WO2003000637A1 - Procede de preparation d'acides $g(a),$g(a)-bis(hydroxymethyl) carboxyliques - Google Patents

Procede de preparation d'acides $g(a),$g(a)-bis(hydroxymethyl) carboxyliques Download PDF

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Publication number
WO2003000637A1
WO2003000637A1 PCT/JP2002/006225 JP0206225W WO03000637A1 WO 2003000637 A1 WO2003000637 A1 WO 2003000637A1 JP 0206225 W JP0206225 W JP 0206225W WO 03000637 A1 WO03000637 A1 WO 03000637A1
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WIPO (PCT)
Prior art keywords
hydroxymethyl
bis
carboxylic acid
crystallization
weight
Prior art date
Application number
PCT/JP2002/006225
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English (en)
Japanese (ja)
Inventor
Shinichi Konishi
Hirotaka Kinoshita
Yukitoshi Fukuda
Original Assignee
Kyowa Yuka Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kyowa Yuka Co., Ltd. filed Critical Kyowa Yuka Co., Ltd.
Publication of WO2003000637A1 publication Critical patent/WO2003000637A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation

Definitions

  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • An object of the present invention is to provide a process for producing ⁇ -bis (hydroxymethyl) alkanoic acid with high purity and low metal content in high yield.
  • the present invention provides the following [1] to [14].
  • R represents alkyl, cycloalkyl or aryl
  • a process for purifying bis (hydroxymethyl) carboxylic acid comprising:
  • the crystallization is performed by cooling the crystallization solution to ⁇ 10 to 30 ° C. [11] to [1]
  • 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.
  • aryl examples include phenyl, naphthyl and the like.
  • the metal content is 0.01% by weight or more based on the bis (hydroxymethyl) carboxylic acid.
  • the content is 0.05% by weight or more, and more preferably 0.05 to 0.2% by weight.
  • 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)
  • 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.
  • 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).
  • 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.
  • the addition amount of the metal compound is preferably 0.001 to 0.1% by weight based on the reaction solution.
  • Hi Hi-bis (hydroxymethyl) aldehyde has the general formula (I I I)
  • R is as defined above
  • 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.
  • Hi, Hibis (hydro (Xymethyl) aldehyde can also be produced by the addition reaction of a peralkylacrolein such as 2-ethylacrolein with formalin.
  • acetic ester examples 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.
  • an acetate ester is used.
  • a ketone solvent such as methyl isobutyl ketone
  • 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.
  • 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.
  • 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.
  • Example 1 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de préparation d'acides α,α-bis(hydroxyméthyl) carboxyliques. Ce procédé se caractérise en ce qu'il consiste à soumettre à la cristallisation un mélange contenant un acide α,α-bis(hydroxyméthyl) carboxylique représenté par la formule générale (I), dans un ester d'acide acétique, en présence de 1 à 2 % en poids d'eau: (I), dans laquelle R représente alkyle, cycloalkyle ou aryle.
PCT/JP2002/006225 2001-06-21 2002-06-21 Procede de preparation d'acides $g(a),$g(a)-bis(hydroxymethyl) carboxyliques WO2003000637A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2001-187552 2001-06-21
JP2001187552A JP2003002865A (ja) 2001-06-21 2001-06-21 α，α−ビス（ヒドロキシメチル）カルボン酸の製造法

Publications (1)

Publication Number Publication Date
WO2003000637A1 true WO2003000637A1 (fr) 2003-01-03

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JP (1) JP2003002865A (fr)
WO (1) WO2003000637A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103524331A (zh) * 2012-09-17 2014-01-22 天津雅特生物科技有限公司 一种2.2-二羟甲基丁酸的制备方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006045185A (ja) * 2004-07-02 2006-02-16 Nippon Kasei Chem Co Ltd ２，２’−ビス（ヒドロキシメチル）アルカン酸および２，２’−ビス（ヒドロキシメチル）アルカン酸組成物
JP4647952B2 (ja) * 2004-07-30 2011-03-09 ペルストルプ スペシヤルテイ ケミカルズ アーベー ２，２’−ビス（ヒドロキシメチル）ブタン酸粉体および水性ポリウレタン樹脂の製造方法
JP2014152133A (ja) * 2013-02-08 2014-08-25 Toyobo Co Ltd 高純度な２，２’−ビス（ヒドロキシメチル）アルカン酸およびその製造法
CN110483277A (zh) * 2019-09-21 2019-11-22 河南精众生物科技有限公司 二羟甲基丁酸萃取精致结晶的制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1177555A (en) * 1966-12-27 1970-01-14 Perstorp Ab Process for the Production of Methylolalkanoic Acids.
JPH11217351A (ja) * 1997-11-25 1999-08-10 Mitsubishi Chemical Corp ジメチロールアルカン酸の製造方法
JPH11228489A (ja) * 1998-02-17 1999-08-24 Nippon Kasei Chem Co Ltd ２，２’−ビス（ヒドロキシメチル）アルカン酸の製造方法
EP0937701A1 (fr) * 1998-02-18 1999-08-25 Nippon Kasei Chemical Co., Ltd. Procédé pour la préparation de l'acide 2,2-bis (hydroxyméthyl)alcanoique
WO2002038527A1 (fr) * 2000-11-08 2002-05-16 Basf Aktiengesellschaft Procede de production d'acides d'alcane de polymethylol ou d'alcane de monomethylol

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1177555A (en) * 1966-12-27 1970-01-14 Perstorp Ab Process for the Production of Methylolalkanoic Acids.
JPH11217351A (ja) * 1997-11-25 1999-08-10 Mitsubishi Chemical Corp ジメチロールアルカン酸の製造方法
JPH11228489A (ja) * 1998-02-17 1999-08-24 Nippon Kasei Chem Co Ltd ２，２’−ビス（ヒドロキシメチル）アルカン酸の製造方法
EP0937701A1 (fr) * 1998-02-18 1999-08-25 Nippon Kasei Chemical Co., Ltd. Procédé pour la préparation de l'acide 2,2-bis (hydroxyméthyl)alcanoique
WO2002038527A1 (fr) * 2000-11-08 2002-05-16 Basf Aktiengesellschaft Procede de production d'acides d'alcane de polymethylol ou d'alcane de monomethylol

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103524331A (zh) * 2012-09-17 2014-01-22 天津雅特生物科技有限公司 一种2.2-二羟甲基丁酸的制备方法

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