JPS6043337B2 - Process for producing 3,3',5,5'-tetrahydroxymethyl-4,4'-dihydroxydiphenylmethanes - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 3,3',5,5'-tetrahydroxymethyl-4,4'-dihydroxydiphenylmethane in high yield by reacting phenols with formaldehyde.

3.3'5.5'-tetrahydroxymethyl-4.4
'-Dihydroxydiphenylmethanes are compounds used as raw materials for polymerization of phenol resins, epoxy resins, polyester resins, and the like.

Conventionally, 3.3 from phenols and formaldehyde
' ・ 5 ・ 5'-tetrahydroxymethyl-4
・4'-dihydroxydiphenylmethanes, e.g. 3
・ 3' ・ 5 ・ 5'-tetrahydroxymethyl-4 ・Many methods for synthesizing 4'-dihydroxydiphenylmethane have been reported in the literature. However, all of these methods involve the treatment of phenols and formaldehyde with an alkali metal or alkali. The reaction is carried out in the presence of a basic compound containing an earth metal, but since there are many by-products of high-boiling condensation products, 3.3'', 5.5''-tetrahydroxymethyl-4●4'- The yield of dihydroxydiphenylmethanes is low and cannot be satisfactorily adopted as an industrial production method.
Also when producing 3″, 5, 5″-tetrahydroxymethyl-4, 4″-dihydroxydiphenylmethane,
Usually, the reaction mixture of phenols and formaldehyde is directly precipitated with acid, or crystallized by reaction
A method has been adopted in which a basic salt of 3''/5●5''-tetrahydroxymethyl-4●4''-dihydroxydiphenylmethane is taken from house to house, then resuspended in water and precipitated with an acid.

In the reaction between phenols and formaldehyde, generally 3
●3″・5●5″-tetrahydroxymethyl-4.4″
In addition to the basic salts of -dihydroxydiphenylmethanes, large amounts of high-boiling condensates are produced, so when the former method described above is adopted, the product obtained by acid precipitation contains a large amount of high-boiling condensates. Contains an oily substance, 3.3″, 5.5″
The purity of -tetrahydroxymethyl-4,4''-dihydroxydiphenylmethane is also low, and the 3,4'' produced in the reaction system is
There is also a drawback that the recovery rate of the product isolated for 3'', 5, 5''-tetrahydroxymethyl-4●4''-dihydroxydiphenylmethane is also extremely low.
Even if the latter method described above is adopted, 3,3″,5,5″-tetrahydroxymethyl-4● crystallizes in the reaction mixture.
Since the basic salts of 4''-dihydroxydiphenylmethanes are extremely fine crystals, it is extremely difficult to separate them by conventional centrifugation methods.
The basic salt of this product was separated and 3.3"
Even if ●5●5''-tetrahydroxymethyl-4●4''-dihydroxydiphenylmethane is isolated, this product will also contain a large amount of high-boiling condensation products as mentioned above, so it will not be pure. The degree of 3.3 generated in the reaction system is low.
The recovery of the product isolated for ``.5.5''-tetrahydroxymethyl-4.4''-dihydroxydiphenylmethanes is similarly low. Highly purified 3.3".5.5
As a result of studying a method for isolating ``-tetrahydroxymethyl-4●4'-dihydroxydiphenylmethanes in high yield, it was found that when the reaction mixture is brought into contact with a water-soluble organic solvent, the high-boiling condensation products in the reaction mixture are selected. found that basic salts of 3,3'',5,5''-tetrahydroxymethyl-4●4''-dihydroxydiphenylmethane can be selectively crystallized and easily separated,
We have arrived at the present invention.

That is, the present invention provides 3.3 which is crystallized by contacting a reaction mixture obtained by reacting phenols with formaldehyde in the presence of a basic compound in an aqueous solution with a water-soluble organic solvent. 3●3″●5●5″-tetrahydroxymethyl-4●, which is characterized by acid precipitation after separating basic salts of 4″-dihydroxydiphenylmethanes. This is a method for producing 4″-dihydroxydiphenylmethanes.

The phenols used as raw materials in the method of the present invention are phenols selected from the group consisting of phenol and bis(4-hydroxyphenyl)methanes, and specifically phenols, bis(4-hydroxyphenyl)methanes, etc. , 2●bis(4-hydroxyphenyl)methanes such as 2-bis(4-hydroxyphenyl)propane.

Among these phenols, it is preferable to use monohydric phenols, and it is particularly preferable to apply the method of the present invention to phenol. In addition to formaldehyde, the formaldehyde used in the method of the present invention for reacting phenols with formaldehyde may include formalin, which is an aqueous solution thereof, or a polymer of formaldehyde, which can easily produce formaldehyde. Paraformaldehyde can be exemplified.

Among these, formalin is preferably used in the method of the present invention. The amount of formaldehyde used is usually in the range of 0.5 to 5, preferably 2 to 3.5 in terms of molar ratio to the above-mentioned phenols. The basic compound used in the method of the present invention is a basic compound containing an alkali metal or an alkaline earth metal.
More specifically, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal oxides such as sodium oxide and potassium oxide, sodium methoxide, sodium ethoxide, sodium propoxide, and potassium propoxide. , basic compounds containing alkali metals such as alkoxides of alkali metals such as potassium butoxide, alkaline earth metals such as magnesium hydroxide, calcium hydroxide, barium hydroxide, magnesium oxide, calcium oxide, barium oxide, etc. Examples include basic compounds. At least one of these basic compounds is used. Among these basic compounds, it is preferable to use a basic compound containing an alkali metal, and it is particularly preferable to use a basic compound containing sodium. In the method of the present invention, when phenols are reacted in the presence of the above-mentioned basic compound containing an alkali metal or alkaline earth metal, the phenols are changed into an alkali metal salt or an alkaline earth metal salt. Alkali metal salts or alkaline earth metal salts of phenols can also be used in place of the phenols and the above-mentioned basic compounds, which naturally fall within the scope of the present invention. The amount of the basic compound used is usually 0.5 to 1.5s in molar ratio to the phenol.
Preferably it is in the range of 0.7 to 1.2. In the method of the present invention, when the reaction is carried out together with the basic compound in the coexistence of an alkali metal salt or alkaline earth metal salt, particularly in the coexistence of a metal salt containing a metal ion common to the basic compound, the formation of It is more preferred because the yield of 3,3'',5,5''-tetrahydroxymethyl-4,4''-dihydroxydiphenylmethane is improved.

The amount of these metal salts to be used can be selected in a wide range from the concentration in the solution in the reaction system, usually from 0.2 mol/l' to the saturation solubility, but economically it is 0.5 to 0.2 mol. /
It is preferably within the range of e. The reaction of the present invention is carried out in an aqueous solution, but if necessary, other water-soluble organic solvents such as alcohols, ketones or It can also be used in combination with water-soluble organic solvents such as nitriles.

In the process of the invention, the reaction is usually carried out at a temperature of 20 to 100°C, preferably 40 to 90°C.

Methods for reacting phenols with formaldehyde include: 1) stirring a mixture consisting of phenols, formaldehyde, a basic compound, a solvent and, if necessary, a metal salt at the above temperature; 2) phenols, a basic compound, and a solvent; A method of continuously supplying formaldehyde with stirring to a mixture consisting of 3 formaldehyde, a solvent, and a metal salt as necessary; Any method such as a method of continuously supplying a mixture consisting of a solvent and a solvent can be adopted. Among these methods, if method 3 is adopted, 3.3"
This is preferred because 5.5"-tetrahydroxymethyl-4.4"-dihydroxydiphenylmethane can be obtained in high yield. In the method of the present invention, highly purified 3
●3″●5●5″-tetrahydroxymethyl-4.4″
This method is characterized by the ability to isolate basic groups of -dihydroxydiphenylmethanes in high yield. In the method of the present invention, basic salts of 3,3",5,5"-tetrahydroxymethyl-4,4"-dihydroxydiphenylmethane are selectively crystallized by contacting these reaction mixtures with a water-soluble organic solvent. The basic salt of the high-boiling condensation product produced as a by-product is selectively dissolved in a solvent.The water-soluble organic solvent here is an organic solvent that is compatible with water. Specifically, for example, ketones such as acetone, methyl ethyl ketone, diethyl ketone, alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, nitriles such as acetonitrile and probionitrile, dimethyl sulfoxide, diethyl Examples include sulfoxide, dimethylsulfone, dimethylformamide, N-methylpyrrolidone, hexamethylphosphortriamide, etc., and one or a mixture of two or more of these water-soluble organic solvents is used. A small amount of an organic solvent that is incompatible with water, such as benzene, hexane, ether, or methyl isobutyl ketone, can also be added to the solvent as long as it does not impair the compatibility with the aqueous solution of the reaction mixture. Among the solvents, it is preferable to use water-soluble ketones or water-soluble alcohols, such as acetone,
It is particularly preferred to use at least one organic solvent selected from the group consisting of methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol and butyl alcohol. The method of bringing the reaction mixture and the water-soluble organic solvent into contact with each other according to the method of the present invention is not particularly limited, and the purpose can be sufficiently achieved by simply stirring and mixing the two. If basic salts of 3●3″・5●5″-tetrahydroxymethyl-4,4″-dihydroxydiphenylmethane are precipitated in the reaction mixture, dissolve them by heating or adding water. After that, it is preferable to contact it with a water-soluble organic solvent.

The temperature at the time of contact between the two is usually in the range of -30 to 40°C, preferably in the range of 0 to 30°C. The amount of the water-soluble organic solvent used is usually in the range of 1 to 8, preferably in the range of 1.5 to 6, based on the weight ratio to water in the reaction mixture. When the reaction mixture is contacted with a water-soluble organic solvent according to the method of the present invention, the desired product is a basic salt of 3,3'',5,5''-tetrahydroxymethyl-4,4''-dihydroxydiphenylmethane. , is selectively crystallized, and the basic salt of the high-boiling condensation product, which is a by-product, is selectively dissolved in the solvent. 3.3".5.5"-tetrahydroxymethyl- 4●Basic salts of 45-dihydroxydiphenylmethanes have large particles and can be easily separated by standard separation methods such as centrifugation.
3.3".5.5"-tetrahydroxymethyl-4.4"-dihydroxydiphenylmethane is obtained by acid precipitation of a basic salt of ".5.5"-tetrahydroxymethyl-4.4"-dihydroxydiphenylmethane. can be obtained. The method of acid precipitation is usually 3.3"
When a basic salt of 5,5"-tetrahydroxymethyl-4,4"-dihydroxydiphenylmethane is suspended in water or other organic solvent and an acid is added, 3●3"
●5●5″-tetrahydroxymethyl-4,4″-dihydroxydiphenylmethane will precipitate as powdered crystals. xymethyl-4
・4″-dihydroxydiphenylmethanes are obtained.
In the method of the present invention, high-boiling condensation products present in the generated reaction mixture are selectively removed, resulting in highly pure 3●3''●5●5''-tetrahydroxymethyl-4.
4″-dihydroxydiphenylmethanes are obtained.

In addition, 3・3″・5・
5″-tetrahydroxymethyl-4●4″-dihydroxydiphenylmethane can be isolated with a high recovery rate. Next, the method of the present invention will be specifically explained using examples.

Example 1 (1) Reaction process After replacing the inside of a separable flask with an internal volume of 1.0e equipped with a condenser, a stirrer, and a dropping load with N2 gas, 37% by weight formalin 243f was added inside the flask.
(contains 3.0 moles of formaldehyde) and 30y of sodium chloride (a). Add 94 g (1.0 mole) of phenol from the dropwise load while stirring while maintaining the temperature at 40°C.
mol), sodium hydroxide (1.0 mol) and water 80
A mixed solution consisting of q was added dropwise in one drop.

After the dropwise addition was completed, stirring was continued for 1 hour at that temperature, and then the temperature was further raised to 70°C and stirring was continued for 5 hours. After the completion of the reaction, a certain amount of the reaction mixture 487y was taken, acetic acid was added thereto to precipitate the product, and then the product was measured by liquid chromatography (G.P.C.).・
The amount of 3'', 5, 5''-tetrahydroxymethyl-4●4''-dihydroxydiphenylmethane was determined.As a result, the amount of 3,3'',5,5-tetrahydroxymethyl-4,4''- produced by the reaction was determined. The total amount of dihydroxydiphenylmethane was 108.89, and the yield based on the charged phenol was 68 mol%. (2) Recovery step After the reaction, 320 ml of water was added to 487 g of the reaction mixture, and the crystallized product was After completely dissolving in water at ℃, add 1500 TnL of acetone, cool to 5℃ and stir to dissolve sodium salt of 3,3'', 5,5''-tetrahydroxymethyl-4,4''-dihydroxydiphenylmethane. It crystallized.

This suspension could be easily separated by centrifugation (using 300 mesh cloth). The crystals thus separated were suspended again in 150 ml of water, and ? 3.3".5 by acid precipitation with hydrochloric acid until the pH becomes 2.
・5″-tetrahydroxymethyl-4●4″-dihydroxydiphenylmethane was precipitated. After separating the crystals, they are washed with water and dried to produce 3, 3", 5,
86.4y of powdered crystals of 5"-tetrahydroxymethyl-4.4"-dihydroxydiphenylmethane were isolated. The purity of this 3●3″●5●5″-tetrahydroxymethyl-4●4″-dihydroxydiphenylmethane is 96
%, and what is the yield based on the phenol used? It was mole hot. Comparative Example 1 A reaction was carried out in exactly the same manner as in Example 1 (1), and 3●
3″・5●5″-tetrahydroxymethyl-4,4″-dihydroxydiphenylmethane sodium salt 108.
After cooling the reaction mixture 487y containing 8y, it was separated into 3.3".
The sodium salt of 5,5″-tetrahydroxymethyl-4,4″-dihydroxydiphenylmethane was isolated.
Separation was difficult because the crystals were fine.

The separated crystals were dried to obtain the sodium salt of 3.3''.5.5''-tetrahydroxymethyl-4.4''-dihydroxydiphenylmethane.
) by acid precipitation using the same method as 3.3
A sticky solid 75.1y of ".5.5"-tetrahydroxymethyl-4.4"-dihydroxydiphenylmethane was isolated. This 3.3".5.5"-tetrahydroxymethyl-4.4"-dihydroxydiphenylmethane The purity of . The yield was 85%, and the yield was 47 mol% based on the phenol used. Comparative Example 2 A reaction was carried out in exactly the same manner as in Example 1 (1), and 3.
Sodium salt of 3″.5.5″-tetrahydroxymethyl-4.4″-dihydroxydiphenylmethane 108.
After cooling the reaction mixture 487q containing 8y, direct acid precipitation was performed with Δ hydrochloric acid until the pH became 2.

However, the product obtained by this method is a viscous oil56
．． 0y, and was no longer a powdery crystal like that obtained in Example 1. The purity of this 3,3'',5,5''-tetrahydroxymethyl-4,4''-dihydroxydiphenylmethane was 80%, and it contained a large amount of high-boiling condensation products.The yield based on the phenol used was 35%.
It was mol%. Large Example 21) Reaction process After replacing the inside of a separable flask with an internal volume of 1.0e equipped with a condenser, a stirrer, and a dropping load with N2 gas, 37% by weight formalin 243y was added inside the flask.
(contains 3.0 moles of formaldehyde) and 30 V of sodium chloride (a). Phenol 94y (1.0
A mixed solution consisting of sodium hydroxide (1.0 mol) and 80 y of water was added dropwise in one drop.

After the dropwise addition was completed, stirring was continued for 1 hour at that temperature, and then the temperature was further raised to 60°C and stirring was continued for 1 hour. After the reaction was completed, the reaction mixture was subjected to liquid chromatography (
G. P. C. ) generated by measuring 3.3
The amount of ``・5,5''-tetrahydroxymethyl-4●4''-dihydroxydiphenylmethane was determined.As a result, the amount of 3●3'',5,5''-tetrahydroxymethyl-4,4''- produced by the reaction was determined. The total amount of dihydroxydiphenylmethane was 124.9y, and the yield based on the phenol charged was 78 mol%. F) Recovery step After adding 320 ml of water to the reaction mixture 487y after the completion of the reaction and completely dissolving the crystallized product at 60°C, 1500 mL of acetone was added, and the mixture was cooled to 5°C and stirred. 3″・5・5″-tetrahydroxymethyl-4・
The sodium salt of 4''-dihydroxydiphenylmethane was crystallized.

This suspension could be easily separated by centrifugation (using 300 mesh cloth). The crystals separated in this way were suspended in 150 ml of water again, and acidified with △ hydrochloric acid until the pH reached 2, resulting in 3●3″●5
●5″-tetrahydroxymethyl-4●4′-dihydroxydiphenylmethane was precipitated. After filtering this crystal, washing with water and drying it, 3.3″, 5.5
100.7y of powdered crystals of "-tetrahydroxymethyl-4.4"-dihydroxydiphenylmethane were isolated. The purity of this 3.3".5.5"-tetrahydroxymethyl-4●4'-dihydroxydiphenylmethane is 96.
%, and the yield was 63 mol based on the phenol charged. Comparative Example 3 A reaction was carried out in exactly the same manner as in Example 2 (1), and 3.
3″●5.5″-tetrahydroxymethyl-4●4″-dihydroxydiphenylmethane sodium salt 124.
After cooling the reaction mixture 487y containing 9V, it was separated by centrifugation (using 300 mesh fabric) to 3.3"
An attempt was made to separate the sodium salt of 5.5"-tetrahydroxymethyl-4.4"-dihydroxydiphenylmethane, but the crystals were fine and the reaction mixture was viscous, so it could not be separated.

Comparative Example 4 A reaction was carried out in exactly the same manner as in Example 2 (1), and 3
●3″●5●5-tetrahydroxymethyl-4●4″-dihydroxydiphenylmethane sodium salt 124.
After cooling the reaction mixture 487y containing 9f, direct acid precipitation was performed with hydrochloric acid until the pH reached 2.0.

However, the product obtained by this method is a viscous oil 88
．． 0y, and was no longer a powdery crystal like that obtained in Example 2. The purity of this 3.3''●5●5f-tetrahydroxymethyl-4●4''-dihydroxydiphenylmethane was 80%, and the yield based on phenol was 55 mol%. This product contained a large amount of high-boiling condensation products. Examples 3 to 11 The same procedure as in Example 2 was conducted except that the organic solvents shown in Table 1 were used as water-soluble organic solvents in the recovery step (2).

The results are shown in Table 1. Examples 12 to 13 (1) Reaction process After replacing the inside of a separable flask with an internal volume of 1.0e equipped with a condenser, a stirrer, and a dropping load with N2 gas, 37% by weight formalin 243y was added inside the flask.
(contains 3.0 moles of formaldehyde) and 30y of sodium chloride (a). Add phenol 94f (1.5 mol) from the dropwise load while stirring while maintaining the temperature at 40'C.
A mixed solution consisting of sodium hydroxide (1.0 mol) and 80 g of water was added dropwise in one drop.

After the dropwise addition was completed, stirring was continued for 1 hour at that temperature, and then the temperature was further raised to 60°C and stirring was continued for 1 hour. 3 produced by measuring the reaction mixture after the completion of the reaction by liquid chromatography (G.P.C.) in the same manner as in Example 1.
・3″・5.5″-tetrahydroxymethyl-4.4″
-dihydroxydiphenylmethane was determined. As a result, the total amount of 3●3''●5●5''-tetrahydroxymethyl-4,4''-dihydroxydiphenylmethane produced by the reaction was 116.9y, and the yield was 73 mol based on the charged phenol. (2) Recovery step Add 320T of water to 487f of the reaction mixture obtained in (1) above.
! The product crystallized by adding Lt was completely dissolved in water at 60°C, and then treated in the same manner as in Example 2 (2), except that acetone was added in the amount shown in Table 2. did. The results are shown in Table 2. Examples 14 to 16 The same procedure as in Example 12 was carried out except that the temperature of contact between the aqueous solution of the reaction mixture and acetone in the recovery step (2) was changed as shown in Table 3.

The results are shown in Table 3. Examples 17 to 18 1) Reaction process After replacing the inside of a separable flask with an internal volume of 1.0' equipped with a condenser, a stirrer, and a dropping load with N2 gas, 37% by weight formalin 243f was added inside the flask.
1 (containing 3.0 moles of formaldehyde) and 30y of sodium chloride (4). Phenol 94y (1.5 mol) was added from the dropwise load while stirring at 40°C.
A mixed solution consisting of sodium hydroxide (1.0 mol) and 80 y of water was added dropwise in one drop.

After the dropwise addition was completed, stirring was continued at that temperature for 1 hour, and then the temperature was further raised to 60° C. and stirring was continued for 1 full hour. After the reaction was completed, the reaction mixture was measured using liquid chromatography (G.P.C.) in the same manner as in Example 1 to obtain 3.
The amount of 3", 5, 5"-tetrahydroxymethyl-4●4"-dihydroxydiphenylmethane was determined. As a result, the amount of 3●3"●5●5"-tetrahydroxymethyl-4●4" produced by the reaction was determined. -dihydroxydiphenylmethane was determined. As a result, 3,3'',5,5-tetrahydroxymethyl-4,4 produced by the reaction
The total amount of ``-dihydroxydiphenylmethane is 97.6y
The yield was 61 mol based on the phenol used. 2) Recovery step Add 320 g of water to 487 q of the reaction mixture obtained in (1) above.
was added to completely dissolve the crystallized product at 60°C, and then acetone was added in the amount shown in Table 4.
It was treated in the same manner as in 2).

Claims (1)

[Claims] 1. A reaction obtained by reacting formaldehyde with a phenol selected from the group consisting of phenol and bis(4-hydroxyphenyl)methane in the presence of a basic compound in an aqueous solution. 3,3',5, crystallized by contacting the mixture with a water-soluble organic solvent.
-3,3',5,5'-hydroxymethyl-4,4 which is characterized by filtering out the basic salt of 5'-tetrahydroxymethyl-4,4'-dihydroxydiphenylmethane and then precipitating it with acid. A method for producing '-dihydroxydiphenylmethanes. 2. The method according to claim 1, wherein water-soluble ketones or alcohols are used as the water-soluble organic solvent. 3. The method according to claim 1, wherein at least one organic solvent selected from the group consisting of acetone, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and butyl alcohol is used as the water-soluble organic solvent. Method. 4. The method according to claim 1, wherein the water-soluble organic solvent is used in a weight ratio of 1.5 to 6 to water in the reaction mixture. 5. The method according to claim 1, wherein the reaction mixture and the water-soluble organic solvent are contacted at a temperature of -30 to 40°C. 6. The method according to claim 1, wherein the reaction is carried out in an aqueous solution in the coexistence of a basic compound and a metal salt containing a metal ion common to the basic compound.