JPH075696B2 - Process for producing hydroxycarboxylic acid derivative - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a specific hydroxycarboxylic acid derivative, which can be expected as a raw material of a polymer or an epoxy resin curing agent, with good productivity.

(Prior Art) Various polyols and polycarboxylic acid derivatives have been conventionally known as polymer raw materials and epoxy resin curing agents.

It is also known that compounds having two or more kinds of functional groups in one molecule are put into practical use according to various required properties, and for example, polymers can be obtained as these raw materials.

However, the performance required for polymers and the like has become more sophisticated with recent technological advances, and conventional raw materials have not always been sufficient.

As one of such raw materials, a hydroxycarboxylic acid derivative represented by the following formula (I) is considered (Chem.Abs.V
ol.108 No26, 27 p129), a method for efficiently producing such a compound has not yet been known.

(Problems to be Solved by the Invention) A main object of the present invention is to efficiently and economically obtain the above-mentioned hydroxycarboxylic acid derivative which can be expected as a raw material of a polymer having more excellent heat resistance and mechanical strength and an epoxy resin curing agent. It is to provide a manufacturing method.

(Means for Solving the Problems) The object of the present invention is to provide at least one aldehyde represented by the following formula (II-1): [However, in the formula (II-1), it represents a hydrogen atom of R or a carbon-hydrogen group having 10 or less carbon atoms. ] At least one aldehyde and / or ketone represented by the following formula (II-2), [However, in the formula (II-2), R ′ and R ″ represent a hydrogen atom or a hydrocarbon group having 10 or less carbon atoms] At least one aromatic hydroxy compound represented by the following formula (III) Is Ar- (OH) _m (III) [wherein, in the formula (III), Ar is an aromatic hydrocarbon group having 20 or less carbon atoms, which may be substituted with a halogen atom, m
Is an integer of 1 to 3] A method for producing a hydroxycarboxylic acid derivative of the above formula (I) by reacting in the presence of an acidic catalyst,
Achieved by

Hereinafter, the present invention will be described in detail.

The hydroxycarboxylic acid derivative which is the target compound in the method of the present invention has a chemical structure represented by the above formula (I). Of the X in the above formula (I), the following formula (A)
The structure represented by It constitutes 15 to 70 mol%, preferably 20 to 65 mol%, particularly preferably 25 to 60 mol%.

In formula (A), R is the number of hydrogen atoms and / or carbon atoms
Represents 10 or less hydrocarbon groups. Examples of the hydrocarbon group having 10 or less carbon atoms include aliphatic hydrocarbon groups such as methyl, ethyl and propyl, alicyclic hydrocarbon groups such as cyclohexyl, and aromatic hydrocarbon groups such as phenyl, benzyl and naphthyl. Examples thereof include a hydrogen atom and / or an aliphatic hydrocarbon group such as methyl, ethyl, propyl and the like are preferable. When the formula (I) includes a plurality of structures represented by (A), R does not necessarily have to be the same group.

Further, in X in the above formula (I), the structure represented by the following formula (B) is The remaining 85 to 30 mol%, preferably 80 to 35 mol%, particularly preferably 75 to 40 mol%.

The above R'and R "represent a hydrogen atom and / or a hydrocarbon group having 10 or less carbon atoms. These R'and R" may be the same or different from each other.

Preferred examples of R'and R "are a water atom and / or an aliphatic hydrocarbon group and / or cyclohexyl or phenyl.

In the above formula (I), n is 0 or an integer of 1 to 20, preferably 0 or an integer of 1 to 10, particularly preferably 0, 1 or 2
Is. If n is too large, the melting point of the obtained compound will be high and the handling will be poor.

The hydroxycarboxylic acid derivative according to the present invention generally has a molecular weight distribution, and the molecular weight of the hydroxycarboxylic acid derivative means its average. However, depending on the intended use, there are cases where only the compound with n = 0 is desired,
This can be achieved by selecting synthesis conditions and purifying the resulting crude product.

In the above formulas (I) and (III), m represents an integer of 1 to 3, and preferably 1 or 2. Note that the three m's in these equations are not necessarily the same numbers.

In the above formulas (I) and (III), Ar is an aromatic hydrocarbon group having 10 or less carbon atoms which may be substituted with a halogen atom, and two of Ar have a (1 + m) valence and the remaining one has (2+
m) is a valence group. As a specific example, skeleton names when Ar is unsubstituted are benzene, toluene, xylene, naphthalene, chlorobenzene, dichlorobenzene,
Chlortoluene, Chlornaphthalene, Trichlorobenzene, Bromobenzene, Dibromobenzene, Tribromobenzene, Tetrabromobenzene, Bromonaphthalene, 2,2
-Diphenylpropane, diphenyl, diphenylmethane, diphenyl ether, diphenyl sulfide, 2,2-
Bis (3-chlorophenyl) propane, 2,2-bis (3,5
-Dichlorophenyl) propane, 2,2-bis (3-bromophenyl) propane, 2,2-bis (3,5-dibromophenyl) propane.

Of these, preferred ones are benzene, toluene,
Naphthalene, chlorobenzene, dichlorobenzene, bromobenzene and dibromobenzene are preferred, and benzene, toluene, naphthalene and dibromobenzene are particularly preferred. These Ars may contain the above-mentioned plural types in one molecule. That is, the three Ars in the above formula (I) do not necessarily have to be the same group.

The hydroxycarboxylic acid derivative obtained by the present invention contains 60% or more, preferably 70% or more, particularly preferably 80% or more of the structure represented by the above formula (I).

Next, an efficient method for producing the hydroxycarboxylic acid derivative according to the present invention will be described.

According to the method of the present invention, the above-mentioned hydroxycarboxylic acid derivative comprises the aldehyde component represented by the above formula (II-1), the aldehyde and / or ketone component represented by the above formula (II-2), and the above formula (III). Reacting with an aromatic hydroxy compound (phenolic compound) represented by the formula (1) in the presence of an acidic catalyst to form a hydroxycarboxylic acid derivative represented by the above formula (I), and hydrolyzing the compound if necessary. To be manufactured efficiently and economically.

In the method of the present invention, as the aldehyde component which is one component of the raw material, one represented by the following formula (II-1) is used.

[However, in the formula (II-1), R represents hydrogen or a hydrocarbon group having 10 or less carbon atoms.] Specific examples of R include hydrogen, methyl, ethyl, propyl, pentyl, hexyl, octyl and the like. Aliphatic hydrocarbon groups, alicyclic hydrocarbon groups such as cyclohexyl and methylcyclohexyl, phenyl, benzyl, chlorophenyl,
Examples thereof include aromatic hydrocarbon groups such as bromphenyl and naphthyl. Specific examples of preferable R include hydrogen, methyl and
Aliphatic hydrocarbon groups such as ethyl and propyl are mentioned.

Typical aldehyde components represented by the formula (II-1) which are preferably used in the present invention are P-formyl benzoic acid and methyl P-formyl benzoate. These aldehyde components (II-1) may be used alone or in admixture of two or more.

In the method of the present invention, a compound represented by the following formula (II-2) is mainly used as the aldehyde and / or ketone component which is another raw material.

[However, in the formula (II-2), R ′ and R ″ represent hydrogen or a hydrocarbon group having 10 or less carbon atoms.] Specific examples of R ′ and R ″ include those listed above for R. You can Preferred R'in the compound of formula (II-2),
Specific examples of R ″ include hydrogen, an aliphatic hydrocarbon group such as methyl, ethyl, propyl, butyl, hexyl and octyl, a cyclohexyl group and a phenyl group.

Typical aldehyde and / or ketone components represented by the formula (II-2) which are preferably used in the method of the present invention include formaldehyde, benzaldehyde, acetaldehyde, butyraldehyde, n-hexylaldehyde, n-octylaldehyde, acetone and methylethylketone. , Methyl isopropyl ketone, acetophenone, and benzophenone. Of these, particularly preferred are formaldehyde, benzaldehyde, acetaldehyde, acetone,
Methyl ethyl ketone, these aldehydes and /
Alternatively, the ketone component (II-2) may be used alone or in combination of two or more.

In addition, the aldehyde and / or ketone component (II-
In addition to 2), glyoxal, glutaraldehyde,
It is also possible to add other aldehydes such as terephthalaldehyde and / or ketones to the component (II-2) in an amount of 30 mol% or less, preferably 20 mol% or less.

Hereinafter, the aldehyde component (II-1) and the aldehyde and / or ketone component (II--2) are collectively referred to as the total aldehyde component (II), but the component (II-1) and the component (II-
The molar ratio of 2) is preferably 15:85 to 70:30, more preferably 20:80 to 65:35, and particularly preferably 25:75 to 60:40.

In the method of the present invention, by using the above-mentioned components (II-1) and (II-2) together in the above proportion, a hydroxycarboxylic acid derivative which can be a precursor of an epoxy compound having good handleability is obtained.

A compound represented by the following formula (III) is mainly used as the aromatic hydroxy compound component which is the other raw material in the method of the present invention.

Ar- (OH) _m ... (III) Specific examples of the aromatic hydroxy compound include phenol, cresol, xylenol, α-naphthol, β-naphthol, and bromophenol in which m = 1 in the above formula (III). , Aromatic monohydroxy compounds such as chlorophenol, chlorocresol, chloronaphthol, dibromophenol, dichlorophenol, tribromophenol, tetrabromophenol, bromonaphthol, trichlorophenol, etc .; resorcinol, m = 2, dihydroxynaphthalene, bromoresorcinol , Chlorlenzorcinol, dibromoresorcinol, dichlororesorcinol, tribromoresorcinol, trichlororesorcinol, hydroquinone, chlorohydroquinone, bromohydroquinone, 2,5-dichlorohi Hydroquinone, t- butyl hydroquinone, catechol, 2,2
Bis (4-hydroxyphenyl) propane, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dividoxydiphenyl sulfide, 4,
4'-dihydroxydiphenylmethane, 2,2-bis (3-
Methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane,
2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) ) Propane, 2,2-bis (3,5-dibromo-
Aromatic dihydroxy compounds such as 4-hydroxyphenyl) propane; and aromatic trihydroxy compounds such as 1,3,5-trihydroxybenzene and pyrogallol where m = 3.

Among them, phenol, cresol, α-naphthol,
β-naphthol, bromophenol, 2,6-dibromophenol and resorcinol are preferred. These aromatic hydroxy compounds (III) are also used alone or as a mixture of two or more kinds.

Each of the above raw materials can be manufactured at a low cost, and the fact that such raw materials can be used is one of the advantages of the present invention.

According to the method of the present invention, first, an aldehyde component and an aromatic hydroxy compound are reacted in the presence of an acidic catalyst to produce a target hydroxycarboxylic acid derivative. In this reaction. The charging ratio of the total aldehyde component represented by the above formula (II) and the aromatic hydroxy compound represented by the above formula (III) is adjusted depending on the degree of polymerization of the desired hydroxycarboxylic acid derivative, The aromatic hydroxy compound (II) is used in the range of 0.5 to 2.0 mol per mol of the aldehyde component (III).

Moreover, as the acidic catalyst used in the reaction, specifically,
Protonic acid such as nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, methanesulfonic acid, toluenesulfonic acid, boron trifluoride, boron trifluoride ether complex, aluminum chloride, tin chloride, zinc chloride, iron chloride, titanium chloride, etc. Lewis Acid, oxalic acid, etc. can be used. Among these, it is preferable to use a protonic acid, and hydrochloric acid, boric acid, methanesulfonic acid, toluenesulfonic acid and the like are particularly preferably used.

The amount of these catalysts used is selected from 0.001 to 0.05 mol times with respect to the total aldehyde component (II) of the raw material. The above catalysts are used alone or as a mixture of two or more kinds.

In the present invention, the reaction between the aromatic hydroxy compound (III) and the aldehyde component (II) in the presence of an acidic catalyst is usually carried out at 80 to 250 ° C.

The reaction temperature is 80 to 150 ° C. in the initial stage, and the reaction temperature is further raised if necessary. The reaction time can be selected in the range of 1 hour to 24 hours.

The above reaction of the present invention is carried out by the aromatic hydroxy compound (III)
It is also possible to use an excessive amount of it and use a part of it as a reaction solvent, whereby it is possible to prevent an increase in the viscosity of the reaction system due to an increase in the degree of polymerization.

When the aromatic hydroxy compound (III) is used as a solvent, the ratio of the total aldehyde component (II) and the aromatic hydroxy compound component (III) used is not limited to the above range.

Further, in the above reaction, aromatic hydrocarbons such as toluene, chlorobenzene, dichlorobenzene, nitrobenzene and diphenyl ether, dimethyl ethers such as ethylene glycol and diethylene glycol, and ethers such as tetrahydrofuran and dioxane can be used as a solvent.

Thus, the hydroxycarboxylic acid derivative of the above formula (I) is obtained with good productivity. When R is not hydrogen, this compound can be hydrolyzed to hydrolyze R, if necessary.

The method of hydrolysis can be carried out in the presence of water using an acid and alkali catalyst according to known methods.

Thus, the hydroxycarboxylic acid derivative of the present invention represented by the above formula (I) is obtained.

(Effect of the Invention) According to the method of the present invention, a hydroxycarboxylic acid derivative useful as a high-performance polymer raw material and a curing agent for an epoxy resin can be obtained, and this product, for example, glycidylates a carboxylic acid and a phenolic hydroxyl group. This makes it possible to synthesize a highly heat-resistant epoxy compound having good handleability. Then, according to the method of the present invention, the above compound can be produced efficiently and inexpensively.

(Examples) Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

In the examples, “part” means “part by weight” unless otherwise specified.

The analysis methods of infrared absorption spectrum analysis (IR) and nuclear magnetic resonance spectrum analysis (NMR) used for identifying the hydroxycarboxylic acid derivative obtained in each example are as follows.

a) Infrared absorption spectrum analysis (IR) KBr powder obtained by crushing a compound was press-molded and measured by a conventional method.

b) Nuclear magnetic resonance spectrum analysis (NMR) It measured using deuterated dimethyl sulfoxide as a solvent and tetramethylsilane as a standard sample.

Example 1 778 parts of phenol and 0.6 part of P-toluenesulfonic acid monohydrate were dissolved in 1000 parts of toluene, and P- was added to a solution heated to 95 ° C.
Formyl benzoic acid (210 parts) was uniformly dispersed in a 35% formalin aqueous solution (120 parts), and the mixture was added dropwise in a nitrogen stream over 1.5 hours with stirring. The water that came out during the reaction was distilled off to the outside of the system for a further 1 hour reaction, and then at 100 ° C. for a further 1 hour, and then 6 parts of concentrated hydrochloric acid was added and the reaction was carried out for 2 hours. The reaction was performed at 0 ° C for 2 hours. The reaction product obtained here was taken out of the reactor, and after adding 300 parts of toluene,
After washing 3 times with 100 parts of water, unreacted phenol was removed at 80 ℃
It was distilled off under reduced pressure at mmHg and then removed by flushing with steam to obtain 550 parts of hydroxycarboxylic acid.

The melting point of the obtained hydroxycarboxylic acid is 90 to 117 ° C, and the molecular weight determined by the freezing point depression method using dioxane is
It was 276. The result of elemental analysis is C (%) = 73.98, H
(%) Was 5.01.

From the results of IR and NMR elemental analysis, it was confirmed that the following compounds were obtained.

Example 2 Phenol 141 parts, P-formyl methyl benzoate 8.2 parts, P-
To a solution of toluenesulfonic acid monohydrate (0.2 parts) and concentrated hydrochloric acid (0.2 parts) uniformly dissolved in a nitrogen stream at 95 ° C with stirring, 4.3 parts of a 35% aqueous formalin solution was added dropwise over 1 hour, and the reaction was continued for another 1 hour. The reaction was carried out at ℃ for 2 hours, and further at 115 ℃ for 2 hours. At this time, water generated as a result of the reaction was distilled out of the reaction system. The reaction product obtained here was taken out of the reactor, added with 200 parts of toluene, washed with 60 parts of water three times, and then the toluene was distilled off under reduced pressure. Further, unreacted phenol was distilled under reduced pressure at 80 ° C. and 5 mmHg. And then removed by flushing with steam to remove the hydroxycarboxylic acid derivative 16.0
Got

The hydroxycarboxylic acid derivative obtained has a melting point of 85 to 110.
C., and the molecular weight determined by the freezing point depression method using dioxane was 280. The result of elemental analysis is C (%) = 75.9
It was 8, H (%) = 4.99.

Further, by NMR, it was confirmed that 60% of the obtained hydroxycarboxylic acid derivative was a methyl ester, and it was found that the following compound was obtained.

[However, 60 mol% is -CH _3, 40 mol% of hydrogen of R] Example 3 obtained in Example 2 was added 150 parts of 5% sodium hydroxide solution in 16 parts of a hydroxycarboxylic acid derivative 2 hours After heating and refluxing to hydrolyze the methyl ester, the product was acidified with a 10% aqueous hydrochloric acid solution, the obtained solid was washed with 100 parts of water three times, and dried under reduced pressure at 80 ° C. 14.3 parts of the obtained hydroxycarboxylic acid was confirmed to be completely hydrolyzed by NMR. The melting point of the obtained hydroxycarboxylic acid was 90 to 117 ° C., and the molecular weight determined by the freezing point depression method using dioxane was 282. The results of elemental analysis were C (%) = 73.96 and H (%) = 5.00.

The IR spectrum of this compound was very similar to that of Example 1, and the compound of the structural formula shown in Example 1 was obtained.

Examples 4 to 7 A predetermined amount of the phenol compound shown in Table 1 below, 0.3 part of P-toluenesulfonic acid monohydrate and 23.0 parts of methyl P-formylbenzoate were dissolved in 250 parts of toluene and heated to 95 ° C. 36.0 parts of 35% formalin aqueous solution was added dropwise to the above solution under stirring in a nitrogen stream for 1.5 hours. The water that came out during the reaction was distilled off to the outside of the system and reacted for an additional 1 hour, and then reacted at 100 ° C for an additional 1 hour, 6 parts of concentrated hydrochloric acid was added thereto and reacted for another 2 hours. The reaction was carried out for 2 hours. To the reaction product obtained here, 350 parts of a 5% sodium hydroxide aqueous solution was added and hydrolyzed under heating and reflux for 2 hours, the toluene layer was separated and removed, and the aqueous layer was acidified with a 10% hydrochloric acid aqueous solution to obtain The solid thus obtained was washed three times with 300 parts of water, and then unreacted phenolic compound was removed by distillation under reduced pressure and flushing with steam to obtain a hydroxycarboxylic acid.

The yield of the obtained hydroxycarboxylic acid is shown in Table 1 below.
The melting point, the molecular weight obtained by the freezing point depression method using dioxane, and the results of elemental analysis are shown.

The structures of the compounds obtained by NMR and IR are also shown in Table 1. In addition, n shown in the "Structure" column of Table 1 shows the average value of n in the formula (I) in the obtained compound.

Further, X in the formula (I) in the compounds produced in Examples 4 to 7 is 25 mol% , And the remaining 75 mole% is -CH ₂ - is.

Examples 8-10 Phenol 316 parts and P-toluenesulfonic acid monohydrate 0.6 parts were dissolved in toluene 280 parts, and P- was added to a solution heated to 95 ° C.
55 parts of methyl formyl benzoate and a predetermined amount of the aldehyde shown in Table 2 below were dissolved or evenly dispersed in 400 parts of toluene, and the resulting mixture was added dropwise under stirring in a nitrogen stream over 1.5 hours. The water that comes out during the reaction is distilled off to the outside of the system
After reacting for 1 hour, the mixture was further reacted at 100 ° C for 1 hour, 6 parts of concentrated hydrochloric acid was added thereto and further reacted for 2 hours.
And reacted for 2 hours.

The reaction product obtained here was added with a 5% aqueous sodium hydroxide solution 60.
After addition of 0 part and hydrolysis for 2 hours under heating and refluxing, the toluene layer was separated and removed, the aqueous layer was acidified with a 10% hydrochloric acid aqueous solution, and the obtained solid was washed with 300 parts of water three times, Unreacted phenolic compounds were removed by distillation under reduced pressure and flushing with steam to obtain hydroxycarboxylic acid. Table 2 shows the yield of the obtained hydroxycarboxylic acid, the melting point, the molecular weight determined by the freezing point depression method using dioxane, and the result of elemental analysis. The structures of the compounds confirmed by NMR and IR are also shown in Table 2.
Also described in. Note that n shown in Table 2 is n in the formula (I).
The average value of is shown.

Further, 60 mol% of X in Examples 8 to 9 is Further, 60 mol% of X in Example 10 is

Claims (1)

[Claims] 1. When producing a hydroxycarboxylic acid derivative mainly composed of a structure represented by the following formula (I), At least one aldehyde represented by the following formula (II-1) [However, in the formula (II-1), the definition of R is the same as the above formula (I). ] At least one aldehyde and / or ketone represented by the following formula (II-2) [However, in the formula (II-2), the definitions of R ′ and R ″ are the same as those in the above formula (I).] At least one aromatic hydroxy compound represented by the following formula (III): Ar- (OH) _m (III) [However, the definition of Ar, m in the formula (III) is the same as that of the above formula (I).] It is characterized by reacting in the presence of an acidic catalyst. A method for producing a hydroxycarboxylic acid derivative.