JPH09241215A - Purification of acrylic ester derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a purified acrylic ester derivative low in impurities content, prevented from crosslinking during its polymerization, suppressed in its gelling, copolymerizable with other monomer(s) in and proportion, thus useful in various applications. SOLUTION: This purified acrylic ester derivative is obtained by washing an acrylic ester derivative contaminated with a crosslinkable component having two or more double bonds in the molecule as impurities and expressed by the formula (R1 and R2 are each H or an organic residue; R3 is an organic residue; (n) is a positive number of 1-3; (m) is a positive number of 1-100) with such an organic solvent (<=8.5 in solubility parameter) as to be more soluble for the crosslinkable component than this derivative, or a cleaning agent containing at least water (containing an organic solvent subject to two-layer separation with water and <=10 in solubility parameter).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for purifying an acrylic acid ester derivative.

[0002]

2. Description of the Related Art Conventionally, as disclosed in JP-A-5-70408, dehydration condensation products (hereinafter referred to as ether dimers) and acetal products (. Hereinafter, it is known that a compound called "acetal dimer" is contained.

[0003]

Therefore, as a result of various studies by the inventors of the present invention on impurities in the acrylic ester derivative using the above-mentioned α-hydroxyalkyl acrylic ester as a raw material, the α-hydroxyalkyl acrylic ester has a cyclic structure. It was found that a side reaction occurs when the ether compound is added and the above-mentioned ether dimer and acetal dimer increase. Further, it has been found that a transesterification reaction occurs between the hydroxyl group and the ester group of the α-hydroxyalkyl acrylic acid ester or acrylic acid ester derivative, and a dimer linked by an ester bond is obtained as an impurity.

Each of these impurities is composed of a crosslinkable component having a double bond in the molecule, and when an acrylic acid ester derivative containing the crosslinkable component as an impurity is polymerized, a crosslinking reaction may occur and gelation may occur. There is. That is, an object of the present invention is to provide a method for purifying an acrylic acid ester derivative containing a crosslinkable component as an impurity.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, the crosslinkable component as an impurity and the acrylic ester derivative have different solubility in water or a solvent. There is a crosslinkable impurity from the acrylic acid ester derivative by washing the acrylic acid ester derivative containing the crosslinkable component as an impurity with a specific solvent, water, or a mixed system of water and a specific solvent. They have found that they can be separated and removed, and have completed the present invention.

That is, the method for purifying an acrylic acid ester derivative according to claim 1 of the present invention is one in which a double bond is formed in the molecule.
General formula (1) containing one or more crosslinkable components as impurities

[0007]

Embedded image

(In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or an organic residue, R ₃ represents an organic residue,
(n represents a positive number of 1 to 3 and m represents a positive number of 1 to 100)
The acrylic ester derivative represented by is washed with an organic solvent (A) in which the solubility of the crosslinkable component is higher than the solubility of the acrylic ester derivative.

The method for purifying an acrylic acid ester derivative according to claim 2 of the present invention is the method for purifying an acrylic acid ester derivative according to claim 1, wherein the solubility parameter of the organic solvent (A) is 8.5 or less. Is characterized by.

The method for purifying an acrylic acid ester derivative according to claim 3 of the present invention is the method for purifying an acrylic acid ester derivative according to claim 1 or 2, wherein the organic solvent (A) is used for the acrylic acid ester derivative. Quantity
It is characterized in that the weight ratio is within the range of 0.01 to 100.

According to the above constitution, the acrylic ester derivative containing the crosslinkable component as an impurity is washed with the organic solvent (A) to remove the crosslinkable component from the acrylic ester derivative into the organic solvent (A). The layers can be extracted and removed. Thereby, impurities can be reduced, and at the same time, there is no problem of gelation at the time of polymerization, copolymerization with other monomer can be carried out at an arbitrary ratio, and an acrylate derivative which can be utilized for various purposes can be obtained.

According to a fourth aspect of the present invention, there is provided a method for purifying an acrylic acid ester derivative, which comprises a double bond in the molecule.
General formula (1) containing one or more crosslinkable components as impurities

[0013]

Embedded image

(In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or an organic residue, R ₃ represents an organic residue,
(n represents a positive number of 1 to 3 and m represents a positive number of 1 to 100)
It is characterized in that the acrylic ester derivative represented by is washed with a detergent containing at least water.

The method for purifying an acrylic acid ester derivative according to a fifth aspect of the present invention is the method for purifying an acrylic acid ester derivative according to the fourth aspect, wherein the amount of water used with respect to the acrylic acid ester derivative is a weight ratio. It is characterized by being in the range of 0.01 to 100.

The method for purifying an acrylic acid ester derivative according to claim 6 of the present invention is the same as the method for purifying an acrylic acid ester derivative according to claim 4 or 5, wherein the detergent is an organic solvent (2) that separates from water into two layers. B) is further included, and
The organic solvent (B) has a solubility parameter of 10 or less.

The method for purifying an acrylic acid ester derivative according to claim 7 of the present invention is the same as the method for purifying an acrylic acid ester derivative according to claim 6, wherein the amount of the organic solvent (B) used relative to the acrylic acid ester derivative is The weight ratio is more than 0 and 100 or less.

According to the above constitution, the acrylic ester derivative containing the crosslinkable component as an impurity is washed with the detergent containing at least water to extract the acrylic ester derivative into the water layer, whereby The crosslinkable component can be separated and removed. Thereby, impurities can be reduced, and at the same time, there is no problem of gelation at the time of polymerization, copolymerization with other monomer can be carried out at an arbitrary ratio, and an acrylate derivative which can be utilized for various purposes can be obtained.

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS One embodiment of the present invention will be described below in detail. The acrylic ester derivative according to the present invention has the general formula (1)

[0020]

Embedded image

(In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or an organic residue, R ₃ represents an organic residue,
(n represents a positive number of 1 to 3 and m represents a positive number of 1 to 100)
And is obtained by, for example, adding a cyclic ether compound to the corresponding α-hydroxyalkyl acrylic acid ester by a known method.

The above acrylic ester derivative has the following formula:
The substituents represented by R ₁ and R ₂ are each independently composed of a hydrogen atom or an organic residue, the substituent represented by R ₃ is composed of an organic residue, and the repeating unit represented by n is 1 ~ Represents a positive number of 3 and the repeating unit represented by m is 1
It is a compound that represents a positive number of -100. And, a portion derived from the cyclic ether compound, that is, —CH ₂ (CHR
Repeating structure of oxyalkylene groups represented by _{2) n} O-has the following structure. That is, the substituent represented by R ₂ may be independently composed of a hydrogen atom or an organic residue for each oxyalkylene group, and these oxyalkylene groups are bonded to each other in a block or random manner. Good. Among these acrylic ester derivatives, compounds in which the repeating unit represented by m represents a positive number of 1 to 80 are preferable, and compounds in which a repeating number of 1 to 50 represents a positive number are more preferable.

As the acrylic ester derivative,
Specifically, for example, methyl-2- (2-hydroxyethoxy) methyl acrylate, ethyl-2- (2-hydroxyethoxy) methyl acrylate, butyl-2- (2-hydroxyethoxy) methyl acrylate, methyl-2- 〔2- (2-
Hydroxyethoxy) ethoxy] methyl acrylate,
Ethyl-2- [2- (2-hydroxyethoxy) ethoxy] methyl acrylate, butyl-2- [2- (2-hydroxyethoxy) ethoxy] methyl acrylate, methyl-2- (ω
-Hydroxypolyethyleneglycoxy) methyl acrylate, ethyl-2- (ω-hydroxypolyethyleneglycoxy) methyl acrylate, butyl-2- (ω-hydroxypolyethyleneglycoxy) methylacrylate, 2-ethylhexyl-2- (ω-hydroxypolyethylene Glyoxy) methyl acrylate and other α-hydroxyalkyl acrylate ethylene oxide adducts; methyl-2- (2-hydroxypropoxy) methyl acrylate,
Ethyl-2- (2-hydroxypropoxy) methyl acrylate, butyl-2- (2-hydroxypropoxy) methyl acrylate, methyl-2- [2- (2-hydroxypropoxy) propoxy] methyl acrylate, ethyl-2- [2
-(2-Hydroxypropoxy) propoxy] methyl acrylate, butyl-2- [2- (2-hydroxypropoxy) propoxy] methyl acrylate, methyl-2- (ω-hydroxypolypropyleneglycoxy) methyl acrylate, ethyl-2- ( ω-hydroxypolypropyleneglycoxy) methyl acrylate, butyl-2- (ω-hydroxypolypropyleneglycoxy) methyl acrylate, 2-
Propylene oxide adducts such as ethylhexyl-2- (ω-hydroxypolypropyleneglycoxy) methyl acrylate; alkylene oxides such as butylene oxide to α-hydroxymethyl acrylate, tetrahydrofuran compounds, allyl glycidyl ether, phenyl glycidyl ether, Examples thereof include adducts of alkyl glycidyl ether compounds such as epichlorohydrin. Among these acrylic acid ester derivatives, ethylene oxide adducts and propylene oxide adducts are particularly preferably used.

The above acrylic ester derivative can be easily homopolymerized or copolymerized with other polymerizable monomers in the presence of heat, ultraviolet rays, ionizing radiation, radical polymerization initiators and the like. Then, the acrylic acid ester derivative and the polymer thereof, like other compounds having a polymerizable vinyl group and a hydroxyl group in the same molecule, adhesion improver of the paint, urethane crosslinking monomer, melamine crosslinking monomer, paint,
Adhesives, surfactants, detergent builders, plasticizers, solid electrolytes, antistatic monomers, antifog agents, flocculants, dyeability improvers,
It can be suitably used as a fiber modifier, a fiber processing agent, a wood size stabilizer, and the like.

However, the above acrylic ester derivative contains a crosslinkable component as an impurity due to the side reaction during the reaction. When an acrylic acid ester derivative containing a crosslinkable component as an impurity is polymerized, a crosslinking reaction may occur and gelation may occur.

According to the purification method of the present invention, an acrylic acid ester derivative containing the above crosslinkable component, that is, an acrylic acid ester derivative before purification (hereinafter referred to as a crude acrylic acid ester derivative) is converted into an acrylic acid ester derivative. An organic solvent in which the solubility of the crosslinkable component is higher than the solubility (hereinafter,
By washing with the organic solvent (A), the crosslinkable component can be extracted from the acrylic ester derivative into the organic solvent (A) layer and removed.

The crosslinkable component to be removed in the present invention is a compound having two or more double bonds in the molecule, and has the general formula (2)

[0028]

[Chemical 6]

An ether dimer represented by the formula (wherein R ₁ represents a hydrogen atom or an organic residue and R ₃ represents an organic residue); general formula (3)

[0030]

Embedded image

(Wherein R ₁ represents a hydrogen atom or an organic residue, and R ₃ represents an organic residue); an acetal dimer; a hydroxyl group of an α-hydroxyalkyl acrylic acid ester or an acrylic acid ester derivative. A dimer (hereinafter referred to as an ester-type dimer) which is bound by an ester bond due to an ester exchange reaction between the ester group and the ester group is exemplified. As the ether dimer represented by the general formula (2) and the acetal dimer represented by the general formula (3), the substituent represented by R ₃ in the formula is mainly a methyl group, an ethyl group, a butyl group, Alternatively, a compound having an octyl group may be mentioned.

In the present invention, the organic solvent (A) used for washing the crude acrylic acid ester derivative is an organic solvent in which the solubility of the crosslinkable component is higher than the solubility of the acrylic acid ester derivative. The organic solvent (A) is preferably a compound having a solubility parameter of 8.5 or less, more preferably a compound having a solubility parameter of 7.0 to 8.3. If the solubility parameter is larger than 8.5, it is not preferable because only the crosslinkable component cannot be selectively dissolved.

The above solubility parameter [δ] (unit: (cal / c
m ³ ) ^1/2 ) is a measure of solubility,

[0034]

[Equation 1]

(In the formula, V represents a molar volume (cm ³ / mol),
ΔH represents the heat of vaporization (cal / mol), R represents the gas constant,
T represents absolute temperature (K)).

The organic solvent (A) is not particularly limited, but specifically, for example, hexane (
Solubility parameter 7.3: Hereinafter, in the exemplified compounds, the values in the parentheses () indicate solubility parameter values), and aliphatic hydrocarbons such as cyclohexane (8.2) and methylcyclohexane (7.8).

The amount of the organic solvent (A) used for washing the crude acrylic ester derivative is preferably 0.01 to 100, and 0.1 to 10 by weight ratio with respect to the crude acrylic ester derivative. Is more preferable.
If the amount of the organic solvent (A) used with respect to the crude acrylic acid ester derivative is less than 0.01 by weight, the crosslinkable component cannot be sufficiently removed, which is not preferable. On the other hand, if the amount of the organic solvent (A) used exceeds 100, the productivity is lowered, which is not preferable.

The washing method for washing the crude acrylic ester derivative is not particularly limited, and various conventionally known methods can be used. As the above-mentioned washing method, for example, an effective method such as stirring and line mixing may be used, and after standing to separate the two layers, an organic solvent (A) layer and an acrylic ester derivative layer which are crosslinkable component layers. By separating and, the crosslinkable component can be extracted and removed from the crude acrylic acid ester derivative.

When the removal of the above-mentioned crosslinkable component is not sufficient, the organic solvent (A) may be further added for washing. The number of times of washing is not particularly limited and may be repeated until the effect is sufficiently exhibited.

After removing the crosslinkable component, the obtained acrylic ester derivative can be used as it is for various purposes. However, the acrylic ester derivative may contain a small amount of the organic solvent (A) used for washing. Therefore, the residual organic solvent (A) may be removed after washing depending on the application.

The removing method for removing the organic solvent (A) is not particularly limited, and various conventionally known methods can be used. Examples of the removal method include a method by evaporation and distillation, a method of blowing a gas without danger of explosion, a method of water extraction, a method of separation by a column and the like. The organic solvent (A) used can be recovered and reused.

The acrylic ester derivative is
Since it contains a vinyl group in the molecule, it has the property of being easily polymerized. Therefore, it is preferable to add a polymerization inhibitor or molecular oxygen in order to suppress the polymerization of the vinyl group in the acrylic ester derivative at the time of washing or concentration for taking out the acrylic ester derivative.

Examples of the above-mentioned polymerization inhibitor include, but are not particularly limited to, hydroquinone, hydroquinone monomethyl ether, p-benzoquinone, t-butylcatechol, phenothiazine and the like. Only one kind of these polymerization inhibitors may be used, or two or more kinds thereof may be appropriately mixed and used. The amount of the polymerization inhibitor added is not particularly limited, but it is preferably used within the range of 0.001% by weight to 5% by weight with respect to the acrylic ester derivative.

As the molecular oxygen, for example, air can be used. In this case, the concentration may be performed while blowing air during the removal of the organic solvent (A), that is, while performing so-called bubbling. In order to sufficiently suppress the above polymerization, it is preferable to use a polymerization inhibitor in combination with molecular oxygen.

The pressure at the time of washing and at the time of removing the organic solvent (A) is not particularly limited and may be normal pressure (atmospheric pressure), reduced pressure or increased pressure.

As described above, the acrylic ester derivative containing a crosslinkable component as an impurity is used as the organic solvent (A).
The crosslinkable component can be extracted from the acrylic ester derivative into the organic solvent (A) layer and removed by washing with. Thereby, impurities can be reduced, and at the same time, there is no problem of gelation at the time of polymerization, copolymerization with other monomer can be carried out at an arbitrary ratio, and an acrylate derivative which can be utilized for various purposes can be obtained. Further, according to the above method, the organic solvent (A) can selectively dissolve the crosslinkable component, so that the crosslinkable component can be removed even from the water-insoluble acrylic acid ester derivative. it can.

According to another purification method of the present invention, an acrylate derivative containing the above-mentioned crosslinkable component, that is,
By washing the crude acrylic ester derivative with a detergent containing at least water, only the acrylic ester derivative can be extracted into the aqueous layer. Thereby, the crude acrylic acid ester derivative and the crosslinkable component can be separated, and the crosslinkable component can be removed from the acrylic acid ester derivative.

In the present invention, the cleaning agent used for cleaning the crude acrylic acid ester derivative is a cleaning agent containing at least water, and water or an organic solvent that separates water and water into two layers (hereinafter, organic solvent). A mixed solution of the solvent (B) may be used.

The amount of water used for washing the above crude acrylic ester derivative, that is, the amount of water contained in the above-mentioned detergent, is the same as that of the detergent even when only water is used as the detergent. Even when a mixed solution of water and an organic solvent (B) that separates water into two layers is used, a weight ratio of 0.01 to 100 to the crude acrylic ester derivative is used.
Is preferable, and the range of 0.1 to 50 is more preferable. If the amount of water used relative to the crude acrylic acid ester derivative is less than 0.01 by weight, the yield of the resulting acrylic acid ester derivative decreases, which is not preferable.
On the other hand, if the amount of water used relative to the crude acrylic acid ester derivative is more than 100 by weight, the productivity is lowered, which is not preferable.

The organic solvent (B) is not particularly limited as long as it is an organic solvent which is insoluble in water, but is preferably an organic solvent having a solubility parameter of 10 or less and having a solubility parameter in the range of 7.0 to 9.5. Solvents within are more preferred. When the solubility parameter exceeds 10, it takes time to separate the two layers from water and productivity is lowered, which is not preferable.

The organic solvent having a solubility parameter of 10 or less is not particularly limited, but specifically,
For example, hexane (solubility parameter 7.3: in the following compounds, the values in the parentheses () indicate solubility parameter values), aliphatic hydrocarbons such as cyclohexane (8.2) and methylcyclohexane (7.8); benzene (9.2), Aromatic hydrocarbons such as toluene (8.9) and xylene (8.8); Acetates such as ethyl acetate (9.1) and butyl acetate (8.5); Propionates such as ethyl propionate (8.4); Methyl ethyl ketone (9.3), methyl Examples thereof include ketones such as propyl ketone (8.7) and methyl isobutyl ketone (8.4). Among these organic solvents, solvents having a solubility parameter of 8.5 or more, for example, aromatic hydrocarbons such as benzene, toluene and xylene, and acetic acid esters such as ethyl acetate and butyl acetate are particularly preferable because of good solubility of the acrylate derivative. . When the cleaning agent contains the organic solvent in addition to water, there is an advantage that the liquid separating property is improved and the productivity is improved.

The amount of the organic solvent (B) used in washing the crude acrylic acid ester derivative, that is, the case where a mixed solution of water and an organic solvent (B) for separating water into two layers is used as the detergent. In addition, the amount of the organic solvent (B) contained in the detergent is preferably more than 0 and 100 or less, and more preferably more than 0 and 10 or less by weight ratio with respect to the crude acrylic acid ester derivative. The amount of the organic solvent (B) used with respect to the crude acrylic acid ester derivative is in a weight ratio.
When it exceeds 100, the productivity is lowered, which is not preferable.

The washing method for washing the crude acrylic acid ester derivative with the detergent is not particularly limited, and various conventionally known methods can be used. As the above-mentioned cleaning method, for example, an effective method such as stirring or line mixing may be used.
After the layers are separated, the aqueous layer containing the acrylic acid ester derivative layer and the crosslinkable component layer are separated to remove the crosslinkable component from the crude acrylic acid ester derivative.

When the removal of the above-mentioned crosslinkable components is not sufficient, the above cleaning agent may be further added for cleaning.
The number of times of washing is not particularly limited and may be repeated until the effect is sufficiently exhibited.

After removing the crosslinkable component, the aqueous solution of the acrylic ester derivative obtained can be used as it is for various purposes. However, the aqueous solution of the acrylic ester derivative may contain a small amount of the organic solvent (B) used for washing. Therefore, after cleaning, the remaining organic solvent (B) may be removed depending on the application.

The method for removing the organic solvent (B) is not particularly limited, and various conventionally known methods can be used. Examples of the removal method include a method by evaporation and distillation, and a method of blowing a gas that has no risk of explosion.

Further, if an acrylic ester derivative which is not an aqueous solution is desired, water can be removed.
The method for removing water is not particularly limited,
For example, it is possible to use a method of evaporating water or adding and evaporating by adding another organic solvent which is azeotropic with water to lower the boiling point. Each organic solvent used can be recovered and reused.

Further, the acrylic ester derivative is
Since it contains a vinyl group in the molecule, it has the property of being easily polymerized. Therefore, it is preferable to add a polymerization inhibitor or molecular oxygen in order to suppress the polymerization of the vinyl group in the acrylic ester derivative at the time of washing or concentration for taking out the acrylic ester derivative.

As the above-mentioned polymerization inhibitor and molecular oxygen, the same compounds as those exemplified above can be used.

The pressure during washing and when removing the organic solvent (B) and water is not particularly limited, and may be normal pressure (atmospheric pressure), reduced pressure, or increased pressure. Good.

As described above, the acrylic acid ester derivative containing the crosslinkable component as an impurity is washed with the detergent containing at least water to extract the acrylic acid ester derivative into the aqueous layer. Separating the ingredients,
Can be removed. This makes it possible to reduce impurities, and there is no problem of gelation during polymerization,
It is possible to obtain an acrylic acid ester derivative which can be copolymerized with other monomers at an arbitrary ratio and can be used for various purposes. Further, by treating the water-soluble acrylic acid ester derivative using the above-mentioned purification method, the cost for purification can be suppressed and the desired acrylic acid ester derivative can be obtained at low cost.

By the way, in the acrylic acid ester derivative after the above-mentioned purification treatment, polyalkylene glycols such as polyethylene glycol and polyalkylene glycol monoalkyl ethers are present as impurities other than the above-mentioned crosslinkable component. ing. All of these impurities are non-polymerizable alcohols. When the acrylic ester derivative containing these non-polymerizable alcohols is reacted with, for example, an isocyanate compound or the like, the non-polymerizable alcohol also reacts with the isocyanate compound. It is desirable to increase the addition amount.

Therefore, by removing these non-polymerizable alcohols depending on the application, it is possible to obtain an acrylic ester derivative having higher purity and capable of efficiently performing urethane crosslinking and melamine crosslinking.

When the number of moles of cyclic ether addition is small among the acrylic acid ester derivatives, the non-polymerizable alcohol is easily separated and removed from the acrylic acid ester derivative by washing with a detergent containing at least water. be able to. When the number of moles of the cyclic ether added is large, the acrylic acid ester derivative is also easily dissolved in water, which makes separation difficult. Therefore, among the acrylic acid ester derivatives containing the non-polymerizable alcohol, by washing the acrylic acid ester derivative in which the repeating unit represented by m is a positive number of 1 to 10 with a detergent containing at least water. The non-polymerizable alcohol can be extracted from the acrylic acid ester derivative by extracting the non-polymerizable alcohol into the aqueous layer.

The cleaning agent used for removing the non-polymerizable alcohol is a cleaning agent containing at least water, and is water or an organic solvent that separates water and water into two layers (hereinafter, organic solvent (C )) Can be used as a mixed solution.

The amount of water used for removing the non-polymerizable alcohol, that is, the amount of water contained in the cleaning agent is the same as the cleaning agent even when only water is used as the cleaning agent. Even when a mixed solution of water and an organic solvent (C) that separates water and two layers is used, the weight ratio with respect to the acrylic ester derivative containing the non-polymerizable alcohol is preferably in the range of 0.001 to 100, 0.01 ~
The range of 10 is more preferable. If the amount of water used relative to the acrylic ester derivative is less than 0.001 in weight ratio, the removal efficiency of the non-polymerizable alcohol becomes poor, which is not preferable. On the other hand, if the amount of water used relative to the acrylic ester derivative is more than 100 by weight, the yield and productivity of the finally obtained acrylic ester derivative will decrease, which is not preferable.

The organic solvent (C) is not particularly limited as long as it is an organic solvent which is insoluble in water, but a solvent having a solubility parameter of 7 or more is preferable, and a solvent having a solubility parameter of 8 or more is preferable. A solvent having a solubility parameter of 8.5 or more is particularly preferable. If the dissolution parameter is less than 7, the flammability is high and the handling becomes complicated, which is not preferable.

The organic solvent having a solubility parameter of 7 or more is not particularly limited, but specifically,
For example, hexane (solubility parameter 7.3: in the following compounds, the values in the parentheses () indicate solubility parameter values), aliphatic hydrocarbons such as cyclohexane (8.2) and methylcyclohexane (7.8); benzene (9.2), Aromatic hydrocarbons such as toluene (8.9) and xylene (8.8); Acetates such as ethyl acetate (9.1) and butyl acetate (8.5); Propionates such as ethyl propionate (8.4); Methyl ethyl ketone (9.3), methyl Examples include ketones such as propyl ketone (8.7) and methyl isobutyl ketone (8.4); higher alcohols such as n-heptanol (10.6) and n-octanol (10.3). Among these, the dissolution parameter is 8.
Five or more solvents, for example, aromatic hydrocarbons such as benzene, toluene and xylene; and acetic acid esters such as ethyl acetate and butyl acetate are preferable because of good solubility of the acrylate derivative. When the cleaning agent contains the organic solvent in addition to water, there is an advantage that the liquid separating property is improved and the productivity is improved.

The amount of the organic solvent (C), that is, the amount of the organic solvent (C) contained in the detergent when a mixed solution of water and the organic solvent (C) is used as the detergent is The weight ratio to the acrylic ester derivative containing the non-polymerizable alcohol is preferably more than 0 and 100 or less,
It is more preferably more than 0 and 10 or less. The amount of the organic solvent (C) used relative to the acrylic ester derivative is a weight ratio.
When it exceeds 100, the productivity is lowered, which is not preferable.

The washing method for washing the acrylic ester derivative containing the non-polymerizable alcohol is not particularly limited, and the same washing method as described above can be used. However, in this case, since the non-polymerizable alcohol is transferred to the aqueous layer, for example, after stirring or line mixing, the two layers are allowed to stand by separating, and the aqueous layer containing the non-polymerizable alcohol and the acrylic acid are separated. By separating the ester derivative layer (organic solvent layer), the non-polymerizable alcohol can be removed from the acrylic ester derivative.

Also in this case, the number of times of washing is not particularly limited, and the washing may be repeated until the effect is sufficiently exhibited. The acrylic ester derivative finally obtained after removing the non-polymerizable alcohol can be used as it is for various purposes. However, the acrylic acid ester derivative may contain a small amount of the organic solvent (C) used for washing and water. Therefore, the residual organic solvent (C) and water may be removed after washing depending on the application. The method for removing the organic solvent (C) is not particularly limited, and for example, a method similar to the above-described method such as a method by evaporation or distillation or a method of blowing a gas without danger of explosion is used. be able to. The used organic solvent (C) can be recovered and reused.

The order of removing the impurities is not particularly limited, and the non-polymerizable alcohol may be removed after removing the crosslinkable component, or after the non-polymerizable alcohol is removed first. Alternatively, the crosslinkable component may be removed. Further, if each organic solvent and water can be used in common in each washing step, it is possible to proceed to the next step without being removed after each step.

The acrylic acid ester derivative purified by the above-mentioned purification method has high quality and can be suitably used for the above various uses.

[0074]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited thereto.

First, a production example of the acrylic ester derivative represented by the general formula (1) is shown below. [Production Example 1] In a 1000 ml pressure-resistant reaction vessel equipped with a thermometer, a gas blowing tube, and a stirrer, 130 g of ethyl-α-hydroxymethyl acrylate as an acrylic acid ester, 100 g of toluene as a solvent, and a catalyst as a catalyst. 1.4 g of boron trifluoride ethyl ether complex and 0.065 g of hydroquinone as a polymerization inhibitor were charged and stirred. Next, after blowing nitrogen gas as an inert gas into the above reaction vessel so as to have a pressure of 2.5 kg / cm ² ,
While maintaining the temperature in the reaction vessel within the range of 35 ° C to 45 ° C, 462 g of ethylene oxide as a cyclic ether compound
Was gradually pressed into the reaction solution.

After completion of the press-fitting, the reaction solution was stirred at 50 ° C. for 2 hours to complete the reaction. After the completion of the reaction, the temperature in the vessel was raised to 40 ° C. and the pressure was reduced to 100 mmHg to remove unreacted ethylene oxide. Then, add 3 g of magnesium oxide as an adsorbent to the above reaction solution.
Was added, and the mixture was stirred at 50 ° C. for 2 hours to adsorb the boron trifluoride ethyl ether complex in the solution to magnesium oxide to form an insoluble matter. After that, the reaction solution was suction-filtered to remove the insoluble matter. Then, the obtained filtrate was transferred to a rotary evaporator, and 40 mmHg, 70
Toluene was removed at ℃ to obtain 568 g of a pale yellow transparent liquid as a reaction product, that is, a crude acrylic ester derivative.

The hydroxyl value of the crude acrylic acid ester derivative measured by a predetermined method was 96.9 mgKOH / g, and from this result, 10.2 mol of ethylene oxide was added to 1 mol of ethyl-α-hydroxymethyl acrylate. I understood.

[Production Example 2] Ethyl-α-hydroxymethyl acrylate 130 was placed in a 1000 ml reaction vessel equipped with a thermometer, a gas blowing tube, a dropping device and a stirring device.
g, 1.4 g of tungstophosphoric acid as a catalyst, and 0.065 g of hydroquinone were charged and stirred. On the other hand, propylene oxide 3 as a cyclic ether compound was added to the dropping device.
19g was put. Next, air was blown into the above reaction solution and propylene oxide in the dropping apparatus was gradually added dropwise to the reaction solution while maintaining the temperature in the reaction vessel within the range of 45 ° C to 55 ° C.

After completion of the dropping, the reaction solution was stirred at 50 ° C. for 2 hours to complete the reaction. After the reaction was completed, the temperature inside the container was raised to 70 ° C and the temperature was 100 mmHg.
The pressure was reduced to 2, and unreacted propylene oxide was removed over 2 hours. Further, 3 g of magnesium oxide was added to the reaction solution, and the mixture was stirred at 50 ° C. for 2 hours to adsorb tungstophosphoric acid in the solution to the magnesium oxide to form an insoluble matter. Then, the reaction solution was suction filtered to remove the insoluble matter, and 413 g of a pale yellow transparent liquid was added as a reaction product,
That is, it was obtained as a crude acrylic acid ester derivative.

The hydroxyl value of the crude acrylic ester derivative measured by a predetermined method was 126.6 mg KOH / g, and from this result, 5.4 mol of propylene oxide was added per mol of ethyl-α-hydroxymethyl acrylate. I found out that

Example 1 100 g of the crude acrylic acid ester derivative obtained in Production Example 1 and 50 g of cyclohexane were placed in a 500 ml separating funnel. Next, the above separating funnel was shaken and mixed 10 times, and then allowed to stand at room temperature. After standing still, the solution in the separating funnel was immediately separated into two layers. Then, after 30 minutes, the lower acrylic acid ester derivative layer was extracted. Then, the acrylic ester derivative layer was transferred to a rotary evaporator, and cyclohexane was removed at 40 mmHg and 50 ° C. to obtain 86 g of a pale yellow transparent liquid. The components of the obtained pale yellow transparent liquid were analyzed using liquid chromatography.

Further, to the test tube, 10.0 g of the above pale yellow transparent liquid in terms of acrylic acid ester derivative and 0.03 g of 2,2-azobisisobutyronitrile as a polymerization initiator were added, and the atmosphere was replaced with nitrogen. . Then, tightly stopper the test tube, and
The acrylic ester derivative was polymerized while maintaining the temperature at 0 ° C., and it was confirmed whether gelation occurred during the polymerization. The results of analysis by the above liquid chromatography and the results of the polymerization test are shown together in Table 1.

Example 2 In a 500 ml separating funnel, 100 g of the crude acrylic acid ester derivative obtained in Production Example 1 and water were added.
100 g and 10 g of toluene were added. Next, the above separating funnel was shaken and mixed 10 times, and then allowed to stand at room temperature. After standing still, the solution in the separating funnel was immediately separated into two layers. Then, after 30 minutes, the lower aqueous layer containing the acrylic acid ester derivative was extracted. Then, the solution extracted from this separating funnel, that is, the acrylic ester derivative layer was transferred to a rotary evaporator, and water and toluene were removed at 40 mmHg and 70 ° C. to obtain a pale yellow transparent 80% by weight aqueous solution.
108 g was obtained. The components of the obtained aqueous solution were analyzed using liquid chromatography.

Further, the above aqueous solution was sampled in a test tube so as to be 10.0 g in terms of acrylic acid ester derivative, and diluted with water to a monomer concentration of 40% by weight. Then, in this test tube, further ammonium persulfate as a polymerization initiator 0.
3 g and 0.15 g of sodium hydrogen sulfite were added, and the atmosphere was replaced with nitrogen. Next, the test tube was sealed, and the acrylic ester derivative was polymerized while maintaining the temperature at 50 ° C., and it was confirmed whether gelation occurred during the polymerization. The results of the above liquid chromatography analysis and the results of the polymerization test are summarized in Table 1.
Shown in

Example 3 In a 500 ml separating funnel, 100 g of the crude acrylic acid ester derivative obtained in Production Example 1 and water were added.
200 g and 10 g of ethyl acetate were added. Next, the above separating funnel was shaken and mixed 10 times, and then allowed to stand at room temperature. After standing still, the solution in the separating funnel was immediately separated into two layers. Then, after a lapse of 30 minutes, the lower aqueous layer containing the acrylic ester derivative was extracted. Then, the solution extracted from this separating funnel, that is, the acrylic ester derivative layer was transferred to a rotary evaporator, and water and ethyl acetate were removed at 40 mmHg and 70 ° C. to obtain 108 g of a pale yellow transparent 80 wt% aqueous solution. . The components of the obtained aqueous solution were analyzed using liquid chromatography. Example 2
The same polymerization test as above was conducted to confirm the presence or absence of gelation during polymerization. Analysis results by the above liquid chromatography,
The results of the polymerization test are shown together in Table 1.

Comparative Example 1 The components of the crude acrylic acid ester derivative obtained in Production Example 1 were analyzed by liquid chromatography. Further, the same polymerization test as in Example 1 was performed to confirm the presence or absence of gelation during polymerization. The results of analysis by the above liquid chromatography and the results of the polymerization test are shown together in Table 1.

Comparative Example 2 100 g of the crude acrylic acid ester derivative obtained in Production Example 1 and 50 g of toluene were placed in a 500 ml separating funnel. Then, use the above separating funnel for 10
After shaking and shaking, the mixture was left standing at room temperature. However, the inside of the separating funnel had a uniform layer, and there was no appearance of separation.

Example 4 100 g of the crude acrylic acid ester derivative obtained in Production Example 2 and 50 g of cyclohexane were placed in a 1000 ml separating funnel. Next, the above separating funnel was shaken and mixed 10 times, and then allowed to stand at room temperature. After standing still, the solution in the separating funnel was immediately separated into two layers. Then, after 30 minutes, the lower acrylic acid ester derivative layer was extracted.

Then, the acrylic ester derivative layer was transferred to a 1000 ml separating funnel, and 300 g of water and toluene were added.
After adding 10 g and shaking and mixing 10 times, the mixture was allowed to stand at room temperature. After standing still, the solution in the separating funnel was immediately separated into two layers. Then, after 30 minutes, the lower aqueous layer containing the acrylic acid ester derivative was extracted. Then, the solution extracted from this separating funnel, that is, the acrylic ester derivative layer was transferred to a rotary evaporator, 40mmHg, 70 ℃,
Water, toluene, and cyclohexane were removed to obtain 83 g of a pale yellow transparent 80% by weight aqueous solution. The components of the obtained aqueous solution were analyzed using liquid chromatography. Further, the same polymerization test as in Example 2 was performed to confirm the presence or absence of gelation during polymerization. The results of analysis by the above liquid chromatography and the results of the polymerization test are shown together in Table 1.

[Comparative Example 3] The components of the crude acrylic acid ester derivative obtained in Production Example 2 were analyzed by liquid chromatography. Further, the same polymerization test as in Example 1 was performed to confirm the presence or absence of gelation during polymerization. The results of analysis by the above liquid chromatography and the results of the polymerization test are shown together in Table 1.

[0091]

[Table 1]

As is clear from the results shown in Table 1 above, the crude acrylic acid ester derivative was purified by the method according to this example to obtain the ether dimer and acetal dimer contained in the crude acrylic acid ester derivative. It is possible to remove a crosslinkable component such as an ester type dimer and prevent gelation during polymerization.

[0093]

As described above, the method for purifying an acrylic ester derivative according to the first aspect of the present invention comprises the general formula (1) containing as an impurity a crosslinkable component having two or more double bonds in the molecule. )

[0094]

Embedded image

(In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or an organic residue, R ₃ represents an organic residue,
(n represents a positive number of 1 to 3 and m represents a positive number of 1 to 100)
The acrylic ester derivative represented by is washed with an organic solvent (A) in which the solubility of the crosslinkable component is higher than the solubility of the acrylic ester derivative.

As described above, the method for purifying an acrylic acid ester derivative according to the second aspect of the present invention is such that, in the method for purifying an acrylic acid ester derivative according to the first aspect, the solubility parameter of the organic solvent (A) is The configuration is 8.5 or less.

As described above, the method for purifying an acrylic acid ester derivative according to the present invention is the same as the method for purifying an acrylic acid ester derivative according to claim 1, wherein the organic solvent for the acrylic acid ester derivative is The amount of (A) used is in the range of 0.01 to 100 by weight.

According to the above constitution, the acrylic ester derivative containing the crosslinkable component as an impurity is washed with the organic solvent (A) to remove the crosslinkable component from the acrylic ester derivative into the organic solvent (A). ) Extract into layers,
Can be removed. This makes it possible to reduce impurities, and there is no problem of gelation during polymerization,
It is possible to obtain an acrylate derivative that can be copolymerized with other monomers at an arbitrary ratio and can be used for various purposes.

As described above, the method for purifying an acrylic acid ester derivative according to claim 4 of the present invention comprises, as an impurity, the general formula (1) containing a crosslinkable component having two or more double bonds in the molecule.

[0100]

Embedded image

(In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or an organic residue, R ₃ represents an organic residue,
(n represents a positive number of 1 to 3 and m represents a positive number of 1 to 100)
The acrylic ester derivative represented by is washed with a detergent containing at least water.

As described above, the method for purifying an acrylic acid ester derivative according to the fifth aspect of the present invention is the same as the method for purifying an acrylic acid ester derivative according to the fourth aspect. Is in the range of 0.01 to 100 by weight.

The method for purifying an acrylic acid ester derivative according to claim 6 of the present invention is, as described above, the method for purifying an acrylic acid ester derivative according to claim 4 or 5, wherein the cleaning agent is water and two layers. The organic solvent (B) to be separated is further included, and the solubility parameter of the organic solvent (B) is 10 or less.

As described above, the method for purifying an acrylic acid ester derivative according to the present invention is the same as the method for purifying an acrylic acid ester derivative according to claim 6, wherein the organic solvent (B The amount used of () is more than 0 and 100 or less by weight.

According to the above constitution, the acrylic ester derivative containing the crosslinkable component as an impurity is washed with the detergent containing at least water to extract the acrylic ester derivative into the aqueous layer, whereby The crosslinkable component can be separated and removed. With this, it is possible to reduce impurities and to obtain an acrylic acid ester derivative which can be copolymerized with other monomers at an arbitrary ratio and can be used for various purposes without causing a problem of gelation during polymerization. Produce an effect.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Yuichi Kita 992, Nishioki, Okihama-shi, Aboshi-ku, Himeji-shi, Hyogo

Claims (7)

[Claims] 1. A general formula (1) containing a crosslinkable component having two or more double bonds in the molecule as an impurity. (In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or an organic residue, R ₃ represents an organic residue, n represents a positive number of 1 to 3, and m represents a positive number of 1 to 100. The acrylic ester derivative represented by the formula (3) is washed with an organic solvent (A) in which the solubility of the crosslinkable component is higher than the solubility of the acrylic ester derivative. Purification method. 2. The solubility parameter of the organic solvent (A) is
The method for purifying an acrylic acid ester derivative according to claim 1, wherein the purification method is 8.5 or less. 3. The purification of the acrylic ester derivative according to claim 1 or 2, wherein the amount of the organic solvent (A) used with respect to the acrylic ester derivative is in the range of 0.01 to 100 in weight ratio. Law. 4. A compound represented by the general formula (1): wherein a crosslinkable component having two or more double bonds in the molecule is contained as an impurity. (In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or an organic residue, R ₃ represents an organic residue, n represents a positive number of 1 to 3, and m represents a positive number of 1 to 100. A method for purifying an acrylic acid ester derivative, which comprises washing the acrylic acid ester derivative represented by a number) with a detergent containing at least water. 5. The method for purifying an acrylic acid ester derivative according to claim 4, wherein the amount of water used with respect to the acrylic acid ester derivative is in the range of 0.01 to 100 in weight ratio. 6. The cleaning agent further contains an organic solvent (B) that separates from water into two layers, and the solubility parameter of the organic solvent (B) is 10 or less. A method for purifying an acrylic acid ester derivative as described. 7. The method for purifying an acrylic ester derivative according to claim 6, wherein the amount of the organic solvent (B) used with respect to the acrylic ester derivative is more than 0 and 100 or less by weight.