JP5220253B2 - Method for producing adamantyl (meth) acrylates - Google Patents

Description

TECHNICAL FIELD The present invention relates to a process for producing (meth) acrylic acid esters having a cyclic skeleton such as adamantyl (meth) acrylates useful as raw material monomers for various plastic molded articles and optical materials.

BACKGROUND ART A polymer of (meth) acrylic acid ester having an adamantane skeleton such as adamantyl (meth) acrylates has high heat resistance and impact resistance, and has excellent optical properties, so that various plastics are used. Use as optical materials such as molded products and resist resins is expected. In addition, a polymer of (meth) acrylic acid ester having a lactone skeleton is also attracting attention as a monomer for a resist resin because of its excellent adhesion to a substrate.

As a method for producing adamantyl mono (meth) acrylates, Japanese Patent Publication No. 7-61980 discloses that adamantanediols are dissolved in a solvent such as toluene and (meth) acrylic in the presence of a catalyst such as p-toluenesulfonic acid. After the reaction with heat and monoesterification, the reaction solution is neutralized with alkali to remove insolubles and solvent, and then recrystallized using n-hexane to obtain the adamantyl mono (meth) acrylates. A method of obtaining is disclosed.

When adamantyl (meth) acrylates are used as a monomer raw material for optical materials, for example, a high-purity product with a low impurity content is required in order to sufficiently exhibit optical characteristics. However, in the above-described method of neutralizing the reaction mixture and recrystallizing from n-hexane, impurities such as coloring substances are easily taken into the crystal, and high-quality adamantyl (meth) acrylates cannot be efficiently obtained. . This is also true for (meth) acrylic acid esters having other cyclic skeletons.

Conventionally, there is no known method for efficiently obtaining a compound that is a (meth) acrylic ester having an adamantane skeleton or a lactone skeleton and is liquid at room temperature.

DISCLOSURE OF THE INVENTION Accordingly, an object of the present invention is to provide a method for efficiently producing a (meth) acrylic acid ester having a high-quality cyclic skeleton with a low impurity content.

Another object of the present invention is to provide a method for efficiently obtaining a (meth) acrylic acid ester having a cyclic skeleton such as adamantyl (meth) acrylate that is liquid at room temperature with high purity.

As a result of intensive studies to achieve the above object, the present inventors have produced a reaction product produced by a reaction between an alcohol having a cyclic skeleton such as adamantanols and (meth) acrylic acid or a reactive derivative thereof. When the product was subjected to molecular distillation, it was found that (meth) acrylic acid esters [adamantyl (meth) acrylates and the like] having a high-purity cyclic skeleton can be efficiently produced, and the present invention was completed.

［式（１ｄ）中、環に結合しているメチル基の個数ｎは０〜５の整数であり、式（１ｅ´）中、環に結合しているメチル基の個数ｎは２〜５の整数である］
で表される環式骨格を有するアルコールと（メタ）アクリル酸又はその反応性誘導体とから、それぞれ対応する下記式（２ｄ）又は（２ｅ´）

［式中、Ｒは水素原子又はメチル基を示す。ｎは前記に同じ］
で表されるレジスト樹脂モノマー用環式骨格を有する（メタ）アクリル酸エステルを製造する方法であって、前記式（１ｄ）又は（１ｅ´）で表される環式骨格を有するアルコールと（メタ）アクリル酸又はその反応性誘導体との反応生成物を、圧力０．０００１〜０．５ｍｍＨｇ（０．０１３３〜６８Ｐａ）、温度１０〜１００℃の条件で分子蒸留に付して、前記環式骨格を有する（メタ）アクリル酸エステルを留出させる工程を含むレジスト樹脂モノマー用環式骨格を有する（メタ）アクリル酸エステルの製造法を提供する。 That is, the present invention provides the following formula ( 1d) or (1e ′ )

[In Formula (1d), the number n of methyl groups bonded to the ring is an integer of 0 to 5 , and in Formula (1e ′), the number n of methyl groups bonded to the ring is 2 to 5. Is an integer ]
The following formula ( 2d) or (2e ' ) corresponding to (meth) acrylic acid or a reactive derivative thereof, respectively, having the cyclic skeleton represented by

[Wherein, R represents a hydrogen atom or a methyl group. n is the same as above]
(Meth) acrylic acid ester having a cyclic skeleton for a resist resin monomer represented by formula ( 1d) or (1e ′ ) and an alcohol having a cyclic skeleton represented by the formula ( 1d) ) The cyclic skeleton is obtained by subjecting a reaction product with acrylic acid or a reactive derivative thereof to molecular distillation under the conditions of a pressure of 0.0001 to 0.5 mmHg (0.0133 to 68 Pa) and a temperature of 10 to 100 ° C. A method for producing a (meth) acrylic acid ester having a cyclic skeleton for a resist resin monomer, which includes a step of distilling a (meth) acrylic acid ester having a dimer is provided.

In the formula (1d) , n is preferably 0.

In the production method, a reaction product of an alcohol having a cyclic skeleton represented by the formula ( 1d) or (1e ′ ) and (meth) acrylic acid or a reactive derivative thereof is obtained from water, an aqueous alkali solution, and an aqueous salt solution. After washing with at least one selected washing solution, it may be subjected to molecular distillation. In the cleaning, the amount of the cleaning liquid used is preferably 10 to 200 parts by weight with respect to 100 parts by weight of the liquid to be cleaned per cleaning process. After washing with a washing solution, it is preferably subjected to molecular distillation after being desolvated under conditions of a temperature of 10 to 100 ° C. and a pressure of 5 to 300 mmHg. In addition, a reaction product of an alcohol having a cyclic skeleton represented by the formula ( 1d) or (1e ′ ) and (meth) acrylic acid or a reactive derivative thereof, activated carbon, chelate resin, chelate fiber, and zeta potential film It is also preferable to subject it to molecular distillation after subjecting it to an adsorption treatment using at least one kind of adsorbent selected from the following.

［式（１ａ）中、Ｒ ^a は水素原子又はメチル基を示し、Ｘは水素原子、ヒドロキシル基又は（メタ）アクリロイルオキシ基を示す。式（１ｂ）〜（１ｅ）中、環に結合しているメチル基の個数ｎは０〜５の整数である］
で表される環式骨格を有するアルコールと（メタ）アクリル酸又はその反応性誘導体とから、それぞれ対応する下記式（２ａ）、（２ｂ）、（２ｃ）、（２ｄ）又は（２ｅ）
【化４】

［式中、Ｒは水素原子又はメチル基を示し、Ｙは水素原子、ヒドロキシル基又は（メタ）アクリロイルオキシ基を示す。Ｒ ^a 、ｎは前記に同じ］
で表される環式骨格を有する（メタ）アクリル酸エステルを製造する方法であって、前記式（１ａ）、（１ｂ）、（１ｃ）、（１ｄ）又は（１ｅ）で表される環式骨格を有するアルコールと（メタ）アクリル酸又はその反応性誘導体との反応生成物を分子蒸留に付して、前記環式骨格を有する（メタ）アクリル酸エステルを留出させる工程を含む環式骨格を有する（メタ）アクリル酸エステルの製造法についても説明する。
In the present specification, in addition to the above invention, the following formula (1a), (1b), (1c), (1d) or (1e)
[Chemical 3]

[In the formula (1a), R ^a represents a hydrogen atom or a methyl group, and X represents a hydrogen atom, a hydroxyl group or a (meth) acryloyloxy group. In formulas (1b) to (1e), the number n of methyl groups bonded to the ring is an integer of 0 to 5.
The following formula (2a), (2b), (2c), (2d) or (2e) respectively corresponding to the alcohol having a cyclic skeleton represented by formula (2), (meth) acrylic acid or a reactive derivative thereof.
[Formula 4]

[Wherein, R represents a hydrogen atom or a methyl group, and Y represents a hydrogen atom, a hydroxyl group or a (meth) acryloyloxy group. R ^a and n are as defined above]
A method for producing a (meth) acrylic acid ester having a cyclic skeleton represented by the formula (1a), (1b), (1c), (1d) or (1e) A cyclic skeleton comprising a step of subjecting a reaction product of an alcohol having a skeleton and (meth) acrylic acid or a reactive derivative thereof to molecular distillation to distill the (meth) acrylic acid ester having the cyclic skeleton. A method for producing a (meth) acrylic acid ester having benzene is also described.

BEST MODE FOR CARRYING OUT THE INVENTION The method for producing a (meth) acrylic acid ester having a cyclic skeleton of the present invention is represented by the formula (1a), (1b), (1c), (1d) or (1e). A reaction product of an alcohol having a cyclic skeleton represented by (meth) acrylic acid or a reactive derivative thereof is subjected to molecular distillation, and the formulas (2a), (2b), (2c) corresponding to the alcohol , (2d) or (2e) at least a step of distilling a (meth) acrylic acid ester having a cyclic skeleton.

In the 1-adamantanols represented by the formula (1a) used as a reaction raw material, two R ^a may be the same group or different from each other. X is a hydrogen atom, a hydroxyl group or a (meth) acryloyloxy group.

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- (meth) acryloyloxy-1-adamantanol, 3- (meth) acryloyloxy-5,7-dimethyl-1-adamantanol, and the like.

The 1-adamantanols represented by the formula (1a) can be obtained by converting a corresponding adamantane having no hydroxyl group or having one hydroxyl group with an N-hydroxyimide-based catalyst such as N-hydroxyphthalimide and the like. In the presence of a metal compound promoter such as a vanadium compound (eg, vanadium acetylacetonate, vanadyl acetylacetonate), a cobalt compound (eg, cobalt acetate, cobalt acetylacetonate, etc.), it is oxidized with oxygen to adamantane It can be obtained by introducing a hydroxyl group at the bridge head position of the ring. In this method, the amount of the N-hydroxyimide catalyst used is, for example, about 0.000001 to 0.5 mol, preferably about 0.00001 to 0.3 mol, relative to 1 mol of adamantanes. Moreover, the usage-amount of a metal compound promoter is 0.0001-0.5 mol with respect to 1 mol of adamantanes, Preferably it is about 0.0005-0.1 mol. The oxidation reaction is carried out in an organic solvent such as an organic acid such as acetic acid, a nitrile such as acetonitrile or benzonitrile, or a halogenated hydrocarbon such as trifluoromethylbenzene at normal pressure or under pressure [eg 5 to 40 atm (0. About 505 to 4.04 MPa)], for example, at a temperature of about 40 to 150 ° C., preferably about 60 to 120 ° C.

The 1-adamantanols may be obtained by bromating adamantanes with bromine and then treating with hydrochloric acid to give adamantane monool, or by reacting the adamantane monool with sulfuric acid to give adamantane diol. Yes (Japanese Patent Publication No. 7-61980). However, a method using the above-mentioned N-hydroxyimide catalyst is preferable because halogen which becomes a problem when used as a resist polymer is not used, and it can be easily produced under mild conditions.

Of the 1-adamantanols represented by the formula (1a), a compound in which X is a (meth) acryloyloxy group is a (meth) acrylic compound in which X is a hydroxyl group according to the esterification method described later. It can be obtained by reacting with an acid or a reactive derivative thereof.

In the adamantanemethanol represented by the formula (1b), the number of methyl groups bonded to the ring is about 0 to 3. Methyl groups are often bonded to bridgehead carbon atoms.

Representative examples of adamantane methanol represented by the formula (1b) include, for example, α, α-dimethyl-1-adamantane methanol, α, α, 3-trimethyl-1-adamantane methanol, α, α, 3, Examples include 5-tetramethyl-1-adamantane methanol.

The adamantane methanol represented by the formula (1b) is, for example, an acylating agent composed of (a) biacetyl, (b) oxygen, and (c) a metal compound in an adamantane compound having a hydrogen atom at the bridgehead position. To obtain the corresponding acetyladamantane derivative, and this acetyladamantane derivative can be obtained by reacting methylmagnesium halide (Grignard reagent).

As the metal compound (c), for example, a cobalt compound such as cobalt acetylacetonate is preferably used. The usage-amount of biacetyl (a) is 1 mol or more (for example, 1-50 mol) with respect to 1 mol of adamantane compounds which have a hydrogen atom in a bridge head position, Preferably it is about 1.5-20 mol. Oxygen is often used in excess with respect to the adamantane compound. The usage-amount of a metal compound (c) is 0.00001-1 mol with respect to 1 mol of said adamantane compounds, Preferably it is about 0.0001-0.7 mol. The acylation reaction is performed at a temperature of about 40 to 150 ° C. in a suitable solvent such as acetic acid. The reaction between the acetyladamantane derivative and methylmagnesium halide can be carried out under the general Grignard reaction conditions.

In the 2-adamantanols represented by the formula (1c), n is usually about 0 to 3, preferably about 0 to 2. In many cases, n methyl groups are bonded to a bridge-top carbon atom.

As representative examples of 2-adamantanols represented by the formula (1c), for example, 2-methyl-2-adamantanol, 2,5-dimethyl-2-adamantanol, 2,5,7-trimethyl- Examples include 2-adamantanol.

The 2-adamantanols represented by the formula (1c) can be obtained, for example, by reacting a 2-adamantanone derivative with methylmagnesium halide (Grignard reagent). This reaction can be performed according to a general Grignard reaction.

In the β-hydroxy-γ-butyrolactone represented by the formula (1d), n is usually about 0 to 5, preferably about 0 to 3.

As typical examples of β-hydroxy-γ-butyrolactone represented by the formula (1d), β-hydroxy-γ-butyrolactone, β-hydroxy-α, α-dimethyl-γ-butyrolactone, β-hydroxy-γ , Γ-dimethyl-γ-butyrolactone, β-hydroxy-α, α, β-trimethyl-γ-butyrolactone, β-hydroxy-β, γ, γ-trimethyl-γ-butyrolactone, β-hydroxy-α, α, β , Γ, γ-pentamethyl-γ-butyrolactone, and the like.

In the α-hydroxy-γ-butyrolactone represented by the formula (1e), n is usually about 0 to 5, preferably about 0 to 3.

Representative examples of the α-hydroxy-γ-butyrolactone represented by the formula (1e) include, for example, 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-γ-butyrolactone and the like.

As the reactive derivative of (meth) acrylic acid in the present invention, a derivative capable of reacting with alcohol to form a corresponding ester, for example, (meth) acrylic acid halide such as (meth) acrylic acid chloride; ) Acid anhydrides such as acrylic acid; (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, vinyl (meth) acrylate, 2-propenyl (meth) acrylate (eg alkyl Ester, alkenyl ester, etc.).

The reaction (esterification) of an alcohol having a cyclic skeleton such as the adamantanol with (meth) acrylic acid is usually performed in a solvent inert to the reaction. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; aliphatic hydrocarbons such as hexane, heptane, octane, and decane; alicyclic hydrocarbons such as cyclohexane; methylene chloride, chloroform, 1, Halogenated hydrocarbons such as 2-dichloroethane, chlorobenzene, and trifluoromethylbenzene; esters such as ethyl acetate and butyl acetate; ethers such as diethyl ether, diisopropyl ether, dibutyl ether, and anisole; and mixed solvents thereof. As the solvent, a solvent that is azeotropic with the by-product water and can be separated from water (solvent capable of azeotropic dehydration), such as toluene, is preferable.

Examples of the catalyst used in the esterification reaction include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and heteropolyacid (for example, silicotungstic acid, silicomolybdic acid, phosphotungstic acid, and phosphomolybdic acid); benzenesulfonic acid, p -Toluenesulfonic acid, naphthalenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, ethanesulfonic acid, sulfonic acids such as sulfonic acid-based strongly acidic ion exchange resins, and the like. These can be used alone or in admixture of two or more.

In order to prevent polymerization during the reaction, it is preferable to add a polymerization inhibitor such as methoquinone or hydroquinone into the system or supply oxygen into the system. Oxygen can be used after being diluted with an inert gas such as nitrogen.

The esterification reaction between an alcohol having a cyclic skeleton such as the adamantanols and (meth) acrylic acid is performed at normal temperature or reduced pressure, for example, at a temperature of about 50 to 150 ° C. Although the usage-amount of (meth) acrylic acid should just be 1 mol or more with respect to 1 mol of hydroxyl groups which should be esterified, 1.1 mol or more (for example, 1.1-10 mol) is used in many cases. In order to increase the conversion rate of the raw material, the reaction is preferably performed while distilling off by-produced water out of the system.

On the other hand, the reaction between an alcohol having a cyclic skeleton such as adamantanol and a reactive derivative of (meth) acrylic acid can be carried out in the presence of a base or a transesterification catalyst depending on the type of the reactive derivative. it can. For example, when (meth) acrylic acid halide or acid anhydride is used as the reactive derivative of (meth) acrylic acid, 0 to 0 in the presence of a base (acid scavenger) such as triethylamine or pyridine. The reaction is carried out at a temperature of about 100 ° C. In addition, when (meth) acrylic acid ester is used as the reactive derivative of (meth) acrylic acid, when a conventional transesterification catalyst or alkenyl (meth) acrylic acid is used as the reactive derivative, particularly The reaction is carried out in the presence of a periodic table group 3 element compound catalyst (for example, a samarium compound such as samarium acetate, samarium trifluoromethanesulfonate, a samarium complex, etc.), for example, at a temperature of about 0 to 150 ° C. in the solvent. .

By reacting an alcohol having a cyclic skeleton such as the adamantanol with (meth) acrylic acid or a reactive derivative thereof, the corresponding formula (2a), (2b), (2c), (2d) or (2e), respectively. (Meth) acrylic acid ester having a cyclic skeleton such as adamantyl (meth) acrylates represented by In the formula (2a), Y represents a hydrogen atom, a hydroxyl group or a (meth) acryloyloxy group. A compound in which Y is a hydroxyl group (monoester form) or a compound (diester form) in which (meth) acryloyloxy group is obtained is a compound (diol form) in which X is a hydroxyl group in formula (1a) (meth) acrylic acid. Or it produces | generates by making it react with the reactive derivative. The said monoester body or diester body can be selectively obtained by adjusting the usage-amount of (meth) acrylic acid or its reactive derivative, reaction temperature, reaction time, etc. suitably. Moreover, the said diester body is obtained by making the compound whose X is a (meth) acryloyloxy group among the adamantanols represented by Formula (1a) react with (meth) acrylic acid or its reactive derivative. You can also. In addition, as a component to be reacted with an alcohol having a cyclic skeleton such as adamantanols, (meth) acrylic acid is not included in the reaction product since halogen that deteriorates performance when used as a resist resin or the like is not included in the reaction product. Etc. are preferable.

Representative examples of 1-adamantyl (meth) acrylates represented by the formula (2a) include, for example, 1-acryloyloxyadamantane, 1-methacryloyloxyadamantane, 1-acryloyloxy-3,5-dimethyladamantane, 1-methacryloyloxy-3,5-dimethyladamantane, 1-acryloyloxy-3-hydroxy-5,7-dimethyladamantane, 1-hydroxy-3-methacryloyloxy-5,7-dimethyladamantane, 1,3-bisacryloyl Examples thereof include oxy-5,7-dimethyladamantane and 1,3-bismethacryloyloxy-5,7-dimethyladamantane. These compounds are liquid at room temperature.

As typical examples of the (meth) acrylic acid ester having an adamantylmethyl group represented by the formula (2b), for example, 1- (1-acryloyloxy-1-methylethyl) adamantane, 1- (1-acryloyl) Oxy-1-methylethyl) -3-methyladamantane, 1- (1-acryloyloxy-1-methylethyl) -3,5-dimethyladamantane, 1- (1-methacryloyloxy-1-methylethyl) adamantane, 1 -(1-Methacryloyloxy-1-methylethyl) -3-methyladamantane, 1- (1-methacryloyloxy-1-methylethyl) -3,5-dimethyladamantane and the like can be mentioned.

Representative examples of the 2-adamantyl (meth) acrylates represented by the formula (2c) include, for example, 2-acryloyloxy-2-methyladamantane, 2-acryloyloxy-2,5-dimethyladamantane, 2- Examples include acryloyloxy-2,5,7-trimethyladamantane, 2-methacryloyloxy-2-methyladamantane, 2-methacryloyloxy-2,5-dimethyladamantane, 2-methacryloyloxy-2,5,7-trimethyladamantane. It is done.

Representative examples of the (meth) acrylic acid ester having a γ-butyrolactone ring represented by the formula (2d) include, for example, β-acryloyloxy-γ-butyrolactone, β-acryloyloxy-α, α-dimethyl- γ-butyrolactone, β-acryloyloxy-γ, γ-dimethyl-γ-butyrolactone, β-acryloyloxy-α, α, β-trimethyl-γ-butyrolactone, β-acryloyloxy-β, γ, γ-trimethyl-γ -Butyrolactone, β-acryloyloxy-α, α, β, γ, γ-pentamethyl-γ-butyrolactone, β-methacryloyloxy-γ-butyrolactone, β-methacryloyloxy-α, α-dimethyl-γ-butyrolactone, β- Methacryloyloxy-γ, γ-dimethyl-γ-butyrolactone, β-methacryloyloxy-α, α , Β-trimethyl-γ-butyrolactone, β-methacryloyloxy-β, γ, γ-trimethyl-γ-butyrolactone, β-methacryloyloxy-α, α, β, γ, γ-pentamethyl-γ-butyrolactone .

Representative examples of (meth) acrylic acid ester having a γ-butyrolactone ring represented by the formula (2e) include, for example, α-acryloyloxy-γ-butyrolactone, α-acryloyloxy-α-methyl-γ-butyrolactone. , Α-acryloyloxy-β, β-dimethyl-γ-butyrolactone, α-acryloyloxy-α, β, β-trimethyl-γ-butyrolactone, α-acryloyloxy-γ, γ-dimethyl-γ-butyrolactone, α- Acryloyloxy-α, γ, γ-trimethyl-γ-butyrolactone, α-acryloyloxy-β, β, γ, γ-tetramethyl-γ-butyrolactone, α-acryloyloxy-α, β, β, γ, γ- Pentamethyl-γ-butyrolactone, α-methacryloyloxy-γ-butyrolactone, α-methacryloyloxy-α-methyl Ru-γ-butyrolactone, α-methacryloyloxy-β, β-dimethyl-γ-butyrolactone, α-methacryloyloxy-α, β, β-trimethyl-γ-butyrolactone, α-methacryloyloxy-γ, γ-dimethyl-γ -Butyrolactone, α-methacryloyloxy-α, γ, γ-trimethyl-γ-butyrolactone, α-methacryloyloxy-β, β, γ, γ-tetramethyl-γ-butyrolactone, α-methacryloyloxy-α, β, β , Γ, γ-pentamethyl-γ-butyrolactone, and the like.

[Washing step (A)]
The reaction product (reaction mixture) thus obtained may be directly subjected to a molecular distillation step, but before that, it is subjected to a washing step in which it is washed with at least one washing liquid selected from water, an aqueous alkali solution and an aqueous salt solution. It is preferable to provide. By this washing treatment, unreacted raw materials [alcohol having a cyclic skeleton such as adamantanol, (meth) acrylic acid], catalyst, and other 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; alkali metal carbonates such as sodium carbonate and potassium carbonate; aqueous solutions such as alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate. Is exemplified. Preferred aqueous alkali solutions include aqueous solutions of alkali metal carbonates such as sodium carbonate.

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

The cleaning may be performed using any one type of cleaning liquid among water, an aqueous alkali solution, and an aqueous salt solution, but is preferably performed by combining at least two cleaning liquids. The number of washings may be once or plural times for each washing 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 with respect to 100 parts by weight of the liquid to be cleaned per cleaning process. The temperature at the time of washing is, for example, about 10 to 50 ° C. When the temperature at the time of washing is too high, a (meth) acrylic acid ester having a cyclic skeleton such as hydroxyadamantyl (meth) acrylates may be polymerized.

In the washing step, an aliphatic hydrocarbon such as hexane, octane or decane or an aromatic hydrocarbon such as toluene may be added to the liquid to be washed in order to improve the liquid separation property.

Washing can be performed by a known or conventional method such as a batch system, a continuous system, or a multistage system. Unreacted raw materials such as (meth) acrylic acid can be recovered from the aqueous layer after washing and reused.

[Adsorption treatment process (B)]
The reaction product of an alcohol having a cyclic skeleton such as adamantanol and (meth) acrylic acid or a reactive derivative thereof is adsorbed after the washing step (A) or without the washing step. You may use for a process (B). In the adsorption treatment step (B), the reaction mixture solution or the washing treatment solution obtained above is subjected to adsorption treatment after solvent replacement (exchange) 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 treatment using at least one kind of adsorbent selected from activated carbon, chelate resin, chelate fiber, and zeta potential membrane. The method is preferred. The adsorption treatment may be performed by combining two or more treatment methods.

Solvent replacement can be performed, for example, by distilling off the reaction solvent in the reaction mixture or the washing treatment liquid obtained in the washing step (A) and adding a solvent used for the adsorption treatment. Although the reaction solvent varies depending on the type of the solvent, for example, the reaction solvent is distilled at a pressure of about 5 to 100 mmHg (665 to 13300 Pa) and a temperature of about 10 to 50 ° C. If the temperature is too high, a (meth) acrylic acid ester having a cyclic skeleton such as adamantyl (meth) acrylates may be polymerized. In the solvent replacement, the reaction solvent does not necessarily need to be distilled off completely, and may be concentrated, for example, about 4 to 15 times. The reaction solvent distilled off can be reused.

The activated carbon used for the activated carbon treatment is not particularly limited, and any of a gas activated activated carbon and a chemical activated activated carbon can be used. The origin of the activated carbon is not particularly limited, and activated carbon obtained from plant materials such as wood, sawdust, fruit shells, and fruit shell charcoal; obtained from mineral materials such as peat, lignite, lignite, coke, coal pitch, and petroleum pitch. Any activated carbon obtained from synthetic resin raw materials such as phenol resin and acrylic resin can be used. The shape of the activated carbon is not particularly limited, and may be any of powder, granule, fiber, and the like. Moreover, the specific surface area of activated carbon is about 10-3000 m < ² > / g, for example.

The treatment liquid to be subjected to the activated carbon treatment is not particularly limited as long as it is a solution. For example, alcohols such as methanol and ethanol are preferable as the solvent of the treatment liquid from the viewpoint of the effect of removing impurities. The concentration of the (meth) acrylic acid ester having a cyclic skeleton in the liquid to be treated for activated carbon treatment can be appropriately selected within a range that does not impair the treatment efficiency, workability, etc., but is generally about 1 to 50% by weight, preferably Is about 5 to 30% by weight. In addition, the usage-amount of alcohol when using alcohol, such as methanol, as an activated carbon treatment solvent is about 200-1000 weight part with respect to 100 weight part of (meth) acrylic acid ester which has cyclic skeleton. The amount of activated carbon used can also be appropriately selected in consideration of processing efficiency, workability, and the like, for example, 5 to 1000 weights with respect to 100 parts by weight of (meth) acrylic acid ester having a cyclic skeleton contained in the liquid to be treated. Part, preferably about 10 to 100 parts by weight.

The treatment temperature in the activated carbon treatment is, for example, about 10 to 50 ° C. If the treatment temperature is too high, a (meth) acrylic acid ester having a cyclic skeleton such as adamantyl (meth) acrylates may be polymerized. 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 (meth) acrylic acid ester having a cyclic skeleton excellent in hue can be easily obtained.

The chelate resin used for the chelate resin treatment is not particularly limited as long as the resin has a functional group capable of forming a chelate with a metal, but typical examples thereof include iminodiacetic acid type and polyamine type chelate resins. Can be mentioned. Although there is no restriction | limiting in particular as the exchange capacity of chelate resin, For example, the thing of about 0.1-2 mol / l is used.

The liquid to be treated for the chelate resin treatment is not particularly limited as long as it is a solution. From the viewpoint of the effect of removing impurities, for example, the solvent for the liquid to be treated includes alcohols such as methanol and ethanol, ethyl acetate, and butyl acetate. Esters such as are preferred. The concentration of the (meth) acrylic acid ester having a cyclic skeleton in the liquid to be treated for the chelate resin treatment can be appropriately selected within a range that does not impair the treatment efficiency, workability, etc., but generally about 1 to 50% by weight, Preferably, it is about 5 to 30% by weight. The amount of the chelate resin used can also be appropriately selected in consideration of processing efficiency, workability, and the like.

The treatment temperature in the chelate resin treatment is, for example, about 10 to 50 ° C. If the treatment temperature is too high, a (meth) acrylic acid ester having a cyclic skeleton such as adamantyl (meth) acrylates may be polymerized. For the chelate resin treatment, a known method such as a patch method, a continuous method, a fixed bed method, or a fluidized bed method can be employed. By the chelate resin treatment, mainly trace metal components (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 the chelate functional group is fixed to the natural fiber by a chemical bond, but a typical example is a chelate fiber based on cellulose ( Trade name “Kyrest Fiber”, manufactured by Kyrest Co., Ltd.) and the like.

The treatment liquid to be subjected to the chelate fiber treatment is not particularly limited as long as it is a solution, but from the viewpoint of the effect of removing impurities, for example, as a solvent of the treatment liquid, alcohol such as methanol, ethanol, isopropyl alcohol, octanol; Esters such as ethyl acetate and butyl acetate; aromatic hydrocarbons such as toluene; aliphatic hydrocarbons such as hexane and heptane; halogenated hydrocarbons such as methylene chloride and 1,2-dichloroethane; ethers such as tetrahydrofuran are preferable. . The concentration of the (meth) acrylic acid ester having a cyclic skeleton in the liquid to be treated for the chelate fiber treatment can be appropriately selected within a range that does not impair the treatment efficiency, workability, etc., but generally about 1 to 50% by weight, Preferably, it is about 5 to 30% by weight. The amount of chelate fiber used can also be appropriately selected in consideration of processing efficiency and workability.

The treatment temperature in the chelate fiber treatment is, for example, about 10 to 50 ° C. If the treatment temperature is too high, a (meth) acrylic acid ester having a cyclic skeleton such as adamantyl (meth) acrylates may be polymerized. For the chelate fiber 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 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 the zeta potential membrane through the liquid to be treated. 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. For example, trade name “Zeta Plus” manufactured by Cuno Co., Ltd. Can be used. Examples of the material for the zeta potential film include resin, cellulose, pearlite, diatomaceous earth, and glass fiber.

The solvent of the liquid to be treated for the zeta potential membrane treatment is not particularly limited, but representative examples include alcohols such as methanol and ethanol; esters such as ethyl acetate and butyl acetate; aromatics such as toluene and xylene. Examples include hydrocarbons. The concentration of the (meth) acrylic acid ester having a cyclic skeleton in the liquid to be treated for the zeta potential membrane treatment can be appropriately selected within a range that does not impair the treatment efficiency and workability, but generally 1 to 50% by weight, Preferably, it is about 5 to 30% by weight.

The processing amount of the liquid to be processed is, for example, about 1 to 30 kg per 1 m ^{2 of} the zeta potential film. The processing speed is, for example, about 0.02 to ² m ³ / m ² / hour.

The treatment temperature in the zeta potential membrane treatment is, for example, about 10 to 50 ° C. If the treatment temperature is too high, a (meth) acrylic acid ester having a cyclic skeleton such as adamantyl (meth) acrylates may be polymerized. By the zeta potential film treatment, mainly trace metal components (for example, Fe, Al, etc.) can be efficiently removed.

[Molecular distillation step (C)]
The reaction product of an alcohol having a cyclic skeleton such as adamantanol and (meth) acrylic acid or a reactive derivative thereof is subjected to the washing step (A) and / or the adsorption treatment step (B), or the Without passing through the process, the solvent is usually removed and then subjected to the molecular distillation process (C).

Desolvation varies depending on the type of solvent, but for example, the temperature is 10 to 100 ° C. (preferably 10 to 50 ° C.) and the pressure is 5 to 300 mmHg (665 to 39900 Pa) [preferably 5 to 100 mmHg (665 to 13300 Pa)]. Done on condition.

In the molecular distillation step (C), (meth) acrylic acid ester having a cyclic skeleton such as adamantyl (meth) acrylates is distilled by molecular distillation. Molecular distillation can be performed using a conventional molecular distillation apparatus, for example, a pot type molecular distillation apparatus, a falling film molecular distillation apparatus, a centrifugal molecular distillation apparatus, or the like. Among these, a centrifugal molecular distillation apparatus is particularly preferable because an extremely thin liquid film can be formed and a sample can be heated and evaporated instantaneously.

The operating conditions in molecular distillation can be appropriately selected within a range that does not impair the quality of the target adamantyl (meth) acrylates. The temperature is, for example, about 10 to 100 ° C, preferably 10 to 80 ° C, more preferably about 10 to 65 ° C, and particularly preferably about 10 to 50 ° C. The pressure is, for example, 0.0001 to 0.5 mmHg (0.0133 to 66.5 Pa), preferably 0.0001 to 0.2 mmHg (0.0133 to 26.6 Pa), and more preferably 0.0001 to 0.1 mmHg. (0.0133 to 13.3 Pa), particularly about 0.001 to 0.05 mmHg (0.133 to 6.65 Pa).

If the operation temperature is too high, (meth) acrylic acid ester having a cyclic skeleton such as adamantyl (meth) acrylate is polymerized, and the purification yield decreases, and the product is easily colored or the purity tends to decrease. Become. Therefore, the present invention is useful for the production of (meth) acrylate adamantyl (meth) acrylates that are liquid at room temperature or have a cyclic skeleton having a melting point of 100 ° C. or lower, particularly 50 ° C. or lower.

By the molecular distillation, by-products and the like produced by the reaction can be efficiently removed, and a (meth) acrylic acid ester having a cyclic skeleton such as a high purity adamantyl (meth) acrylate having a small coloring degree can be obtained.

FIG. 1 is a production process diagram showing an example of the production method of the present invention. In this example, a raw material alcohol having a cyclic skeleton (adamantanol, etc.), (meth) acrylic acid, a reaction solvent, a catalyst (acid catalyst), and, if necessary, a polymerization inhibitor are supplied to the reactor 1. (Reaction process). In order to suppress polymerization, air diluted with nitrogen may be supplied into the liquid in the reactor 1 and bubbled. In order to increase the reaction rate, it is preferable to carry out the reaction while distilling off by-produced water.

The reaction mixture is transferred from the reactor 1 to the washing tank 2 and washed with at least one washing liquid among water, an aqueous alkali solution, and an aqueous salt solution (washing step). The organic layer after washing usually contains (meth) acrylic acid ester (such as adamantyl (meth) acrylates) having a cyclic skeleton generated by the reaction and a reaction solvent. On the other hand, the unreacted raw material and the catalyst are contained in the washed water layer. Unreacted raw materials can be recovered and reused by conventional methods.

The washed organic layer is supplied to the evaporator 3 and the reaction solvent and the like are distilled off (desolvation step). The concentrated liquid is supplied to the molecular distillation apparatus 4, and after the low-boiling components are cut, (meth) acrylic acid esters (adamantyl (meth) acrylates, etc.) having a target cyclic skeleton are obtained from the top of the tower (molecular distillation). Process). High-boiling components such as polymerization inhibitors are discharged from the bottom of the column.

INDUSTRIAL APPLICABILITY According to the present invention, (meth) acrylic acid esters (such as adamantyl (meth) acrylates) having a high-quality cyclic skeleton with excellent hue and low impurity content can be efficiently produced. In addition, (meth) acrylic acid esters (such as adamantyl (meth) acrylates) having a cyclic skeleton that is liquid at room temperature can be efficiently obtained with high purity.

EXAMPLES Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. Examples 1 , 2 , 3, and 5 are described as reference examples.

Example 1
1-Methacryloyloxy-3,5-dimethyladamantane was produced according to the production process diagram of FIG.
A glass reactor 1 having an internal volume of 10 L was charged with 1,200 g of 3,5-dimethyl-1-adamantanol, 1147 g of methacrylic acid, 20.2 g of sulfuric acid, 1.2 g of methoquinone, and 5211 g of toluene. % Oxygen-nitrogen mixed gas was supplied at a flow rate of 3 l / min. The temperature of the liquid was raised to 110 ° C., water produced as a by-product in the reaction was distilled off by azeotropy with toluene, and the reaction was carried out for about 7.5 hours while returning only the toluene to the reactor. As a result of analyzing the reaction solution by gas chromatography, 1400 g of 1-methacryloyloxy-3,5-dimethyladamantane was produced.
The reaction solution was transferred to a glass washing tank 2 equipped with a stirrer, and 8000 g of hexane was added. Then, under conditions of a temperature of 40 ° C., twice with 3000 g of a 10 wt% sodium carbonate aqueous solution and three times with 3000 g of water. Batch washed 5 times. By this washing operation, unreacted 3,5-dimethyl-1-adamantanol, methacrylic acid and sulfuric acid are removed, and a toluene-hexane solution of 1-methacryloyloxy-3,5-dimethyladamantane is obtained as an organic layer. It was.
This organic layer was concentrated using a glass evaporator 3 having an internal volume of 10 L [10 mmHg (1330 Pa), 35 ° C.] to obtain 1091 g of a concentrated liquid. This concentrated solution was subjected to a pressure of 0.02 mmHg (2.66 Pa) and a temperature of 40 ° C. using a glass centrifugal molecular distillation apparatus 4 (trade name “MS-150” manufactured by Nippon Vehicle Manufacturing Co., Ltd.). Molecular distillation yielded 1004 g of 1-methacryloyloxy-3,5-dimethyladamantane (purity 98.1%).

Example 2
1-methacryloyloxyadamantane (= 1-adamantyl methacrylate) was produced according to the production process diagram of FIG.
A glass reactor 1 having an internal volume of 10 L is charged with 1100 g of 1-adamantanol, 1245 g of methacrylic acid, 21.2 g of sulfuric acid, 1.1 g of methoquinone, and 4774 g of toluene. Was fed at a flow rate of 3 l / min. The temperature of the liquid was raised to 110 ° C., water produced as a by-product in the reaction was distilled off by azeotropy with toluene, and the reaction was carried out for about 6 hours while returning only the toluene to the reactor. As a result of analyzing the reaction solution by gas chromatography, 1337 g of 1-methacryloyloxyadamantane was produced.
This reaction solution was transferred to a glass washing tank 2 equipped with a stirrer, and 4774 g of toluene was added. Then, under conditions of a temperature of 40 ° C., twice with 5500 g of water and once with 3300 g of 10 wt% aqueous sodium carbonate solution. Batch washed 3 times. By this washing operation, unreacted 1-adamantanol, methacrylic acid and sulfuric acid were removed, and a toluene solution of 1-methacryloyloxyadamantane was obtained as an organic layer.
This organic layer was concentrated using a glass evaporator 3 having an internal volume of 10 L [10 mmHg (1330 Pa), 35 ° C.] to obtain 2968 g of a concentrated liquid. The concentrated liquid was desolvated using a glass centrifugal molecular distillation apparatus 4 (trade name “MS-150” manufactured by Nippon Vehicle Manufacturing Co., Ltd.), and then again made of glass centrifugal molecular distillation apparatus 4 (Japan). (Manufactured by Vehicle Manufacturing Co., Ltd., trade name “MS-150”), subjected to molecular distillation under the conditions of pressure 0.03 mmHg (3.99 Pa) and temperature 40 ° C., and 984 g of 1-methacryloyloxyadamantane (purity 98 0.0%).

Example 3
Acrylic acid 1- (adamantan-1-yl) -1-methylethyl ester [= 1- (1-acryloyloxy-1-methylethyl) adamantane] was produced according to the production process diagram of FIG.
A glass reactor 1 having an internal volume of 10 L was charged with 600.4 g of 2- (adamantan-1-yl) -1-propan-2-ol (= α, α-dimethyladamantane methanol), 4000 g of tetrahydrofuran and 1093 g of triethylamine. Under a nitrogen atmosphere, 364 g of acrylic acid chloride was added dropwise over 1 hour. After aging for 48 hours, the reaction was terminated. During this time, the temperature of the liquid was controlled at 50 to 55 ° C. As a result of analyzing the reaction solution by liquid chromatography, 499 g of acrylic acid 1- (adamantan-1-yl) -1-methylethyl ester was produced.
This reaction solution was transferred to a washing tank 2 equipped with a stirrer, and under conditions of a temperature of 40 ° C., once with water, once with a 10 wt% sodium carbonate aqueous solution, and once with a 10 wt% sodium chloride aqueous solution, three times in total. Batch washed. In each case, 60 parts by weight of the cleaning liquid was used with respect to 100 parts by weight of the liquid to be cleaned. By this washing operation, unreacted 2- (adamantan-1-yl) -1-propan-2-ol and acrylic acid chloride are removed, and as an organic layer, acrylic acid 1- (adamantan-1-yl) -1 -A tetrahydrofuran solution of methyl ethyl ester was obtained.
The organic layer was concentrated using a glass evaporator 3 having an internal volume of 10 L [50 mmHg (6664 Pa), 60 ° C.] to obtain 1491 g of a concentrated liquid.
To the obtained concentrated liquid, 3973 g of methanol was added to precipitate a polymer. This slurry was separated by filtration and further concentrated [200 mmHg (26658 Pa), 60 ° C.] to obtain 799 g of a concentrated liquid.
This concentrated solution was subjected to a pressure of 0.007 mmHg (0.93 Pa) and a temperature of 58 ° C. using a glass centrifugal molecular distillation apparatus 4 (manufactured by Nippon Vehicle Manufacturing Co., Ltd., trade name “MS-150”). Molecular distillation was performed to obtain 452 g of acrylic acid 1- (adamantan-1-yl) -1-methylethyl ester (purity 95.0%).

Example 4
According to the production process diagram of FIG. 1, methacrylic acid 5-oxotetrahydrofuran-3-yl ester (= β-methacryloyloxy-γ-butyrolactone) was produced.
To a glass reactor 1 having an internal volume of 10 L, 400.2 g of 4-hydroxydihydrofuran-2-one (= β-hydroxy-γ-butyrolactone), 0.405 g of phenothiazine, 496 g of triethylamine and N, N-dimethylformamide 4384. 9 g was added, and a mixed solution of 496 g of methacrylic acid chloride and 1964 g of N, N-dimethylformamide was added dropwise over 2 hours under a nitrogen atmosphere. After aging for 1 hour, the reaction was terminated. During this time, the temperature of the liquid was controlled to −32 ° C. or lower.
1600 g of water was added to the resulting reaction solution to quench the acid chloride, and 5133 g of toluene was further added. This liquid was transferred to a washing tank 2 equipped with a stirrer and washed with water three times under the condition of a temperature of 40 ° C. In any case, 100 parts by weight of the cleaning liquid was used with respect to 100 parts by weight of the liquid to be cleaned. By this quenching and washing operation, unreacted 4-hydroxydihydrofuran-2-one and methacrylic acid chloride are removed, and as an organic layer, N, N-dimethylformamide / methacrylic acid 5-oxotetrahydrofuran-3-yl ester / A toluene solution was obtained. As a result of analyzing this liquid by liquid chromatography, 254.4 g of 5-oxotetrahydrofuran-3-yl ester of methacrylic acid was produced.
This liquid was concentrated using a glass evaporator 3 having an internal volume of 10 L [50 mmHg (6664 Pa), 60 ° C.], and the generated slurry was filtered off. After separation by filtration, the resultant was rinsed with 868 g of toluene, and the obtained filtrate was further concentrated to obtain 899 g of a crude concentrated solution.
The obtained crude concentrated liquid was further concentrated by WFE (Wiped Film Evaporator) [200 mmHg (26658 Pa), 60 ° C.] to obtain 572 g of concentrated liquid. This concentrated solution was subjected to a pressure of 0.34 mmHg (45.3 Pa) and a temperature of 90 ° C. using a glass centrifugal molecular distillation apparatus 4 (trade name “MS-150” manufactured by Nippon Vehicle Manufacturing Co., Ltd.). Molecular distillation yielded 133.1 g of methacrylic acid 5-oxotetrahydrofuran-3-yl ester (purity 98.6%).

Example 5
According to the production process diagram of FIG. 1, methacrylic acid 2-methyladamantan-2-yl ester (= 2-methacryloyloxy-2-methyladamantane) was produced.
Into a glass reactor 1 having an internal volume of 10 L, 513.3 g of 2-methyladamantan-2-ol (= 2-methyl-2-adamantanol), 3764 g of toluene and 1093.2 g of triethylamine were placed, and methacrylic acid was added in a nitrogen atmosphere. A mixture of 420 g and 144 g of chloride was added dropwise over 1 hour. After aging for 48 hours, the reaction was terminated. During this time, the temperature of the liquid was controlled to 55 ° C. or lower. As a result of analyzing the reaction solution by liquid chromatography, 734.1 g of 2-methyladamantan-2-yl methacrylate was formed.
This reaction solution was transferred to a washing tank 2 equipped with a stirrer, and under conditions of a temperature of 40 ° C., once with water, twice with a 15% by weight aqueous sodium carbonate solution, and once with a 10% by weight aqueous sodium chloride solution. Batch washed twice. In each case, 50 parts by weight of the cleaning liquid was used with respect to 100 parts by weight of the liquid to be cleaned. By this washing operation, unreacted 2-methyladamantan-2-ol and methacrylic acid chloride were removed, and a toluene solution of 2-methyladamantan-2-yl methacrylate was obtained as an organic layer.
The organic layer was concentrated using a glass evaporator 3 having an internal volume of 10 L [50 mmHg (6664 Pa), 80 ° C.] to obtain 954 g of a concentrated liquid.
This concentrated solution was subjected to molecular distillation under the conditions of a pressure of 0.15 mmHg (20 Pa) and a temperature of 72 ° C. using a glass centrifugal molecular distillation apparatus 4 (product name “MS-150” manufactured by Nippon Vehicle Manufacturing Co., Ltd.). As a result, 491.9 g of 2-methyladamantan-2-yl methacrylate (purity 98.2%) was obtained.

Example 6
According to the production process diagram of FIG. 1, methacrylic acid 5,5-dimethyl-2-oxotetrahydrofuran-3-yl ester (= α-methacryloyloxy-γ, γ-dimethyl-γ-butyrolactone) was produced.
In a glass reactor 1 having an internal volume of 10 L, 510 g of 3-hydroxy-5,5-dimethyldihydrofuran-2-one (= α-hydroxy-γ, γ-dimethyl-γ-butyrolactone), 4325 g of toluene and 525 g of triethylamine were added. In a nitrogen atmosphere, a mixed solution of 528 g of methacrylic acid chloride and 1821 g of toluene was added dropwise over 1 hour. After aging for 1 hour, the reaction was terminated. During this time, the temperature of the liquid was controlled to 20 to 30 ° C. or lower. As a result of analyzing the reaction liquid by gas chromatography, 734 g of methacrylic acid 5,5-dimethyl-2-oxotetrahydrofuran-3-yl ester was produced.
This reaction solution was transferred to a washing tank 2 equipped with a stirrer, and was subjected to a temperature of 40 ° C. once with water, once with a 10 wt% sodium carbonate aqueous solution, and once with a 10 wt% sodium chloride aqueous solution. Batch washed twice. In any case, 100 parts by weight of the cleaning liquid was used with respect to 100 parts by weight of the liquid to be cleaned. By this washing operation, unreacted 3-hydroxy-5,5-dimethyldihydrofuran-2-one and methacrylic acid chloride are removed, and as an organic layer, methacrylic acid 5,5-dimethyl-2-oxotetrahydrofuran-3- A toluene solution of yl ester was obtained.
The organic layer was concentrated [45 mmHg (5998 Pa), 50 ° C.] using a glass evaporator 3 having an internal volume of 10 L. Subsequently, the concentrated solution was subjected to a pressure of 0.03 mmHg (4.0 Pa) and a temperature of 60 using a glass centrifugal molecular distillation apparatus 4 (product name “MS-150”, manufactured by Nippon Vehicle Manufacturing Co., Ltd.) having a can capacity of 10 L. Batch distillation was performed under the condition of ° C to obtain 409.5 g of methacrylic acid 5,5-dimethyl-2-oxotetrahydrofuran-3-yl ester (purity 95.2%).

[Brief description of the drawings]
FIG. 1 is a production process diagram showing an example of the method of the present invention.

Claims (6)

The following formula ( 1d) or (1e ′ )
[Chemical 1]

[In Formula (1d), the number n of methyl groups bonded to the ring is an integer of 0 to 5 , and in Formula (1e ′), the number n of methyl groups bonded to the ring is 2 to 5. Is an integer ]
The following formula ( 2d) or (2e ' ) corresponding to (meth) acrylic acid or a reactive derivative thereof, respectively, having the cyclic skeleton represented by
[Chemical 2]

[Wherein, R represents a hydrogen atom or a methyl group. n is the same as above]
(Meth) acrylic acid ester having a cyclic skeleton for a resist resin monomer represented by formula ( 1d) or (1e ′ ) and an alcohol having a cyclic skeleton represented by the formula ( 1d) ) The cyclic skeleton is obtained by subjecting a reaction product with acrylic acid or a reactive derivative thereof to molecular distillation under the conditions of a pressure of 0.0001 to 0.5 mmHg (0.0133 to 68 Pa) and a temperature of 10 to 100 ° C. The manufacturing method of the (meth) acrylic acid ester which has the cyclic | annular frame | skeleton for resist resin monomers including the process of distilling the (meth) acrylic acid ester which has.
The method for producing a (meth) acrylic acid ester having a cyclic skeleton for a resist resin monomer according to claim 1, wherein n is 0 in the formula (1d) .
The reaction product of an alcohol having a cyclic skeleton represented by the formula ( 1d) or (1e ′ ) and (meth) acrylic acid or a reactive derivative thereof is selected from water, an aqueous alkali solution, and an aqueous salt solution. A method for producing a (meth) acrylic acid ester having a cyclic skeleton for a resist resin monomer according to claim 1 or 2, which is subjected to molecular distillation after washing with a seed washing solution.
  The (meth) acrylic acid having a cyclic skeleton for a resist resin monomer according to claim 3, wherein the amount of the cleaning liquid used is 10 to 200 parts by weight per 100 parts by weight of the liquid to be cleaned per cleaning process. Esters manufacturing method.
  After cleaning with the cleaning solution, the solvent is removed under the conditions of a temperature of 10 to 100 ° C. and a pressure of 5 to 300 mmHg.
5. A method for producing a (meth) acrylic acid ester having a cyclic skeleton for a resist resin monomer according to claim 3 or 4, which is subjected to molecular distillation.
A reaction product of an alcohol having a cyclic skeleton represented by the formula ( 1d) or (1e ′ ) and (meth) acrylic acid or a reactive derivative thereof is selected from activated carbon, a chelate resin, a chelate fiber, and a zeta potential membrane. The (meth) acrylic acid ester having a cyclic skeleton for a resist resin monomer according to claim 1 or 2, which is subjected to molecular distillation after being subjected to an adsorption treatment using at least one kind of adsorbent. Manufacturing method.

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