inhibiting properties.

On the other hand, in the field of polymers, research is underway to add various functions to polymer substances, and the functions of phosphoric acid groups and phosphoric esters, such as surfactant ability, chelating ability, antistatic ability, etc. In recent years, research has been actively conducted to add this function to polymer compounds.

The method of incorporating such a phosphorus compound into a polymer compound is as follows: (1) Blending the phosphorus compound into the polymer compound.

(2) Phosphorylating a reactive functional group, such as a hydroxyl group, in a polymer compound.

■Molecularization using a phosphorus compound as a monomer.

There are three possible methods. However, method (2) has the disadvantage that the blended phosphorus compound comes out of the polymer compound due to elution, etc., and method (2) has the disadvantage that the phosphorylating agent is limited and phosphorylation cannot be performed as expected. have. Therefore, it has been desired to develop a phosphorus compound, such as a phosphoric acid ester having a polymerizable group, as a monomer to be used in the method (1).

Furthermore, in the field of polymer membranes, which is one of the ways in which polymers are used, the functions possessed by biological membranes, such as compartment formation and selective transport functions of substances, are artificially created, and a wide range of engineering and In recent years, research has been actively conducted to try to apply it to a wide range of fields such as medicine and pharmacy. This biological membrane differs from an artificial polymer membrane in its structure; in biological membranes, molecules are oriented in an orderly manner, forming, for example, a bilayer membrane structure. This orientation is due to the physical function of phospholipid molecules, which are constituent components of biological membranes, and the property of self-assembling and organizing, which is unique to amphipathic compounds that have a hydrophobic group and a hydrophilic group. Therefore, when considering monomers used as materials for membranes, etc., attention is being paid not only to the chemical properties of the monomers but also to compounds having physical properties such as surfactant ability and self-organizing ability. In addition to surface activity and self-assembly properties, lipids also have biocompatibility functions, and when considering the application of polymers to pharmaceuticals and medical polymer materials, it is important to introduce polymerizable groups into phospholipids. These compounds are very interesting compounds2, such as Rega
A compound represented by the following formula (■) has been synthesized by Nl et al. [Journal of the American Chemical Society (J. Arner, Chem.
Soc,, 105. 2975 (1983)).

Therefore, it has been desired to develop a substance similar to phosphoric acid esters or phospholipids that has surface activity, self-assembly properties, and has a polymerizable group in a hydrophobic group or a hydrophilic group.

However, it has been difficult to obtain these substances industrially.

[Problem that the invention seeks to solve]

Therefore, it has been desired to develop a phosphoric acid ester compound having surfactant ability and polymerizability, which can be easily produced industrially and has few safety problems.

[Means for solving problems]

Under these circumstances, the present inventors conducted extensive research and found that highly purified phosphoric acid monoester has excellent surfactant ability, and that monoalkali metal salts of phosphoric acid monoester are water-soluble. and that a polymerizable group can be selectively introduced into a phosphoric acid ester by utilizing the fact that a monoalkali metal □ group salt of a phosphoric acid monoester reacts with an epoxy compound in an aqueous solution system. Furthermore, it has been found that the target compound can be easily obtained with high purity. In addition, the obtained compound has surfactant ability,
The present invention was completed by discovering that this compound has self-assembly ability, that this compound has polymerizability, and that this polymer has excellent film-forming ability.

That is, the present invention has the following formula: or a phenyl group substituted with a linear or branched alkyl group having 1 to 15 carbon atoms, where ``bird'' is an alkylene group having 2 to 3 carbon atoms, n is a number from 0 to 30, and M is an alkali group. (indicating that it is a metal) and a phosphoric acid monoester salt represented by the general formula (Ill
, (wherein R3 represents hydrogen or methyl group) A general formula (seal) characterized by reacting a compound represented by: (wherein Rt , F6 , R3, n, M are Formula (Il,
The present invention provides a method for producing a phosphoric ester represented by (same as that shown in (1)).

The phosphoric acid monoester salt represented by the general formula (I) used in the present invention includes monooctyl phosphate,
Monolinear alkyl phosphates such as monolauryl phosphate and monostearyl phosphate; monoisostearyl phosphate, mono-8-methyl-heptadecyl phosphate [1, mono-2-
Monobranched alkyl phosphates such as hexylutecyl phosphate; monoalkyl phenyl phosphates such as monooctylphenyl phosphate and heptanonylphenyl phosphate;
Monopolyoxyalkylenes such as monopolyoxyethylene (3 mol) lauryl ether phosphate, monopolyoxypropylene (3 mol) decyl ether phosphate, monopolyoxyethylene (8 mol) polyoxypropylene (3 mol) lauryl ether phosphate Alkyl ether phosphate; monopolyoxyethylene (5 mol) nonylphenyl ether phosphate, monopolyoxypropylene (2
Examples include monopolyoxyalkylene alkylphenyl ether phosphates such as mol) octylphenyl ether phosphates.

As the alkyl metal salt, sodium salt and potassium salt are preferred.

These phosphoric acid monoester salts can be obtained by reacting the corresponding organic hydroxy compound with a phosphorylating agent such as phosphorus pentoxide, phosphorus oxychloride, or polyphosphoric acid to obtain a phosphoric acid monoester, and then neutralizing it. . However, it is preferable that the phosphoric acid monoester salt used in the present invention has high purity. In other words, if phosphoric acid diester, which is produced as a by-product when phosphorus pentoxide or phosphorus oxychloride is used as a phosphorylating agent, is included, the surfactant ability and self-assembly ability of the phosphoric acid monoester will decrease or disappear. The purity of the target compound decreases in the reaction with the epoxy compound, and purification to obtain a highly pure target compound becomes difficult. In addition, orthophosphoric acid, which is produced as a by-product when polyphosphoric acid is used as a phosphorylating agent, also reduces the yield of the desired reaction in the reaction with the epoxy compound, and further reduces the purity of the desired compound, making it difficult to obtain a highly pure desired compound. This makes purification difficult. That is, when carrying out the present invention, it is preferable to use a phosphoric acid monoester having a purity of 90% by weight or more. Note that a method for industrially producing high-purity monoalkyl phosphoric acid has been developed by some of the inventors (Japanese Patent Application No. 1388-1983).
No. 29), and a method for removing orthophosphoric acid from a mixture of monopolyoxyethylene or polyoxypropylene alkyl ether phosphoric acid and orthophosphoric acid has been developed by some of the inventors (Japanese Patent Application No. 1983-251).
No. 409).

In the production method of the present invention, the epoxy compound represented by the formula (old) is a monoalkali metal salt of phosphoric acid monoester (■)
It is preferable to react 1 to 10 mol per mol, and 3 to 5 mol per mol.

The solvent used for the reaction is an inert polar solvent, water,
Methyl alcohol, ethyl alcohol, etc. are used, but water is preferred. The fact that water can be used as a solvent is extremely preferable from the standpoint of safety in industrial production.

The reaction temperature is 30 to 100°C, especially 50 to 90°C.
It is preferable to carry out the reaction.

If this reaction is carried out without converting the phosphoric acid monoester into a monoalkali metal salt, as mentioned above, the reaction cannot be carried out in an aqueous solvent, and the reaction will not only result in the target compound, but also in the reaction. 1 mole of the compound represented by the formula (old) reacts with phosphoric acid triester, which is produced as a by-product and reduces the yield of the target compound, which is undesirable.Furthermore, at the end of the reaction, the ester bond is hydrated because the system is acidic. This reduces the yield of the target compound which is susceptible to decomposition.That is, in carrying out the present invention, it is necessary to react a monoalkali metal salt of a phosphoric acid monoester with a compound represented by formula (U).

Furthermore, polymerization inhibitors or polymerization inhibitors may be added during the reaction, such as hydroquinone mo/L-thyl ether, hydroquinone, 2,2'-methylene bis(4
It is preferable to add 50 to 110,000 pp of glycidyl methacrylate or glycidyl acrylate to glycidyl methacrylate or glycidyl acrylate.

In addition to the target compound represented by formula (I), the reaction solution thus obtained contains unreacted formulas (compounds represented by
Alternatively, a hydrolyzate of the compound represented by formula (If) is included. Depending on the purpose of use, it is possible to use the reaction product obtained from this reaction solution as it is, but
A highly purified product can be obtained by further purification.

For example, sodium dodecyl 2-hydroxy-3-methacryloyloxybrobyl phosphate [in the compound of formula ([) R+= ClAs + n = O, R1= CH
3, M = Na, hereinafter referred to as compound (V)], after reacting glycidyl methacrylate with an aqueous solution of sodium dodecyl phosphate, water is distilled off, or sodium chloride or potassium chloride is added to the reaction solution. After saturating the electrolyte such as ethyl ether and extracting the organic matter into an organic solvent such as ethyl ether, the ethyl ether is distilled off to separate it from water, and the unreacted glycidyl methacrylate is added to a nonpolar solvent such as n
-After extraction and separation with hexane, acetone is further added,
By precipitating the produced sodium dodecyl 2-hydroxy-3-methacryloyloxyprobyl phosphate and separating it from the acetone-soluble glycidyl methacrylate hydrolyzate, a highly pure target product can be obtained.

Further, in the above purification, if unreacted glycidyl methacrylate is completely hydrolyzed after the reaction is completed, the subsequent purification step will be facilitated.

Furthermore, the present compound ([1] may be used after being acidified if necessary or further neutralized with a base such as ammonium, alkylamine, alkanolamine, etc.).

[Effect]

In the present invention, the fact that the compound represented by formula (1) has surface activity and self-assembly property means that, for example, compound (V)
The phase diagram in an aqueous system is shown in Figure 1, and this can be seen from the fact that liquid crystals are formed.

In addition, the fact that the compound shown in the present invention has polymerizability can be confirmed, for example, by adding a photopolymerization initiator or a general water-based polymerization initiator to the above-mentioned aqueous solution of the compound (Vl) and applying light or heat. This can be seen from the fact that these polymers are polymerized and that these polymers have film-forming ability.

〔Effect of the invention〕

According to the present invention, it has surfactant ability, self-assembly ability, polymerizability, and film-forming ability, and is highly safe for the human body.
Phosphate esters that can be widely used in fields such as engineering and medicine can be produced industrially with great advantage.

〔Example〕

Next, the present invention will be explained with reference to Examples.

Example 1 200PC0 of monolauryl phosphoric acid with a purity of 97% was added to the reactor.
, 73 mol, but the AVI of this sample (Q number of KOH required to neutralize 1 ton of sample of this phosphoric acid monoester from the first equivalent point to the second equivalent point, the same applies below) m42
0.8], 75 Qm/l of 1N aqueous sodium hydroxide solution was added, stirred, and heated to 70°C to make it uniform. At this time, the acid value of the reaction system (the η number of KOI required to neutralize 1 g of sample, hereinafter the same) was 41L9.Next, while maintaining the reaction system at 70°C, glycidyl methacrylate 533 ? (3.75 mol) was gradually added and stirred at this temperature for 9 hours. At this time, the acid value of the reaction system became almost 0, indicating that the reaction was completed. When the sample was analyzed by HPLC (high performance liquid chromatography, hereinafter the same applies), a peak of unreacted glycidyl methacrylate was observed. After further stirring, the reaction continued for a total of 20 hours, and glycidyl methacrylate was completely hydrolyzed. Next, the reaction solution was cooled to room temperature, transferred to a separating port, and after being saturated with common salt,
Extracted twice with 005' ethyl ether. Acetone 5009- was added to the nonvolatile liquid residue obtained by distilling off ethyl ether under reduced pressure, and the mixture was left refrigerated at 5°C. After one day, the precipitated crystals were collected and recrystallized with acetone to yield white crystals of sodium dodecyl 2-hydroxy-3-methacryloyloxyprobyl phosphate 178? was gotten. .

1) I NMR.

δ0.8pI)m (t, 3)I, -P-OCR,
(CH,),. CH,)δ1.2ppm (broad
a, 20H, -P-OCH, ((H2), 0H5
) δloppm (a, 3H,CH, -C-CH,)
δ3.7-4.3 ppm (broad, 8H,C
o, CH, Cl5CH, 0 POC shi) 0■ 'CNMR.

δ tppml: n14.1. δ18.3. m
23. o, j26.1.1k30.2,131. δ6
5.2. e68.7. b126.5°c136.2 Standard sample: Si(Cf(,14) Elemental analysis: As a result of HPLC analysis, the purity was 98-99%.

Test Example 1 Sodium dodecyl 2-hydroxy-3-methacryloyloxyprobyl phosphate obtained in Example 1 [Compound (V)]
To a mixed system of 50150 and 50150 of water, benzoin isobutyl ether as a photopolymerization initiator was added as a counter compound (V), and the mixture was irradiated with light for 2 hours under a nitrogen stream to obtain a colorless and transparent rubbery substance.

In addition, when this sample [a sample in which a photopolymerization initiator was added to a mixed system of Compound (V) and water 50150] was thinly spread between slide glasses and exposed to light for 2 hours, a colorless and transparent film was formed. Substance obtained.

In addition, a polymerization initiator was added to about 10% aqueous solution of compound m.
KtstOs was added to the counter compound (V) (7) at 1%,
When heated at 60 to 70°C for 4 to 5 hours, a colorless and transparent high viscosity aqueous solution was obtained. Furthermore, when this polymer was placed on a slide glass and left to stand, a colorless and transparent film-like substance was obtained. Additionally, this polymer had the property of gelling water and methanol.

Example 2 Similar to Example 1, 200 g of monooctadecyl phosphoric acid with a purity of 97% (0.55 mol, but this sample (7)
AV1 = 160.7, A'V2 = 321.5) t
” lNormal sodium hydroxide aqueous solution 573rILl 5
Glycidyl methacrylate 4075' (2.86 mol) was gradually added to the mixture, and the mixture was stirred at this temperature for 20 hours. It can be seen that the acid value of the reaction system at this time was approximately O, and the reaction rate of the phosphoric acid monoester was approximately 100%.

The reaction solution was cooled with O'CT, the precipitated crystals were filtered out, and the resulting cake was washed with acetate and dried to obtain white crystals of sodium octadecyl 2-hydroxy-3-methacryloyloxyprobyl phosphate. 198y- was obtained.

Elemental analysis: As a result of HPLC analysis, the purity was 99% or more.

Example 3 Mono-2-hexyldecyl phosphoric acid 2°P (0
,057 mol, &ri L co0 sample (7) A V 1
m167.2, AV 2 = 329.8 ) in 1N sodium hydroxide aqueous solution 59.6 #17! (The acid value of the reaction system at this time was 39.5), and glycidyl methacrylate was 25.4 at 70°C. (0,178 mol) was gradually added and stirred at this temperature for 30 hours. It can be seen that the acid value of the reaction system at this time was 1.1, and the reaction rate of the phosphoric acid monoester was about 97. When the reaction solution was analyzed by HPLC, peaks of a hydrolyzate of glycidyl methacrylate and a new round product were observed. The product was separated from the reaction solution by HPLC, and the solvent was distilled off under reduced pressure to obtain 2-
Sodium hexyldecyl 2-hydroxy-3-methacryloyloxyprobyl phosphate is 23.5? Obtained.

II (NMR.

δ0.9 ppm (t, at 6, -CH, CJi,
X2) δ1.3ppm (broad a, 24H
, -P-OCH,CH (C, 11g1vCHt1 (C horse 1scHs δ1.9ppm (s, 3H,CH, -C-CHs
)IsCNMR.

δ (PPm): q 14.2. δ18.3.
p2L7. k27. o, n29.8. m30.
1. j30.8.131.1. o32. o.

δ38.6. g64.8. f 65.6. e68
．． 2. δ71.1°δ126.3. (!136.1.
d167.5 standard sample: S i (CH,, 14 Elemental analysis; As a result of HPLC analysis, the purity was 98-99%.

Example 4 A reactor was charged with 94% pure mono-2-decyltetradecyl phosphate 2 Q P (0,043 mol, except for this sample (
7) AV1=1342, AV2=267.1>
and 1N potassium hydroxide aqueous solution 47.8 at
was added, stirred, and heated to 70°C to uniformly disperse it (
The acid value of the reaction system at this time was 37.9). Next, while keeping the reaction system at 70°C, glycidyl methacrylate 20,
4) (0,143 mol) was gradually added dropwise and stirred at this temperature for 20 hours. It can be seen that the acid value of the reaction system at this time was 1.5, and the reaction rate of the phosphoric acid monoester was about 96%. ) (The product was separated by P'LC and the solvent was distilled off under reduced pressure to give 2-decyltetradecyl 2-hydroxy-3-
Potassium methacryloyloxyprobyl phosphate is 23.4
9- Obtained.

Elemental analysis: As a result of HP LC analysis, the purity was 98-99%.

Example 5 Motuptil phosphoric acid 20P (0,
13% le, only 1. This Og charge OA V 1 =360.
6, AV2=721.3), 1291 nl of 1N aqueous sodium hydroxide solution was added and stirred, and dissolved at 70°C (the acid value of the reaction system at this time was 46.7).

Next, while maintaining the reaction system at 70°C, 91.4p (0°64 mol) of glycidyl methacrylate was gradually added dropwise, and the mixture was stirred at this temperature for 20 hours. At this time, the acid value of the reaction system is almost 0.
It can be seen that the reaction rate of phosphoric acid monoester is approximately 100m. The product was separated by HPLC and the solvent was distilled off under reduced pressure to obtain 37.2% sodium butyl 2-hydroxy-3-methacryloyloxyprobyl phosphate.

Elemental analysis: As a result of HPLC analysis, the purity was 98-99%.

Example 6 98% purity monotrioxyethylene dodecyl phosphate 205F- (0,049 mol, however, O sample 0AV1=14L8, AV2=288.2) was charged into a reactor, and 1N potassium hydroxide was added. An aqueous solution of 50.9- was added, stirred, and dissolved at 70°C (the acid value of the reaction system at this time was 3).
9.5). Next, the reaction system was kept at 70°C and from the table, glycidyl methacrylate 20.9 F (0.15 mol)
was gradually added dropwise and stirred at this temperature for 20 hours. It can be seen that the acid value of the reaction system at this time was 1.5, and the reaction rate of the phosphoric acid monoester was approximately 96. The product was separated by HPLC, and the solvent was distilled off under reduced pressure, yielding 25.5% potassium trioxyethylenedodecyl 2-hydroxy-3-methacryloyloxyprobyl phosphate. Obtained.

Example 7 Diethylene nonylphenyl phosphoric acid (average number of added moles of ethylene oxide =
5+20? (0,035 mol, however, (7)
V 1 = 97.1, AV 2 = 194.1 +
was added, 34.6 mm of a 1N aqueous potassium hydroxide solution was added, and the mixture was stirred and dissolved at 70°C (the acid value of the reaction system at this time was 34.4). Next, while maintaining the reaction system at 70°C, 24.5 ji' (0,17
mol) was gradually added dropwise and stirred at this temperature for 20 hours.

At this time, the acid value of the reaction system was approximately 0, indicating that approximately 100% of the phosphoric acid monoester had reacted.

Comparative Example 1 Monolauryl phosphoric acid 5°5' (purity 9711) was placed in a reactor.
0,19-v-ru, 7tLko0FeR (DAV1=2
09.5, AV2=420.6) was dissolved in 187m of Te)rahi)'o fly.At this time, the reaction system was
8.8, AV2=97.9. Next, the reaction system was
Glycidyl methacrylate 1345' (
0.94 mol) was gradually added and stirred at this temperature for 1 hour. At this time, the acid value of the reaction system is A V l = 7.6, A
V2=10.3, and it was found that 9 mol of unreacted phosphoric acid monoester, 16 mol of phosphoric acid diester, and 75 mol of phosphoric acid triester were produced. Further stirring was continued, and after a total of 4 hours of reaction, the acid value was measured and found to be almost O, indicating that almost 100% of the phosphoric acid monoester had reacted, and that all of the phosphoric acid triester had been converted.

Comparative Example 2 Monolauryl phosphoric acid 50S' (0
, 19 mol, &Tashi and (7) inノAV1-209.5
,AV2=420.6) f-) Rahi)”a75y1
It was dissolved in 87ml. At this time, the reaction system is AV1=48.
8, A V 2 = 97.9. Next, while maintaining the reaction system at 70°C, glycidyl methacrylate 27de(
0.19 mol) was gradually added and stirred at this temperature for 5 hours. At this time, the acid value of the reaction system is AV1=30.8, AV2=
49.0, indicating that 42 molt of unreacted phosphoric acid monoester, 29 molt of phosphoric acid diester, and 29 molt of phosphoric acid triester were produced.

[Brief explanation of the drawing]

Figure 1 shows the phosphoric acid ester compound (V)/H,0 of the present invention.
This is a phase diagram of the system, and FIG. 2 is a drawing showing the IR spectrum of the same compound (V). Margin rules for the following areas Invitation p Procedural amendment uF (Voluntary) May 10, 1985 Patent Application No. 71340 2. Name of the invention Method for producing phosphate ester 3. Relationship with the case of the person making the amendment Filed Address: 1-141110 Kayabacho, Nihonbashi, Chuo-ku, Tokyo
Title (091) Kao Soap Co., Ltd. Representative Yoshi Maruyama Department 4, Agent 6 Column 7 of “Detailed Description of the Invention” of the specification to be amended, Contents of the amendment (1) In the specification, No. The words "Dodecyl 2" on page 13, lines 1-2 and line 13, page 16, line 11, and page 18, line 3 are corrected to "Dodecyl 2." 12) Same, page 19, line 12, ``Octadecyl 2'' is corrected to ``Octadecyl 2''. (3) Same, page 24, lines 11-12, "monotrioxyethylene dodecyl phosphoric acid" is corrected to "monotrioxyethylene dodecyl ether phosphoric acid". (4) Same, page 25, lines 7-8, "mono-lioxyethylene nonyl phenyl phosphoric acid" is corrected to "mono-lioxyethylene nonyl phenyl ether phosphoric acid".

Claims (1)

[Claims] 1. General formula (I), ▲Mathematical formula, chemical formula, table, etc.▼(I) (In the formula, R_1 is a straight or branched alkyl group having 1 to 36 carbon atoms, or a carbon It is a phenyl group substituted with a linear or branched alkyl group of numbers 1 to 15, and R_
2 is an alkylene group having 2 to 3 carbon atoms, and n is 0 to 30
, where M is an alkali metal) and the general formula (II), ▲Mathematical formula, chemical formula, table, etc.▼(II) (In the formula, R_3 is There are general formulas (III), ▲mathematical formulas, chemical formulas, tables, etc.▼(III) (in the formula, R_1, R_2, R_3, n, M are formulas (I)
, which is the same as that shown in (II)).