WO2016047655A1

WO2016047655A1 - Method for producing (meth)acrylate compound, method for purifying (meth)acrylate compound, and (meth)acrylate compound

Info

Publication number: WO2016047655A1
Application number: PCT/JP2015/076853
Authority: WO
Inventors: 北川　浩隆
Original assignee: 富士フイルム株式会社
Priority date: 2014-09-26
Filing date: 2015-09-24
Publication date: 2016-03-31
Also published as: JP6282353B2; JPWO2016047655A1; KR20170036765A; KR101882717B1

Abstract

　Provided are a method for producing a (meth)acrylate compound and a method for purifying a (meth)acrylate compound with which it is possible to prevent the polymerization of a (meth)acrylate compound during distillation and to highly productively produce a (meth)acrylate compound having a low impurity content, and a (meth)acrylate compound having a low impurity content. The method for producing and method for purifying a (meth)acrylate compound of the present invention involve conducting distillation after adding an N-oxyl compound A having a molecular weight of from 150 to less than 270 and an N-oxyl compound B having a molecular weight of 270 or higher to a mixture including a target (meth)acrylate compound, and recovering the target (meth)acrylate compound. The (meth)acrylate compound of the present invention is obtained by the above method, the (meth)acrylate compound having a HPLC purity of 98% or higher and/or a Na content of 10 ppb or lower.

Description

Method for producing (meth) acrylate compound, method for purifying (meth) acrylate compound, and (meth) acrylate compound

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.

A (meth) acrylate compound is added with a polymerization inhibitor in order to prevent polymerization during storage. N-oxyl compounds and the like are known as polymerization inhibitors.
For example, Patent Document 1 describes a method of stabilizing acrylic acid by adding 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl to acrylic acid.

Further, when the (meth) acrylate compound is purified by distillation, the (meth) acrylate compound may be polymerized in a distillation kettle or a distillation column during distillation. In the unlikely event that polymerization occurs in a distillation kettle or distillation column, the facility must be stopped and repaired, which significantly reduces productivity.
For example, 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. Examples of N-oxyl compounds 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.

Japanese Examined Patent Publication No. 45-1054 Japanese Patent Publication No. 58-46496

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. Distillation is carried out by adding 1-oxyl or 2,2-dimethyl-4,4-dipropylazetidine-1-oxyl, but this method cannot solve the above problem, and the target (meth) It has been found that it is difficult to produce a (meth) acrylate compound with a low content of impurities other than the acrylate compound with high productivity.

Therefore, 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.

As a result of intensive studies by the present inventors, 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. As a result, it was found that the above-mentioned object can be achieved, and the present invention has been completed. Accordingly, the present invention provides the following.
<1> After adding 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.
<2> The N-oxyl compound A is a compound represented by the following general formula (I), and the N-oxyl compound B is a compound represented by the following general formula (II). A process for producing a (meth) acrylate compound of

In the formula, 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.
<3> The amount of N-oxyl compound A added is 10 to 300 ppm relative to the mass of the mixture,
The method for producing a (meth) acrylate compound according to <1> or <2>, wherein the addition amount of the N-oxyl compound B is 300 ppm or more with respect 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.
<6> 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)
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.
<8> In the formula (M1), 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 manufacturing method of the (meth) acrylate compound as described in <7>.
<9> 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 The (meth) acrylate compound according to any one of Manufacturing method.
<10> 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.
<11> 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):

In the formula, 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> A (meth) acrylate compound which is a compound and has a purity (HPLC purity) of 98% or more determined from a peak area ratio by high performance liquid chromatography.
<13> The (meth) acrylate compound according to <12>, wherein the Na content is 10 ppb or less.
<14> The (meth) acrylate compound obtained by the production method according to any one of <1> to <9>, or the (meth) acrylate compound obtained by the purification method according to <10> or <11> A (meth) acrylate compound having an Na content of 10 ppb or less.

According to the present invention, 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 and ( It has become possible to provide a method for purifying a meth) acrylate compound and a (meth) acrylate compound with a low impurity content.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, “to” is used in the sense of including the numerical values described before and after it as lower and upper limits.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, “(meth) acryloyl” represents acryloyl and methacryloyl, and “(meth) ) "Acryloyloxy" represents acryloyloxy and methacryloyloxy.
In the description of a group (atomic group) in this specification, 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. For example, 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 (hereinafter referred to as the method 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.
According to the method of the present invention, by performing distillation using the N-oxyl compound A and the N-oxyl compound B in combination, it is possible to prevent impurities from being polymerized while preventing polymerization of the (meth) acrylate compound during distillation. 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. Furthermore, it is difficult to flow out with the vaporized (meth) acrylate compound, and it is difficult to mix in the distillate.
Further, by using the N-oxyl compound A and the N-oxyl compound B in combination, the polymerization of the (meth) acrylate compound in the distillation kettle and the distillation column can be suppressed, and the content of impurities is small. A (meth) acrylate compound can be produced with high productivity.
When the N-oxyl compound A is used alone, it tends to flow out with the vaporized (meth) acrylate compound, so that the polymerization inhibition effect in the liquid tends to decrease as the distillation proceeds. For this reason, as the distillation proceeds, the (meth) acrylate compound is easily polymerized and gelled in the distillation kettle. In order to carry out stable distillation of N-oxyl compound A alone, it is necessary to add a large amount of N-oxyl compound A. As a result, the amount of N-oxyl compound flowing into the distillate also increases. Therefore, the purity of the target (meth) acrylate compound tends to decrease. Further, when the N-oxyl compound B is used alone, the (meth) acrylate compound in the gas cannot be sufficiently suppressed, and the (meth) acrylate compound is easily polymerized in a distillation column or piping.
Hereinafter, the method of the present invention will be described in detail.

In the method of the present invention, 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. In addition, 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.
For example, neopentyl glycol diacrylate (NPGDA) can be produced by dehydrating and condensing neopentyl glycol and acrylic acid in the presence of an acid catalyst. Commercially available nepentyl glycol diacrylate thus produced contains compounds of formulas (1) to (3) as impurities. As a mechanism for generating these impurities, a mechanism represented by the following formula is conceivable. That is, after neopentyl glycol and acrylic acid are dehydrated and condensed to produce a compound of formula (1), the compound of formula (1) and acrylic acid are dehydrated and condensed to produce NPGDA. Acrylic acid is added to the resulting conjugated double bond of NPGDA by Michael to form a by-product of the compound of formula (2). Furthermore, neopentyl is added to the carbonyl group of the ester bond of the compound of formula (2). It is thought that glycol dehydrates and condenses, and the compound of Formula (3) is by-produced.

In this invention, it is preferable to use what performed liquid separation extraction as a mixture containing the target (meth) acrylate compound. By performing liquid separation extraction, 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.

In the present invention, 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. Although 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. Taking neopentyl glycol diacrylate as an example, 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.
Examples of the 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.

Specific examples of 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. 2-ethylhexyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 1 -Naphtylmethyl (meth) acrylate, 2-naphthylmethyl (meth) acrylate, phenethyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) Acrylate, 2- (2-butoxyethoxy) ethyl (meth) acrylate, glycidyl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (2-methyl -2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, α- (meth) acryloyloxy-γ-butyrolactone, β- (meth) acryloyloxy-γ-butyrolactone, dimethylaminoethyl (meth) ) Acrylate, diethylamino Examples include ethyl (meth) acrylate, tetramethylpiperidinyl (meth) acrylate, and pentamethylpiperidinyl (meth) acrylate.
Specific examples of the polyfunctional (meth) acrylate compound 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.
Among these, in particular, neopentyl glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, and 2-hydroxy-3-acryloyloxypropyl One selected from 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).

In the formula, 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.

In the present invention, 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. For example, the upper limit is preferably 250 ppm or less, and more preferably 200 ppm or less. For example, the lower limit is preferably 25 ppm or more, and more preferably 50 ppm or more. Within this range, the polymerization of the (meth) acrylate compound in the gas can be efficiently prevented while suppressing the inflow of the N-oxyl compound A into the distillate.

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. As an alkyl group, it is the same as the range demonstrated by R, and its preferable range is also the same.
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.

In the present invention, 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. Although there is no restriction | limiting in particular in an upper limit, From a viewpoint of cost, 5000 ppm or less is preferable, for example, and 3000 ppm or less is still more preferable. If it is this range, superposition | polymerization of the (meth) acrylate compound in a liquid can be prevented efficiently.

Next, 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. To do.
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.

According to 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. Furthermore, since there is little metal content, such as Na, it can use suitably for the photocurable composition for imprints for semiconductor lithography.
Moreover, since there are few impurities, it can use suitably for medical materials, such as dental cement and medical bone cement.
The (meth) acrylate compound obtained by the method of the present invention preferably has a purity (HPLC purity) of 98% or more. When components other than the target (meth) acrylate compound are contained, the viscosity tends to increase. In addition, 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. As a measuring device, 7500cs manufactured by Agilent Technologies can be used.

The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “%” is based on mass.

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. 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. In addition, 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. To the organic layer, 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.
When the distillation tower was confirmed, solid was not adhering to the glass wall.

(Comparative Example 1-1)
“Light acrylate NP-A” manufactured by Kyoeisha Chemical Co., Ltd. had an HPLC purity of 93.5%. Further, the Na content was 2500 ppb, and the viscosity was 5.5 mPa · s at 25 ° C.

(Comparative Example 1-2)
When 10 mg (100 ppm) of 4-HO-TEMPO was added to 100 g of “Light acrylate NP-A” manufactured by Kyoeisha Chemical Co., Ltd., and vacuum distillation was performed at 0.67 kPa, white turbidity occurred in the flask during the process. The distillation under reduced pressure was stopped.

(Comparative Example 1-3)
When 500 mg (5000 ppm) of 4-HO-TEMPO was added to 100 g of “Light acrylate NP-A” manufactured by Kyoeisha Chemical Co., Ltd. and distilled under reduced pressure at 0.67 kPa, 4-HO-TEMPO was azeotroped. Since the distillate showed an orange color, the distillation under reduced pressure was stopped. 4-HO-TEMPO in the distillate was 3100 ppm.

(Comparative Example 1-4)
100 mg (1000 ppm) of 4-BzO-TEMPO was added to 100 g of “Light acrylate NP-A” manufactured by Kyoeisha Chemical Co., Ltd., and vacuum distillation was performed at 0.67 kPa to obtain purified neopentyl glycol diacrylate. The retention point was 108 ° C., the yield was 73 g, and the yield was 73%.
The purified neopentyl glycol diacrylate had a HPLC purity of 98.3%, a Na content of 1 ppb or less, a 4-BzO-TEMPO content of 10 ppm or less, and was slightly cloudy. In addition, the viscosity was 4.7 mPa · s at 25 ° C.
As a result of checking the distillation tower, the solid was slightly adhered to the glass wall.

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%.
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.

(Comparative Example 2-1)
Unpurified 1,4-butanediol diacrylate (Tokyo Chemical Industry Co., Ltd.) had an HPLC purity of 97.4%. The viscosity at 5.3C was 5.3 mPa · s.

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.

(Comparative Example 3-1)
Shin Nakamura Chemical Co., Ltd. “NK Ester A-HD-N” had an HPLC purity of 92.9%. The viscosity at 25 ° C. was 5.9 mPa · s.

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.

(Comparative Example 4-1)
The crude diethylene glycol diacrylate (Sigma-Aldrich) had an HPLC purity of 82.3%. The viscosity at 25 ° C. was 8.9 mPa · s.

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%.
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.
When the distillation tower was confirmed, solid was not adhering to the glass wall.

(Comparative Example 5-1)
Shin Nakamura Chemical Co., Ltd. “NK Ester APG-100” had a viscosity of 8.4 mPa · s at 25 ° C.

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) A transparent liquid having a Na content of 1 ppb or less. The viscosity at 25 ° C. was 36.2 mPa · s.
When the distillation tower was confirmed, solid was not adhering to the glass wall.

(Comparative Example 6-2)
The crude 2-hydroxy-3-acryloyloxypropyl methacrylate (Sigma-Aldrich) had an HPLC purity of 88.8% (isomer mixture). The viscosity at 25 ° C. was 44.8 mPa · s.

<Measurement of HPLC purity of (meth) acrylate compound>
The target (meth) acrylate compound in the sample was analyzed by high performance liquid chromatography (HPLC) under the following conditions. The HPLC purity of the target (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
Column: Shimadzu GLC Shim-pack CLC-ODS (15 mm x 4.6 mm)
Column temperature: 35 ° C
Mobile phase: acetonitrile / water (50/50)
Flow rate: 1 mL / min Sample concentration: 1 mg / mL
Injection volume: 10 μl
Measurement time: 40 minutes

<Viscosity measurement>
Using an E-type viscometer (RE85L manufactured by Toki Sangyo Co., Ltd.), the viscosity was measured at 25 ± 0.2 ° C. and at a rotation speed of 50 rpm.

<Measurement of Na content>
Measurement was performed by ICP-MS (inductively coupled plasma) method using Agilent Technologies 7500cs.

<Measurement of content of N-oxyl compound>
The content of the N-oxyl compound in the sample was analyzed by high performance liquid chromatography (HPLC) under the following conditions. The content of the N-oxyl compound was calculated based on a calibration curve prepared from a standard.
HPLC apparatus: 2695 manufactured by Waters
Detector: Waters 2996 Photodiode array Detection wavelength: 240 nm
Column: Shimadzu GLC Shim-pack CLC-ODS (15 mm x 4.6 mm)
Column temperature: 35 ° C
Mobile phase: acetonitrile / water (50/50)
Flow rate: 1 mL / min Sample concentration: 10 mg / mL
Injection volume: 10 μl
Measurement time: 40 minutes

Claims

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 to obtain the target (meth) The manufacturing method of the (meth) acrylate compound which collect | recovers an acrylate compound.
The N-oxyl compound A is a compound represented by the following general formula (I):
The method for producing a (meth) acrylate compound according to claim 1, wherein the N-oxyl compound B is a compound represented by the following general formula (II):

In the formula, 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.
The addition amount of the N-oxyl compound A is 10 to 300 ppm with respect to the mass of the mixture,
The method for producing a (meth) acrylate compound according to claim 1 or 2, wherein an addition amount of the N-oxyl compound B is 300 ppm or more with respect to a mass of the mixture.
The method for producing a (meth) acrylate compound according to any one of claims 1 to 3, wherein the distillation is performed under conditions of 0.1 to 1.0 kPa and 80 to 180 ° C.
The method for producing a (meth) acrylate compound according to any one of claims 1 to 4, wherein the mixture is purified by separation extraction.
The objective (meth) acrylate compound is a polyfunctional (meth) acrylate compound having two or more (meth) acryloyloxy groups in one molecule. A method for producing a (meth) acrylate compound.
The method for producing a (meth) acrylate compound according to any one of claims 1 to 6, wherein the target (meth) acrylate compound is 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.
In the formula (M1), L is 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—. 8. A method for producing a (meth) acrylate compound according to 7.
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, di The method according to any one of claims 1 to 8, which is one selected from propylene glycol di (meth) acrylate, glycerol-1,3-di (meth) acrylate and 2-hydroxy-3-acryloyloxypropyl methacrylate. (Meth) acrylate compound described in The method of production.
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 to obtain the target (meth) A method for purifying a (meth) acrylate compound, wherein the acrylate compound is recovered.
The N-oxyl compound A is a compound represented by the following general formula (I):
The method for purifying a (meth) acrylate compound according to claim 10, wherein the N-oxyl compound B is a compound represented by the following general formula (II):

In the formula, 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.
A (meth) acrylate compound obtained by the production method according to any one of claims 1 to 9, or a (meth) acrylate compound obtained by the purification method according to claim 10 or 11, A (meth) acrylate compound having a purity determined by high-performance liquid chromatography peak area ratio of 98% or more.
The (meth) acrylate compound according to claim 12, wherein the Na content is 10 ppb or less.
A (meth) acrylate compound obtained by the production method according to any one of claims 1 to 9, or a (meth) acrylate compound obtained by the purification method according to claim 10 or 11, The (meth) acrylate compound whose Na content is 10 ppb or less.