JPH0660184B2 - Method for producing phosphate ester - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a phosphoric acid ester, and more particularly to a method for producing a phosphoric acid ester having polymerizability.

[Conventional technology]

Phosphate esters are used in a wide range of fields as detergents, fiber treatment agents, emulsifiers, rust preventives, liquid ion exchangers, pharmaceuticals and the like.

Thus, among the phosphoric acid esters, the alkali metal salts of phosphoric acid monoesters are far superior to other phosphoric acid esters, for example, the alkali metal salts of phosphoric acid diesters in terms of functions such as surface activity. . For example, alkali metal salts or alkanolamine salts of long-chain alkyl alcohol phosphoric acid monoesters are water-soluble, and their aqueous solutions have very good foaming power and detergency, whereas phosphoric acid diester salts are water-soluble. It hardly dissolves, has almost no foaming power, and on the contrary exhibits foam suppressing properties.

On the other hand, in the field of polymers, research is underway to add various functions to polymeric substances, and the functions possessed by phosphate acidic groups and phosphate esters, such as surface-active ability, chelating ability, antistatic ability, etc. In recent years, much research has been done on adding the function of the above to a polymer compound.

The method of incorporating such a phosphorus compound into the polymer compound is to blend the polymer compound with the phosphorus compound.

A reactive functional group in a polymer compound, for example, a hydroxyl group is phosphorylated.

Polymerize using a phosphorus compound as a monomer.

There are three possible methods. However, the method (1) has a drawback that the blended phosphorus compound is released from the polymer compound by elution and the like, and the method (3) has a limitation that the phosphorylating agent is limited. Have Therefore, it has been desired to develop a phosphorus compound as a monomer used in the above method, for example, a phosphoric acid ester having a polymerizable group.

Furthermore, in the field of polymer membranes, which is one of the usage forms of polymers, artificially creating functions possessed by biological membranes, such as compartment formation and selective transport functions of substances, are widely used in engineering, In recent years, research aiming at application to a wide range of fields such as medicine and pharmacy has been actively conducted. This biological membrane is different from the artificial polymer membrane in that its structure is such that molecules are oriented in a well-ordered manner in the biological membrane to form, for example, a bilayer membrane structure. This orientation is due to the physical function of the phospholipid molecule, which is a constituent of biological membranes, and the property of self-assembly and organization, which is unique to amphipathic compounds having so-called hydrophobic groups and hydrophilic groups. Therefore, when considering a monomer as a material used for a film or the like, a compound having not only the chemical property of the monomer but also the physical property, for example, the surface activity ability and the self-organization ability is attracting more and more attention. Phospholipids have functions of biocompatibility in addition to such surface activity and self-organization property, and when considering the application of polymers to pharmaceuticals and medical polymer materials, phospholipids have a polymerizable group. The introduced compounds are very interesting compounds, for example Regan
Have synthesized a compound represented by the following formula (IV) [Journal of the American Chemical Society (J. Amer. Chem. Soc., 105 , 2975 (1983)]].

Therefore, it has been desired to develop a phosphoric acid ester or a phospholipid-like substance having a surface-active property and a self-organizing property and having a polymerizable group in a hydrophobic group or a hydrophilic group. However, it was difficult to obtain these substances industrially.

[Problems to be solved by the invention]

Therefore, it has been desired to develop a compound having a phosphoric acid ester-based surfactant activity and a polymerizable property, which can be easily produced industrially and has little problem in safety.

[Means for solving problems]

Under such circumstances, as a result of intensive studies conducted by the present inventors, it was found that high-purity phosphoric acid monoester has excellent surface-active ability, and that the monoalkali metal salt of phosphoric acid monoester is water-soluble. And, by utilizing the fact that the monoalkali metal salt of phosphoric acid monoester and the epoxy compound react with good selectivity in an aqueous solution system, it is possible to introduce a polymerizable group into the phosphoric ester with good selectivity, It was found that the compound was easily obtained in high purity. Further, the obtained compound has a surface-active ability and a self-organizing ability, and further, this compound has a polymerizing property, and further, this polymer has an excellent film-forming ability. Found and completed the present invention.

That is, the present invention is represented by the general formula (I), (In the formula, R ₁ is a linear or branched alkyl group having 1 to 36 carbon atoms, or a phenyl group substituted with a linear or branched alkyl group having 1 to 15 carbon atoms, and R ₂ is carbon. Which is an alkylene group of the formula 2 to 3, n is a number of 0 to 30 and M is an alkali metal), and a monoester of phosphoric acid represented by the general formula (II), (Wherein R ₃ represents hydrogen or a methyl group), a compound represented by the general formula (III), (Wherein R ₁ , R ₂ , R ₃ , n, and M are the same as those represented by formulas (I) and (II)), and a method for producing a phosphoric acid ester represented by the formula: .

Examples of the phosphoric acid monoester salt represented by the general formula (I) used in the present invention include mono-linear alkyl phosphates such as monooctyl phosphate, monolauryl phosphate and monostearyl phosphate; Stearyl phosphate, mono 8-methyl-heptadecyl phosphate, mono 2-
Mono-branched alkyl phosphates such as hexyl-decyl phosphate; monoalkyl phenyl phosphates such as monooctyl phenyl phosphate, monononyl phenyl 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
Mol) octyl phenyl ether phosphates and other monopolyoxyalkylene alkyl phenyl ether phosphates.

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

These phosphoric acid monoester salts can be obtained by reacting a corresponding organic hydroxy compound with a phosphorylating agent such as phosphorus pentoxide, phosphorus oxychloride, polyphosphoric acid, etc. to obtain a phosphoric acid monoester and then neutralizing it. . However, in the phosphoric acid monoester salt used in the present invention, it is preferable that the monoester has a high purity. That is, when a phosphoric acid diester by-produced when phosphorus pentoxide or phosphorus oxychloride is used as a phosphorylating agent is contained, the surfactant activity as a phosphoric acid monoester, the self-organizing ability is reduced or disappears, and further In the reaction with the epoxy compound, the purity of the target compound is lowered, and the purification for obtaining the high-purity target compound becomes difficult. Further, orthophosphoric acid, which is a by-product when polyphosphoric acid is used as a phosphorylating agent, also lowers the yield of the desired reaction in the reaction with the epoxy compound, further reduces the purity of the desired compound, and produces a highly pure target compound. Purification to obtain becomes difficult. That is, in carrying out the present invention, it is preferable to use phosphoric acid monoester having a purity of 90% by weight or more as the purity of phosphoric acid monoester. A method for industrially producing high-purity monoalkyl phosphoric acid has been developed by a part of the present inventors (Japanese Patent Application No. 59-138829).
No.), 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 present inventors (Japanese Patent Application No. 59-251409). ).

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

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

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

When this reaction is carried out without converting the phosphoric acid monoester into a monoalkali metal salt, the reaction cannot be carried out in a water solvent as described above, and not only the target compound in the reaction but also another mol The phosphoric acid triester reacted with the compound represented by the formula (II) is by-produced to reduce the yield of the target compound, which is not preferable. Furthermore, at the end of the reaction,
Since the system is acidic, the ester bond is susceptible to hydrolysis and the yield of the target compound is reduced. 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 the formula (II).

Further, a polymerization inhibitor or a polymerization inhibitor may be added during the reaction, for example, hydroquinone monomethyl ether, hydroquinone, 2,2'-methylenebis (4
-Ethyl-6-t-butylphenol) and the like with respect to glycidyl methacrylate or glycidyl acrylate.
It is preferable to add 0 to 10,000 ppm.

In the reaction solution thus obtained, in addition to the compound represented by the target formula (III), the unreacted compound represented by the formula (II),
Alternatively, it contains a hydrolyzate of the compound represented by the formula (II). Depending on the purpose of use, the reaction product obtained from this reaction solution can be used as it is, but a high-purity product can be obtained by further purification. For example, sodium dodecyl 2-hydroxy-3-methacryloyloxypropyl phosphate [in the compound of formula (III), R ₁ = C ₁₂ H ₂₅ , n = 0, R ₃ = CH ₃ , M = Na, and In the case of (V)], glycidyl methacrylate is reacted with an aqueous solution of sodium dodecyl phosphate, and then water is distilled off, or the reaction solution is saturated with an electrolyte such as sodium chloride or potassium chloride, and an organic substance is converted into ethyl ether. After extraction with an organic solvent such as ethyl ether, the ethyl ether was distilled off to separate from water, and unreacted glycidyl methacrylate was extracted and separated with a nonpolar solvent, for example, n-hexane, and then acetone was added to generate. Dodecyl 2
A target substance having a high purity can be obtained by precipitating sodium hydroxy-3-hydroxy-3-methacryloyloxypropylphosphate and separating it from the acetone-soluble hydrolyzate of glycidyl methacrylate.

Further, in the above purification, if the unreacted glycidyl methacrylate is completely hydrolyzed after the reaction is completed, the subsequent purification step becomes easy.

If necessary, the compound (III) may be acidified or further neutralized with a base such as ammonium, alkylamine or alkanolamine before use.

[Action]

In the present invention, the compound represented by the formula (I) has surface activity,
The fact that the compound (V) has a self-organizing property can be seen, for example, from the fact that the phase diagram of the compound (V) in an aqueous system is as shown in FIG.

Further, that the compound shown in the present invention is polymerizable, for example, by adding a photopolymerization initiator or a general water-based polymerization initiator in the aqueous solution of the compound (V) to give light and heat It can also be seen from the fact that these polymers have a film forming ability.

〔The invention's effect〕

According to the present invention, having a surfactant ability, a self-organizing ability, a polymerizing ability and a film forming ability, and being highly safe for the human body,
A phosphate ester which can be widely used in the fields of engineering, medicine, etc. can be industrially produced extremely advantageously.

〔Example〕

 Next, the present invention will be described with reference to examples.

Example 1 200 g [0.73] of monolauryl phosphoric acid having a purity of 97% was charged in a reactor.
Mol, but AV1 of this sample (KOH required to neutralize 1 g sample of the present phosphoric acid monoester to the first equivalent point)
, And AV2 (the number of mg of KOH necessary to neutralize 1 g of the sample of the present phosphoric acid monoester to the second equivalent point, the same applies below) = 420.8] Then, 750 m of a 1N aqueous sodium hydroxide solution was added, and the mixture was stirred and heated to 70 ° C. to make the mixture uniform. At this time, the acid value of the reaction system (mg of KOH necessary to neutralize 1 g of the sample, the same applies below) was 42.9. Next, while maintaining the reaction system at 70 ° C, 533 g (3.75 mol) of glycidyl methacrylate
Was gradually added, and the mixture was 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. In addition, when a sample collected from this reaction system was analyzed by HPLC (high performance liquid chromatography, the same shall apply hereinafter), an unreacted glycidyl methacrylate peak was observed. Glycidyl methacrylate was completely hydrolyzed when the mixture was further stirred and reacted for a total of 20 hours. Then, the reaction solution was cooled to room temperature, transferred to a separating funnel, saturated with sodium chloride, and extracted twice with 500 g of ethyl ether. 500 g of acetone was added to the non-volatile liquid residue obtained by distilling off the ethyl ether under reduced pressure, and the mixture was kept refrigerated at 5 ° C. One day later, the precipitated crystals were collected and recrystallized with acetone to obtain 178 g of white crystals of sodium dodecyl 2-hydroxy-3-methacryloyloxypropyl phosphate.

δ (ppm): n14.1, a18.3, m23.0, j26.1, ik30.2, 13
2.3, g65.2, e68.7, b126.5, c136.2 Standard sample: Si (CH ₃ ) ₄ Elemental analysis: As a result of analysis by HPLC, the purity was 98 to 99%.

Test Example 1 Dodecyl 2-hydroxy-3-methacryloyloxypropyl sodium phosphate obtained in Example 1 [Compound (V)]
To a mixed system of 50/50 of water and water, 2% of compound (V) was added as a photopolymerization initiator, and 2% of compound (V) was added, and a colorless transparent rubber-like substance was obtained by irradiating with light for 2 hours under a nitrogen stream. . In addition, this sample [compound (V) and water 5
A sample in which a photopolymerization initiator was added to a 0/50 mixed system] was sandwiched between slide glasses, thinly stretched, and similarly irradiated with light for 2 hours to obtain a colorless and transparent film-like substance.

In addition, K ₂ S ₂ O ₈ as a polymerization initiator was added to a 10% aqueous solution of the compound (V) at 1 to 40% at 60 to 70 ° C.
After heating for ~ 5 hours, a colorless transparent high viscosity aqueous solution was obtained. Furthermore, when this polymer was placed on a slide glass and allowed to stand, a colorless and transparent film-like substance was obtained. Further, this polymer had a property of gelling water or methanol.

Example 2 As in Example 1, 200 g (0.55 mol, but AV1 = 160.
7, AV2 = 321.5) 1N sodium hydroxide aqueous solution 5
Dissolves in 73m at 55 ℃ (The acid value of the reaction system at this time is 4
0.3), 407 g of glycidyl methacrylate (2.8
(6 mol) was gradually added, 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 is almost 0 and the reaction rate of the phosphoric acid monoester is almost 100%. 0 for reaction
The mixture was cooled to 0 ° C., the precipitated crystals were separated, the cake obtained was washed with acetone and dried to obtain 198 g of white crystals of sodium octadecyl 2-hydroxy-3-methacryloyloxypropyl phosphate.

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

Example 3 20 g (0.05%) of mono-2-hexyldecylphosphoric acid having a purity of 92%
7 moles, but for this sample AV1 = 167.2, AV2 = 329.
8) was dispersed in 59.6 m of 1N aqueous sodium hydroxide solution (the acid value of the reaction system at this time was 39.5), and 25.4 g (0.178 mol) of glycidyl methacrylate was gradually added at 70 ° C. And stirred for 30 hours. It can be seen that the acid value of the reaction system at this time is 1.1 and the reaction rate of the phosphoric acid monoester is about 97%. When the reaction solution was analyzed by HPLC, peaks of a hydrolyzate of glycidyl methacrylate and a new product were observed. The product was separated from the reaction solution by HPLC and the solvent was distilled off under reduced pressure to obtain 23.5 g of sodium 2-hexyldecyl 2-hydroxy-3-methacryloyloxypropyl phosphate.

δ (ppm): q14.2, a18.3, p22.7, k27.0, n29.8, m30.
1, j30.8, l31.1, o32.0, i38.6, g64.8, f65.6, e68.
2, h71.1, b126.3, c136.1, d167.5 Standard sample: Si (CH ₃ ) ₄ Elemental analysis: As a result of analysis by HPLC, the purity was 98 to 99%.

Example 4 In a reactor, 20 g (0.043 mol, but AV1 = 13 of this sample) of mono-2-decyltetradecylphosphoric acid having a purity of 94% was used.
4.2, AV2 = 267.1) was added, 47.8 m of 1N potassium hydroxide aqueous solution was added and stirred, and the temperature was raised to 70 ° C. to uniformly disperse (the acid value of the reaction system at this time was 37.9). ). Next, 20.4 g (0.143 mol) of glycidyl methacrylate was gradually added dropwise while maintaining the reaction system at 70 ° C., 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 is 1.5 and the reaction rate of the phosphoric acid monoester is about 96%. The product was separated by HPLC and the solvent was distilled off under reduced pressure.
23.4 g of potassium decyltetradecyl 2-hydroxy-3-methacryloyloxypropyl phosphate were obtained.

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

Example 5 In a reactor, 20 g (0.13%) of monobutylphosphoric acid having a purity of 99% was added.
Mol, but for this sample AV1 = 360.6, AV2 = 721.
3) is charged and 1N sodium hydroxide aqueous solution 129m
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., 91.4 g (0.64 mol) of glycidyl methacrylate was gradually added dropwise, 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 is almost 0 and the reaction rate of the phosphoric acid monoester is almost 100%. The product is separated by HPLC,
The solvent was distilled off under reduced pressure to obtain 37.2 g of sodium butyl 2-hydroxy-3-methacryloyloxypropyl phosphate.

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

Example 6 20 g (0.049 mol, but AV1 = 142.8, AV2 = 288.2 of this sample) of monotrioxyethylene dodecyl ether phosphoric acid having a purity of 98% was placed in a reactor, and 50.9 m of 1N aqueous potassium hydroxide solution was added. The mixture was stirred and dissolved at 70 ° C. (the acid value of the reaction system at this time was 39.5). Next, while maintaining the reaction system at 70 ° C, glycidyl methacrylate
20.9 g (0.15 mol) was gradually added dropwise, 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 is 1.5 and the reaction rate of the phosphoric acid monoester is about 96%. HP
The product was separated by LC and the solvent was distilled off under reduced pressure to obtain 25.5 g of potassium trioxyethylenedodecyl 2-hydroxy-3-methacryloyloxypropyl phosphate.

Example 7 In a reactor, 20 g (0.035 mol, but A of this sample) of monopolyoxyethylene nonylphenyl ether phosphoric acid (average ethylene oxide addition mol number = 5) having a purity of 99%
(V1 = 97.1, AV2 = 194.1), 1N potassium hydroxide aqueous solution (34.6 m) 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, glycidyl methacrylate 24.5
g (0.17 mol) was gradually added dropwise, 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 almost 0, and the phosphoric acid monoester reacted almost 100%.

Comparative Example 1 50 g of monolauryl phosphoric acid having a purity of 97% (0.19
Mol, but AV1 = 209.5, AV2 = 420 for this sample.
6) was dissolved in 187 m of tetrahydrofuran. At this time, the reaction system had AV1 = 48.8 and AV2 = 97.9. Next, while maintaining the reaction system at 70 ° C., 134 g (0.94 mol) of glycidyl methacrylate was gradually added, and the mixture was stirred at this temperature for 1 hour. At this time, the acid value of the reaction system is AV1 = 7.6, AV
It became 2 = 10.3, and it was found that unreacted phosphoric acid monoester was formed in 9 mol%, phosphoric acid diester was formed in 16 mol%, and phosphoric acid triester was formed in 75 mol%. When the acid value was measured when the reaction was continued for a total of 4 hours while stirring was continued, it was found that the acid value was almost 0, and almost 100% of the phosphoric acid monoester was reacted, and it was found that all phosphoric acid triesters were converted.

Comparative Example 2 50 g (0.19%) of monolauryl phosphoric acid having a purity of 97% was charged in a reactor.
Mol, but AM1 = 209.5, AV2 = 420 for this sample.
6) was dissolved in 187 m of tetrahydrofuran. At this time, the reaction system had AV1 = 48.8 and AV2 = 97.9. Next, while maintaining the reaction system at 70 ° C., 27 g (0.19 mol) of glycidyl methacrylate was gradually added, and the mixture was stirred at this temperature for 5 hours. At this time, the acid value of the reaction system is AV1 = 30.8, AV2
= 49.0, 4 unreacted phosphate monoesters
It can be seen that 2 mol%, phosphoric acid diester 29 mol% and phosphoric acid triester 29 mol% were produced.

[Brief description of drawings]

FIG. 1 is a phase diagram of the phosphoric acid ester compound (V) / H ₂ O system of the present invention, and FIG. 2 is a drawing showing an IR spectrum of the compound (V).

Claims (1)

[Claims] 1. A general formula (I), (In the formula, R ₁ is a linear or branched alkyl group having 1 to 36 carbon atoms, or a phenyl group substituted with a linear or branched alkyl group having 1 to 15 carbon atoms, and R ₂ is carbon. Which is an alkylene group of the formula 2 to 3, n is a number of 0 to 30 and M is an alkali metal), and a monoester of phosphoric acid represented by the general formula (II), (Wherein R ₃ represents hydrogen or a methyl group), a compound represented by the general formula (III), (Wherein R ₁ , R ₂ , R ₃ , n and M are the same as those represented by formulas (I) and (II)).