JPH03275707A - New hydroxycarboxylic acid derivative and production thereof - Google Patents

Abstract

PURPOSE:To efficiently obtain the subject new derivative useful as a raw material of polymer excellent in heat resistance and strength, etc., at a low cost by reacting a specific aromatic aldehydes and carbonyl compound with an aromatic hydroxy compound in the presence of an acid catalyst. CONSTITUTION:An aldehyde expressed by formula I (R is H or 1-10C hydrocarbon) is reacted with an aldehyde and/or ketone expressed by formula II (R' and R'' are H or 1-10C hydrocarbon) and aromatic hydroxy compound expressed by formula III (Ar is <=20C aromatic hydrocarbon substitutable with halogen; m is 1-3) in the presence of an acid catalyst to afford the aimed hydroxycarboxylic acid derivative mainly composed of structures expressed by formula IV (15-70mol% of X is expressed by formula V and 85-39mol% is expressed by formula VI; n is 0 or 1-20).

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel hydroxycarboxylic acid derivative that is expected to be used as a raw material for polymers or a curing agent for epoxy resins, and a method for producing the same.

(Prior Art) Various polyols and polycarboxylic acid derivatives have been known as raw materials for polymers and curing agents for epoxy resins.

It is also known that a compound '\IA (J) having two or more types of functional groups in one molecule according to various required properties can be put to practical use and a polymer can be obtained if the compound is used.

However, as technology advances in recent years, the performance required of polymers and the like has become more sophisticated, and conventional raw materials are no longer always sufficient.

(Objective of the Invention) The first object of the present invention is to improve ripening resistance and I! The purpose is to provide a novel hydroxycarboxylic acid derivative that can be expected as a raw material for polymers with excellent mechanical strength and as a curing agent for epoxy resins, and another purpose is to develop a method for efficiently and economically producing the hydroxycarboxylic acid derivative. It is about providing.

(Archives of the Invention) The objects of the present invention as described above are: (1) A human 0-1r dicarboxylic acid derivative mainly composed of a structure represented by the following formula (I).

8r -X So ^r-X + Ar (2) At least one aldehyde represented by the following formula 1-1) and c++a Oco□R...<II-1)[
However, in formula (n-1), R represents hydrogen or a hydrocarbon group having 10 or less carbon atoms. At least one aldehyde and/or ketone represented by the following formula (n-2) and Ar- (Kano), ・・・・・・(III)
[However, in formula (II [), the definitions of Ar and ra are the same as in the above formula (I)]] The method according to the above (1), characterized in that it is reacted in the presence of an acidic catalyst. This is achieved by a method for producing hydroxycarboxylic acid derivatives.

The present invention will be explained in detail below.

The novel hydroxycarboxylic acid derivative according to the present invention has a novel chemical structure represented by the above formula (I>) [wherein the formula (I
I-2>, R', l'l'' represent hydrogen, carbon, or a hydrocarbon group having 10 or less atoms] The following formula (III)
At least one aromatic hydroxy compound represented by

The represented structure is 15 to 70 mol%, preferably 20 to 65 mol%, particularly preferably 25 to 60 mol%.

The above R represents a hydrogen atom and/or a hydrocarbon group having 10 or less carbon atoms. Examples of the hydrocarbon group having 10 or less carbon atoms include aliphatic hydrocarbon groups such as methyl, ethyl, propyl, etc., and fatty acids such as cyclohexyl. Examples include cyclic hydrocarbon groups and aromatic hydrocarbon groups such as phenyl, benzyl, and naphthyl.

Preferred examples of R include a hydrogen atom and/or an aliphatic hydrocarbon group such as methyl, ethyl, propyl, etc. When a plurality of R's are included in formula 6, they do not necessarily all have to be the same group.

Among R and X, the i-structure represented by -C- is 85 to 30 mol%, preferably 80 to 35 mol%, particularly preferably 75 to 40 mol%.

The above R', R'' is a hydrogen atom and/or has 10 carbon atoms.
The following hydrocarbon groups R' and 11'' may be the same or different from each other.

Preferred examples of R' and R'' include a hydrogen atom and/or an aliphatic hydrocarbon group and/or cyclohexyl.

It is phenyl.

In formula (I), n is O or an integer of 1 to 20, preferably 0 or an integer of 1 to 10, particularly preferably 0°1 or 2.
It is. If n is too large, the resulting compound will have a high melting point and will be difficult to handle.

The hydroxycarboxylic acid derivative of the present invention generally has a molecular weight distribution, and the molecular weight of the hydroxycarboxylic acid derivative indicates the average thereof.

However, depending on the intended use, only a product with n=o may be desired, and this can be achieved by selecting synthesis conditions or purifying the obtained crude product.

In the formula, the number represents an integer of 1 to 3, preferably 1 or 2.
It is. Note that the three m's in the formula are not necessarily the same number.

In the formula, A" is an aromatic hydrocarbon group having 10 or less carbon atoms which may be substituted with a halogen atom, two of Ar in formula (I) have a valence of (1,000 l), and the remaining one is (2
-1-a) It is a valent group. Specific examples of skeleton names when Ar is unsubstituted include benzene, toluene, and A.
Silene, naphthalene, chlorobenzene, dichlorobenzene, chlorotoluene, chlornaphthalene, trichlorobenzene, bromobenzene, dibromobenzene, tribromobenzene.

butrabromobenzene, bromnaphthalene, 2,2-diphenylpropane, diphenyl, diphenylmethane diphenyl ether, diphenyl sulfide, 2.2-
his(3-chlorophenyl)propane, 2,2-bis(
3,5-dichlorophenyl)propane, 2,2-bis(
3-bromophenyl)propane, 2,2-bis(3,5
-dibromophenyl)propane.

Among these, preferred are benzene, toluene,
These are naphthalene, chlorobenzene, dichlorobenzene, bromobenzene, and dibromobenzene, and particularly preferred are benzene, toluene, naphthalene, and dibromobenzene. The plurality of forms described above may be contained in the molecule. That is, the three Ars in formula (I) do not necessarily need to be the same.

In the hydroxycarboxylic acid derivative according to the present invention,
It contains 60% or more, preferably 70% or more, particularly preferably 80% or more of the structure represented by the above-mentioned - pattern hole (I>).

Next, a preferred method for producing the novel hydroxycarboxylic acid derivative of the present invention will be described.

The novel hydroxycarboxylic acid derivative of the present invention comprises an aldehyde component represented by the above formula (II-1) and the above formula (I).
An aldehyde and/or ketone component represented by I-2) and an aromatic hydroxy compound represented by the above formula (1)! t
i (phenolic compound) in the presence of an acidic catalyst to form a polyol represented by the above formula (I), and optionally hydrolyze the compound to produce it efficiently and economically. be able to.

In the present invention, as the aldehyde component which is one of the raw material components, those represented by the following formula (n-1) are mainly used.

coo ()'co□R... (II-1) [However, in formula (I [-1), 1 (represents hydrogen or a hydrocarbon group having 10 or less carbon atoms]) Examples are hydrogen, methyl, and ethyl.

Examples include aliphatic hydrocarbon groups such as propyl, pentyl, hexyl, and octyl, alicyclic hydrocarbon groups such as cyclohexyl and methylcyclohexyl, and aromatic hydrocarbon groups such as phenyl-benzyl, chlorphenyl-bromophenyl, and naphthyl. Preferred specific examples of H include hydrogen, aliphatic hydrocarbon groups such as methyl, ethyl, and propyl. Representative aldehyde components represented by formula (n-1) that are preferably used in the present invention are: P-pormylbenzoic acid and methyl P-formylbenzoate. These aldehyde components (I[-1) may be used alone or in combination of 211 or more.

As the aldehyde component serving as another raw material in the present invention, a compound represented by the following formula (II-2) is mainly used.

[However, in formula (n-2), It', It'' represents hydrogen or a hydrocarbon group having 10 or less carbon atoms] R',
Specific examples of It'" include those listed for R above. Preferred specific examples of R' and R'" include hydrogen,
Examples include aliphatic hydrocarbon groups such as methyl, ethyl, propyl, butyl, hexyl, and octyl, cyclohexyl, and phenyl groups.

Representative aldehyde and/or ketone components represented by formula (II-2>) preferably used in the present invention include formaldehyde, benzaldehyde, acetaldehyde, butyraldehyde, n-hexylaldehyde, n-octylaldehyde, acetone, methyl ethyl ketone, and methyl Isoprovir getone.

Acetophenone and benzophenone. Among these, formaldehyde, benzaldehyde,
Acetaldehyde, acetone, methyl ethyl ketone, and these aldehyde and/or ketone components (II-
2> may be used alone or in combination of two or more.

In addition, the above aldehyde and/or ketone component (II-2
), from the viewpoint of improving physical properties, other aldehydes and/or ketones such as glyoxal, glutaraldehyde, terephthalaldehyde, etc.
It is also possible to add up to mol %, preferably up to 20 mol %.

Hereinafter, the aldehyde component (It-1) and the aldehyde and/or ketone component (II-2) will be collectively referred to as the total aldehyde component (n), but component (II-1) and component (
The preferred usage ratio of II-2) is 15:85 in molar ratio.
~70:230, more preferably 20:80~6
5:35, particularly preferably 25 near 5 to 60:4
It is 0.

<1l-1) By using the component (II-2) in the above ratio, a hydroxycarboxylic acid derivative can be obtained which can be a precursor of an epoxy compound with good handling properties.

As the aromatic hydroxy compound component serving as another raw material in the present invention, a compound represented by the following formula (■) is mainly used.

Ar-(011), -----
--(I[) A specific example of such an aromatic hydroxy compound is a phenol where m=1 in the above formula (III).

Cresol, xylenol, α-naphthol 1β-naphthol, bromophenol, chlorophenol, chlorocresol, chloronaf! -L, dibromophenol,
Aromatic monohydroxy compounds such as dichlorophenol, tribromophenol, tetrabromophenol, 1-bromonaphthol, trichlorophenol, etc., resorcinol where m=2, dihydro-15 sinaphthalene, bromoresorcinol, chlorresorcinol, dibromoresorcinol, dichlorophenol, etc. Chlorresorcinol, tribromoresorcinol, trichlororesorcinol.

Hydroquinone, chlorohydroquinone, bromohydroquinone, 2,5-dichlorohydroquinone, L-butylhydroquinone, catechol. 2,2-bis(4-hydroxyphenyl)propane, 4.4'-dihydroxydiphenyl, 4.4'-dihydroxydiphenyl ether, 4
,4°-Dividroxydiphenyl sulfide 44゛-
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(
Such as 3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane Aromatic dihydroxy compounds include aromatic trihydroxy compounds such as 1,3,5-trihydroxybenzene, pyrogallol, etc., including phenol and cresol.

α-naphthol, β-naphthol, bromophenol,
2,6-dibromophenol and resorcinol are preferred, and these aromatic hydroxy compounds (m) may be used alone or in a mixture of two or more.

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

According to the production method of the present invention, first, an aldehyde component and an aromatic hydroΔc compound are reacted in the presence of an acidic catalyst,
In this reaction, a polyol compound is produced. The ratio of the total aldehyde component represented by the above formula (II) to the aromatic hydroxy compound represented by the above formula (II[) is adjusted depending on the degree of polymerization of the desired hydroxycarboxylic acid derivative, but generally all aldehyde components Aromatic hydroxy compound (n
) is used in a range of 0.5 to 2.0 mol.

Further, specific examples of acidic catalysts used during the reaction include protonic acids such as nitric acid, P acid, hydrochloric acid, phosphoric acid, methanesulfonic acid, and toluenesulfonic acid.

Lewis acids such as boron trifluoride, boron trifluoride ether, aluminum chloride, tin chloride, zinc monochloride, iron chloride, titanium chloride, oxalic acid, and the like can be used.

Among these, it is preferable to use protonic acids,
In particular, hydrochloric acid, boric acid, methanesulfonic acid, toluenesulfonic acid, etc. are preferably used.

The amount of these catalysts used is based on the total aldehyde component (II) of the raw material.
The amount is selected between 0.001 and 0.05 times by mole. The above catalysts may be used alone or in a mixture of two or more.

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.

Further, this reaction temperature is carried out at an initial stage of 80 to 150°C, and the reaction temperature is further increased as necessary. Moreover, the reaction time can be selected within the range of 1 hour to 24 hours.

The above reaction of the present invention is performed on aromatic hydroxy compounds (III
) can be used in excess as a solvent, thereby preventing the viscosity of the reaction system from increasing as the degree of polymerization increases.

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

In addition, the above reaction uses toluene and chlorobenzene.

Aromatic hydrocarbons such as dichlorobenzene, nitrobenzene and diphenyl ether, dimethyl ether such as ethylene glycol and diethyl glycol, ethers such as tetrahydrofuran and dioxane can also be used as solvents.

Thus, the hydroxycarboxylic acid derivative of the above formula (I) is obtained. This compound (I) can be hydrolyzed to hydrogenate R if necessary when R is not hydrogen.

The method of hydrolysis is carried out in the presence of water according to a known method.
It can be carried out using acid and alkaline catalysts.

In this way, the hydroxycarboxylic acid derivative of the present invention represented by the following formula (I>) is obtained.

8 "-x + ^" -x →-^rThe hydroxycarboxylic acid derivative of the present invention can be used for molecular weight measurement, infrared analysis (
IR) and nuclear magnetic resonance analysis (NMR).

(Effects of the Invention) The novel hydroxycarboxylic acid derivative according to the present invention can be expected to be used as a raw material for high-performance polymers and as a curing agent for epoxy resins. Highly heat-resistant epoxy compounds can be synthesized. Moreover, according to the production method of the present invention, the above-mentioned novel epoxy compound can be produced efficiently and at low cost.

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

In the examples, "parts" simply refer to parts by weight unless otherwise specified.

Furthermore, the analytical methods of infrared absorption spectroscopy (IR) and nuclear magnetic resonance spectroscopy (NMR) used to identify the hydroxycarboxylic acid derivatives obtained in each example are as follows.

a) Infrared absorption spectroscopy (IR) The compound and pulverized KBr powder were press-molded and measured using a conventional method.

b) Nuclear Magnetic Resonance Spectroscopy (NMR) Measurement was performed using deuterated dimethyl sulfoxide as a solvent and tetramethylsilane as a standard sample.

Example 1 778 parts of phenol and 0.6 parts of P-toluenesulfonic acid monohydrate were diluted in 1000 parts of toluene, heated to 95°C, and 210 parts of P-formylbenzoic acid was added to 120 parts of a 35% formalin aqueous solution. The mixture was uniformly dispersed and added dropwise over 1.5 hours under stirring in a nitrogen stream.

After reacting for another hour while distilling the water that comes out of the reaction system, the reaction was further carried out at 100°C for one hour. 6 parts of salt #M was added thereto and the reaction was carried out for two hours.
The reaction was carried out at ℃ for 2 hours. The reaction product obtained here was taken out from the reactor, 300 parts of toluene was added, and 10 parts of water was added.
After washing 3 times with 0 parts, unreacted phenol was removed at 80℃5
The residue was distilled off under reduced pressure using amH (J) and further removed by flushing with steam to obtain 550 parts of hydroxycarboxylic acid.

The melting point of the obtained hydroxycarboxylic acid is 90-117°C
The molecular weight determined by the freezing point depression method using dioxane was 276.0 The result of elemental analysis was C (%) = 7
3.98, H (%) = 5.01.

From the results of IR and NM elemental analysis, it was confirmed that the following compound was obtained.

X: 50 mol% Average value of n=0.1 1011□ Example 2 141 parts of phenol, methyl P-formylbenzoate 8.
Part 2! -Toluenesulfonic acid monohydrate 0.2 part, l!
4.3 parts of 35% formalin water ffiMf was added dropwise over 1 hour to a homogeneous solution of 0.2 parts of hydrochloric acid at 95°C in a nitrogen stream using a stirrer, and the reaction was continued for another 1 hour. The reaction was carried out for 2 hours at 'C. At this time, water produced as a result of the reaction was distilled out of the reaction system.

The reaction product obtained here was taken out from the reactor, 200 parts of toluene was added thereto, and after washing with 60 parts of water three times, the toluene was distilled off under reduced pressure, and further 80 parts of unreacted phenol was removed.
The hydroxycarboxylic acid derivative 16 was removed by distillation under reduced pressure at 5 aatlQ and further flushed with steam.
．． I got 0.

The obtained human oxygen carboxylic acid derivative has a melting point of 85-1
The temperature was 10°C, and the molecular weight determined by freezing point depression method using dioxane was 280. The result of elemental analysis is C (%
) =75.98, H(%)-,1,99.

Moreover, the hydroxycarboxylic acid derivative obtained by NMR is 6
It was confirmed that 0% was methyl ester, and the following compound was obtained.

"However, 60 mol 25 of R is -CI + 3.40 mol χ is hydrogen] X 250 mol% - Average value of C112n =
0.1 Example 3 To 16 parts of the hydroxycarboxylic acid derivative obtained in Jikho-12, 150 parts of aqueous solution of 5 (3 ≦ hydroxy acid) was added and the mixture was heated and left for 2 hours to hydrolyze the methyl ester. After that, acid precipitation was performed with 109≦hydrochloric acid aqueous solution, and the obtained solid was washed three times with 100 parts of water and then dried under reduced pressure at 8G'C.The obtained hydroxycarboxylic acid was completely hydrated with 14.3 parts of NMll. It was found that the hydroxycarboxylic acid was decomposed.The melting point of the obtained hydroxycarboxylic acid was 90 to 117°C.
The molecular weight determined by the freezing point depression method using Geokichisan is 28
It was 2. Also, the result of elemental analysis is C (%') = 73.
96, H (%) = 5. It was OO.

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

Examples 4 to 7 Predetermined amounts of phenol compounds shown in Table 1, P-toluenesulfonic acid monohydrate! t110.3 parts and 23.0 parts of methyl P-polmylbenzoate were dissolved in 250 parts of toluene,
Add 35% formalin aqueous solution to the solution heated to 95°C 36.
6. Reacting water was added dropwise to Part 0 over 1.5 hours under stirring in a nitrogen stream.The resulting water was distilled out of the system and allowed to react for an additional hour. 6 parts of concentrated hydrochloric acid was added to the mixture, and the mixture was further reacted for 2 hours, and the mixture was further reacted at 115°C for 2 hours. To the reaction product obtained here, 350 parts of a 5% aqueous sodium hydroxide solution was added and heated for 2 hours to cause water decomposition on the lower side.The toluene layer was separated and removed, and the aqueous layer was precipitated with a 10% aqueous hydrochloric acid solution. After washing the obtained solid substance three times with 300 parts of water, unreacted phenolic compounds were removed by distillation under reduced pressure and flushing with steam to obtain a hydroxycarboxylic acid.Table 1 shows the yield of the hydroxycarboxylic acid obtained. , melting point, and results of molecular I5 elemental analysis determined by freezing point depression method using dioxane are shown.

J/ of the compound obtained from the above results as well as NMR and IR
The dispatch is shown in Table 1. Note that i, which is not shown in the "Structure" column of Table 1, indicates the average value of n in the formula (I>) in the compound.

Table-1 Example 11i118-10 Phenol 316 parts pt~Luenesulfonic acid hydration Th 0.6 part was dissolved in 280 parts of toluene, 95 parts
55 parts of methyl P-formylbenzoate and a predetermined amount of aldehyde shown in Table 2 were added to a solution heated to 400 °C of toluene.
The solution was dissolved or uniformly dispersed in a nitrogen stream, and was added dropwise over 1.5 hours under stirring.The resulting water was distilled out of the system, and the reaction was continued for another hour.
The mixture was reacted at 00°C for 1 hour, 6 parts of concentrated hydrochloric acid was added thereto and reacted for further 2 hours, and then at 115°C for 2 hours. Add 60% of a 5% aqueous sodium hydroxide solution to the reaction product obtained here.
0 parts was added and hydrolyzed under heating for 2 hours, the toluene layer was separated and removed, the aqueous layer was precipitated with a 10% aqueous hydrochloric acid solution, the obtained solid was washed 3 times with 300 parts of water, and then heated under reduced pressure. Unreacted phenolic compounds were removed by distillation and steam flushing to obtain hydroxycarboxylic acids.

Table 2 shows the yield of hydroxycarboxylic acid obtained.

The melting point and molecular weight determined by the freezing point depression method using dioxane are shown. Results of nine element analysis are shown. Table 2 shows these results as well as the tlA structures of the compounds confirmed by NMR and IR. Note that n shown in Table 2 represents the average value of n in formula (I).

Table-2

Claims (2)

[Claims] (1) A hydroxycarboxylic acid derivative mainly composed of a structure represented by the following formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) [However, in formula (I), Ar is an aromatic hydrocarbon group having 20 or less carbon atoms that may be substituted with a halogen atom, and Of these, 15 to 70 mol% are ▲mathematical formulas, chemical formulas,
There are tables etc. ▼, and 85 to 30 mol% is ▲ mathematical formula,
There are chemical formulas, tables, etc.The structure is represented by ▼,
R is a hydrogen atom and/or a hydrocarbon group having 10 or less carbon atoms,
R' and R'' represent a hydrogen atom and/or a hydrocarbon group having 10 or less carbon atoms. m is an integer of 1 to 3, and n is 0 or 1.
Represents an integer between ~20. ] (2) At least one aldehyde represented by the following formula (II-1) and ▲There is a mathematical formula, chemical formula, table, etc.▼...(II-1) [However, in formula (II-1), R represents hydrogen or a hydrocarbon group having 10 or less carbon atoms. ] The following formula (II-2)
At least one aldehyde and/or ketone represented by or represents a hydrocarbon group having 10 or less carbon atoms] The following formula (I
At least one aromatic hydroxy compound Ar-(OH)_m...(III) represented by II) [However, in formula (III), the definitions of Ar and m are the same as in formula (I) above. ] The method for producing a hydroxycarboxylic acid derivative according to claim 1, characterized in that the reaction is carried out in the presence of an acidic catalyst.