JP7405557B2 - Method for producing phosphate ester of hydroxy compound having aromatic ring - Google Patents

Description

The present invention relates to a method for producing a phosphoric ester of a hydroxy compound having an aromatic ring.

Phosphate esters of organic hydroxy compounds are suitably used for applications such as flame retardants, cleaning agents, fiber treatment agents, emulsifiers, rust preventives, liquid ion exchangers, pharmaceuticals, and cosmetics.

This phosphoric acid ester of an organic hydroxy compound is obtained by phosphorylating the organic hydroxy compound with a phosphorylating agent. As a method for phosphorylating an organic hydroxy compound with a phosphorylating agent, for example, Patent Document 1 describes a method in which an organic hydroxy compound is phosphorylated with polyphosphoric acid and then further oxidized with diphosphorus pentoxide. However, when diphosphorus pentoxide is used for phosphorylation, there is a problem in that the resulting phosphoric acid ester of an organic hydroxy compound is colored due to heat generation during phosphorylation. Therefore, Patent Document 2 describes that coloring of the phosphate ester of an organic hydroxy compound is suppressed by setting the residual rate of diphosphorus pentoxide in the reaction solution within a specific range.

On the other hand, in some applications of phosphoric acid esters of organic hydroxy compounds, transparency is required, so colored phosphoric acid esters of organic hydroxy compounds cannot be used. However, among organic hydroxy compounds, when hydroxy compounds having an aromatic ring were phosphorylated with diphosphorus pentoxide, many compounds were significantly colored.

Patent No. 3115489 Patent No. 4498910

An object of the present invention is to provide a manufacturing method that can easily suppress coloring of a phosphoric acid ester of a hydroxy compound having an aromatic ring obtained by phosphorylating a hydroxy compound having an aromatic ring.

（一般式（Ｉ）中、Ａｒは、芳香環を有する基であり（ただし、該芳香環を有する基は、式中に示すｍ個のＸおよび－Ｏ－（ＲＯ）_ｎ－Ｈ基以外の置換基は有さない）、ｍ個のＸは、炭素数１～４の直鎖状又は分枝状のアルキル基であって、互いに同一であっても、異なっていてもよく、ｍは０～３の整数であり、ｎ個のＲＯは、炭素数２～４のオキシアルキレン基であって、互いに同一であっても、異なっていてもよく、ｎは、ＲＯの平均付加モル数を示す０～２０の数であり、ＲＯの付加形式は、ホモ、ランダム、ブロック及び交互のいずれでもよい。）
［２］前記リン酸化剤が、ポリリン酸である［１］の芳香環を有するヒドロキシ化合物のリン酸エステルの製造方法。
［３］前記一般式（Ｉ）で表される化合物中にリン酸化剤を投入する工程において、冷却を行わない、［１］又は［２］の芳香環を有するヒドロキシ化合物のリン酸エステルの製造方法。
［４］前記一般式（Ｉ）中のｎが０～１０の数である、［１］～［３］のいずれかの芳香環を有するヒドロキシ化合物のリン酸エステルの製造方法。
［５］前記一般式（Ｉ）中のＡｒがフェニル基又はナフチル基である、［１］～［４］のいずれかの芳香環を有するヒドロキシ化合物のリン酸エステルの製造方法。 The present invention includes, for example, the following [1] to [5].
[1] A method for producing a phosphoric acid ester by reacting a phosphorylating agent with a compound represented by the following general formula (I), comprising:
As the phosphorylating agent, only a phosphorylating agent that is liquid at 25° C. under atmospheric pressure is used.
A method for producing a phosphoric acid ester of a hydroxy compound having an aromatic ring.

(In the general formula (I), Ar is a group having an aromatic ring (However, the group having the aromatic ring is a group other than the m X and -O-(RO) _n -H groups shown in the formula) (has no substituent), m number of X's is a linear or branched alkyl group having 1 to 4 carbon atoms, and may be the same or different from each other, and m is 0 is an integer of ~3, n ROs are oxyalkylene groups having 2 to 4 carbon atoms, and may be the same or different from each other, and n represents the average number of moles of RO added. It is a number from 0 to 20, and the RO addition format may be homo, random, block, or alternate.)
[2] The method for producing a phosphoric acid ester of a hydroxy compound having an aromatic ring according to [1], wherein the phosphorylating agent is polyphosphoric acid.
[3] Production of a phosphoric acid ester of a hydroxy compound having an aromatic ring according to [1] or [2] in which cooling is not performed in the step of adding a phosphorylating agent into the compound represented by the general formula (I). Method.
[4] The method for producing a phosphoric ester of a hydroxy compound having an aromatic ring according to any one of [1] to [3], wherein n in the general formula (I) is a number from 0 to 10.
[5] The method for producing a phosphoric acid ester of a hydroxy compound having an aromatic ring according to any one of [1] to [4], wherein Ar in the general formula (I) is a phenyl group or a naphthyl group.

According to the production method of the present invention, coloring of the phosphoric acid ester of the hydroxy compound having an aromatic ring obtained by phosphorylating the hydroxy compound having an aromatic ring can be easily suppressed.

（一般式（Ｉ）中、Ａｒは、芳香環を有する基であり（ただし、芳香環を有する基は、式中に示すｍ個のＸおよび－Ｏ－（ＲＯ）_ｎ－Ｈ基以外の置換基は有さない）、ｍ個のＸは、炭素数１～４の直鎖状又は分枝状のアルキル基であって、互いに同一であっても、異なっていてもよく、ｍは０～３の整数であり、ｎ個のＲＯは、炭素数２～４のオキシアルキレン基であって、互いに同一であっても、異なっていてもよく、ｎは、ＲＯの平均付加モル数を示す０～２０の数であり、ＲＯの付加形式は、ホモ、ランダム、ブロック及び交互のいずれでもよい。） The present invention is a method for producing a phosphoric acid ester by reacting a phosphorylating agent with a compound represented by the following general formula (I), comprising:
As the phosphorylating agent, only a phosphorylating agent that is liquid at 25° C. under atmospheric pressure is used.
The present invention relates to a method for producing a phosphoric ester of a hydroxy compound having an aromatic ring (hereinafter also referred to as a "phosphoric ester").

(In the general formula (I), Ar is a group having an aromatic ring (However, the group having an aromatic ring is a substituent other than the m X and -O-(RO) _n -H groups shown in the formula) m X's are linear or branched alkyl groups having 1 to 4 carbon atoms, and may be the same or different from each other, and m is 0 to 4. is an integer of 3, and n ROs are oxyalkylene groups having 2 to 4 carbon atoms, and may be the same or different from each other, and n represents the average number of moles of RO added. ~20, and the RO addition format may be homo, random, block, or alternate.)

In the production method of the present invention, a phosphorylating agent that is liquid at 25° C. under atmospheric pressure is used. By using such a phosphorylating agent, it is possible to suppress the coloring of the obtained phosphoric acid ester of the hydroxy compound having an aromatic ring. Examples of the phosphorylating agent that is liquid at 25° C. under atmospheric pressure include polyphosphoric acid and phosphorus oxychloride, and from the viewpoint of safety in the working environment, polyphosphoric acid is preferable.

The compound represented by the general formula (I) is a hydroxy compound having an aromatic ring.
In the general formula (I), Ar is a group having an aromatic ring. However, the group having an aromatic ring does not have any substituents other than the m X and -O-(RO) _n -H groups shown in the formula. Preferred examples of the group having an aromatic ring include a group consisting only of an aromatic ring and a group in which a plurality of aromatic rings are bonded via a single bond or an alkylene chain, and a group consisting only of 1 to 5 aromatic rings; More preferred examples include groups in which 1 to 5 aromatic rings are bonded via a single bond or a linear or branched alkylene chain having 1 to 5 carbon atoms. Examples of groups having such aromatic rings include phenyl, naphthyl, cumylphenyl, biphenyl, phenanthryl, anthryl, terphenyl, pyrenyl, fluorenyl, and perylenyl groups. , cumylphenyl group is preferable, phenyl group and naphthyl group are more preferable, and phenyl group is still more preferable.

In the general formula (I), m number of X's are linear or branched alkyl groups having 1 to 4 carbon atoms, and may be the same or different from each other. Examples of the linear or branched alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, and tertiary butyl group. Among these, linear alkyl groups having 1 to 2 carbon atoms are preferred. If the number of carbon atoms in The inhibitory effect is significant.

In the general formula (I), m is an integer of 0 to 3, preferably an integer of 0 to 1.

In the general formula (I), n RO's are oxyalkylene groups having 2 to 4 carbon atoms, and may be the same or different. R is a linear or branched alkylene group having 2 to 4 carbon atoms; ethylene group, n-propylene group, propylene group (-CH ₂ -CH(CH ₃ )-), n-butylene group, 1-methylpropylene group (-CH ₂ -CH ₂ -CH(CH ₃ )-), 2-methylpropylene group (-CH ₂ -CH(CH ₃ )-CH ₂ -), dimethylethylene group (-CH ₂ - C(CH ₃ ) ₂ -), ethylethylene group (-CH ₂ -CH(CH ₂ CH ₃ )-), and the like. Further, in R, the number of carbon atoms in the portion constituting the main chain of (RO) _n is preferably 2 or less. That is, R preferably has at least one selected from the group consisting of an ethylene group, a propylene group, and an ethylethylene group. The ROs may be the same or different, and their addition format may be homo, random, block, or alternating, but it is preferable that they are the same and in the homo format. As RO, oxyethylene group, oxypropylene (-O-CH ₂ -CH(CH ₃ )-) group, combination of oxyethylene group and oxypropylene group (-O-CH ₂ -CH(CH ₃ )-) is preferred, and oxyethylene group is more preferred.

n, which indicates the average number of moles of RO added, is from 0 to 20, preferably from 0 to 10, and more preferably from 2 to 10. Those within the above range show significant coloring when phosphorylated with diphosphorus pentoxide, and have a significant coloring suppression effect when phosphorylated using a phosphorylating agent that is liquid at 25°C under atmospheric pressure. . A compound in which n is greater than 0 has a polyoxyalkylene chain and is a polyoxyalkylene aryl ether.

The method for producing the compound represented by the general formula (I) when n exceeds 0 is not particularly limited, but usually involves reacting an arylhydroxy compound having m X with an alkylene oxide in the presence of an alkali. It can be obtained by The reaction is performed by heating and pressurizing as appropriate.

The phosphoric acid ester of the hydroxy compound having an aromatic ring to be obtained may be a phosphoric acid monoester, a phosphoric acid diester, or a mixture thereof, and is appropriately selected depending on the purpose.

The reaction between the phosphorylating agent and the compound represented by the general formula (I) is carried out as follows.
(Step 1: Phosphorizing agent injection step)
The temperature of the compound represented by the general formula (I) is raised while bubbling nitrogen and stirring. The temperature should be raised to 100°C or less. A phosphorylating agent is added to the compound at a temperature of 100°C or lower, preferably 50°C or lower. The phosphorylating agent is usually used in a molar amount (in terms of phosphorus pentoxide) 0.5 to 1.0 times, preferably 0.6 to 0.8 times the amount of the compound represented by the general formula (I). .

The reaction generates heat, which causes the coloring of the phosphoric ester obtained. However, by using the above-mentioned phosphorylating agent as the phosphorylating agent and keeping the temperature at the time of charging within the above range, the coloring of the phosphoric ester obtained can be reduced. can be suppressed. In order to effectively suppress coloring, the phosphorylating agent may be added in portions. The greater the number of divisions, the more heat generated during charging is suppressed, but generally, if divided into 2 to 5 times, heat generation that would cause coloring can be suppressed. When using a phosphorylating agent that is solid at 25°C under atmospheric pressure, it is necessary to divide it into several dozen doses in order to suppress coloring; The present invention using a liquid phosphorylating agent is also preferable from the viewpoint of improving work efficiency. When charging, it is possible to suppress coloring by cooling, but cooling is not necessary as long as the liquid temperature of the compound represented by the general formula (I) is 100° C. or less. When using a phosphorylating agent that is liquid at 25°C under atmospheric pressure, when using a phosphorylating agent that is solid at 25°C under atmospheric pressure, there is significant heat generation during injection, especially localized heat generation due to aggregation of the phosphorylating agent. Therefore, by appropriately adjusting the number of divisions of charging, the charging process can be performed without cooling.

(Step 2: Reaction step)
The reaction solution obtained in Step 1 is allowed to react for 3 to 10 hours while being kept at 60 to 100°C, preferably 70 to 90°C, while continuing bubbling nitrogen and stirring.
During the reaction, coloring can be suppressed by cooling, but as long as the temperature of the reaction liquid is 100° C. or less, cooling is not necessary. When using a phosphorylating agent that is liquid at 25°C under atmospheric pressure, compared to using a phosphorylating agent that is solid at 25°C under atmospheric pressure, heat generation during the reaction occurs, especially in local areas due to aggregation of the phosphorylating agent. Since the heat generation is suppressed, it is also possible to carry out the reaction step without cooling.

(Step 3: Hydrolysis step)
Water is added to the reaction solution obtained in step 2, and the unreacted phosphorylating agent is hydrolyzed at 60 to 90°C, preferably 70 to 80°C. The amount of water is not particularly limited, but from the viewpoint of effectively hydrolyzing the remaining pyrophosphate ester, it is determined in molar amount relative to the amount of the compound represented by the general formula (I) in Step 1. Usually used 1 to 10 times.

After Step 3, if necessary, the phosphoric acid monoester and the phosphoric diester may be separated by distillation, column separation, or the like.

<Application>
The phosphoric acid ester of a hydroxy compound having an aromatic ring obtained by the production method of the present invention can be used in applications such as detergents, emulsifiers, fiber treatment agents, rust preventives, medical products, and cosmetics. The phosphoric acid ester of a hydroxy compound having an aromatic ring obtained by the production method of the present invention has suppressed coloration, so it is particularly suitable for applications where aesthetics are important (paints, surface treatment agents, cosmetics), etc. Can be used.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
In Examples and Comparative Examples, polyoxyethylene aryl ether was used as the hydroxy compound having an aromatic ring.

<How to measure color tone>
The color tone of the raw material polyoxyethylene aryl ether and the obtained polyoxyethylene aryl ether phosphoric ester was measured by the following method.

(1) APHA index The APHA index was measured in accordance with JIS K 0071-1:1998 by comparing it with a standard solution containing a phosphoric acid ester of polyoxyethylene aryl ether in a colorimetric tube.

(2) Gardner Index According to JIS K 0071-2:1998, the phosphoric acid ester of polyoxyethylene aryl ether was measured by comparing it with the Gardner color number standard solution.

The average number of moles of ethylene oxide added to polyoxyethylene aryl ether was calculated from the hydroxyl value of polyoxyethylene aryl ether. The hydroxyl value was measured according to JIS K 1557-1:2007 (Method B).

<Synthesis of polyoxyethylene aryl ether>
[Synthesis example 1]
After charging 94 parts by mass of phenol and 0.5 parts by mass of potassium hydroxide into an autoclave and raising the temperature to 150°C, 88 parts by mass of ethylene oxide was injected under conditions of 0.5 MPa or less, and the mixture was reacted for 5 hours to produce oxyethylene. Polyoxyethylene phenyl ether having an average number of added moles of 2 was obtained.

[Synthesis example 2]
Polyoxyethylene phenyl ether having an average number of added moles of oxyethylene of 3 was obtained in the same manner as in Synthesis Example 1 except that the amount of ethylene oxide was 132 parts by mass.

[Synthesis example 3]
Polyoxyethylene phenyl ether having an average number of added moles of oxyethylene of 10 was obtained in the same manner as in Synthesis Example 1 except that the amount of ethylene oxide was 440 parts by mass.

[Synthesis example 4]
Polyoxyethylene phenyl ether having an average number of added moles of oxyethylene of 20 was obtained in the same manner as in Synthesis Example 1 except that the amount of ethylene oxide was 880 parts by mass.

[Synthesis example 5]
Polyoxyethylene phenyl ether having an average number of added moles of oxyethylene of 30 was obtained in the same manner as Synthesis Example 1 except that the amount of ethylene oxide was 1320 parts by mass.

[Synthesis example 6]
Polyoxyethylene phenyl ether having an average number of added moles of oxyethylene of 40 was obtained in the same manner as in Synthesis Example 1 except that the amount of ethylene oxide was 1760 parts by mass.

[Synthesis example 7]
After charging 108 parts by mass of cresol and 0.5 parts by mass of potassium hydroxide into an autoclave and raising the temperature to 150°C, 176 parts by mass of ethylene oxide was introduced under pressure at a pressure of 0.5 MPa or less, and the mixture was reacted for 5 hours to produce oxyethylene. Polyoxyethylene cresyl ether having an average number of added moles of 4 was obtained.

[Synthesis example 8]
After charging 144 parts by mass of β-naphthol and 0.7 parts by mass of potassium hydroxide into an autoclave and raising the temperature to 150°C, 176 parts by mass of ethylene oxide was injected under conditions of 0.5 MPa or less, and reacted for 5 hours. Polyoxyethylene β-naphthyl ether having an average number of added moles of ethylene of 4 was obtained.

[Synthesis example 9]
After charging 212 parts by mass of cumylphenol and 1.0 parts by mass of potassium hydroxide into an autoclave and raising the temperature to 150°C, 352 parts by mass of ethylene oxide was introduced under pressure at a pressure of 0.5 MPa or less and reacted for 5 hours. Polyoxyethylene cumyl phenyl ether having an average number of added moles of ethylene of 8 was obtained.

[Synthesis example 10]
After charging 220 parts by mass of nonylphenol and 1.1 parts by mass of potassium hydroxide into an autoclave and raising the temperature to 150°C, 352 parts by mass of ethylene oxide was introduced under pressure at a pressure of 0.5 MPa or less, and the mixture was reacted for 5 hours to produce oxyethylene. Polyoxyethylene nonylphenyl ether having an average number of added moles of 8 was obtained.

[Example 1]
Polyphosphoric acid (manufactured by Nihon Kagaku Kogyo Co., Ltd., orthophosphoric acid equivalent: 116 Weight %) 0.8 mol (in terms of phosphorus pentoxide) was added in two portions. During the charging operation, the polyoxyethylene phenyl ether liquid temperature was 25 to 80°C, so cooling was not performed.
Thereafter, the reaction solution was kept at 80 to 100°C and reacted for 5 hours.
After the reaction, 2 mol of water was added to the reaction solution and hydrolysis was carried out at 80 to 90°C for 2 hours to obtain a phosphoric acid ester of polyoxyethylene phenyl ether (yield 99.5%). It was confirmed by a liquid chromatograph mass spectrometer (LC-MS) that a phosphoric acid ester of polyoxyethylene phenyl ether was obtained.

[Examples 2 to 7]
Except that the polyoxyethylene aryl ether obtained in Synthesis Examples 2 to 4 and 7 to 9 was used instead of polyoxyethylene phenyl ether having an average number of added moles of oxyethylene of 2 as the polyoxyethylene aryl ether. In the same manner as in Example 1, a phosphoric acid ester of polyoxyethylene aryl ether was obtained.

[Comparative Examples 1 to 3]
Example 1 except that the polyoxyethylene aryl ether obtained in Synthesis Examples 5, 6, and 10 was used instead of polyoxyethylene phenyl ether having an average number of added moles of oxyethylene of 2 as the polyoxyethylene aryl ether. In the same manner as above, a phosphoric acid ester of polyoxyethylene aryl ether was obtained.

[Comparative example 4]
0.5 mol of diphosphorus pentoxide was added in 20 portions into 1.0 mol of polyoxyethylene phenyl ether of Synthesis Example 1 with an average number of added moles of oxyethylene of 2 at 30° C. while bubbling with nitrogen and stirring. The temperature was maintained at 60°C while cooling.
Thereafter, the reaction solution was kept at 50 to 70°C and allowed to react for 5 hours.
After the reaction, 2 mol of water was added to the reaction solution, and hydrolysis was carried out at 80 to 90°C for 2 hours to obtain a phosphoric acid ester of polyoxyethylene phenyl ether. (Yield 99.4%). It was confirmed by a liquid chromatograph mass spectrometer (LC-MS) that a phosphoric acid ester of polyoxyethylene phenyl ether was obtained.

[Comparative Examples 5 to 13]
Same as Comparative Example 4 except that polyoxyethylene aryl ether obtained in Synthesis Examples 2 to 10 was used instead of polyoxyethylene phenyl ether having an average added mole number of 2 of oxyethylene as polyoxyethylene aryl ether. Then, a phosphoric acid ester of polyoxyethylene aryl ether was obtained.

It can be seen that when Ar is a phenyl group and does not have a substituent X, when phosphorylated with polyphosphoric acid, the resulting phosphoric acid ester becomes more markedly colored as the number of repeating units of oxyethylene decreases.
It can be seen that when Ar is a naphthylene group, phosphorylation with diphosphorus pentoxide causes significant discoloration, but phosphorylation with polyphosphoric acid suppresses discoloration.
Comparing the cases where Ar is a phenyl group and X is a cresyl group with 1 carbon number and the case where X is a nonylphenyl group with 9 carbon atoms, in nonylphenyl, diphosphorus pentoxide is used as a phosphorylating agent. In Cresyl, when diphosphorus pentoxide is used as the phosphorylating agent, the coloration is significant, whereas when polyphosphoric acid is used, there is little coloration. It can be seen that coloring is suppressed.

The phosphoric acid ester of a hydroxy compound having an aromatic ring obtained by the production method of the present invention can be used in applications such as detergents, emulsifiers, fiber treatment agents, rust preventives, medical products, and cosmetics.

Claims (4)

A method for producing a phosphoric acid ester by reacting a phosphorylating agent with a compound represented by the following general formula (I) which is a polyoxyalkylene aryl ether , the method comprising:
A method for producing a phosphoric acid ester of a hydroxy compound having an aromatic ring, using only a phosphorylating agent that is liquid at 25° C. under atmospheric pressure as the phosphorylating agent ,
the phosphorylating agent is polyphosphoric acid;
A method for producing a phosphoric acid ester of a hydroxy compound having an aromatic ring .

(In the general formula (I), Ar is a phenyl group, a naphthyl group, a cumylphenyl group, a biphenyl group, a phenanthryl group, an anthryl group, a terphenyl group, a pyrenyl group, a fluorenyl group, or a perylenyl group (however, Ar is a formula m Xs are linear _or branched alkyl groups having 1 to 4 carbon atoms. , which may be the same or different from each other, m is an integer of 0 to 3, and n ROs are oxyalkylene groups having 2 to 4 carbon atoms, and may be the same or different from each other. n is a number greater than 0 and less than or equal to 20 indicating the average number of moles of RO added, and the addition form of RO may be homo, random, block, or alternating.) The method for producing a phosphoric ester of a hydroxy compound having an aromatic ring according to claim 1 , wherein cooling is not performed in the step of adding a phosphorylating agent into the compound represented by the general formula (I). The method for producing a phosphoric acid ester of a hydroxy compound having an aromatic ring according to claim 1 or 2 , wherein n in the general formula (I) is a number greater than 0 and less than or equal to 10. The method for producing a phosphoric acid ester of a hydroxy compound having an aromatic ring according to any one of claims 1 to 3 , wherein Ar in the general formula (I) is a phenyl group or a naphthyl group.