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WO2016047655A1 - Procédé de production d'un composé (méth)acrylate, procédé de purification d'un composé (méth)acrylate et composé (méth)acrylate associé - Google Patents

Procédé de production d'un composé (méth)acrylate, procédé de purification d'un composé (méth)acrylate et composé (méth)acrylate associé Download PDF

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Publication number
WO2016047655A1
WO2016047655A1 PCT/JP2015/076853 JP2015076853W WO2016047655A1 WO 2016047655 A1 WO2016047655 A1 WO 2016047655A1 JP 2015076853 W JP2015076853 W JP 2015076853W WO 2016047655 A1 WO2016047655 A1 WO 2016047655A1
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Prior art keywords
meth
acrylate
compound
acrylate compound
group
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PCT/JP2015/076853
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English (en)
Japanese (ja)
Inventor
北川　浩隆
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富士フイルム株式会社
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Priority to JP2016550340A priority Critical patent/JP6282353B2/ja
Priority to KR1020177005276A priority patent/KR101882717B1/ko
Publication of WO2016047655A1 publication Critical patent/WO2016047655A1/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
    • C07C67/62—Use of additives, e.g. for stabilisation
    • 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
    • C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
    • 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

Definitions

  • the present invention relates to a method for producing a (meth) acrylate compound, a method for purifying a (meth) acrylate compound, and a (meth) acrylate compound.
  • Patent Document 1 describes a method of stabilizing acrylic acid by adding 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl to acrylic acid.
  • Patent Document 2 describes a popcorn polymerization prevention method in which an N-oxyl compound is added to a (meth) acrylate compound and the (meth) acrylate compound is distilled.
  • N-oxyl compounds examples include 2,2,5,5-tetramethyl-3-oxopyrrolidine-1-oxyl, 2,2,6,6-tetramethyl-4-acetoxypiperidine-1-oxyl in the examples, 2,2-dimethyl-4,4-dipropylazetidine-1-oxyl is used.
  • the N-oxyl compound is a compound that suppresses polymerization of the (meth) acrylate compound, but according to the study of the present inventors, the N-oxyl compound was added to the mixture containing the (meth) acrylate compound and distilled. However, it has been found that the polymerization of the (meth) acrylate compound during distillation cannot be prevented, and there are problems such as a large amount of N-oxyl compound added during distillation being mixed into the distillate. Further, in Patent Document 2, 2,2,5,5-tetramethyl-3-oxopyrrolidine-1-oxyl, 2,2,6,6-tetramethyl-4-acetoxypiperidine- is added to the (meth) acrylate compound.
  • this invention prevents the polymerization of the (meth) acrylate compound during distillation, and can produce a (meth) acrylate compound with a low impurity content with high productivity and ( It aims at providing the purification method of a meth) acrylate compound, and the (meth) acrylate compound with little content of impurities.
  • an N-oxyl compound having a molecular weight of 150 or more and less than 270 and an N-oxyl compound having a molecular weight of 270 or more were added to a mixture containing the target (meth) acrylate compound, and then distilled.
  • the present invention provides the following.
  • N-oxyl compound A having a molecular weight of 150 or more and less than 270 and N-oxyl compound B having a molecular weight of 270 or more to a mixture containing the target (meth) acrylate compound
  • distillation is performed, A method for producing a (meth) acrylate compound, wherein a (meth) acrylate compound is recovered.
  • the N-oxyl compound A is a compound represented by the following general formula (I)
  • the N-oxyl compound B is a compound represented by the following general formula (II).
  • ⁇ 3> The amount of N-oxyl compound A added is 10 to 300 ppm relative to the mass of the mixture
  • ⁇ 4> The method for producing a (meth) acrylate compound according to any one of ⁇ 1> to ⁇ 3>, wherein the distillation is performed under conditions of 0.1 to 1.0 kPa and 80 to 180 ° C.
  • ⁇ 5> The method for producing a (meth) acrylate compound according to any one of ⁇ 1> to ⁇ 4>, wherein a mixture purified by separation extraction is used.
  • the target (meth) acrylate compound is a polyfunctional (meth) acrylate compound having two or more (meth) acryloyloxy groups in one molecule, according to any one of ⁇ 1> to ⁇ 5> (Meth) acrylate compound production method.
  • ⁇ 7> The method for producing a (meth) acrylate compound according to any one of ⁇ 1> to ⁇ 6>, wherein the target (meth) acrylate compound is a compound represented by the following formula (M1); L- (X) m (M1)
  • L represents an m-valent linking group having 3 to 10 carbon atoms constituting a chain linking X to each other
  • X represents a (meth) acryloyloxy group
  • m represents 2 or more.
  • L represents a hydrocarbon group that may have a hydroxy group, or a group that includes a combination of a hydrocarbon group that may have a hydroxy group and —O—.
  • the target (meth) acrylate compound is 1,2-propanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 3-methyl-1 , 5-pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate ⁇ 1> to ⁇ 8>, which is one selected from dipropylene glycol di (meth) acrylate, glycerol-1,3-di (meth) acrylate and 2-hydroxy-3-acryloyloxypropyl methacrylate
  • N-oxyl compound A having a molecular weight of 150 or more and less than 270 and N-oxyl compound B having a molecular weight of 270 or more are added to a mixture containing the target (meth) acrylate compound, followed by distillation.
  • a method for purifying a (meth) acrylate compound, which recovers a (meth) acrylate compound is a method for purifying a (meth) acrylate compound, which recovers a (meth) acrylate compound.
  • N-oxyl compound A is a compound represented by the following general formula (I): The method for purifying a (meth) acrylate compound according to ⁇ 10>, wherein the N-oxyl compound B is a compound represented by the following general formula (II):
  • Z represents a hydrogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 4 carbon atoms, or an acyloxy group having 2 to 4 carbon atoms
  • R represents a substituent
  • n represents an integer of 0 to 5, and when n is 2 or more, a plurality of R may be the same or different.
  • ⁇ 12> The (meth) acrylate compound obtained by the production method according to any one of ⁇ 1> to ⁇ 9>, or the (meth) acrylate obtained by the purification method according to ⁇ 10> or ⁇ 11>
  • ⁇ 13> The (meth) acrylate compound according to ⁇ 12>, wherein the Na content is 10 ppb or less.
  • a method for producing a (meth) acrylate compound capable of preventing the polymerization of a (meth) acrylate compound during distillation and producing a (meth) acrylate compound having a low impurity content with high productivity It has become possible to provide a method for purifying a meth) acrylate compound and a (meth) acrylate compound with a low impurity content.
  • the description which does not describe substitution and unsubstituted includes the group which has a substituent with the group which does not have a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • the production method and purification method of the (meth) acrylate compound of the present invention are each carried out by adding an N-oxyl compound A having a molecular weight of 150 to less than 270 to a mixture containing the desired (meth) acrylate compound And N-oxyl compound B having a molecular weight of 270 or more, followed by distillation to recover the desired (meth) acrylate compound.
  • N-oxyl compound A having a molecular weight of 150 to less than 270
  • N-oxyl compound B having a molecular weight of 270 or more
  • a small amount of (meth) acrylate compound can be produced with high productivity. It is estimated that the mechanism for obtaining such an effect is as follows. Since the N-oxyl compound A has a low molecular weight, it tends to volatilize during distillation. For this reason, it is considered that the polymerization of the (meth) acrylate compound in the gas can be efficiently suppressed by adding the N-oxyl compound A. Since the N-oxyl compound B has a large molecular weight, it is difficult to volatilize during distillation. For this reason, it is considered that by adding the N-oxyl compound B, polymerization of the (meth) acrylate compound in the liquid can be efficiently suppressed.
  • an N-oxyl compound A having a molecular weight of 150 or more and less than 270 and an N-oxyl compound B having a molecular weight of 270 or more are added to a mixture containing the target (meth) acrylate compound.
  • Examples of the mixture containing the target (meth) acrylate compound include commercially available (meth) acrylate compounds, reaction solutions after the synthesis of (meth) acrylate compounds, and the like.
  • a catalyst, unreacted acrylic acid, a by-product, etc. are mixed as impurities in the commercially available (meth) acrylate compound and the synthesized reaction liquid in addition to the target (meth) acrylate compound.
  • NPGDA neopentyl glycol diacrylate
  • NPGDA neopentyl glycol diacrylate
  • Commercially available nepentyl glycol diacrylate thus produced contains compounds of formulas (1) to (3) as impurities.
  • liquid separation extraction it is preferable to use what performed liquid separation extraction as a mixture containing the target (meth) acrylate compound.
  • an acid catalyst, unreacted acrylic acid, or the like can be removed, and a (meth) acrylate compound with fewer impurities can be obtained.
  • Separation extraction can be performed by dissolving a mixture containing the target (meth) acrylate compound in an organic solvent, mixing water, separating the mixture into an aqueous layer and an organic layer, and collecting the organic layer. . Distillation may be performed after removing the organic solvent contained in the organic layer, or a solution containing the organic solvent may be distilled as it is.
  • the target (meth) acrylate compound may be a monofunctional (meth) acrylate compound having one or more (meth) acryloyloxy groups in one molecule, and two or more in one molecule.
  • a polyfunctional (meth) acrylate compound having a (meth) acryloyloxy group may be used, a polyfunctional (meth) acrylate compound is preferred.
  • Polyfunctional (meth) acrylate compounds are generally easy to polymerize and gel during distillation, but according to the method of the present invention, (meth) acrylate compounds during distillation are also used for polyfunctional (meth) acrylate compounds. Polymerization can be prevented.
  • the polyfunctional (meth) acrylate compound preferably has 2 to 6 (meth) acryloyloxy groups, more preferably 2 to 4, and still more preferably 2.
  • the polyfunctional (meth) acrylate compound is preferably a compound represented by the following formula (M1).
  • L- (X) m (M1) In the formula, L represents an m-valent linking group having 3 to 10 carbon atoms constituting a chain linking X to each other, X represents a (meth) acryloyloxy group, and m represents 2 or more. Represents an integer.
  • m represents an integer of 2 or more, preferably 2 to 6, more preferably 2 to 4, and still more preferably 2.
  • L represents an m-valent linking group having 3 to 10 carbon atoms constituting a chain linking X to each other.
  • L preferably has 3 to 8 carbon atoms constituting a chain connecting Xs to each other.
  • the number of carbon atoms constituting a chain connecting Xs means the number of atoms constituting the shortest chain when there are a plurality of chains due to branching or ringing.
  • the chain connecting two acryloyloxy groups is three carbon atoms, as shown below.
  • the m-valent linking group represented by L includes an optionally substituted hydrocarbon group, an optionally substituted hydrocarbon group, —O—, —CO—, —COO—, and —NR. And a group formed by combining one or more selected from L1-.
  • the hydrocarbon group is preferably an aliphatic hydrocarbon group, and more preferably a linear or branched aliphatic hydrocarbon group.
  • Examples of the divalent hydrocarbon group include an alkylene group, an arylene group, and a group formed by a combination of an arylene group and an alkylene group, and an alkylene group is preferable.
  • the alkylene group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
  • the alkylene group may be linear, branched or cyclic, and is preferably linear or branched.
  • the carbon number of the arylene group is preferably 6 to 20, and more preferably 6 to 12.
  • Examples of the trivalent or higher valent hydrocarbon group include groups obtained by removing one or more hydrogen atoms from a divalent hydrocarbon group.
  • R L1 includes a hydrogen atom or an alkyl group.
  • the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, but is preferably linear or branched, particularly preferably linear.
  • substituent that the hydrocarbon group may have include a hydroxy group, an alkoxy group, a fluorine atom, and a chlorine atom, and a hydroxy group is more preferable.
  • the m-valent linking group represented by L is a hydrocarbon group that may have a substituent, or a hydrocarbon group that may have a substituent, and one selected from —O—, —CO—, and the like.
  • a group formed by combining the above is preferable, and a hydrocarbon group which may have a substituent, or a group formed by combining a hydrocarbon group which may have a substituent and —O— is more preferable.
  • a hydrocarbon group which may have a group, or a group formed by a combination of a hydrocarbon group which may have a hydroxy group and —O— is more preferable.
  • the monofunctional (meth) acrylate compound include, for example, octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, and isodecyl (meth) acrylate.
  • polyfunctional (meth) acrylate compound examples include 1,2-propanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 3- Methyl-1,5-pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di ( Examples thereof include meth) acrylate, dipropylene glycol di (meth) acrylate, glycerol-1,3-di (meth) acrylate, and 2-hydroxy-3-acryloyloxypropyl methacrylate.
  • methacrylate is preferred.
  • the N-oxyl compound A used in the present invention has a molecular weight of 150 or more and less than 270, preferably a molecular weight of 150 or more and less than 250, and more preferably a molecular weight of 150 or more and less than 220.
  • the N-oxyl compound A is preferably a compound represented by the following formula (I).
  • Z represents a hydrogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 4 carbon atoms, or an acyloxy group having 2 to 4 carbon atoms.
  • the alkoxy group has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.
  • the alkoxycarbonyl group has 2 to 4 carbon atoms, and more preferably 2 to 3 carbon atoms.
  • the acyloxy group has 2 to 4 carbon atoms, and more preferably 2 to 3 carbon atoms.
  • Z is preferably a hydrogen atom, a hydroxy group, a methoxy group or an acetoxy group. Specific examples of the compound represented by the formula (I) include the following.
  • the addition amount of the N-oxyl compound A is preferably 10 to 300 ppm relative to the mass of the mixture containing the target (meth) acrylate compound.
  • the upper limit is preferably 250 ppm or less, and more preferably 200 ppm or less.
  • the lower limit is preferably 25 ppm or more, and more preferably 50 ppm or more.
  • the N-oxyl compound B used in the present invention has a molecular weight of 270 or more, preferably a molecular weight of 270 or more and less than 500, and more preferably a molecular weight of 270 or more and less than 450. Further, the difference between the molecular weight of the N-oxyl compound B and the molecular weight of the N-oxyl compound A is preferably 20 or more, and more preferably 50 or more.
  • the N-oxyl compound B is preferably a compound represented by the following formula (II). In the formula, R represents a substituent, n represents an integer of 0 to 5, and when n is 2 or more, a plurality of Rs may be the same or different.
  • Examples of the substituent include an alkyl group, an alkoxy group, and a group represented by —NR 1 R 2 .
  • Examples of the alkyl group include straight chain, branched, and cyclic, and straight chain or branched is preferable.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 5 carbon atoms.
  • Examples of the alkoxy group include linear, branched and cyclic groups, and linear or branched are preferable.
  • the alkoxy group preferably has 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 5 carbon atoms.
  • R 1 and R 2 each independently represents a hydrogen atom or an alkyl group.
  • n represents an integer of 0 to 5, preferably 0 to 3, more preferably 0 to 2, and still more preferably 0 to 1.
  • Specific examples of the compound represented by the formula (II) include the following.
  • the addition amount of the N-oxyl compound B is preferably 300 ppm or more, more preferably 500 ppm or more, and still more preferably 800 ppm or more with respect to the mass of the mixture containing the target (meth) acrylate compound.
  • the N-oxyl compound B is preferably 300 ppm or more, more preferably 500 ppm or more, and still more preferably 800 ppm or more with respect to the mass of the mixture containing the target (meth) acrylate compound.
  • 5000 ppm or less is preferable, for example, and 3000 ppm or less is still more preferable. If it is this range, superposition
  • a composition obtained by adding the N-oxyl compound A and the N-oxyl compound B to a mixture containing the target (meth) acrylate compound is distilled to recover the target (meth) acrylate compound.
  • Distillation can be carried out under reduced pressure or normal pressure, but is preferably performed under reduced pressure.
  • Distillation conditions vary depending on the target (meth) acrylate compound, but are preferably 0.1 to 10 kPa and 80 to 220 ° C.
  • the pressure is more preferably from 0.1 to 5 kPa, and even more preferably from 0.1 to 1 kPa.
  • the temperature is more preferably from 80 to 200 ° C, and even more preferably from 80 to 180 ° C.
  • the method of the present invention polymerization of the (meth) acrylate compound during distillation can be prevented, and contamination of various N-oxyl compounds added before distillation into the distillate can be reduced. For this reason, a (meth) acrylate compound with a low impurity content can be obtained with high productivity.
  • the (meth) acrylate compound obtained by the method of the present invention has a low viscosity, and is excellent in, for example, fillability when used in a photocurable composition for imprints. In addition, since there is little mixing of various N-oxyl compounds added before distillation, the curing sensitivity when used in the photocurable composition for imprinting is excellent.
  • the (meth) acrylate compound obtained by the method of the present invention preferably has a purity (HPLC purity) of 98% or more.
  • the purity (HPLC purity) of the target (meth) acrylate compound is a value obtained from the peak area ratio by high performance liquid chromatography (HPLC) measured under the conditions described in Examples described later.
  • the (meth) acrylate compound obtained by the method of the present invention preferably has a Na content of 10 ppb or less, and more preferably 5 ppb or less.
  • the Na content is a value measured by an ICP-MS (inductively coupled plasma) method.
  • ICP-MS inductively coupled plasma
  • 7500cs manufactured by Agilent Technologies can be used.
  • Example 1-1 To 100 g of “Light acrylate NP-A” manufactured by Kyoeisha Chemical Co., Ltd., which is a neopentyl glycol diacrylate mixture, 4-hydroxy-2,2-6,6-tetramethylpiperidine N-oxyl, free radical (4-HO— 10 mg (100 ppm) of TEMPO, manufactured by Wako Pure Chemical Industries), 4-benzoyloxy-2,2-6,6-tetramethylpiperidine N-oxyl, free radical (4-BzO-TEMPO, manufactured by Wako Pure Chemical Industries) 100 mg (1000 ppm) was added and distilled under reduced pressure at 0.67 kPa to obtain purified neopentyl glycol diacrylate.
  • “Light acrylate NP-A” manufactured by Kyoeisha Chemical Co., Ltd. which is a neopentyl glycol diacrylate mixture, 4-hydroxy-2,2-6,6-tetramethylpiperidine N-oxyl, free radical (4-HO— 10
  • the distillation point was 108 ° C., the yield was 77 g, and the yield was 77%.
  • Purified neopentyl glycol diacrylate is a transparent liquid with an HPLC purity of 98.6%, a 4-HO-TEMPO content of 53 ppm, a 4-BzO-TEMPO content below the lower limit of quantification (10 ppm or less), and an Na content of 1 ppb or less. there were.
  • the viscosity was 4.6 mPa ⁇ s at 25 ° C. When the distillation tower was confirmed, solid was not adhering to the glass wall.
  • Example 1-2 100 g of heptane and 10 mg (100 ppm) of heptane and 100 mg of 4-HO-TEMPO were added to 100 g of “Light acrylate NP-A” manufactured by Kyoeisha Chemical Co., Ltd., followed by liquid separation extraction with 100 mL of pure water.
  • 10 mg (100 ppm) of 4-HO-TEMPO and 100 mg (1000 ppm) of 4-BzO-TEMPO were added and concentrated under reduced pressure, followed by distillation under reduced pressure at 0.67 kPa to obtain purified neopentyl glycol diacrylate. Obtained.
  • the distillation point was 109 ° C., the yield was 74 g, and the yield was 74%.
  • Purified neopentyl glycol diacrylate is a transparent liquid with an HPLC purity of 99.2%, 4-HO-TEMPO content of 59 ppm, 4-BzO-TEMPO content below the lower limit of quantification (10 ppm or less), and Na content of 1 ppb or less. there were.
  • the viscosity at 25 ° C. was 4.5 mPa ⁇ s.
  • Example 2-1 10 mg of 2,2-6,6-tetramethylpiperidine N-oxyl and free radical (TEMPO, manufactured by Wako Pure Chemical Industries) are added to 100 g of unpurified 1,4-butanediol diacrylate (Tokyo Chemical Industry Co., Ltd.) (100 ppm) and 100 mg (1000 ppm) of 4-BzO-TEMPO were added and distilled under reduced pressure at 0.67 kPa to obtain purified 1,4-butanediol diacrylate. The distillation point was 110 to 112 ° C., the yield was 89 g, and the yield was 89%.
  • TEMPO 2,2-6,6-tetramethylpiperidine N-oxyl and free radical
  • the purified 1,4-butanediol diacrylate is a transparent liquid having an HPLC purity of 98.3%, a TEMPO content of 93 ppm, a 4-BzO-TEMPO content below the lower limit of quantification (10 ppm or less), and an Na content of 1 ppb or less. It was. In addition, the viscosity was 4.1 mPa ⁇ s at 25 ° C. When the distillation tower was confirmed, solid was not adhering to the glass wall.
  • Example 3-1 100 mg of 4-HO-TEMPO and 100 mg of 4-BzO-TEMPO are added to 100 g of “NK Ester A-HD-N”, Shin-Nakamura Chemical Co., Ltd., which is a 1,6-hexanediol diacrylate mixture. 1000 ppm) and vacuum distillation at 0.40 kPa to obtain purified 1,6-hexanediol diacrylate. The retention point was 124 to 126 ° C., the yield was 86 g, and the yield was 86%.
  • the purified 1,6-hexanediol diacrylate has a HPLC purity of 98.3%, a 4-HO-TEMPO content of 84 ppm, a 4-BzO-TEMPO content of less than the lower limit of quantification (10 ppm or less), and a Na content of 1 ppb or less. It was a liquid. The viscosity at 25 ° C. was 5.4 mPa ⁇ s. When the distillation tower was confirmed, solid was not adhering to the glass wall.
  • Example 4-1 To 100 g of unpurified diethylene glycol diacrylate (Sigma-Aldrich), 10 mg (100 ppm) of 4-HO-TEMPO and 100 mg (1000 ppm) of 4-BzO-TEMPO were added and purified by distillation under reduced pressure at 0.44 kPa. Diethylene glycol diacrylate was obtained. The retention point was 117 to 120 ° C., the yield was 69 g, and the yield was 69%.
  • the purified diethylene glycol diacrylate was a transparent liquid with an HPLC purity of 99.3%, a 4-HO-TEMPO content of 78 ppm, a 4-BzO-TEMPO content below the lower limit of quantification (10 ppm or less), and an Na content of 1 ppb or less. . Further, the viscosity was 6.7 mPa ⁇ s at 25 ° C. When the distillation tower was confirmed, solid was not adhering to the glass wall.
  • Example 5-1 10 mg (100 ppm) of 4-HO-TEMPO and 100 mg (1000 ppm) of 4-BzO-TEMPO were added to 100 g of “NK Ester APG-100”, which is a mixture of dipropylene glycol diacrylate. Then, vacuum distillation was performed at 0.31 kPa to obtain purified dipropylene glycol diacrylate. The retention point was 108 to 112 ° C., the yield was 77 g, and the yield was 77%.
  • NK Ester APG-100 is a mixture of dipropylene glycol diacrylate.
  • the purified dipropylene glycol diacrylate was a transparent liquid having a 4-HO-TEMPO content of 81 ppm, a 4-BzO-TEMPO content below the lower limit of quantification (10 ppm or less), and an Na content of 1 ppb or less.
  • the viscosity at 25 ° C. was 6.8 mPa ⁇ s.
  • Example 6-1 To 100 g of unpurified 2-hydroxy-3-acryloyloxypropyl methacrylate (Sigma-Aldrich), 10 mg (100 ppm) of 4-HO-TEMPO and 100 mg (1000 ppm) of 4-BzO-TEMPO were added to give 0.36 kPa. Distilled under reduced pressure to obtain purified 2-hydroxy-3-acryloyloxypropyl methacrylate. The retention point was 128 to 133 ° C., the yield was 65 g, and the yield was 65%.
  • Purified 2-hydroxy-3-acryloyloxypropyl methacrylate has an HPLC purity of 98.1% (isomer mixture), 4-HO-TEMPO content of 92 ppm, and 4-BzO-TEMPO content is below the lower limit of quantification (10 ppm or less)
  • HPLC purity of (meth) acrylate compound was calculated as the ratio (area%) of the largest peak area value to the sum of the area values of all peaks.
  • HPLC apparatus 2695 manufactured by Waters Detector: Waters 2996 Photodiode array Detection wavelength: 210 nm
  • Injection volume 10 ⁇ l Measurement time: 40 minutes
  • Measurement was performed by ICP-MS (inductively coupled plasma) method using Agilent Technologies 7500cs.

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Abstract

　L'invention concerne un procédé de production d'un composé (méth)acrylate et un procédé de purification d'un composé (méth)acrylate, dans lesquels, la polymérisation du composé (méth)acrylate au moment de la distillation est évitée et dans lesquels il est possible d'obtenir avec un bon rendement un composé (méth)acrylate contenant peu d'impuretés. L'invention concerne également ce composé (méth)acrylate contenant peu d'impuretés.　Ces procédés de production et de purification d'un composé (méth)acrylate consistent, après avoir ajouté à un mélange contenant le composé (méth)acrylate voulu un composé (A) N-oxyle de masse moléculaire supérieure ou égale à 150 et inférieure à 270 et un composé (B) N-oxyle de masse moléculaire supérieure ou égale à 270, à effectuer une distillation, puis à récupérer le composé (méth)acrylate voulu. Le composé (méth)acrylate obtenu par les procédés susmentionnés présente un degré de pureté HPLC supérieur ou égal à 98%, et/ou sa teneur en Na est égale ou inférieure à 10ppb.
PCT/JP2015/076853 2014-09-26 2015-09-24 Procédé de production d'un composé (méth)acrylate, procédé de purification d'un composé (méth)acrylate et composé (méth)acrylate associé WO2016047655A1 (fr)

Priority Applications (2)

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JP2016550340A JP6282353B2 (ja) 2014-09-26 2015-09-24 （メタ）アクリレート化合物の製造方法、（メタ）アクリレート化合物の精製方法および、（メタ）アクリレート化合物
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JP2021113181A (ja) * 2020-01-21 2021-08-05 精工化学株式会社 重合禁止剤及び重合性不飽和結合を有する化合物の製造方法
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EP4538757A1 (fr) 2023-10-10 2025-04-16 Nitto Denko Corporation Stratifié optique et appareil d'affichage

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