WO2003000637A1

WO2003000637A1 - PROCESS FOR PREPARATION OF α,α-BIS(HYDROXYMETHYL)- CARBOXYLIC ACIDS

Info

Publication number: WO2003000637A1
Application number: PCT/JP2002/006225
Authority: WO
Inventors: Shinichi Konishi; Hirotaka Kinoshita; Yukitoshi Fukuda
Original assignee: Kyowa Yuka Co., Ltd.
Priority date: 2001-06-21
Filing date: 2002-06-21
Publication date: 2003-01-03
Also published as: JP2003002865A

Abstract

A process for the preparation of α,α-bis- (hydroxymethyl)carboxylic acids, characterized by comprising the step of subjecting a mixture containing an α,α- bis(hydroxymethyl)carboxylic acid represented by the general formula (|) to crystallization in an acetic acid ester in the presence of 1 to 2 wt% of water: (|) wherein R is alkyl, cycloalkyl, or aryl.

Description

Specification

a, Hibis- (hydroxymethyl) carboxylic acid production method

The present invention relates to a process for producing bis (hydroxymethyl) carboxylic acid, which is useful as a raw material for polyurethane, polyester, alkyd resin and the like.

Background art

Hitherto, as a method for producing perfluorobis (hydroxymethyl) carboxylic acid, a method of oxidizing perfluorobis (hydroxymethyl) aldehyde has been known. The raw material, i-bis (hydroxymethyl) aldehyde, is obtained by subjecting an aliphatic aldehyde having two hydrogen atoms to a suitable amount of formaldehyde to a condensation reaction in an aqueous solution in the presence of a basic catalyst. Is obtained by Then, a, bis- (hydroxymethyl) carboxylic acid is obtained by oxidation of bis (hydroxymethyl) aldehyde (see the chemical formula below).

Basic catalyst CH ₂ OH

R CH ₂ -CHO + HCHO ► RC-CHO

CH ₂ OH

CH ₂ OH oxidation CH ₂ OH

R-C-CHO ► R-C-COOH

CH ₂ OH CH ₂ OH

(Wherein, R represents alkyl, cycloalkyl or aryl)

Examples of the basic catalyst in the production of bis (hydroxymethyl) aldehyde include basic inorganic compounds such as sodium hydroxide and potassium hydroxide.

In addition, as a method for producing bis (hydroxymethyl) carboxylic acid, the method of oxidizing hydrogen peroxide with hydrogen peroxide (US Pat. No. 3,312,736), cerium, A method of oxidizing with hydrogen peroxide in the presence of a catalyst such as titanium or zirconium (JP-A-62-263141) More method for oxidizing [Organic Synthesis Chemistry Association Journal, 2 109 ⁵ (1978)] and the like. The reaction solution containing bis (hydroxymethyl) carboxylic acid obtained by the above-mentioned method or the like contains a small amount of peroxide. Therefore, in order to decompose this peroxide, a metal compound is generally used. Etc. are added.

As described above, perfluorobis (hydroxymethyl) carboxylic acid is usually used in the production of perfluorobis (hydroxymethyl) aldehyde to produce metal components derived from basic catalysts and decomposition of peroxides. Therefore, it is desirable to remove the metal component in a purification step such as crystallization.

For example, JP-A-11-228489 discloses, in a comparative example, a method of crystallizing dimethylolbutanoic acid in ethyl acetate in the presence of 0.7% by weight of water.

亍ヽ

An object of the present invention is to provide a process for producing α-bis (hydroxymethyl) alkanoic acid with high purity and low metal content in high yield.

The present invention provides the following [1] to [14].

[1] General formula (I)

CH ₂ OH R— C-COOH (I)

CH ₂ OH

(Wherein R represents alkyl, cycloalkyl or aryl), a mixture containing a bis- (hydroxymethyl) carboxylic acid, in an acetic acid ester, water :! A process for subjecting the product to crystallization in the presence of from 2% by weight to 2% by weight.

[2] The production method according to [1], wherein the acetate is ethyl acetate.

[3] The concentration of bis- (hydroxymethyl) carboxylic acid in the crystallization solution is 25 ~

The production method according to [1] or [2], wherein the amount is 45% by weight.

[4] The production method according to any one of [1] to [3], wherein the crystallization is performed by cooling the crystallization solution to -10 to 30 ° C. [5] When the metal content in the mixture containing “-bis (hydroxymethyl) carboxylic acid, which is subjected to crystallization, is 0.01% by weight or more based on the amount of the bis (hydroxymethyl) carboxylic acid. The production method according to any one of [1] to [4].

[6] The process according to any one of [1] to [5], wherein the metal content in the bis (hydroxymethyl) carboxylic acid obtained after crystallization is 15 ppm or less.

[7] The production method according to any one of [1] to [6], wherein R is alkyl having 1 to 6 carbon atoms.

[8] The production method according to any one of [1] to [6], wherein R is ethyl.

[9] Bis (hydroxymethyl) butanoic acid having a metal content of lOppm or less.

[10] Hibis- (hydroxymethyl) butanoic acid with a sodium content of lOppm or less.

[11] General formula (I)

CH ₂ OH R— C— COOH (I)

CH ₂ OH

(Wherein R represents alkyl, cycloalkyl or aryl), crystallization of a bis (hydroxymethyl) carboxylic acid in acetic acid ester in the presence of 1-2% by weight of water A process for purifying bis (hydroxymethyl) carboxylic acid, comprising:

[12] The purification method according to [11], wherein the acetate is ethyl acetate.

[13] The concentration of bis (hydroxymethyl) carboxylic acid in the crystallization solution was 25%.

The purification method according to [11] or [12], wherein the amount is up to 45% by weight.

[14] The crystallization is performed by cooling the crystallization solution to −10 to 30 ° C. [11] to [1]

The purification method according to any one of 3).

Hereinafter, the monobis (hydroxymethyl) carboxylic acid represented by the general formula (I) may be simply referred to as the monobis (hydroxymethyl) carboxylic acid. In the definition of the group in the general formula, alkyl represents, for example, a linear or branched alkyl having 1 to 18 carbon atoms, and specifically, methyl, ethyl, propyl, isopropyl, butyl, isopropyl, sec -Butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octyldecyl, etc., of which alkyl having 1 to 6 carbon atoms is preferable, and ethyl is more preferable. . Cycloalkyl represents cycloalkyl having 3 to 8 carbon atoms, and specific examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like.

Examples of aryl include phenyl, naphthyl and the like.

For the mixture containing the bis (hydroxymethyl) carboxylic acid to be subjected to crystallization, the metal content is 0.01% by weight or more based on the bis (hydroxymethyl) carboxylic acid. Preferably, the content is 0.05% by weight or more, and more preferably 0.05 to 0.2% by weight. Here, examples of the metal include those belonging to the genus I to VI of the periodic table. Among them, alkali metals such as lithium, sodium, potassium, rubidium and cesium, beryllium, magnesium, calcium, strontium, barium Are preferred, and sodium and potassium are more preferred. Further, sodium is more preferable.

The mixture containing the bis- (hydroxymethyl) carboxylic acid to be subjected to crystallization is not particularly limited, but may be, for example, a compound represented by the general formula (II)

CH ₂ OH

R— C— CHO (||) CH ₂ OH

(Wherein R is as defined above), water obtained from the oxidation of a bis (hydroxymethyl) aldehyde, and water from a reaction solution containing a bis (hydroxymethyl) carboxylic acid. Examples thereof include those distilled off. Hereinafter, the bis (hydroxymethyl) aldehyde represented by the general formula (II) will be simply referred to as the bis (hydroxymethyl) aldehyde. Mouth xymethyl) Sometimes referred to as aldehyde.

The method of oxidizing high bis (hydroxymethyl) aldehyde is the method of oxidizing with hydrogen peroxide (US Pat. No. 3,312,736), the method of oxidizing with hydrogen peroxide in the presence of a catalyst such as cerium, titanium, and zirconium. A known method such as a method (Japanese Patent Application Laid-Open No. Sho 62-263141) and a method of oxidizing with peroxybutyric acid [Journal of the Society of Synthetic Organic Chemistry, 36, 1095 (1978)] can be applied.

For example, when oxidizing using hydrogen peroxide, an aqueous solution of 20 to 60% by weight of hydrogen peroxide is usually used. The amount of hydrogen peroxide used is usually 0: !! per mole of bis- (bis (hydroxymethyl) aldehyde). To 10 mol, preferably 0.1 to 2 mol, more preferably 0.8 to: 1.2 mol. The concentration of bis (hydroxymethyl) aldehyde in the reaction solution is usually 5 to 60% by weight, preferably 20 to 40% by weight. The temperature of the oxidation reaction is usually 20 to 100 ° C, preferably 40 to 80 ° C.

To the reaction solution after the oxidation reaction, for peroxide decomposition, _{_{optionally, Co (CH 3 COO) 2}} - 4H 2 0, Mn (CH 3 COO) 2 '4H 2 0, Cu (CH 3 _{_{COO) 2 · H 2 0,}} 5% Pd / C ( carbon), 5% Pt / C (carbon containing), 5% Ru / C (carbon), a _{Pd / Si0 2, Pt / Si0} 2 or the like of a metal compound It may be added. In this case, the addition amount of the metal compound is preferably 0.001 to 0.1% by weight based on the reaction solution.

In addition, Hi, Hi-bis (hydroxymethyl) aldehyde has the general formula (I I I)

R-CH ₂ -CHO (III)

(Wherein R is as defined above) using a basic catalyst with an aldehyde represented by the formula (for example, propionaldehyde, n-butyraldehyde, etc.) [for example, Journal of Organic Synthetic Chemistry, 1095 (1978) etc.] to formaldehyde. Examples of the basic catalyst include common basic inorganic compounds such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, and potassium hydrogencarbonate. formula

It is used in an amount of 0.01 to 0.2 equivalent (molar ratio) to the aldehyde represented by (III). Further, the amount of formaldehyde used is preferably at least 1 times (mole) of the aldehyde represented by the general formula (III). In addition, Hi, Hibis (hydro (Xymethyl) aldehyde can also be produced by the addition reaction of a peralkylacrolein such as 2-ethylacrolein with formalin.

By subjecting the mixture containing the bis (hydroxymethyl) carboxylic acid obtained by the above method and the like to crystallization in acetic acid ester in the presence of 1 to 2% by weight of water, a metal with high purity can be obtained. Low bis- (hydroxymethyl) carboxylic acid content can be obtained in high yield.

Examples of the acetic ester include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, and isoamyl acetate. Of these, ethyl acetate is preferable.

The acetate is used in such an amount that the concentration of bis (hydroxymethyl) carboxylic acid in the crystallization solution is preferably 25 to 45% by weight, more preferably 30 to 40% by weight.

In the production method of the present invention, an acetate ester is used. However, as compared with the crystallization method using a ketone solvent such as methyl isobutyl ketone, a smaller amount of solvent and a higher purity of HI, HIbis ( (Hydroxymethyl) carboxylic acid can be obtained, and it is excellent in terms of volumetric efficiency of the crystallization tank.

The water content in the crystallization solution is preferably adjusted to 1 to 2% by weight, preferably 1.2 to 1.8% by weight.

The crystallization solution is cooled to -10 to 30 ° C, preferably 5 to 15 ° (more preferably 8 to 12 ° C. After cooling, the temperature is maintained. 1 to: The crystals may be aged for 100 hours.

After completion of the crystallization, the crystals of the bis (hydroxymethyl) carboxylic acid are separated from the crystallization solution by filtration or the like, and the crystals are further dried by heat under reduced pressure if necessary. You may.

The bis (hydroxymethyl) carboxylic acid obtained by the production method of the present invention preferably has a metal content of 15 ppm or less, more preferably 10 ppm or less.

Hibis (hydroxymethyl) carboxylic acid obtained by the production method of the present invention Has the following advantages: (1) high solubility in solvents (acetone, etc.) in the production of water-soluble polyurethane, and (2) it can be used for electronic materials. Have.

In addition, polybis (hydroxymethyl) carbonic acid obtained by the production method of the present invention is useful as a raw material for polyurethane, polyester, alkyd resin and the like.

The production method of the present invention is a production method for producing high-purity, low-metal content polybis (hydroxymethyl) alkanoic acid in low yield.

Invention >> 卖 The shape of a tortoise bear

Example 1

150 g of the reaction solution containing bis (hydroxymethyl) butanoic acid obtained in Reference Example 2 was concentrated under reduced pressure, and 67 g of water and low-boiling components were distilled off from the reaction solution. 49 g was added to obtain a crystallization solution. The water content in the crystallization solution was 1.5% by weight. The crystallization solution was cooled to 10 ° C to precipitate crystals of monobis (hydroxymethyl) butanoic acid. Next, crystals of sodium bis (hydroxymethyl) butanoic acid were separated from the crystallization solution by filtration, and the crystals were dried under reduced pressure at 60 ° C. for 24 hours. Table 1 shows the yield, purity, and Na concentration of the obtained bis (hydroxymethyl) butanoic acid.

The Na concentrations of Example 1 and Comparative Example 1 were measured by an atomic absorption method using an AA-860 atomic absorption flame / light spectrophotometer manufactured by Jarrell Ash Co., Ltd. of Japan. Comparative Example 1: Method according to Comparative Example 1 of Japanese Patent Publication No. 11-228489

The crystallization was carried out in the same manner as in Example 1 except that the concentration and the amount of water in the crystallization solution of sodium bis (hydroxymethyl) butanoate were changed as shown in Table 1. Table 1 shows the crystallization results. Table 1; Crystallization conditions and results

Reference Example 1: Synthesis of Hi, Hiichi bis (hydroxymethyl) butyraldehyde

A mixture of formalin (37%, lOOOOg) and n-butyraldehyde (890g) was vigorously stirred, and an aqueous solution of sodium hydroxide (25%, 60g) was added dropwise at room temperature to 60 ° C over 30 minutes. Stirring was continued for hours. The resulting reaction solution was concentrated under reduced pressure to remove unreacted butyraldehyde, low-boiling by-products, and the solvent, and to give crude 2,2-bis (hydroxymethyl) butyraldehyde (45% by weight) ) 1080 g was obtained.

Reference Example 2: Synthesis of a, hybis (hydroxymethyl) butanoic acid

30 g of water was added to 100 g of crude bis (hydroxymethyl) butyl aldehyde obtained in Reference Example 1, and the mixture was heated to 60 ° C, and 33 g of 35% hydrogen peroxide solution was added dropwise. The reaction was carried out for another 4 hours to obtain 161 g of a reaction solution containing sodium bis (hydroxymethyl) butanoic acid.

の禾 ττ

According to the present invention, there is provided a process for producing high purity and low bis (hydroxymethyl) alkanoic acid with low metal content in high yield.

Claims

The scope of the claims

1. General formula (I)

CH ₂ 〇H

R— C-C〇〇H (I)

CH ₂ 0H

(Wherein R represents alkyl, cycloalkyl or aryl), a mixture containing bis (hydroxymethyl) carboxylic acid in an acetic acid ester in the presence of 1-2% by weight of water, A process for producing bis (hydroxymethyl) carboxylic acid, comprising a step of subjecting the solution to precipitation.

2. The method according to claim 1, wherein the acetate is ethyl acetate.

3. The process according to claim 1 or 2, wherein the concentration of bis- (hydroxymethyl) carboxylic acid in the crystallization solution is 25 to 45% by weight.

4. The production method according to any one of claims 1 to 3, wherein crystallization is performed by cooling the crystallization solution to -10 to 30 ° C.

5. The metal content of the mixture containing the bis (hydroxymethyl) carboxylic acid to be crystallized is 0.01% by weight or more based on the amount of the bis (hydroxymethyl) carboxylic acid. The production method according to any one of claims 1 to 4.

6. The process according to any one of claims 1 to 5, wherein the metal content in the bis (hydroxymethyl) carboxylic acid obtained after crystallization is 15 ppm or less.

7. The method according to any one of claims 1 to 6, wherein R is alkyl having 1 to 6 carbon atoms.

8. The method according to any one of claims 1 to 6, wherein R is ethyl.

9. Bis (hydroxymethyl) butanoic acid with a metal content of less than 10 ppm.

10. Bis (hydroxymethyl) butyric acid with sodium content less than lOppm.

11. General formula (I) CH ₂ OH

R—C-COOH (I)

CH ₂ OH

(Wherein R represents alkyl, cycloalkyl or aryl) Crystallization of bis (hydroxymethyl) carboxylic acid in the presence of 1-2% by weight of water in acetic acid ester A method for purifying bis (hydroxymethyl) carboxylic acid comprising the steps of:

12. The purification method according to claim 11, wherein the acetate is ethyl acetate.

13. The purification method according to claim 11 or 12, wherein the concentration of bis- (hydroxymethyl) carboxylic acid in the crystallization solution is 25 to 45% by weight.

14. The purification method according to any one of claims 11 to 13, wherein crystallization is performed by cooling the crystallization solution to -10 to 30 ° C.