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WO2018221314A1 - Inhibiteur de polymérisation et procédé de production d'ester d'acide (méth)acrylique à l'aide dudit inhibiteur de polymérisation, produit rectifié - Google Patents

Inhibiteur de polymérisation et procédé de production d'ester d'acide (méth)acrylique à l'aide dudit inhibiteur de polymérisation, produit rectifié Download PDF

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WO2018221314A1
WO2018221314A1 PCT/JP2018/019631 JP2018019631W WO2018221314A1 WO 2018221314 A1 WO2018221314 A1 WO 2018221314A1 JP 2018019631 W JP2018019631 W JP 2018019631W WO 2018221314 A1 WO2018221314 A1 WO 2018221314A1
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meth
group
carbon atoms
acrylic acid
acid ester
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加藤　隆
敏貴 今康
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Osaka Organic Chemical Industry Co Ltd
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Osaka Organic Chemical Industry Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • 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
    • C07C67/62—Use of additives, e.g. for stabilisation
    • 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
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/92—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with a hetero atom directly attached to the ring nitrogen atom
    • C07D211/94—Oxygen atom, e.g. piperidine N-oxide

Definitions

  • the present invention relates to a polymerization inhibitor used for rectifying the (meth) acrylic acid ester from a composition containing (meth) acrylic acid ester obtained by dehydration esterification reaction or transesterification reaction, and The present invention relates to a method for producing a (meth) acrylic acid ester using a polymerization inhibitor. Moreover, this invention relates to the rectified product of the composition containing the (meth) acrylic acid ester obtained by dehydration esterification reaction or transesterification.
  • 2,2,6,6-tetramethylpiperidine 1-oxyl hereinafter also referred to as TEMPO
  • HTEMPO 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl
  • BTEMPO 2,2,6,6-tetramethylpiperidine-N-oxyl compounds
  • BTEMPO 4- (benzoyloxy) -2,2,6,6-tetramethylpiperidine 1-oxide
  • Patent Document 3 As a method of reducing the polymerization inhibitor as described above in the monomer mixture, a method of contacting an acid is disclosed (Patent Document 3). It is disclosed that this method is more suitable than the distillation operation in that the monomer recovery rate can be increased and the above polymerization inhibitor can be reduced.
  • Patent Document 4 a specific N-oxyl compound is used as a method for distilling the monomer mixture.
  • the present invention has been made in view of the above circumstances, and rectifying the (meth) acrylic acid ester from a composition containing (meth) acrylic acid ester obtained by dehydration esterification reaction or transesterification reaction.
  • An object of the present invention is to provide a polymerization inhibitor.
  • the present invention rectifies the (meth) acrylic acid ester in the presence of the polymerization inhibitor from a composition containing (meth) acrylic acid ester obtained by dehydration esterification reaction or transesterification reaction. It aims at providing the manufacturing method of the (meth) acrylic acid ester containing a process.
  • Another object of the present invention is to provide a rectified product of a composition containing (meth) acrylic acid ester obtained by dehydration esterification reaction or transesterification reaction.
  • the present invention is a polymerization inhibitor used for rectifying the (meth) acrylate ester from a composition containing the (meth) acrylate ester obtained by dehydration esterification reaction or transesterification reaction.
  • the polymerization inhibitor has the general formula (1): (In the general formula (1), R 1 represents an alkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
  • the alkyl group, the alkenyl group, the cycloalkyl group, and the aryl group are each an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and carbon.
  • a compound represented by the formula (2) which may be substituted with any one or more of the aryl groups of formulas 6 to 20, and: (In the general formula (2), R 2 represents a single bond, an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, or a carbon atom having 6 to 20 carbon atoms.
  • the alkylene group, the alkenylene group, the cycloalkylene group, and the arylene group include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and a cycloalkyl group having 3 to 10 carbon atoms.
  • a C 6-20 aryl group which may be substituted with one or more compounds selected from the group consisting of compounds represented by: , Regarding.
  • the present invention also includes a step of rectifying the (meth) acrylic acid ester in the presence of a polymerization inhibitor from a composition containing (meth) acrylic acid ester obtained by dehydration esterification reaction or transesterification reaction.
  • a polymerization inhibitor is represented by the following general formula (1):
  • R 1 represents an alkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
  • the alkyl group, the alkenyl group, the cycloalkyl group, and the aryl group are each an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and carbon.
  • a compound represented by the formula (2) which may be substituted with any one or more of the aryl groups of formulas 6 to 20, and: (In the general formula (2), R 2 represents a single bond, an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, or a carbon atom having 6 to 20 carbon atoms.
  • Represents an arylene group, and the alkylene group, the alkenylene group, the cycloalkylene group, and the arylene group include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and a cycloalkyl group having 3 to 10 carbon atoms. Or an aryl group having 6 to 20 carbon atoms, which may be substituted with at least one selected from the group consisting of compounds represented by (meth)
  • the present invention relates to a method for producing an acrylic ester.
  • the present invention is a rectified product of a composition containing a (meth) acrylic acid ester obtained by dehydration esterification reaction or transesterification reaction, wherein the (meth) acrylic acid ester has (meth) in the molecule.
  • the present invention relates to a rectified product of a composition containing a (meth) acrylic acid ester, which is a polyfunctional monomer having two or more acryloyl groups and has an APHA of 15 or less.
  • the compound represented by the general formula (1) and the compound represented by the general formula (2) of the present invention does not have a hydroxyl group or an ester bond in the molecular skeleton, the above-described raw materials and target products are used.
  • it is suitable as a polymerization inhibitor for rectifying a (meth) acrylic acid ester having a relatively high boiling point (for example, 200 ° C. or higher under 1 atm).
  • the compound represented by the general formula (1) and the compound represented by the general formula (2) of the present invention rectifies a polyfunctional monomer having two or more (meth) acryloyl groups in the molecule. It is also suitable as a polymerization inhibitor.
  • the compound represented by the general formula (1) and the compound represented by the general formula (2) of the present invention have a 2,2,6,6-tetramethylpiperidine-N-oxyl structure
  • the synthesis step of (meth) acrylate ester and the rectification (distillation) step are carried out using the polymerization inhibitor.
  • the rectified product of the composition containing (meth) acrylic acid ester obtained by the dehydration esterification reaction or transesterification reaction of the present invention does not substantially contain a polymerization inhibitor that can be a coloring component.
  • a polymerization inhibitor that can be a coloring component. Since the APHA is 15 or less, when the (meth) acrylic acid ester is a polyfunctional monomer having two or more (meth) acryloyl groups in the molecule, printing ink, binder for photocurable coating, It has a high commercial value as a raw material monomer used in compositions such as adhesives, photocuring reaction diluents and coating materials.
  • the rectified product of the present invention Is a dehydration esterification reaction or transesterification reaction, and an oligomer by-produced by distillation operation or the like (a molecular weight higher than that of a target product such as a polymer derived from a raw material and a target product, an adduct, or an unintentionally polymerized product).
  • a target product such as a polymer derived from a raw material and a target product, an adduct, or an unintentionally polymerized product.
  • the polyfunctional monomer has excellent properties such as high purity and low viscosity. Such characteristics are useful in that the blending ratio of the polyfunctional monomer in the composition can be increased without deteriorating the handling property due to the increase in the viscosity of the composition as described above.
  • the polymerization inhibitor of the present invention has the general formula (1):
  • R 1 represents an alkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
  • the alkyl group, the alkenyl group, the cycloalkyl group, and the aryl group are each an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and carbon.
  • a compound represented by the formula (2) which may be substituted with any one or more of the aryl groups of formulas 6 to 20, and:
  • R 2 represents a single bond, an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, or a carbon atom having 6 to 20 carbon atoms.
  • Represents an arylene group, and the alkylene group, the alkenylene group, the cycloalkylene group, and the arylene group include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and a cycloalkyl group having 3 to 10 carbon atoms. And at least one selected from the group consisting of compounds represented by the following: a dehydrating esterification reaction or an ester It is used for rectifying the (meth) acrylic acid ester from the composition containing the (meth) acrylic acid ester obtained by the exchange reaction.
  • R 1 represents an alkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms. From the viewpoint of solubility in (meth) acrylic acid ester and difficulty in vaporization at the temperature used, an alkyl group having 6 to 15 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, An aryl group having 6 to 14 carbon atoms is preferable.
  • the alkyl group, the alkenyl group, the cycloalkyl group, and the aryl group may be unsubstituted, but the alkyl group having 1 to 10 carbon atoms, the alkenyl group having 2 to 10 carbon atoms, the carbon number It may be substituted with any one or more of a 3 to 10 cycloalkyl group and an aryl group having 6 to 20 carbon atoms, and from the viewpoint of solubility in (meth) acrylic acid ester and compatibility, It may be substituted with any one or more of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 4 to 6 carbon atoms, and an aryl group having 6 to 14 carbon atoms.
  • R 1 is preferably 4 or more, more preferably 6 or more, and a (meth) acrylic acid ester or a solvent from the viewpoint that R 1 is not easily vaporized even under reduced pressure.
  • the total carbon number of R 1 is preferably 20 or less, and preferably 18 or less. More preferred.
  • Examples of the compound represented by the general formula (1) include 4-benzoylamino-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-cinnamoylamino-2,2,6,6. -Tetramethylpiperidine-N-oxyl, 4-crotonylamino-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-propionylamino-2,2,6,6-tetramethylpiperidine-N- Oxyl, 4-butyrylamino-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-isobutyrylamino-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-valerylamino-2 , 2,6,6-tetramethylpiperidine-N-oxyl, 4-isovalerylamino-2,2,6,6-tetramethylpiperidine-N-oxyl, 4, Examples include pivaloylamino-2,2,6,6-tetramethylpiperidine-N-
  • the production method of the compound represented by the general formula (1) is not particularly limited.
  • 4-amino-2,2,6,6-tetramethylpiperidine and a halide or esterified product By a reaction (amidation reaction) to obtain an amide (hereinafter also referred to as step 1-1), and a step of oxidizing the obtained amide with an oxidizing agent (hereinafter also referred to as step 1-2). Obtainable.
  • halide and esterified products examples include halides such as benzoyl chloride, cinnamoyl chloride, crotonyl chloride, naphthyl chloride, tert-butyl chloride, and esterified products such as methyl benzoate and methyl cinnamoate.
  • benzoyl chloride and methyl benzoate are preferable from the viewpoint of availability at a relatively low cost.
  • the oxidizing agent examples include hydrogen peroxide, formic acid, peracetic acid and the like. Among these, hydrogen peroxide is preferable from the viewpoint of easy handling and availability at a relatively low cost.
  • a halide such as benzoyl chloride or an esterified product such as methyl benzoate has the yield of the target product relative to 1 mol of 4-amino-2,2,6,6-tetramethylpiperidine. From the viewpoint of increasing, it is preferable to react at 1.0 mol or more, more preferably at least 1.05 mol, and preferably at 2.0 mol or less, and at 1.5 mol or less. More preferred.
  • an alkoxide catalyst such as sodium methylate, sodium ethylate or t-butoxy potassium, or a basic catalyst such as triethylamine, pyridine or potassium carbonate.
  • the reaction temperature in the step 1-1 varies depending on the raw materials and the organic solvent described later, and thus cannot be generally determined, but is usually about 30 ° C. or higher and 150 ° C. or lower. Further, the reaction time in the step 1-1 varies depending on the raw materials and the reaction temperature and cannot be determined unconditionally, but is usually about 6 hours to 50 hours.
  • the oxidizing agent is preferably reacted in an amount of 1.5 mol or more, and 2.0 mol or more with respect to 1 mol of the amide, from the viewpoint of increasing the yield of the target product. More preferably, the reaction is preferably performed at 5.0 mol or less, more preferably at 3.0 mol or less.
  • a catalyst such as sodium tungstate, ethylenediaminetetraacetic acid / disodium salt, hydroxyethylethylenediamine It is preferable to use a promoter such as acetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid.
  • the reaction temperature in the step 1-2 is preferably 25 ° C. or higher, more preferably 30 ° C. or higher, and preferably 50 ° C. or lower from the viewpoint of increasing the yield of the target product. More preferably, the temperature is 45 ° C. or lower.
  • the reaction time in the step 1-2 varies depending on the raw materials and reaction temperature and cannot be determined unconditionally. However, usually, from the viewpoint of improving the yield of the target product, it is preferably 8 hours or more, and 12 hours or more. More preferably, it is preferably 30 hours or shorter, more preferably 24 hours or shorter.
  • steps 1-1 and 1-2 are preferably carried out under normal pressure, in a nitrogen stream or in a nitrogen atmosphere.
  • an organic solvent is not particularly limited, but is preferably an inert organic solvent in the reaction system.
  • the organic solvent include nonpolar compounds such as hexane and toluene; polar compounds such as acetone and acetonitrile.
  • An organic solvent may be used independently and may use 2 or more types together.
  • an alcohol solvent such as methanol, ethanol, propanol, or butanol may be used.
  • the amount of the organic solvent used is not particularly limited, but is usually about 200 to 600 parts by weight with respect to 100 parts by weight of the total amount of raw materials.
  • Identification of the obtained target product is performed by gas chromatography (GC), liquid chromatography (LC), gas chromatography mass spectrometry (GC-MS), nuclear magnetic resonance spectroscopy (NMR), infrared spectroscopy (IR). Or a melting point measurement apparatus.
  • GC gas chromatography
  • LC liquid chromatography
  • GC-MS gas chromatography mass spectrometry
  • NMR nuclear magnetic resonance spectroscopy
  • IR infrared spectroscopy
  • R 2 is a single bond, an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, or a 6 to 20 carbon atom.
  • the alkylene group, the alkenylene group, the cycloalkylene group, and the arylene group may be unsubstituted, but an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a carbon number It may be substituted with any one or more of a 3 to 10 cycloalkyl group and an aryl group having 6 to 20 carbon atoms, and from the viewpoint of solubility in (meth) acrylic acid ester and compatibility, It may be substituted with any one or more of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 4 to 6 carbon atoms, and an aryl group having 6 to 14 carbon atoms.
  • Examples of the compound represented by the general formula (2) include N, N-bis (1-oxyl-2,2,6,6-tetramethylpiperidyl-4) oxalic acid diamide, N, N-bis ( 1-oxyl-2,2,6,6-tetramethylpiperidyl-4) malonic acid diamide, N, N-bis (1-oxyl-2,2,6,6-tetramethylpiperidyl-4) succinic acid diamide, N, N-bis (1-oxyl-2,2,6,6-tetramethylpiperidyl-4) glutaric acid diamide, N, N-bis (1-oxyl-2,2,6,6-tetramethylpiperidyl- 4) Adipic acid diamide, N, N-bis (1-oxyl-2,2,6,6-tetramethylpiperidyl-4) sebacic acid diamide, N, N-bis (1-oxyl-2,2,6, 6-Tetramethylpiperidyl- ) Phthalic acid diamide, N, N-bis (1-oxyl-2,2,6,6-te
  • the production method of the compound represented by the general formula (2) is not particularly limited.
  • 4-amino-2,2,6,6-tetramethylpiperidine and dihalides or diesters By a reaction (amidation reaction) to obtain a diamide body (hereinafter also referred to as step 2-1) and a step of oxidizing the obtained diamide body with an oxidizing agent (hereinafter also referred to as step 2-2). Obtainable.
  • dihalide and diester compound examples include adipic acid dichloride, succinic acid dichloride, phthalic acid dichloride, dimethyl oxalate, dimethyl succinate, and diethyl adipate, and among these, they can be obtained relatively inexpensively. From the viewpoint, succinic dichloride is preferable.
  • the dihalide or diester compound is used in an amount of 0.5 mol from 1 mol of 4-amino-2,2,6,6-tetramethylpiperidine from the viewpoint of increasing the yield of the target product.
  • the reaction is preferably performed as described above, more preferably 0.55 mol or more, more preferably 1.0 mol or less, and even more preferably 0.75 mol or less.
  • the oxidizing agent is preferably reacted in an amount of 3.0 mol or more with respect to 1 mol of the diamide, from the viewpoint of increasing the yield of the target product. It is more preferable to react, and it is preferable to react 10.0 mol or less, and it is more preferable to react at 6.0 mol or less.
  • a mixed solvent aqueous solution and organic solvent
  • pure water washing glass tube oven, distillation, crystallization, gel column chromatography, etc.
  • Identification of the obtained target product is performed by gas chromatography (GC), liquid chromatography (LC), gas chromatography mass spectrometry (GC-MS), nuclear magnetic resonance spectroscopy (NMR), infrared spectroscopy (IR). Or a melting point measurement apparatus.
  • GC gas chromatography
  • LC liquid chromatography
  • GC-MS gas chromatography mass spectrometry
  • NMR nuclear magnetic resonance spectroscopy
  • IR infrared spectroscopy
  • the dehydration esterification reaction is a conventionally known general method, in which an alcohol and (meth) acrylic acid are subjected to a dehydration esterification reaction in the presence of an acidic catalyst (paratoluenesulfonic acid, sulfuric acid, etc.). , (Meth) acrylic acid ester. Further, if necessary, a step of removing water generated during the dehydration esterification reaction may be provided outside the system, and a neutralization step and a water washing step may be provided after the dehydration esterification step.
  • an acidic catalyst paratoluenesulfonic acid, sulfuric acid, etc.
  • the transesterification reaction is a conventionally known general method in which an alcohol and a (meth) acrylic acid alkyl ester are converted into a catalyst (a tin compound such as dioctyl tin oxide, a titanium compound such as tetraisopropyl titanate).
  • a catalyst a tin compound such as dioctyl tin oxide, a titanium compound such as tetraisopropyl titanate.
  • dithiocarbamate metal salts such as sodium dimethyldithiocarbamate, metal alcoholates such as sodium methylate, hydroxides such as lithium hydroxide and calcium hydroxide, acetylacetonate complexes such as zinc acetylacetonate
  • This is a method for producing a composition containing a (meth) acrylic acid ester by performing an exchange reaction.
  • Examples of the (meth) acrylic acid alkyl ester include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, Examples thereof include tert-butyl (meth) acrylate, and among these, methyl (meth) acrylate is preferred from the viewpoint of efficient separation from the reaction product.
  • the dehydration esterification reaction preferably has a reaction temperature of 30 to 150 ° C, more preferably 50 to 120 ° C.
  • the reaction time varies depending on the raw materials and reaction temperature, but is usually preferably within 48 hours, and more preferably within 30 hours from the viewpoint of productivity and polymerization inhibition.
  • the transesterification reaction preferably has a reaction temperature of 30 to 150 ° C, more preferably 60 to 120 ° C.
  • the reaction time varies depending on the raw materials and reaction temperature, but is usually preferably within 48 hours, and more preferably within 30 hours from the viewpoint of productivity and polymerization inhibition.
  • the dehydration esterification reaction or transesterification reaction may be carried out in an organic solvent.
  • the organic solvent include n-hexane, n-heptane, n-octane, cyclohexane, methylcyclohexane, benzene, toluene, Xylene and the like can be mentioned, and among these, n-hexane and cyclohexane are preferable from the viewpoint of easy distillation.
  • the dehydration esterification reaction or transesterification reaction is preferably performed in the presence of a polymerization inhibitor from the viewpoint of preventing polymerization of raw materials and target products.
  • a polymerization inhibitor include a compound represented by the general formula (1); a compound represented by the general formula (2); 4-hydroxy-2,2,6,6-tetramethylpiperidine-N.
  • the polymerization inhibitor is a compound represented by the general formula (1), the general formula (2), from the viewpoint of rectifying the (meth) acrylic acid ester after the transesterification step.
  • the compounds represented are preferred.
  • the polymerization inhibitor is preferably a polymerization inhibitor having no such site.
  • the amount of the polymerization inhibitor used is not particularly limited, but is preferably 0.001 part by weight or more, more preferably 0.002 part by weight or more with respect to 100 parts by weight of (meth) acrylic acid ester, And it is preferable that it is 5 weight part or less, and it is more preferable that it is 0.1 weight part or less.
  • a composition containing a (meth) acrylic acid ester can be obtained by the dehydration esterification reaction or transesterification reaction.
  • the composition containing the (meth) acrylic acid ester includes a part of raw materials, a by-product and the like in addition to the target (meth) acrylic acid ester.
  • the (meth) acrylic acid ester is not limited as long as it is a (meth) acrylate, but is represented by the compound represented by the general formula (1) and / or the general formula (2). From the viewpoint that the (meth) acrylic acid ester having a relatively high boiling point can be efficiently rectified in the presence of the compound, it preferably has a boiling point of 200 ° C. or higher under 1 atm. More preferably, it has a boiling point of 220 ° C. or higher, or preferably has a boiling point of 100 ° C. or higher under 1.4 kPa, and has a boiling point of 110 ° C. or higher under 1.4 kPa. It is more preferable that it has a boiling point of 120 ° C. or higher under 1.4 kPa.
  • Examples of the (meth) acrylic acid ester include isostearyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, isodecyl as a monofunctional monomer having one (meth) acryloyl group in the molecule.
  • Alkyl group-containing (meth) acrylates such as (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, 3,5,5-trimethylhexyl (meth) acrylate ) Acrylate; 2-phenoxyethyl (meth) acrylate, 2- (2-phenoxyethoxy) ethyl (meth) acrylate, 2- (nonylphenoxy) ethyl (meth) acrylate, 2- [2- (nonylphenoxy) ethoxy] ethyl ( A) Aromatic-containing monomers such as acrylate, ethoxyethoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, and chain ether group-containing monomers such as methoxytripropylene glycol (meth)
  • Examples of the (meth) acrylic acid ester include 1,4-butanediol di (meth) acrylate and 1,6-hexane as polyfunctional monomers having two or more (meth) acryloyl groups in the molecule.
  • Multifunctional monomer having two (meth) acryloyl groups in the molecule such as meth) acrylate and tripropylene glycol di (meth) acrylate; trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, EO modified bird
  • Such polyfunctional monomer having in the molecule such as Chi trimethylolpropane tri
  • the (meth) acrylic acid ester is a polyfunctional monomer having two or more (preferably three or more) (meth) acryloyl groups in the molecule
  • a composition containing the (meth) acrylic acid ester obtained has excellent properties such that the purity of the polyfunctional monomer is high and the viscosity is low as compared with the prior art.
  • the method of rectifying the (meth) acrylic acid ester from the composition containing the (meth) acrylic acid ester is represented by the compound represented by the general formula (1) and / or the general formula (2).
  • the (meth) acrylic acid ester is distilled in the presence of a compound.
  • the composition containing the (meth) acrylic acid ester is concentrated (the raw material and the solvent are distilled off), and then the obtained concentrated liquid is heated under reduced pressure. it can.
  • the concentration can be adjusted as appropriate, such as the heating temperature and the degree of pressure reduction, in consideration of the characteristics of raw materials and solvents (such as volatility and heat resistance).
  • the rectification is preferably carried out by heating, and varies depending on the properties of the target (meth) acrylate ester and cannot be determined in general, but usually suppresses the polymerization reaction of the (meth) acrylate ester.
  • the heating temperature is preferably 50 to 220 ° C, more preferably 80 to 170 ° C.
  • the rectification is preferably performed under reduced pressure. Since it differs depending on the heating temperature, it cannot be determined in general, but normally, from the viewpoint of preventing the heating temperature from exceeding 170 ° C., it is preferably 50 kPa or less, and more preferably 10 kPa or less. Further, from the viewpoint of productivity considering factory equipment, the pressure is preferably 10 to 0.01 kPa, more preferably 5 to 0.01 kPa.
  • the amount of the compound represented by the general formula (1) and / or the compound represented by the general formula (2) is a raw material in a composition containing (meth) acrylic acid ester or (meth) acrylic acid ester. It is preferably 0.001 part by weight or more, more preferably 0.002 part by weight or more, and 5 part by weight or less based on 100 parts by weight of the compound having a double bond site. The amount is preferably 0.1 parts by weight or less.
  • the recovered (meth) acrylic acid ester has little coloring and impurities, and becomes a high-quality product.
  • the rectification method is useful for recovering (meth) acrylic acid esters having a relatively high boiling point with high purity.
  • the rectified product of the composition containing (meth) acrylic acid ester obtained by the dehydration esterification reaction or transesterification reaction of the present invention has an APHA of 15 or less.
  • the APHA number of colors
  • the preparation of the standard colorimetric solution is No. No. 500 standard solution is diluted to the required magnification.
  • Each APHA standard colorimetric solution was prepared in 5 increments and colorimetric with this.
  • the APHA is preferably 10 or less, and more preferably 5 or less.
  • the composition containing (meth) acrylic acid ester contains 50 ppm of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (HTEMPO), it is dissolved (meta )
  • HTEMPO 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl
  • the APHA will be about 30.
  • a rectified product of a composition containing a (meth) acrylic acid ester obtained by the dehydration esterification reaction or transesterification reaction of the present invention is a compound represented by the above general formula (1) and / or the general formula
  • the compound represented by (2) as a polymerization inhibitor for rectifying the (meth) acrylic acid ester, as other compounds, for example, from the viewpoint of being difficult to react with a raw material or a target product.
  • the rectified product of the composition containing the (meth) acrylic acid ester obtained by the dehydration esterification reaction or transesterification reaction of the present invention has a purity obtained by gas chromatography of the polyfunctional monomer in the rectified product. It is preferable that it is 95% or more and the ratio of the oligomer by gel permeation chromatography is 5% or less.
  • the oligomer is more detrimental than impurities such as dehydration esterification reaction or transesterification reaction, and by-product impurities such as distillation operation (multimers, adducts derived from raw materials and target products, or unintentionally progressed polymers). Component having a high molecular weight).
  • the purity of the polyfunctional monomer in the rectified product is preferably 97% or more, more preferably 98% or more, and more preferably 99% or more. Further preferred.
  • the ratio of the oligomer by gel permeation chromatography in the rectified product is preferably 3% or less, more preferably 1% or less, and further preferably 0.5% or less.
  • the proportion of the oligomer by gas chromatography in the rectified product is preferably 5% or less, more preferably 2% or less, and preferably 1% or less. Further preferred.
  • the oligomer is preferably not contained in the rectified product, but considering the actual productivity, for example, the lower limit of the ratio of the oligomer by gas chromatography is 0.1% or more, or 0. 2% or more can be exemplified.
  • the structure of 4-benzoylamino-2,2,6,6-tetramethylpiperidine-N-oxyl represented by the above general formula (3) is Agilent Technologies 5975C inert XL EI / CI MSD (Agilent Technology ( And the infrared absorption spectrum measurement (ATR method) using Perkin Elmer Spectrum 100 FT-IR Spectrometer (manufactured by PerkinElmer Co., Ltd.). The obtained infrared absorption spectrum is shown in FIG.
  • Methanol was added to 5 g of the obtained diamide, 0.14 g of ethylenediaminetetraacetic acid disodium salt and 0.04 g of sodium tungstate, and 7.9 g of 35% hydrogen peroxide was added dropwise over 1 hour, and then at 40 ° C. for 17 hours. Stir with heating. Methanol was distilled off, extracted with toluene, washed with aqueous sodium carbonate and water, the solvent was distilled off and N, N-bis (1-oxyl-2, represented by the following general formula (4) 2,6,6-tetramethylpiperidyl-4) succinic acid diamide (viscous material) was obtained.
  • N, N-bis (1-oxyl-2,2,6,6-tetramethylpiperidyl-4) succinic acid diamide represented by the general formula (4) is Agilent Technologies 5975C int XL EI / CI MSD (manufactured by Agilent Technologies, Inc.) gas chromatograph mass spectrometry measurement and infrared absorption spectrum measurement using Perkin Elmer Spectrum 100 FT-IR Spectrometer (manufactured by PerkinElmer Co., Ltd.) (ATR method) Identified. The obtained infrared absorption spectrum is shown in FIG.
  • the toluene solution containing 12.7 g of the amide compound thus obtained was neutralized with a 10% aqueous sodium hydroxide solution, methanol was added to 0.25 g of ethylenediaminetetraacetic acid disodium salt and 0.08 g of sodium tungstate, and 35 % Hydrogen peroxide (13 g) was added dropwise over 20 minutes, and then heated and stirred at 40 ° C. for 27 hours. The organic layer was washed with water, toluene was distilled off and 4-octanoylamino-2,2,6,6-tetramethylpiperidine-N-oxyl represented by the following general formula (5) Crystallization) was obtained.
  • the structure of 4-octanoylamino-2,2,6,6-tetramethylpiperidine-N-oxyl represented by the above general formula (5) is the Thermo SCIENTIFIC LTQ XL / DIONEX Ultimate Mate 3000 (ThermoSciene). And an infrared absorption spectrum measurement (ATR method) using a Perkin Elmer Spectrum 100 FT-IR Spectrometer (manufactured by PerkinElmer Co., Ltd.). The obtained infrared absorption spectrum is shown in FIG.
  • N, N-bis (1-oxyl-2,2,6,6-tetramethylpiperidyl-4) fumaric acid diamide represented by the above general formula (6) is Thermo SCIENTIFIC LTQ XL / DIONEX.
  • N, N-bis (1-oxyl-2,2,6,6-tetramethylpiperidyl-4) terephthalic acid diamide represented by the above general formula (7) is Thermo SCIENTIFIC LTQ XL / DIONEX.
  • Example 1 ⁇ Manufacture of a composition containing (meth) acrylic acid ester>
  • 100 g, dioctyltin oxide 5.2 g, and 0.7 g of 4-benzoylamino-2,2,6,6-tetramethylpiperidine-N-oxyl obtained in Preparation Example 1 above as a polymerization inhibitor were added.
  • the detector used FID and set the heater temperature to 280 ° C.
  • HP-1 length 30 m, inner diameter 0.32 mm, film thickness 0.25 ⁇ m
  • the oven was held at an initial temperature of 80 ° C. for 5 minutes and then heated to 260 ° C. at 12 ° C. per minute.
  • the driving amount was 0.2 ⁇ l.
  • the conversion rate was calculated from the area percentage by the formula of (meth) acrylic acid ester area / ((meth) acrylic acid ester area + raw material alcohol area) ⁇ 100.
  • ⁇ GC (gas chromatography) conditions The GC analysis was performed under the following measurement conditions using a 6850 model manufactured by Agilent.
  • the inlet was set to a heater temperature of 260 ° C., a split ratio of 50: 1, and a pressure of 50 kPa.
  • the detector used FID and set the heater temperature to 280 ° C.
  • HP-1 length 30 m, inner diameter 0.32 mm, film thickness 0.25 ⁇ m
  • the oven was held at an initial temperature of 80 ° C. for 5 minutes and then heated to 260 ° C. at 12 ° C. per minute.
  • the driving amount was 0.2 ⁇ l.
  • area% of (meth) acrylic acid ester was adopted.
  • LC analysis was performed under the following measurement conditions using a Waters 2695 type + 2996 type Photodiode Array Detector.
  • the oven temperature was set to 40 ° C., and the flow rate was set to 0.5 ml per minute.
  • the analyte was dissolved in the mobile phase at a concentration of 0.2%, and 10 ⁇ l was injected.
  • area% of (meth) acrylic acid ester was adopted.
  • Example 2 ⁇ Manufacture of a composition containing (meth) acrylic acid ester and rectification of (meth) acrylic acid ester> Instead of 4-benzoylamino-2,2,6,6-tetramethylpiperidine-N-oxyl in Example 1, N, N-bis (1-oxyl-2,2) obtained in Preparation Example 2 above was used. , 6,6-tetramethylpiperidyl-4) The reaction was conducted in the same manner as in Example 1 except that succinic acid diamide was used. As a result, a composition containing 2-phenoxyethyl acrylate was produced. This compound was a colorless transparent liquid having a GC purity of 99.3%, an LC area percentage purity by ultraviolet (UV) detection of 99.4%, and a color number of APHA5 or less.
  • UV ultraviolet
  • Example 3> ⁇ Manufacture of a composition containing (meth) acrylic acid ester>
  • a composition containing (meth) acrylic acid ester> In a 1 L glass reactor equipped with a stirrer, fractionator, cooler, thermometer, gas inlet tube and sampling port, 383 g (1.42 mol) of isostearyl alcohol, 165 g (1.92 mol) of methyl acrylate, normal hexane 51 g, 0.3 g of 70% tetramethoxytitanium, and 0.2 g of 4-benzoylamino-2,2,6,6-tetramethylpiperidine-N-oxyl obtained in Production Example 1 above as a polymerization inhibitor, Under atmospheric pressure, air was heated up to 90-105 ° C while blowing air of 4 ml / min into the liquid, and transesterification was carried out for 20 hours while extracting methanol coming out from the top of the fractionation tower, and (meth) acrylic acid A composition containing isostearyl
  • Example 4 ⁇ Manufacture of a composition containing (meth) acrylic acid ester, rectification of a composition containing (meth) acrylic acid ester> Instead of 4-benzoylamino-2,2,6,6-tetramethylpiperidine-N-oxyl of Example 1, 4-octanoylamino-2,2,6,6 obtained in Preparation Example 3 above As a result of rectification in the same manner as in Example 1 except that -tetramethylpiperidine-N-oxyl was used, the GC purity of 2-phenoxyethyl acrylate was 99.6%, and the LC area percentage purity by ultraviolet (UV) detection was 99. It was a colorless transparent liquid having a color number of 3% and APHA of 5 or less.
  • Example 5 ⁇ Manufacture of a composition containing (meth) acrylic acid ester, rectification of a composition containing (meth) acrylic acid ester> Instead of 4-benzoylamino-2,2,6,6-tetramethylpiperidine-N-oxyl in Example 1, N, N-bis (1-oxyl-2,2) obtained in Production Example 4 above was used. , 6,6-tetramethylpiperidyl-4) rectification was conducted in the same manner as in Example 1 except that fumaric acid diamide was used. As a result, GC purity of 2-phenoxyethyl acrylate was 99.8%, and UV (UV) detection was used. The LC area percentage purity was 99.4%, and the number of colors was a colorless transparent liquid having an APHA of 5 or less.
  • Example 6> ⁇ Manufacture of a composition containing (meth) acrylic acid ester, rectification of a composition containing (meth) acrylic acid ester> Instead of 4-benzoylamino-2,2,6,6-tetramethylpiperidine-N-oxyl in Example 3, N, N-bis (1-oxyl-2,2) obtained in Preparation Example 5 above was used. , 6,6-tetramethylpiperidyl-4) rectification was conducted in the same manner as in Example 3 except that terephthalic acid diamide was used. As a result, the GC purity of isostearyl acrylate was 99.7%, and the LC area was detected by ultraviolet (UV) detection. It was a colorless transparent liquid with a percentage purity of 99.3% and a color number of APHA5 or less.
  • UV ultraviolet
  • Example 7 ⁇ Manufacture of a composition containing (meth) acrylic acid ester> Into a 2 L glass reactor equipped with a stirrer, fractionator, cooler, thermometer, gas inlet tube and sampling port, 1,4-butanediol 150 g (1.66 mol), methyl acrylate 573 g (6.66 mol) 200 g of cyclohexane, 0.47 g of dioctyltin oxide, and 0.16 g of 4-benzoylamino-2,2,6,6-tetramethylpiperidine-N-oxyl obtained in Production Example 1 above as a polymerization inhibitor, Under atmospheric pressure, 5 ml / min of air was blown into the liquid while heating up to 80-95 ° C., and transesterification was carried out for 12 hours while extracting methanol coming out from the top of the fractionation tower, and (meth) acrylic acid A composition containing 1,4-butanediol diacrylate as an ester was prepared
  • the GPC (gel permeation chromatography) area percentage purity with a differential refractometer (RI) detector was 98.3%, and no oligomer peak was detected. Further, at 25 ° C., the viscosity was 4.1 mPa ⁇ s. In addition, the ratio of the oligomer by GC (area% of the total of the detection peaks of all regions having a retention time later than that of the target product) was 0.3%.
  • RI differential refractometer
  • GPC column TSKgel G4000HXL, G3000HXL, G2000HXL, and G1000HXL manufactured by Tosoh Corporation were connected and used, and the oven temperature was set to 40 ° C.
  • the analyte was dissolved in the mobile phase at a concentration of 2.5 mg / ml, and 50 ⁇ l was injected.
  • the proportion of oligomers by GPC the total area% of the detection peaks of all regions having a retention time earlier than that of the target object was adopted.
  • Viscosity depends on the viscosity of the (meth) acrylic acid ester measured using a TVE-25L E-type viscometer manufactured by Toki Sangyo Co., Ltd., but at 25 ° C. a standard cone rotor (1 ° 34 ′ ⁇ R24) The measurement was performed under the conditions of a rotation speed of 10, 50 or 100 rpm.
  • Example 8> ⁇ Manufacture of a composition containing (meth) acrylic acid ester>
  • a 2 L glass reactor equipped with a stirrer, fractionator, cooler, thermometer, gas inlet tube, sampling port, 1,6-hexanediol 150 g (1.27 mol), methyl acrylate 437 g (5.08 mol) 200 g of cyclohexane, 0.36 g of dioctyltin oxide, and 0.14 g of 4-benzoylamino-2,2,6,6-tetramethylpiperidine-N-oxyl obtained in Production Example 1 above as a polymerization inhibitor, Under atmospheric pressure, the temperature was raised to 80 to 95 ° C.
  • the GPC (gel permeation chromatography) area percentage purity by differential refractometer (RI) detector was 99.7%, and no oligomer peak was detected. Further, at 25 ° C., the viscosity was 5.3 mPa ⁇ s. In addition, the ratio of the oligomer by GC (area% of the total of the detection peaks of all regions having a retention time later than that of the target product) was 0.6%.
  • GPC gel permeation chromatography
  • RI differential refractometer
  • Example 1 ⁇ Manufacture of a composition containing (meth) acrylic acid ester and rectification of (meth) acrylic acid ester> Instead of 4-benzoylamino-2,2,6,6-tetramethylpiperidine-N-oxyl in Example 1, 4-acetylamino-2,2,6,6-tetramethylpiperidine-N-oxyl was changed to 0. The same operation as in Example 1 was carried out using .55 g to obtain a fraction of 2-phenoxyethyl acrylate. This fraction was an orange liquid having a color number of APHA50.
  • Example 4 The same operation as in Example 1 was carried out using 4.20 g of phenothiazine instead of 4-benzoylamino-2,2,6,6-tetramethylpiperidine-N-oxyl of Example 1, but at the beginning of distillation. A polymerization reaction occurred and a distilled product could not be obtained.
  • the GC purity of this compound was 91.4%, the LC area percentage purity by ultraviolet (UV) detection was 92.7%, and the color number was a slightly orange liquid having an APHA of 25 or less.
  • the GPC (gel permeation chromatography) area percentage purity with a differential refractometer (RI) detector was 90.1%, and the proportion of oligomers was 9.6%. Further, at 25 ° C., the viscosity was 6.0 mPa ⁇ s.
  • the ratio of the oligomer by GC area% of the total of the detection peaks of all regions having a retention time later than that of the target product was 7.1%.
  • Comparative Example 8 The same operation as in Comparative Example 7 was performed using 140 g (1.04 mol) of trimethylolpropane and 260 g (3.61 mol) of acrylic acid to obtain a concentrated product of trimethylolpropane triacrylate by a dehydration esterification method.
  • the GC purity of this compound was 90.0%
  • the LC area percentage purity by ultraviolet (UV) detection was 78.0%
  • the color number was a slightly orange liquid having an APHA of 25 or less.
  • the GPC (gel permeation chromatography) area percentage purity with a differential refractometer (RI) detector was 75.5% and the proportion of oligomers was 23.7%.
  • the viscosity was 72.0 mPa ⁇ s.
  • the ratio of the oligomer by GC area% of the total of detection peaks of all regions having a retention time later than that of the target product

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  • Chemical & Material Sciences (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Hydrogenated Pyridines (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un inhibiteur de polymérisation destiné à être utilisé pour rectifier un ester d'acide (méth)acrylique à partir d'une composition contenant un ester d'acide (méth)acrylique obtenu par une réaction d'estérification par déshydratation ou par une réaction de trans-estérification, l'inhibiteur de polymérisation étant un ou plusieurs composés sélectionnés parmi des composés représentés par la formule générale (1) et des composés représentés par la formule générale (2). L'inhibiteur de polymérisation peut rectifier l'ester d'acide (méth)acrylique à partir d'une composition contenant un ester d'acide (méth)acrylique obtenu par une réaction d'estérification par déshydratation ou par une réaction de trans-estérification.
PCT/JP2018/019631 2017-05-31 2018-05-22 Inhibiteur de polymérisation et procédé de production d'ester d'acide (méth)acrylique à l'aide dudit inhibiteur de polymérisation, produit rectifié Ceased WO2018221314A1 (fr)

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WO2023204122A1 (fr) * 2022-04-18 2023-10-26 信越化学工業株式会社 Procédé de purification de siloxane contenant un groupe hydroxyle et un groupe (méth)acrylique, et composition de siloxane contenant un groupe hydroxyle et un groupe (méth)acrylique
US12098070B2 (en) 2019-04-02 2024-09-24 Ecolab Usa Inc. Pure chlorine dioxide generation system with reduced acid usage
US12304980B2 (en) 2022-04-01 2025-05-20 Ecolab Usa Inc. Antifoulant compositions for vapor-space applications
US12344581B2 (en) 2022-04-01 2025-07-01 Ecolab Usa Inc. Antifoulant compositions for high-severity processing of vinylic monomer streams
US12428360B2 (en) 2022-04-01 2025-09-30 Ecolab Usa Inc. Abating unwanted emulsion polymerization during extractive distillation of conjugated diene monomers

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US12098070B2 (en) 2019-04-02 2024-09-24 Ecolab Usa Inc. Pure chlorine dioxide generation system with reduced acid usage
US12304980B2 (en) 2022-04-01 2025-05-20 Ecolab Usa Inc. Antifoulant compositions for vapor-space applications
US12344581B2 (en) 2022-04-01 2025-07-01 Ecolab Usa Inc. Antifoulant compositions for high-severity processing of vinylic monomer streams
US12428360B2 (en) 2022-04-01 2025-09-30 Ecolab Usa Inc. Abating unwanted emulsion polymerization during extractive distillation of conjugated diene monomers
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