WO2017069104A1 - Procédé de purification d'un dérivé d'acide acrylique - Google Patents

Procédé de purification d'un dérivé d'acide acrylique Download PDF

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Publication number
WO2017069104A1
WO2017069104A1 PCT/JP2016/080790 JP2016080790W WO2017069104A1 WO 2017069104 A1 WO2017069104 A1 WO 2017069104A1 JP 2016080790 W JP2016080790 W JP 2016080790W WO 2017069104 A1 WO2017069104 A1 WO 2017069104A1
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group
acrylic acid
acid derivative
aldehyde
carbon atoms
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PCT/JP2016/080790
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English (en)
Japanese (ja)
Inventor
真帆 富岡
章広 後藤
誠 松浦
智仁 濱田
洋介 岸川
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ダイキン工業株式会社
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Publication of WO2017069104A1 publication Critical patent/WO2017069104A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/60—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/62—Halogen-containing esters
    • C07C69/65—Halogen-containing esters of unsaturated acids
    • C07C69/653—Acrylic acid esters; Methacrylic acid esters; Haloacrylic acid esters; Halomethacrylic acid esters

Definitions

  • the present invention relates to a method for purifying an acrylic acid derivative, and more particularly to a method for purifying an acrylic acid derivative characterized in that the aldehyde is removed from a composition containing an acrylic acid derivative and an aldehyde having 2 to 6 carbon atoms.
  • Acrylic acid derivatives are (1) raw materials for water-absorbing polymers, (2) as substitutes for inorganic glass, window materials for buildings or vehicles, covers for lighting equipment, lantern signs, road signs, daily necessities, office supplies, crafts, It is also widely used as a raw material for acrylic resins used for windshields of watches and (3) acrylic resin paints.
  • fluorine-containing acrylic acid derivatives are synthetic intermediates for pharmaceuticals (for example, antibiotics), synthetic intermediates for optical fiber sheath materials, synthetic intermediates for coating materials, and semiconductor resist materials. It is useful as an intermediate and a monomer of a functional polymer.
  • Patent Document 1 discloses a method of reacting 2-fluoropropionic acid ester with a brominating agent having a nitrogen-bromine bond in the presence of a radical initiator.
  • Patent Document 2 discloses that a 3-halo-2-fluoropropionic acid derivative is converted to a substituted 2-fluoroacrylic acid derivative in the presence of at least one base and in the presence of at least one polymerization inhibitor. A method of conversion is disclosed.
  • an aldehyde may be mixed in the composition containing the target acrylic acid derivative.
  • the aldehyde is an acrylic acid derivative, as described above, a pharmaceutical intermediate (for example, antibiotic), a synthetic intermediate for optical fiber sheath materials, a synthetic intermediate for coating materials, and a synthetic intermediate for semiconductor resist materials.
  • a pharmaceutical intermediate for example, antibiotic
  • a synthetic intermediate for optical fiber sheath materials for example, a synthetic intermediate for coating materials
  • a synthetic intermediate for semiconductor resist materials When used in applications such as monomers of functional polymers, etc., there is a risk of adversely affecting the desired reaction. In such cases, it is necessary to remove the aldehyde from the acrylic acid derivative and the composition containing the aldehyde.
  • An object of the present invention is to provide a method for efficiently purifying an acrylic acid derivative, specifically, a method for efficiently removing an aldehyde from a composition containing an acrylic acid derivative and an aldehyde.
  • a method of removing impurities from useful compounds for example, (1) a method of removing the impurities as they are, and (2) a method of removing the impurities by reacting them with other components to convert them into other compounds Can be considered.
  • the structure and physical properties of useful compounds and impurities are often similar, and thus the impurities may not be removed as they are by conventional methods such as distillation.
  • the method (2) such a problem may be avoided, but there is a problem in that the other component itself and / or the other compound can become a new impurity.
  • an object of the present invention is to provide a new method for purifying an acrylic acid derivative, which is highly efficient and highly suppresses the introduction of such new impurities as described above.
  • the present invention includes the following aspects.
  • Item 1 Formula (I): [Where: R a represents an alkyl group, a fluoroalkyl group, an aryl group optionally having one or more substituents, or a hydrogen atom, and X represents an alkyl group, a fluoroalkyl group, a fluorine atom, or a hydrogen atom Represents. ]
  • a method for purifying an acrylic acid derivative represented by A composition A containing an acrylic acid derivative represented by the formula (I) and an aldehyde having 2 to 6 carbon atoms, Contacting with a compound having one or more amino groups, or sulfite, Step A for removing the aldehyde having 2 to 6 carbon atoms A purification method comprising: Item 2. Item 2.
  • a method for efficiently purifying an acrylic acid derivative (I), specifically, a composition containing an acrylic acid derivative (I) and an aldehyde having 2 to 6 carbon atoms, the carbon number 2 A method for efficiently removing -6 aldehydes is provided.
  • room temperature means a temperature within the range of 10 to 40 ° C.
  • the steps, processes, or operations herein can be performed at room temperature unless specifically limited.
  • an “alkyl group” (the term “alkyl group” includes a part of “alkyl group” in “fluoroalkyl group” and the like) is cyclic, linear or branched. It can be an alkyl group.
  • the “alkyl group” is, for example, an alkyl group having 1 to 20 carbon atoms, 1 to 12 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, or 1 to 3 carbon atoms. it can.
  • alkyl group specifically includes, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a neopentyl group.
  • linear or branched alkyl groups such as a hexyl group.
  • alkyl group specifically includes, for example, a cyclic alkyl group having 3 to 6 carbon atoms (cycloalkyl group) such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • cycloalkyl group such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • the “fluoroalkyl group” is an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
  • the number of fluorine atoms of the “fluoroalkyl group” is 1 or more (eg, 1 to 3, 1 to 6, 1 to 12, or the maximum number that can be substituted from one). be able to.
  • the “fluoroalkyl group” is, for example, a fluoroalkyl group having 1 to 20 carbon atoms, 1 to 12 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, or 1 to 3 carbon atoms. be able to.
  • the “fluoroalkyl group” may be a linear or branched fluoroalkyl group.
  • the “fluoroalkyl group” specifically includes, for example, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, a tetrafluoro group.
  • Propyl group eg, HCF 2 CF 2 CH 2 —
  • Hexafluoropropyl group eg, (CF 3 ) 2 CH—
  • Nonafluorobutyl group e.g., HCF 2 CF 2 CF 2 CF 2) CH 2-
  • Octafluoropentyl group eg, HCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 ) CH 2-
  • a tridecafluorohexyl group eg, HCF 2 CF 2 CH 2 —
  • examples of the “aryl group” include a phenyl group and a naphthyl group.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • alkoxy group is an alkyl-O— group.
  • acyl group examples include an alkanoyl group (that is, an alkyl-CO— group) and the like.
  • ester group examples include an alkylcarbonyloxy group (that is, an alkyl-CO—O— group), an alkoxycarbonyl group (that is, an alkyl-O—CO— group), and the like.
  • the “organic group” includes a hydrocarbon group such as an alkyl group.
  • composition A that is, the crudely purified acrylic acid derivative (I)
  • the aldehyde (II) as the impurity
  • the objective of purification by the purification method of the present invention is the acrylic acid derivative (I).
  • R a represents an alkyl group, a fluoroalkyl group, an aryl group optionally having one or more substituents, or a hydrogen atom
  • X represents an alkyl group, a fluoroalkyl group, a fluorine atom, or a hydrogen atom Represents.
  • Preferred examples of the substituent in the “aryl group optionally having one or more substituents” represented by Ra include a fluorine atom, an alkyl group, an alkoxy group, an acyl group, an ester group, a cyano group, A nitro group and a fluoroalkyl group are mentioned, and a more preferred example is a fluorine atom.
  • the number of the “substituents” is preferably 0 (that is, unsubstituted), 1, 2, or 3.
  • R a preferably has 1 to 20 carbon atoms (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, still more preferably 1 to 3 carbon atoms, particularly Preferably, it is a linear alkyl group having 1 or 2 carbon atoms or a linear fluoroalkyl group.
  • X preferably has 1 to 20 carbon atoms (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, still more preferably 1 to 3 carbon atoms, and particularly preferably Is an alkyl group having 1 or 2 carbon atoms, 1 to 20 carbon atoms (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, still more preferably carbon numbers). It is a fluoroalkyl group having 1 to 3, particularly preferably 1 or 2 carbon atoms, a fluorine atom or a hydrogen atom, and more preferably a fluorine atom.
  • R a is a methyl group or an ethyl group (more preferably, a methyl group), and X is a methyl group, a fluorine atom, or a hydrogen atom (more preferably, a methyl group or a fluorine atom). It is.
  • the removal object of the purification method of the present invention is aldehyde (II).
  • aldehyde (II) By the purification method of the present invention, at least a part of the aldehyde (II) is removed. In the purification, it is preferable that more aldehyde (II) is removed.
  • aldehyde (II) examples include acetaldehyde, propionaldehyde, normal butyraldehyde, isobutyraldehyde, and n-valeraldehyde.
  • the aldehyde (II) is preferably an aldehyde having 3 to 6 carbon atoms, more preferably an aldehyde having 4 to 6 carbon atoms, and particularly preferably normal butyraldehyde.
  • the aldehyde (II) may be a single type or a combination of two or more types. In the purification method of the present invention, impurities other than this may be removed together with the aldehyde (II).
  • the object to be treated of the purification method of the present invention is the composition A containing the acrylic acid derivative (I) and the aldehyde (II) (that is, the crudely purified acrylic acid derivative (I)).
  • the manufacturing method and origin of the composition A which is a treatment target of the purification method of the present invention, are not particularly limited.
  • the acrylic acid derivative (I) contained in the composition A can be, for example, a reaction product.
  • the aldehyde (II) contained in the composition A can be, for example, an additive in the production of the acrylic acid derivative (I) or a by-product in the production of the acrylic acid derivative (I).
  • the content of the acrylic acid derivative (I) in the composition A can be, for example, in the range of 80 to 99% by mass, in the range of 85 to 99% by mass, or in the range of 90 to 99% by mass.
  • the content of the aldehyde (II) in the composition A is, for example, in the range of 0.01 to 5% by mass, in the range of 0.01 to 1% by mass, or in the range of 0.05 to 0.5% by mass. Can be.
  • the content of the aldehyde (II) in the composition A can be, for example, 0.0001 parts by mass or more, or 0.0005 parts by mass or more with respect to 1 part by mass of the acrylic acid derivative (I).
  • the content of the aldehyde (II) in the composition A is, for example, 0.005 parts by mass or less, 0.05 parts by mass or less, or 0.01 parts by mass or less with respect to 1 part by mass of the acrylic acid derivative (I).
  • the content of the aldehyde (II) in the composition A is, for example, 0.0001 to 0.05 parts by weight, 0.0001 to 0.01 parts by weight, or 1 part by weight of the acrylic acid derivative (I). It can be 0.0005 to 0.005 parts by mass.
  • step A the composition A is contacted with a compound having one or more amino groups (ie, —NH 2 groups) or sulfite to remove the aldehyde (II).
  • a compound having one or more amino groups ie, —NH 2 groups
  • sulfite to remove the aldehyde (II).
  • the composition A may be used in combination with a compound having one or more amino groups and a sulfite. Specifically, for example, (1) contacting the composition A with a compound having one or more amino groups to remove the aldehyde (II); and (2) converting the composition A into a sulfite. The contact and removal of the aldehyde (II) may be performed sequentially and in combination. Moreover, you may implement the method of this invention in combination with the method of removing other aldehyde (II).
  • the aldehyde (II) to be removed is a part or all of the aldehyde (II) contained in the composition A.
  • Suitable examples of the “compound having one or more amino groups” used in the present invention include (1) amino acids, (2) a compound having one or more amino groups and one or more sulfhydryl groups (ie, —SH groups); and (3) one or more amino groups and one or more hydroxyl groups (ie, —OH). A compound having a group).
  • the “(1) amino acid” used in the present invention can be D-form, L-form, or a mixture of D-form and L-form (eg, racemate).
  • the number of amino groups possessed by the “compound having one or more amino groups” used in the present invention is preferably one.
  • the number of sulfhydryl groups possessed by the “(2) compound having one or more amino groups and one or more sulfhydryl groups” is preferably one.
  • the number of hydroxyl groups that the “(3) compound having one or more amino groups and one or more hydroxyl groups” has is preferably one.
  • the “(2) compound having one or more amino groups and one or more sulfhydryl groups” is preferably one or more (preferably one) hydroxyl group and one (preferably one) or more.
  • a sulfhydryl group is linked via a linker.
  • the linker is preferably a linker having 1 to 3 carbon atoms.
  • the linker is also preferably alkylene which may have one or more substituents, or arylene which may have one or more substituents.
  • the “alkylene” in the “alkylene optionally having one or more substituents” preferably has 1 to 3 carbon atoms.
  • Suitable examples of the “substituent” in the “alkylene optionally having one or more substituents” include a nitro group, a cyano group, a tosyl group, a halogen atom, a phenyl group, an acyl group, and a carboxy group. Include.
  • the “arylene” in the “arylene optionally having one or more substituents” preferably has 6 to 8 carbon atoms.
  • Suitable examples of the “substituent” in the “arylene optionally having one or more substituents” include a nitro group, a cyano group, a tosyl group, a halogen atom, a phenyl group, an acyl group, and a carboxy group. Include.
  • Cysteine can be D-form, L-form, or a mixture of D-form and L-form (eg, racemate).
  • the compounds having one or more amino groups may be used singly or in combination of two or more.
  • the form of the compound having one or more amino groups used in the present invention is not particularly limited, but for example, a compound having one or more amino groups in the form of powder is preferably used. However, the compound having one or more amino groups in the form of the powder can be used in the form of a liquid by being used with a solvent described later.
  • Examples of anions constituting “sulfite” used in the present invention include sulfite anions and pyrosulfite anions.
  • Examples of cations constituting “sulfite” used in the present invention include alkali metal ions such as sodium ion and potassium ion; tetramethylammonium ion, tetraethylammonium ion, tetrapropylammonium ion, tetrabutylammonium ion, benzyl Ammonium ions such as trimethylammonium ion, benzyltriethylammonium ion, and phenyltrimethylammonium ion; and phosphonium ions such as ethyltriphenylphosphonium ion and propyltriphenylphosphonium ion.
  • sulfite used in the present invention are sodium pyrosulfite (ie, sodium disulfite), potassium pyrosulfite, sodium hydrogenbisulfite, potassium hydrogenbisulfite, sodium hydrogensulfite, potassium hydrogensulfite, tetramethylammonium.
  • One kind of sulfite may be used alone, or two or more kinds may be used in combination.
  • the form of sulfite used in the present invention is not particularly limited, but for example, sulfite in the form of powder is preferably used. However, the sulfite in the form of the powder can be preferably used together with the solvent described later to be in a liquid form.
  • the amount of the compound having one or more amino groups and / or the sulfite used in the step A is preferably 0.00002 to about 100 parts by mass of the aldehyde (II) contained in the composition A, for example. It can be in the range of 20 parts by mass, more preferably in the range of 0.001 to 10 parts by mass, and still more preferably in the range of 0.001 to 5 parts by mass.
  • the amount of the compound having one or more amino groups used in Step A is, for example, preferably in the range of 80 to 500 parts by mass with respect to 100 parts by mass of the aldehyde (II) contained in the composition A.
  • the amount is preferably 90 to 300 parts by mass, more preferably 90 to 150 parts by mass.
  • the amount of sulfite used in Step A is, for example, preferably in the range of 40 to 250 parts by mass, more preferably 45 to 150 parts by mass with respect to 100 parts by mass of aldehyde (II) contained in Composition A. More preferably, it can be in the range of 45 to 75 parts by mass.
  • the contact in step A can be preferably carried out in the presence of a solvent.
  • a solvent for example, water; Alcohol solvents such as methanol and ethanol; Non-aromatic hydrocarbon solvents such as pentane, hexane, heptane, octane, cyclohexane, decahydronaphthalene, n-decane, isododecane, tridecane; Aromatic hydrocarbon solvents such as benzene, toluene, xylene, tetralin, veratrol, diethylbenzene, methylnaphthalene, nitrobenzene, o-nitrotoluene, mesitylene, indene, diphenyl sulfide; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, propiophenone, diisobutyl ketone, isophor
  • Suitable examples of such solvents include (1) water, and (2) water, and combinations of other solvents.
  • the solvent may be contained in Composition A; it may be used as a compound having one or more amino groups, or a sulfite solvent or suspending medium; or Composition A, and one or more The compound having an amino group and sulfite may be added separately to the system of Step A.
  • the amount thereof is preferably in the range of 0.1 to 3 parts by weight, more preferably in the range of 0.3 to 2 parts by weight with respect to 1 part by weight of the composition A. And more preferably in the range of 0.5 to 1.2 parts by weight.
  • the compound having one or more amino groups and the sulfite may be in a free form, a salt, or an ion.
  • the compound having one or more amino groups and the sulfite may be changed depending on the presence of the solvent as long as it corresponds to the compound having one or more amino groups and the sulfite described above. Of course, this case is also within the scope of the present invention.
  • the method in which the composition A is contacted with a compound having one or more amino groups or a sulfite includes contacting the composition A with a compound having one or more amino groups or a sulfite.
  • the method may be a batch method or a continuous method. Examples of the batch-type method include a method in which a compound having one or more amino groups or a sulfite is added to the composition A contained in a container and stirred as desired.
  • the temperature at which the composition A is contacted with a compound having one or more amino groups or sulfite is, for example, in the range of 0 to 40 ° C., or in the range of 10 to 30 ° C. Can be.
  • the temperature when the composition A is contacted with a compound having one or more amino groups or sulfite can be room temperature.
  • the time for which the composition A is contacted with the compound having one or more amino groups or sulfite is appropriately set to a necessary and sufficient length capable of removing the desired aldehyde (II). That's fine.
  • the time can be, for example, in the range of 15 minutes to 5 hours or in the range of 30 minutes to 3 hours in the case of a batch system.
  • the content of the aldehyde (II) in the composition A treated by the purification method of the present invention is preferably 1 part by weight of the acrylic acid derivative (I). Is less than 0.003 parts by weight, more preferably 0.002 parts by weight or less, still more preferably 0.001 parts by weight or less, still more preferably 0.0005 parts by weight or less, and particularly preferably 0.0004 parts by weight.
  • the amount is not more than parts by weight, more preferably not more than 0.0002 parts by weight, and most preferably 0.0000 parts by weight.
  • L-cysteine manufactured by Tokyo Chemical Industry Co., Ltd., purity> 98%
  • Sodium disulfite Showa Chemical Co., Ltd., purity> 95%
  • methyl methacrylate is sometimes referred to as Compound A.
  • 2-fluoroacrylic acid methyl ester is sometimes referred to as Compound B.
  • normal butyraldehyde is sometimes referred to as butyraldehyde.
  • Example 1 To 2.0 g of a composition consisting of (1) compound A or B, (2) methanol, and (3) butyraldehyde, 1.6 g of water and L-cysteine in the amount shown in Table 1 were added, and the mixture was stirred at room temperature for 1 hour. Stir. The composition ratio (weight ratio) of compound A or B and butyraldehyde before and after stirring is shown below. The composition was calculated from GC measurement.
  • Example 2 To 2.0 g of the composition consisting of (1) compound A or B, (2) methanol, and (3) butyraldehyde, 1.6 g of water and the amount of Na 2 S 2 O 5 described in Table 2 were added, and For 1 hour. The composition ratio (weight ratio) of compound A and butyraldehyde before and after stirring is shown below. The composition was calculated from GC measurement.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention aborde le problème de la fourniture d'un procédé efficace de purification d'un dérivé d'acide acrylique. Le problème est résolu par un procédé de purification d'un dérivé d'acide acrylique de formule (I) [dans la formule, Ra représente un groupe alkyle, un groupe fluoroalkyle, un atome d'hydrogène ou un groupe aryle possédant éventuellement au moins un substituant, et X représente un groupe alkyle, un groupe fluoroalkyle, un atome de fluor ou un atome d'hydrogène], ledit procédé de purification comprenant une étape A, dans laquelle ledit dérivé d'acide acrylique de formule (I) et une composition contenant un aldéhyde en C2 à C6 sont mis en contact avec un sulfite ou un composé comprenant au moins un groupe amino, puis l'aldéhyde en C2 à C6 est éliminé.
PCT/JP2016/080790 2015-10-20 2016-10-18 Procédé de purification d'un dérivé d'acide acrylique WO2017069104A1 (fr)

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EP4201920A1 (fr) * 2020-08-19 2023-06-28 Daikin Industries, Ltd. Procédé de purification de (méth)acrylate contenant un halogène

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JPS4831087B1 (fr) * 1970-04-09 1973-09-26
JPS5014B1 (fr) * 1973-12-26 1975-01-06
JPS5944338A (ja) * 1982-09-06 1984-03-12 Nippon Shokubai Kagaku Kogyo Co Ltd メタクリル酸の精製方法
JPS5993027A (ja) * 1982-11-17 1984-05-29 Nippon Shokubai Kagaku Kogyo Co Ltd メタクリル酸の精製方法
JPS60152438A (ja) * 1984-01-21 1985-08-10 Nippon Shokubai Kagaku Kogyo Co Ltd メタクリル酸の精製方法
JPH07149687A (ja) * 1993-10-15 1995-06-13 Basf Ag アルデヒドで汚染された（メタ）アクリル酸の精製方法
JP2005500380A (ja) * 2001-08-13 2005-01-06 ビーエーエスエフ アクチェンゲゼルシャフト エチレン性不飽和化合物のアミドキシムによる安定化

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JPS4831087B1 (fr) * 1970-04-09 1973-09-26
JPS5014B1 (fr) * 1973-12-26 1975-01-06
JPS5944338A (ja) * 1982-09-06 1984-03-12 Nippon Shokubai Kagaku Kogyo Co Ltd メタクリル酸の精製方法
JPS5993027A (ja) * 1982-11-17 1984-05-29 Nippon Shokubai Kagaku Kogyo Co Ltd メタクリル酸の精製方法
JPS60152438A (ja) * 1984-01-21 1985-08-10 Nippon Shokubai Kagaku Kogyo Co Ltd メタクリル酸の精製方法
JPH07149687A (ja) * 1993-10-15 1995-06-13 Basf Ag アルデヒドで汚染された（メタ）アクリル酸の精製方法
JP2005500380A (ja) * 2001-08-13 2005-01-06 ビーエーエスエフ アクチェンゲゼルシャフト エチレン性不飽和化合物のアミドキシムによる安定化

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Title
CSJ: THE CHEMICAL SOCIETY OF JAPAN, SHIN JIKKEN KAGAKU KOZA 13 YUKI KOZO I, 20 January 1977 (1977-01-20), pages 63 - 70 *

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