JP2003064027A - Method for producing methacrylic acid ester having cyclic skeleton - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a high quality methacrylic acid ester having a cyclic skeleton and less impurity content, in high efficiency. SOLUTION: This method for producing a methacrylic acid ester having a cyclic skeleton is a method for producing a corresponding methacrylic acid ester by performing a reaction of an alcohol having a cyclic skeleton with methacrylic acid halide, and comprises a process of adding water to a reaction mixture of the alcohol having the cyclic skeleton and methacrylic acid halide and heat-treating. The method of production may further comprise a process of adding a 1-4C aliphatic alcohol to the reaction mixture of the alcohol having the cyclic skeleton and methacrylic acid halide and heat-treating, and also comprise a process of washing the reaction mixture of the alcohol having the cyclic skeleton and methacrylic acid halide with an aqueous acid solution.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a methacrylic acid ester having a cyclic skeleton, which is useful as a raw material monomer for a resist resin.

[0002]

2. Description of the Related Art Methacrylic acid esters having an alicyclic hydrocarbon skeleton such as adamantane or a cyclic skeleton such as a lactone skeleton exhibit a function of imparting plasma etching resistance and adhesion to a substrate when polymerized. ,
It is drawing attention as a monomer raw material for photoresist resins.

As a method for producing such a methacrylic acid ester having a cyclic skeleton, there is known a method of producing an methacrylic acid ester by reacting an alcohol having a cyclic skeleton with a methacrylic acid halide in the presence of a base. ing. In this method, the point that the reaction proceeds smoothly under mild conditions, and the reaction system is generally neutral or basic, so that the methacrylic acid ester generated has an acid leaving group capable of leaving with an acid. Even if it is a compound contained, it is an advantageous method in that the acid-cleavable group does not decompose / eliminate during the reaction.

However, the methacrylic acid halide used in the above-mentioned method, regardless of its production method, undergoes an intermolecular hetero Diels-Alder reaction over time during storage, resulting in a corresponding dimer represented by the following formula. (Methacrylic acid halide dimer) is produced.

[Chemical 1] (In the formula, X represents a halogen atom)

For example, when methacrylic acid chloride is stored in a cool and dark place, the content of dimer is 10% by weight in 3 months.
Increase. Therefore, usually 5% by weight or more of dimer is present in the methacrylic acid halide, and some of them are commercially available products containing 50% by weight or more of dimer. When a methacrylic acid halide containing such a dimer is used in a reaction with an alcohol having a cyclic skeleton, the dimer and a by-product derived from the dimer are present in the reaction mixture. In addition, methacrylic acid anhydride is often produced as a by-product during the reaction. Furthermore, the base used as the acid scavenger may remain in the reaction mixture. These by-products and the like cannot be sufficiently removed by simply washing the reaction mixture with water or by distillation under general conditions, and are often mixed in the product of the target compound. When a polymer obtained by subjecting a methacrylic acid ester containing a large amount of such by-products to polymerization is used as a photoresist resin or the like, there arises a problem that desired performance is not sufficiently exhibited. For example, when a polymer obtained by polymerizing a methacrylic acid ester containing a large amount of a base used as an acid scavenger is used as a photoresist resin, the acid generated by exposure in lithography is trapped by the base, There is a problem in that the acid-eliminating group of is not smoothly eliminated.

[0006]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a method for efficiently producing a methacrylic acid ester having a high-quality cyclic skeleton with a low content of impurities. Another object of the present invention is to provide a methacrylic acid ester having a high-quality cyclic skeleton with a low content of impurities.

[0007]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that a reaction mixture of an alcohol having a cyclic skeleton and a methacrylic acid halide is subjected to a specific treatment. The present invention has been completed by finding that a methacrylic acid ester having a cyclic skeleton with a small amount of impurities and excellent quality can be efficiently produced.

That is, the present invention is a method for producing a corresponding methacrylic acid ester by reacting an alcohol having a cyclic skeleton with a methacrylic acid halide, which comprises reacting an alcohol having a cyclic skeleton with a methacrylic acid halide. Provided is a method for producing a methacrylic acid ester having a cyclic skeleton, which includes the step of adding water to a mixture and performing heat treatment.

This production method has 1 to 1 carbon atoms in a reaction mixture of an alcohol having a cyclic skeleton and a methacrylic acid halide.
It may further include the step of adding the aliphatic alcohol of 4 and heat treatment. Further, this production method may further include a step of washing a reaction mixture of an alcohol having a cyclic skeleton and a methacrylic acid halide with an aqueous acid solution.

The alcohol having a cyclic skeleton includes, for example, an alcohol having a polycyclic alicyclic skeleton having 7 to 20 carbon atoms and an alcohol having a lactone skeleton.
The alcohol having a cyclic skeleton may be an alcohol having an adamantane skeleton.

The present invention also provides a methacrylic acid ester having a cyclic skeleton produced by reacting an alcohol having a cyclic skeleton with a methacrylic acid halide, wherein a methacrylic acid halide dimer as an impurity and methacrylic acid anhydride are used. Provided is a methacrylic acid ester having a cyclic skeleton with a total content of 0.5% by weight or less.

The present invention further relates to a methacrylic acid ester having a cyclic skeleton produced by reacting an alcohol having a cyclic skeleton with a methacrylic acid halide in the presence of a base, and a methacrylic acid halide dimer as an impurity. And methacrylic anhydride, and the total content of the base is 0.
A methacrylic acid ester having a cyclic skeleton of 5% by weight or less is provided.

Further, the present invention is a methacrylic acid ester having a cyclic skeleton produced by reacting an alcohol having a cyclic skeleton with a methacrylic acid halide in the presence of an organic base, wherein an organic base as an impurity is used. A methacrylic acid ester having a cyclic skeleton having a total content of 50 ppm by weight or less is provided.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION In an alcohol having a cyclic skeleton, the cyclic skeleton is not particularly limited.
An aromatic or non-aromatic carbocyclic or heterocyclic ring having about 20 members can be mentioned. These rings may be monocyclic or polycyclic such as condensed ring and bridged ring. As a typical cyclic skeleton, for example, an adamantane ring has 7 to 20 carbon atoms.
Degree polycyclic alicyclic skeleton; 3-oxatricyclo [4.
Lactone skeletons such as 3.1.1 ^4,8 ] undecan-2-one ring, 3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one ring, and γ-butyrolactone ring Can be mentioned. The cyclic skeleton may be directly bonded to the alcoholic hydroxyl group, or may be bonded via a linking group such as a linear or branched alkylene group.

As typical alcohols having a cyclic skeleton, the following formulas (1a), (1b), (1c), (1d), (1e),
Examples thereof include alcohols having a cyclic skeleton represented by (1f) or (1g).

[Chemical 2] (In the formula, R ¹ is a substituent bonded to the ring and represents a methyl group, a hydroxyl group or a methacryloyloxy group, R ² represents a hydrogen atom, a methyl group or an ethyl group, and R ³
Represents a methyl group or an ethyl group. n is an integer of 0 to 3, m
Represents an integer of 0 to 5. An oxo group may be bonded to the ring shown in the formula)

In the 1-adamantanols represented by the above formula (1a), the n R ^1's may be the same or different. R ¹ is often bonded to a carbon atom at the bridgehead position.

As typical 1-adamantanols represented by the formula (1a), for example, 1-adamantanol,
3,5-Dimethyl-1-adamantanol, 1,3-adamantanediol, 5,7-dimethyl-1,3-adamantanediol, 3-methacryloyloxy-1-adamantanol, 3-methacryloyloxy-5,7-
Examples thereof include dimethyl-1-adamantanol and 4-oxo-1-adamantanol.

In the adamantanemethanols represented by the above formula (1b), n R ^{1 s} may be the same group or different from each other. R ¹ is often bonded to a carbon atom at the bridgehead position.

Typical examples of the adamantanemethanols represented by the formula (1b) include, for example, α, α-dimethyl-
1-adamantanemethanol, α, α, 3,5-tetramethyl-1-adamantanemethanol, 3-hydroxy-α, α-dimethyl-1-adamantanemethanol, 3
-Methacryloyloxy-α, α-dimethyl-1-adamantanemethanol and the like can be mentioned.

In the 2-adamantanols represented by the above formula (1c), n R ^{1 s} may be the same group or different from each other. R ¹ is often bonded to a carbon atom at the bridgehead position. As a typical example of 2-adamantanols represented by the formula (1c), for example,
2-Methyl-2-adamantanol, 2-ethyl-2-
Examples thereof include adamantanol and 2,5,7-trimethyl-2-adamantanol.

6-hydroxy-represented by the above formula (1d)
3-Oxatricyclo [4.3.1.1 ^4,8 ] undecane-2-ones (= 1-hydroxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecane-5- On)
In the above, n R ^{1 s} may be the same group or different from each other. R ¹ is often bonded to a carbon atom at the bridgehead position.

6-hydroxy-3-represented by the formula (1d)
Oxatricyclo [4.3.1.1 ^4,8] Undecane
Typical examples of 2-ones include 6-hydroxy.
Ci-3-oxatricyclo [4.3.1.1^4,8] Eun
Decan-2-one, 6,8-dihydroxy-3-oxa
Tricyclo [4.3.1.1^4,8] Undecan-2-O
And the like.

6-hydroxy-3-represented by the formula (1d)
Oxatricyclo [4.3.1.1 ^4,8] Undecane
2-ones are, for example, 1-hydroxy-4-adaman
The perones such as m-chloroperbenzoic acid are allowed to act on the tanones.
Can be obtained by This reaction is
It can be carried out according to the Earbilger reaction.

In the 6-hydroxymethyl-3-oxatricyclo [4.3.1.1 ^4,8 ] undecan-2-ones represented by the above formula (1e), n R ^1's are the same. The groups may be different groups or groups different from each other. R
¹ is often bonded to a carbon atom at the bridgehead position.

As a typical example of 6-hydroxymethyl-3-oxatricyclo [4.3.1.1 ^4,8 ] undecan-2-one represented by the formula (1e), for example, 6-
(1-hydroxy-1-methylethyl) -3-oxatricyclo [4.3.1.1 ^{4, 8]} undecane-2-one, 8-hydroxy-6- (1-hydroxy-1-methylethyl) -3-Oxatricyclo [4.3.1.1
^4,8 ] Undecan-2-one and the like can be mentioned.

5-hydroxy-represented by the above formula (1f)
2-oxo-3-oxatricyclo [4.2.1.0]
^{In the 4,8} ] nonane, n R ^{1 s} may be the same group or different from each other. R ¹ is often bonded to a carbon atom at the bridgehead position.

5-hydroxy-3-represented by formula (1f)
Oxatricyclo [4.2.1.0] ^4,8] Nonan-2-
As a typical example of ones, 5-hydroxy-3-oxy
Satricyclo [4.2.1.0]^4,8] Nonan-2-on
And so on.

Hydroxy-γ-represented by the above formula (1g)
In butyrolactones, m is preferably about 0 to 3. Typical examples of the hydroxy-γ-butyrolactone represented by the formula (1g) include, for example, β-hydroxy-γ-butyrolactone, β-hydroxy-α, α-dimethyl-γ-butyrolactone, β-hydroxy-γ. , Γ
-Dimethyl-γ-butyrolactone, β-hydroxy-
β such as α, α, β-trimethyl-γ-butyrolactone, β-hydroxy-β, γ, γ-trimethyl-γ-butyrolactone, β-hydroxy-α, α, β, γ, γ-pentamethyl-γ-butyrolactone -Hydroxy-γ-butyrolactone; α-hydroxy-γ-butyrolactone, α-hydroxy-α-methyl-γ-butyrolactone, α-hydroxy-β, β-dimethyl-γ-butyrolactone, α-hydroxy-α, β, β-trimethyl-γ
-Butyrolactone, α-hydroxy-γ, γ-dimethyl-γ-butyrolactone, α-hydroxy-α, γ, γ-
Trimethyl-γ-butyrolactone, α-hydroxy-
β, β, γ, γ-tetramethyl-γ-butyrolactone,
α-hydroxy-α, β, β, γ, γ-pentamethyl-
Examples include α-hydroxy-γ-butyrolactones such as γ-butyrolactone.

Examples of the methacrylic acid halide include methacrylic acid chloride and methacrylic acid bromide. Of these, methacrylic acid chloride is preferred.

The reaction (esterification) between the alcohol having a cyclic skeleton and the methacrylic acid halide is usually carried out in a solvent inert to the reaction. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; hexane, heptane, octane,
Aliphatic hydrocarbons such as decane; Alicyclic hydrocarbons such as cyclohexane; Methylene chloride, chloroform, 1,2-
Examples thereof include halogenated hydrocarbons such as dichloroethane, chlorobenzene and trifluoromethylbenzene; esters such as ethyl acetate and butyl acetate; ethers such as diethyl ether, diisopropyl ether, dibutyl ether, anisole and tetrahydrofuran; and mixed solvents thereof.

The amount of the methacrylic acid halide used is 0.9 to 3.0 mol, preferably 1.0 to 2.0 mol, per 1 mol of the alcohol having a cyclic skeleton.

The reaction is usually carried out in the presence of a base in order to capture an acid (hydrogen halide) produced as a by-product. Examples of the base include tertiary amines such as trialkylamine (eg, triethylamine) and organic bases such as nitrogen-containing aromatic heterocyclic compounds such as pyridine. The amount of the base used is, for example, 0.9 to 3 mol, preferably 1.0 to 2.
It is about 5 mol. The reaction temperature varies depending on the type of alcohol having a cyclic skeleton and the like, but is generally 0-10.
It is about 0 ° C.

By the reaction of the alcohol having a cyclic skeleton with the methacrylic acid halide, a methacrylic acid ester having a cyclic skeleton corresponding to the starting alcohol is produced. In addition, in the reaction mixture, in general, in addition to a methacrylic acid ester having a cyclic skeleton which is a target product, an unreacted methacrylic acid halide, an unreacted alcohol, a methacrylic acid halide dimer, and a by-product derived from a methacrylic acid halide dimer. , Methacrylic anhydride, a salt of a hydrogen halide corresponding to the methacrylic acid halide and a base used as a scavenger of an acid, an excessively used base and the like.

The main feature of the method of the present invention is a step of adding water to a reaction mixture of the alcohol having a cyclic skeleton and a methacrylic acid halide to perform heat treatment (hereinafter, simply referred to as "step A"). ) Is included. By this step A, the unreacted methacrylic acid halide or methacrylic acid halide dimer mainly contained in the reaction mixture is hydrolyzed to be the corresponding carboxylic acid. The carboxylic acid can be easily removed by, for example, a washing operation using an alkaline aqueous solution described later.

The amount of water added in step A is 1.0 to 10 times, preferably 1.2 to 3 times the total number of moles of unreacted methacrylic acid halide and methacrylic acid halide dimer in the reaction mixture. is there. The temperature of the heat treatment is, for example, 30 to 100 ° C, preferably about 40 to 80 ° C. The heat treatment time is, for example, 5 minutes to 5 hours, preferably 15 minutes to 2 hours.

In the present invention, further, a step of adding an aliphatic alcohol having 1 to 4 carbon atoms to the reaction mixture of the alcohol having a cyclic skeleton and a methacrylic acid halide and performing heat treatment (hereinafter, simply referred to as "step B"). May be referred to as)) is preferably provided. This step mainly decomposes the methacrylic acid anhydride contained in the reaction mixture into the corresponding methacrylic acid ester. This methacrylic acid ester can be easily removed by, for example, a simple distillation operation.

Examples of the aliphatic alcohol having 1 to 4 carbon atoms in the step B include methanol, ethanol, propanol, isopropyl alcohol, butanol and the like. Among these, methanol is preferable from the viewpoint of reactivity and cost. The amount of the aliphatic alcohol having 1 to 4 carbon atoms used is about 0.1 to 10 mol, preferably about 0.3 to 3 mol, based on 1 mol of the methacrylic acid halide used in the reaction. The temperature of the heat treatment is, for example, 30 to 100 ° C, preferably about 40 to 80 ° C.
The heat treatment time is, for example, 5 minutes to 5 hours, preferably 15 minutes to 2 hours.

Step B may be carried out before Step A, but in that case, since the methacrylic acid halide dimer is converted into the corresponding ester which is difficult to separate and remove by a purification means such as distillation, after Step A It is preferable to provide step B.
Note that the heat treatment in step A and the heat treatment in step B can be performed in parallel.

The production method of the present invention also includes a step of washing a reaction mixture of an alcohol having a cyclic skeleton and a methacrylic acid halide with an aqueous acid solution (hereinafter, simply referred to as "step C"). You may stay. By this process,
Mainly, the excess base (base for acid scavenging) contained in the reaction mixture is removed to obtain a methacrylic acid ester having a cyclic skeleton containing no base or an extremely low base content. You can When a polymer obtained by polymerizing a methacrylic acid ester having such a cyclic skeleton is used as a resin for a photoresist, the acid generated by exposure in lithography functions effectively without being trapped by a base. The elimination of the acid-eliminating group of the above proceeds smoothly.

When the acid aqueous solution is added and the two layers are not separated, the reaction mixture may be added with an organic solvent having a low polarity, or an organic solvent having a high polarity may be distilled off. A washing operation becomes possible.

Examples of the aqueous acid solution include aqueous solutions of inorganic acids such as hydrogen chloride (hydrochloric acid), sulfuric acid, nitric acid and phosphoric acid; and aqueous solutions of organic acids such as acetic acid. Among these,
Aqueous solutions of inorganic acids, especially hydrochloric acid, are preferred. The concentration of the acid in the aqueous acid solution is not particularly limited, but is usually 0.1 to 50% by weight, preferably 0.2 to 10% by weight, more preferably about 0.3 to 5% by weight. The amount of the acid aqueous solution used is, for example, 5 per 100 parts by weight of the liquid to be treated to be subjected to the acid cleaning.
To about 2000 parts by weight, preferably about 10 to 500 parts by weight. The temperature at the time of acid cleaning is, for example, about 10 to 60 ° C.

This step C can be carried out at any time after the reaction is completed, but it is often carried out after step A (when step B is carried out, after steps A and B).

In the method of the present invention, a washing step (hereinafter sometimes simply referred to as "step D") of washing with at least one washing liquid selected from water, an aqueous alkaline solution and an aqueous salt solution is further provided. Good. By this washing step D, water-soluble impurities contained in the reaction mixture can be efficiently removed.

Examples of the alkaline aqueous solution include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide;
Examples thereof include aqueous solutions of alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate. Preferred alkaline aqueous solutions include aqueous solutions of alkali metal carbonates such as sodium carbonate.

Examples of the aqueous salt solution include aqueous solutions of alkali metal or alkaline earth metal halides or sulfates such as sodium chloride, potassium chloride, magnesium chloride, calcium chloride, sodium sulfate and magnesium sulfate.

The washing can be carried out using one kind of washing solution of water, an aqueous alkali solution and an aqueous salt solution, but it is more preferable to carry out washing in combination of two kinds or three kinds. The number of times of cleaning may be once or plural times for each cleaning solution. The amount of the cleaning liquid used is, for example, about 10 to 200 parts by weight, preferably about 20 to 100 parts by weight, per 100 parts by weight of the liquid to be cleaned, per one cleaning process. The temperature at the time of washing is, for example, about 10 to 60 ° C.

These washing steps D can be carried out at any time after completion of the reaction, but after the step A (further step B
And / or after performing these steps, if step C is performed)
Often done in.

In the present invention, an adsorption treatment step may be further provided in order to remove coloring components and metals in the reaction mixture. The adsorption treatment step can be performed at any time after the completion of the reaction, but after the step A (and after the step B and / or the step C and / or the step D, these steps are performed). It is often seen. In addition, before the adsorption treatment, solvent replacement (exchange) may be performed as necessary.

The adsorption treatment method is not particularly limited as long as it is a treatment method capable of removing impurities in the reaction product, but at least one adsorbent selected from activated carbon, chelate resin, chelate fiber and zeta potential membrane is used. The treatment method used is preferred. A treatment method using silica gel as an adsorbent is also preferable.

The activated carbon used for the activated carbon treatment is not particularly limited, and either gas activated carbon or chemical activated carbon can be used. Further, the origin of the activated carbon and the shape of the activated carbon are not particularly limited, and may be any of powdery, granular, fibrous and the like. The specific surface area of activated carbon is, for example, 10 to 30.
It is about 00 m ² / g. The treatment temperature in the activated carbon treatment is, for example, about 10 to 60 ° C. For the activated carbon treatment, a known method such as a batch method, a continuous method, a fixed bed method, or a fluidized bed method can be adopted. By the activated carbon treatment, mainly the colored components can be efficiently removed, and a methacrylic acid ester having a cyclic skeleton excellent in hue can be easily obtained.

The chelate resin used in the chelate resin treatment is not particularly limited as long as it is a resin having a functional group capable of forming a chelate with a metal, and typical examples thereof include iminodiacetic acid type and polyamine type. A chelate resin may be used. The exchange capacity of the chelate resin is not particularly limited, but for example, about 0.1 to 2 mol / l is used. The treatment temperature in the chelate resin treatment is
For example, it is about 10 to 60 ° C. Chelating resin treatment is
Well-known methods such as a batch system, a continuous system, a fixed bed system and a fluidized bed system can be adopted. By the chelate resin treatment, mainly a trace amount of metal component (for example, Fe, Al, etc.) can be efficiently removed.

The chelate fiber used for the chelate fiber treatment is not particularly limited as long as it has a chelate functional group (for example, iminodiacetic acid type resin) immobilized on a natural fiber by a chemical bond, but its typical example is Specific examples thereof include chelate fibers based on cellulose (trade name “Crest Fiber”, manufactured by CREST Co., Ltd.) and the like. The treatment temperature in the chelate fiber treatment is, for example, 1
It is about 0 to 60 ° C (preferably 10 to 50 ° C). For the chelate fiber treatment, known methods such as a batch system, a continuous system, a fixed bed system and a fluidized bed system can be adopted. By the chelate fiber treatment, mainly trace metal components (for example, Fe, Al, etc.) can be efficiently removed.

The zeta-potential membrane treatment is performed by passing a liquid to be treated through the zeta-potential membrane. The zeta potential membrane used for the zeta potential membrane treatment is not particularly limited as long as it is a filtration membrane capable of adsorbing fine particles based on the zeta potential, and for example, a product name "Zeta Plus" manufactured by Cuno Co., Ltd. Can be used. Examples of the material of the zeta potential film include resin, cellulose, perlite, diatomaceous earth, glass fiber and the like. The treatment temperature in the zeta potential membrane treatment is, for example, about 10 to 50 ° C. By the zeta potential membrane treatment, mainly trace metal components (for example, F
e, Al, etc.) can be efficiently removed.

The silica gel used for the silica gel treatment is not particularly limited. The treatment temperature in the silica gel treatment is, for example, about 10 to 60 ° C. For the silica gel treatment, known methods such as a batch system, a continuous system, a fixed bed system and a fluidized bed system can be adopted. By the silica gel treatment, high boiling point organic substances, coloring components, etc. can be efficiently removed.

The methacrylic acid ester having a cyclic skeleton, which is a reaction product, can be obtained by concentrating the mixed solution that has undergone the above-mentioned steps, but a higher purity product can be obtained by further subjecting it to crystallization or molecular distillation. Can be obtained.

The solvent used for crystallization varies depending on the kind of the methacrylic acid ester having a cyclic skeleton,
A solvent selected from (i) a solvent containing at least an aromatic hydrocarbon, (ii) a mixed solvent of an aliphatic hydrocarbon and an ester, and (iii) a mixed solvent of water and a water-miscible solvent is preferable.

Examples of the aromatic hydrocarbon in the solvent (i) include aromatic hydrocarbons having about 6 to 12 carbon atoms such as benzene, toluene, xylene and ethylbenzene. Of these, toluene and the like are particularly preferable. The solvent (i) containing at least an aromatic hydrocarbon includes (i-1) an aromatic hydrocarbon such as toluene, (i-
2) a mixed solvent of an aromatic hydrocarbon and an aliphatic hydrocarbon, (i
-3) A mixed solvent of aromatic hydrocarbon and ether is included. Examples of the aliphatic hydrocarbon in the above (i-2) include aliphatic hydrocarbons having about 5 to 12 carbon atoms such as pentane, hexane, heptane, octane, nonane, decane and dodecane. The ether in (i-3) above is preferably a chain alcohol such as diethyl ether, diisopropyl ether, t-butyl methyl ether, dibutyl ether, dimethoxyethane, anisole and the like. Among these, diisopropyl ether and the like are preferable.

In the mixed solvent (ii) of the aliphatic hydrocarbon and the ester, the aliphatic hydrocarbon is, for example,
Aliphatic hydrocarbons having about 5 to 12 carbon atoms such as pentane, hexane, heptane, octane, nonane, decane and dodecane can be mentioned. Of these, hexane and the like are preferable. Further, as the ester, for example, methyl acetate,
Examples thereof include aliphatic carboxylic acid alkyl esters such as ethyl acetate, isopropyl acetate, butyl acetate and ethyl propionate; and aromatic carboxylic acid alkyl esters such as ethyl benzoate. Among these, acetic acid alkyl esters such as ethyl acetate (in particular, acetic acid C _1-4 alkyl ester) are preferable.

Examples of the water-miscible solvent in (iii) above include cyclic ethers such as tetrahydrofuran and dioxane; alcohols such as methanol, ethanol and isopropyl alcohol; ketones such as acetone; nitriles such as acetonitrile; N, N-dimethyl. Examples include aprotic polar solvents such as formamide. Among these, cyclic ethers such as tetrahydrofuran and alcohols such as isopropyl alcohol are preferable.

Although the amount of the crystallization solvent used varies depending on the type of the solvent, it is generally 20 to 1000 parts by weight, preferably 25 to 800 parts by weight, based on 100 parts by weight of the methacrylic acid ester having a cyclic skeleton. And more preferably about 30 to 300 parts by weight. The crystallization operation is, for example, 3
It is performed by cooling from a temperature of about 0 to 50 ° C to a temperature of about -20 to 10 ° C. The cooling time is, for example, 0.1 to 5 hours, preferably 0.3 to 3 hours, and the aging time is, for example, 0.5 to 10 hours, preferably 1 to 5 hours.

After crystallization, the obtained crystal is washed (rinsed) with a solvent to obtain a methacrylic acid ester having a higher purity cyclic skeleton. Cleaning
For example, it can be performed by stirring a mixed solution of the crystals and a washing solvent (rinsing solvent).

The solvent used for the washing is, for example,
Aliphatic hydrocarbons such as hexane (preferably having 5 carbon atoms
It is preferably an aliphatic hydrocarbon (about 12 to 12), an ether such as diisopropyl ether (for example, a chain ether), a mixed solvent of water and a water-miscible solvent (for example, an alcohol such as isopropyl alcohol), and the like.

The drying conditions of the crystals obtained by crystallization or the crystals that have been further washed can be appropriately set within a range that does not impair the quality and work efficiency, for example, a temperature of about 10 to 60 ° C. (preferably 10 to 50 ° C.). Degree), and under normal pressure or reduced pressure [for example, 0.1 to 760 mmHg (13.3 to 101
About 000 Pa)]. The drying time is, for example, about 0.1 to 24 hours. The drying may be performed in a stream of inert gas such as nitrogen.

The molecular distillation can be carried out by using a conventional molecular distillation apparatus, for example, a pot type molecular distillation apparatus, a falling film type molecular distillation apparatus, a centrifugal type molecular distillation apparatus or the like. Among these, the centrifugal molecular distillation apparatus is particularly preferable because it can form an extremely thin liquid film and can heat and evaporate the sample instantaneously.

The operating conditions in the molecular distillation can be appropriately selected within a range that does not impair the quality of the target methacrylic acid ester having a cyclic skeleton. The temperature is, for example, 10 to 100 ° C.
Degree, preferably 10 to 80 ° C., more preferably 10
It is about 65 ° C, and particularly preferably about 10 ° C to 50 ° C. The pressure is, for example, 0.0001 to 0.5 mmHg
(0.0133-66.5 Pa), preferably 0.00
01-0.2mmHg (0.0133-26.6P
a), more preferably 0.0001 to 0.1 mmHg
(0.0133 to 13.3 Pa).

Molecular distillation is useful for the purification of methacrylic acid esters which are liquid at room temperature or have a cyclic skeleton having a melting point of 100 ° C. or lower, especially 50 ° C. or lower. By the molecular distillation, a methacrylic acid ester having a smaller degree of coloring can be obtained.

According to the method for producing a methacrylic acid ester having a cyclic skeleton of the present invention, water is added to a reaction mixture of an alcohol having a cyclic skeleton and a methacrylic acid halide for heat treatment. Since the contained methacrylic acid halide dimer and methacrylic acid anhydride are converted into easily removable substances by washing operation and distillation operation, methacrylic acid ester with high purity cyclic skeleton containing few impurities can be easily obtained. be able to. Further, when a step of adding an aliphatic alcohol having 1 to 4 carbon atoms to the reaction mixture and performing a heat treatment is further provided, methacrylic anhydride and the like contained in the reaction mixture can be easily removed by distillation or the like. Since it is converted into another substance, methacrylic acid having a cyclic skeleton with higher purity can be easily obtained. Further, when a step of washing the reaction mixture with an aqueous acid solution is further provided, the base used as a scavenger for the by-produced acid can be easily removed, and methacrylic acid having a higher-purity cyclic skeleton can be easily obtained. There is an advantage.

For example, according to the method of the present invention, the total content of methacrylic acid halide dimer and methacrylic anhydride as impurities is 0.5% by weight or less (preferably 0.3% by weight or less, more preferably 0.1% by weight). Methacrylic acid ester having a cyclic skeleton, or methacrylic acid halide dimer as an impurity, and methacrylic anhydride, and the total content of the base is 0.5% by weight or less (preferably 0.3% by weight). % Or less, more preferably 0.
The total content of methacrylic acid ester having a cyclic skeleton (1% by weight or less) or an organic base as an impurity (organic base used as an acid scavenger) is 50 ppm by weight.
Methacrylic acid ester having a cyclic skeleton of the following (preferably 20 ppm by weight or less) can be obtained.

[0069]

According to the method of the present invention, it is possible to efficiently produce a methacrylic acid ester having a high-quality cyclic skeleton with a small amount of impurities. Further, the methacrylic acid ester having a cyclic skeleton of the present invention has a small amount of impurities and is extremely excellent in quality.

[0070]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by these examples.

Example 1 (2-methacryloyloxy-2
-Production of methyl adamantane) In a glass container having an internal volume of 10 L, 513 g (3.09 mol) of 2-methyl-2-adamantanol and toluene 37
50 g and triethylamine 515 g (5.09 mol)
Methacrylic acid chloride 484 g under nitrogen atmosphere
(4.63 mol) was added dropwise over 1 hour and aged for 24 hours. During this period, the temperature of the liquid was controlled at 55 to 60 ° C. After cooling the reaction mixture to room temperature, 56 g of water (3.
09 mol) was added, and the mixture was stirred at a temperature of 55 to 60 ° C. for 0.5 hours. Then, 148 g of methanol (4.63 mol)
Was added and the mixture was stirred at a temperature of 55 to 60 ° C. for 1 hour. To the obtained mixed liquid, 2630 g of 5% by weight dilute hydrochloric acid was added under the condition of a temperature of 20 to 25 ° C. to perform acid cleaning. Next, the temperature 20
10 wt% sodium carbonate aqueous solution 232.
Batch washing was performed three times, twice with 0 g and once with 2200 g of 10 wt% saline. Phenothiazine (1.35 g) was added to the mixed liquid (organic layer) after washing, and the mixture was concentrated under reduced pressure (50 mmHg (6660 Pa); 60 ° C.), 7
06 g of concentrate was obtained. Using a centrifugal molecular distillation apparatus (manufactured by Japan Vehicle Manufacturing Co., Ltd., model “MS-150”), this concentrate was subjected to a pressure of 0.15 mmHg (20 Pa) and a temperature of 72.
Molecular distillation was performed under the condition of ° C to obtain 573 g of 2-methacryloyloxy-2-methyladamantane (purity 99.7).
weight%). The content of impurities contained in the obtained 2-methacryloyloxy-2-methyladamantane was 0.03 wt% or less of methacrylic acid halide dimer, 0.03 wt% or less of methacrylic anhydride, and 8 wt ppm of triethylamine. It was below.

Comparative Example 1 (2-methacryloyloxy-2
-Production of methyl adamantane) In a glass container having an internal volume of 10 L, 513 g (3.09 mol) of 2-methyl-2-adamantanol and toluene 37
50 g and triethylamine 515 g (5.09 mol)
Methacrylic acid chloride 484 g under nitrogen atmosphere
(4.63 mol) was added dropwise over 1 hour and aged for 24 hours. During this period, the temperature of the liquid was controlled at 55 to 60 ° C. The reaction mixture was cooled to room temperature, 2526 g of water was added, and the mixture was stirred at 20 to 25 ° C for 1 hr. After separating lower layer water by liquid separation, the mixed solution (organic layer) was treated twice with 2320 g of a 10 wt% sodium carbonate aqueous solution, and further 10 wt% saline solution 2 was added.
Batch washing was performed once at 200 g, for a total of three times. Phenothiazine (1.35 g) was added to the mixture (organic layer) after washing, and the mixture was concentrated under reduced pressure (50 mmHg (6660P).
a); 60 ° C.), 745 g of concentrate were obtained. A pressure of 0.15 mmHg was applied to this concentrate using a centrifugal type molecular distillation apparatus (manufactured by Japan Vehicle Manufacturing Co., Ltd., model “MS-150”).
(20 Pa), the temperature is 72 ℃, molecular distillation, 376
g of 2-methacryloyloxy-2-methyladamantane was obtained (purity 97% by weight). The content of impurities contained in the obtained 2-methacryloyloxy-2-methyladamantane was 0.3 for the methacrylic acid halide dimer.
% By weight, 1.1% by weight of methacrylic anhydride and 90 ppm by weight of triethylamine.

Example 2 (β-methacryloyloxy-γ
-Production of butyrolactonetone) In a glass container having an internal volume of 10 L, β-hydroxy-γ-
Butyrolactone 316 g (3.09 mol), toluene 2
520 g and triethylamine 563 g (5.56 mol) were added, and methacrylic acid chloride 42 was added under a nitrogen atmosphere.
0 g (4.02 mol) was added dropwise over 2 hours, and the mixture was aged for 1 hour. During this period, the temperature of the liquid was controlled to 0 to 5 ° C.
Water (145 g, 8.04 mol) was added to the reaction mixture, and the mixture was stirred at a temperature of 55 to 60 ° C. for 1 hour. Then, 129 g (4.02 mol) of methanol was added, and the mixture was stirred at a temperature of 50 ° C. for 1 hour. To the obtained mixed liquid, 1910 g of 5% by weight dilute hydrochloric acid was added under the condition of a temperature of 20 to 25 ° C. to perform acid cleaning. Next, under conditions of a temperature of 20 to 25 ° C., batch washing was performed twice with 2350 g of a 10 wt% sodium carbonate aqueous solution and once with 2200 g of 10 wt% sodium chloride solution, for a total of three batch washings. The mixed solution (organic layer) after washing is concentrated under reduced pressure (50 mm
Hg (6660 Pa); 60 ° C.), 412 g of concentrate was obtained. Using a centrifugal type molecular distillation apparatus (manufactured by Japan Vehicle Manufacturing Co., Ltd., model “MS-150”), this concentrate was treated at a pressure of 0.
Molecular distillation was carried out under the conditions of 15 mmHg (20 Pa) and a temperature of 72 ° C. to obtain 371 g of β-methacryloyloxy-γ-butyrolactone (purity 98% by weight). The content of impurities contained in the obtained β-methacryloyloxy-γ-butyrolactone was 0.03 wt% or less of methacrylic acid halide dimer, 0.03 wt% or less of methacrylic anhydride, and 8 wt ppm or less of triethylamine. Met.

Comparative Example 2 (β-methacryloyloxy-γ
-Production of butyrolactonetone) In a glass container having an internal volume of 10 L, β-hydroxy-γ-
Butyrolactone 316 g (3.09 mol), toluene 2
520 g and triethylamine 563 g (5.56 mol) were added, and methacrylic acid chloride 42 was added under a nitrogen atmosphere.
0 g (4.02 mol) was added dropwise over 2 hours, and the mixture was aged for 1 hour. During this period, the temperature of the liquid was controlled to 0 to 5 ° C.
Water (2400 g) was added to the reaction mixture, and the mixture was stirred at 20 to 25 ° C. for 0.5 hr. After separating the lower layer water by liquid separation, the mixed solution (organic layer) was subjected to a temperature of 20 to 25 ° C. twice with 2350 g of a 10 wt% sodium carbonate aqueous solution, and once with 2200 g of 10 wt% saline, a total of three times. Batch cleaning was performed. The mixed solution (organic layer) after washing is concentrated under reduced pressure (50 mm
Hg (6660 Pa); 60 ° C.), 440 g of concentrate was obtained. Using a centrifugal type molecular distillation apparatus (manufactured by Japan Vehicle Manufacturing Co., Ltd., model “MS-150”), this concentrate was treated at a pressure of 0.
Molecular distillation was carried out under the conditions of 15 mmHg (20 Pa) and a temperature of 72 ° C. to obtain 342 g of β-methacryloyloxy-γ-butyrolactone (purity 97% by weight). The content of impurities contained in the obtained β-methacryloyloxy-γ-butyrolactone was 0.2% by weight of methacrylic acid halide dimer, 1.2% by weight of methacrylic anhydride and 120 ppm by weight of triethylamine. .

Example 3 (5-methacryloyloxy-3-oxatricyclo [4.2.1.0 represented by the following formula:
^4,8 ] nonan-2-one production)

[Chemical 3] In a glass container having an internal volume of 10 L, 5-hydroxy-3-
Oxatricyclo [4.2.1.0 ^4,8 ] nonane-2-
Onto 476 g (3.09 mol), toluene 2520 g and triethylamine 563 g (5.56 mol) were added,
In a nitrogen atmosphere, 420 g of methacrylic acid chloride (4.0 g
(2 mol) was added dropwise over 2 hours and aged for 1 hour. During this time,
The temperature of the liquid was controlled at 0 to 5 ° C. Water (145 g, 8.04 mol) was added to the reaction mixture, and the temperature was adjusted to 55-60.
The mixture was stirred at 0 ° C for 1 hour. Then, 129 g of methanol
(4.02 mol) was added, and the mixture was stirred at a temperature of 50 ° C. for 1 hour. The obtained mixed solution was added under the conditions of a temperature of 20 to 25 ° C.
Acid washing was performed by adding 1910 g of dilute hydrochloric acid in weight%. Next, under the condition of the temperature of 20 to 25 ° C., 2350 g of 10 wt% sodium carbonate aqueous solution was added twice, and further 10 wt% saline solution 22 was added.
Batch cleaning was carried out once at a total of three times with 00 g. The obtained organic layer was concentrated using a glass evaporator having an internal volume of 10 L [10 mmHg (1330 Pa), 40 ° C.],
1280 g of concentrated liquid was obtained. To the obtained concentrated liquid, 1120 g of diisopropyl ether was added, and the mixture was stirred and cooled under ice cooling for 3 hours to give 5-methacryloyloxy-3-oxatricyclo [4.2.1.0 ^{4, 8} ] nonan-2-one. Was crystallized and a slurry was obtained. The temperature of this slurry was 2 ° C. After the crystallization was completed, the crystals were separated by filtration, to which 517.5 g of cold diisopropyl ether was added, and the mixture was cooled to 1 with ice.
It was washed by stirring for a time. After the washing was completed, the crystals were separated by filtration and dried in a vacuum dryer for 9 hours to give [10
mmHg (1330 Pa), 60 ° C.], white 5-methacryloyloxy-3-oxatricyclo [4.2.
540 g of 1.0 ^4,8 ] nonan-2-one was obtained. The obtained 5-methacryloyloxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one has a purity of 9
It was 9.9% by weight, and the content of impurities was 0.03% by weight or less of methacrylic acid halide dimer, 0.03% by weight or less of methacrylic anhydride, and 10% by weight or less of triethylamine.

Comparative Example 3 (5-methacryloyloxy-3
-Oxatricyclo [4.2.1.0 ^4,8 ] nonane-2
-Production of ON) In a glass container having an internal volume of 10 L, 5-hydroxy-3-
Oxatricyclo [4.2.1.0 ^4,8 ] nonane-2-
Onto 476 g (3.09 mol), toluene 2520 g and triethylamine 563 g (5.56 mol) were added,
In a nitrogen atmosphere, 420 g of methacrylic acid chloride (4.0 g
(2 mol) was added dropwise over 2 hours and aged for 1 hour. During this time,
The temperature of the liquid was controlled at 0 to 5 ° C. Water (2400 g) was added to the reaction mixture, and the mixture was stirred at 20 to 25 ° C. for 0.5 hr. After separating the lower layer water by liquid separation, the mixed solution (organic layer) is heated at a temperature of 20 to 25 ° C. and a 10 wt% sodium carbonate aqueous solution 2
Batch washing was performed twice with 350 g and once with 2200 g of 10% by weight saline, for a total of three times. The obtained organic layer was concentrated using a glass evaporator having an internal volume of 10 L [10 mmHg (1330 Pa), 40 ° C.], 1280
g of concentrated liquid was obtained. To the obtained concentrated liquid, 1120 g of diisopropyl ether was added, and the mixture was stirred and cooled under ice cooling for 3 hours to give 5-methacryloyloxy-3-oxatricyclo [4.2.1.0 ^{4, 8} ] nonan-2-one. Was crystallized and a slurry was obtained. The temperature of this slurry was 2 ° C. After completion of the crystallization, the crystals were separated by filtration, to which 517.5 g of cold diisopropyl ether was added and washed by stirring for 1 hour under ice cooling. After completion of washing, the crystals were filtered out and dried in a vacuum dryer for 9 hours to obtain [10 mm
Hg (1330 Pa), 60 ° C.], white 5-methacryloyloxy-3-oxatricyclo [4.2.1.0]
543 g of ^4,8 ] nonan-2-one was obtained. Obtained 5-
Methacryloyloxy-3-oxatricyclo [4.
2.1.0 ^4,8 ] Non-2-one has a purity of 97% by weight.
And the content of impurities is 0.5% by weight of methacrylic acid halide dimer and 0.5% by weight of methacrylic anhydride.
The amount of triethylamine was 90 ppm by weight.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C07D 307/00 C07D 307/00 F term (reference) 4C037 AA02 4G075 AA14 BA10 BB01 BB02 BB04 BB05 BB07 BB10 BD15 CA02 CA03 CA51 CA57 CA65 DA18 EB01 4H006 AA02 AC13 AC48 AD16 BA51 BC10 BE60 BJ30 4H039 CA66 CD10 CD20

Claims (8)

[Claims] 1. A method for producing a corresponding methacrylic acid ester by reacting an alcohol having a cyclic skeleton with a methacrylic acid halide, wherein water is added to a reaction mixture of the alcohol having a cyclic skeleton and the methacrylic acid halide. A method for producing a methacrylic acid ester having a cyclic skeleton, which comprises the step of adding and performing heat treatment. 2. The cyclic skeleton according to claim 1, further comprising a step of adding an aliphatic alcohol having 1 to 4 carbon atoms to a reaction mixture of an alcohol having a cyclic skeleton and a methacrylic acid halide and performing heat treatment. Method for producing methacrylic acid ester. 3. The method for producing a methacrylic acid ester having a cyclic skeleton according to claim 1, further comprising a step of washing a reaction mixture of an alcohol having a cyclic skeleton and a methacrylic acid halide with an aqueous acid solution. 4. The alcohol having a cyclic skeleton has 7 carbon atoms.
The method for producing a methacrylic acid ester according to any one of claims 1 to 3, which is an alcohol having a polycyclic alicyclic skeleton or an alcohol having a lactone skeleton. 5. The method for producing a methacrylic acid ester according to claim 1, wherein the alcohol having a cyclic skeleton is an alcohol having an adamantane skeleton. 6. A methacrylic acid ester having a cyclic skeleton produced by reacting an alcohol having a cyclic skeleton with a methacrylic acid halide, wherein the total content of methacrylic acid halide dimer and methacrylic anhydride as impurities is Methacrylic acid ester having a cyclic skeleton of 0.5% by weight or less. 7. A methacrylic acid ester having a cyclic skeleton, which is produced by reacting an alcohol having a cyclic skeleton with a methacrylic acid halide in the presence of a base, wherein a methacrylic acid halide dimer as an impurity and methacrylic anhydride are used. A methacrylic acid ester having a cyclic skeleton in which the total content of the acid and the base is 0.5% by weight or less. 8. A methacrylic acid ester having a cyclic skeleton produced by reacting an alcohol having a cyclic skeleton with a methacrylic acid halide in the presence of an organic base, wherein the total content of the organic base as an impurity is A methacrylic acid ester having a cyclic skeleton of 50 ppm by weight or less.