WO2001030739A1 - Process for the production of adamantyl (meth)acrylates - Google Patents

Abstract

A process for producing adamantyl (meth)acrylates or (meth)acrylates having lactone ring skeletons from adamantyl alcohols or alcohols having lactone ring skeletons and (meth)acrylic acid or reactive derivatives thereof, which comprises subjecting the product obtained by reacting the above cyclic alcohol with (meth)acrylic acid or a reactive derivative thereof to molecular distillation to recover formed (meth)acrylate of the cyclic alcohol as the distillate. This process makes it possible to produce efficiently high-quality (meth)acrylates of the cyclic alcohols little containing impurities.

Description

 Specification Manufacturing method for adamantyl (meta) acrylates Technical field

 The present invention relates to a method for producing a (meth) acrylic acid ester having a cyclic skeleton such as adamantyl (meth) acrylate which is useful as a raw material monomer for various plastic molded articles and optical materials. About. Background art

 Polymers of (meth) acrylic acid esters having an adamantane skeleton such as adamantyl (meth) acrylates have high heat resistance, high impact resistance, and excellent optical properties. It is expected to be used as an optical material such as various plastic molded products and resist resins. In addition, a polymer of a (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 and the like.

 As a method for producing adamantyl mono (meth) acrylates, Japanese Patent Publication No. Hei 7-61880 discloses that adamantandiols are dissolved in a solvent such as toluene and p-toluenesulfonic acid or the like is used. After reacting with (meth) acrylic acid by heating in the presence of the above catalyst to form a monoester, the reaction solution is neutralized with aluminum to remove insolubles and solvent, and then n-hexane is removed. A method for obtaining the adamantyl mono (meth) acrylate by recrystallization using the same is disclosed.

When adamantyl (meth) acrylates are used, for example, as a monomer material for optical materials, impurities must be added to sufficiently exhibit optical characteristics. High purity products with low content are required. However, in the above method of neutralizing the reaction mixture and recrystallizing from n-hexane, impurities such as coloring substances are easily incorporated into the crystal, and high-quality adamantyl (meth) acrylates and the like are efficiently used. You can't get good. This is also true for (meth) acrylic esters having other cyclic skeletons.

 Further, conventionally, there is no known method for efficiently obtaining a liquid compound at room temperature with high purity, which is a (meth) acrylate having an adamantane skeleton and a lactone skeleton. 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) acrylates, which is liquid at room temperature, with high purity and high efficiency. is there.

 The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a reaction between an alcohol having a cyclic skeleton such as adamantanol and (meth) atalinoleic acid or a reactive derivative thereof. When the resulting reaction product was subjected to molecular distillation, it was found that (meth) acrylic acid esters having a high-purity cyclic skeleton [such as adamantyl (meth) acrylates] could be efficiently produced. The present invention has been completed.

That is, the present invention provides the following formula (la), (lb), (lc), (Id) or (le)

(lb) (lc) (Id) ocll

'3 n

 (le)

[In formula (la), R "represents a hydrogen atom or a methyl group, and X represents a hydrogen atom, a hydroxyl group or a (meth) acryloyloxy group. In the formula (lb) (le), a bond to a ring The number n of the methyl groups used is an integer of 0.5] from the alcohol having a cyclic skeleton represented by the formula (1) and (meth) acrylic acid or a reactive derivative thereof corresponding to the following formula (2a) ( 2b) (2c) (2d) or (2e)

(2a) (2b) (2c) (2d)

(2e)

 [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 °, n is the same as above

]

A method for producing a (meth) acrylic acid ester having a cyclic skeleton represented by the following formula (la), (lb), (lc), (Id) or (le) Subjecting the reaction product of the alcohol having a cyclic skeleton to (meth) acrylic acid or a reactive derivative thereof to molecular distillation to distill the (meth) acrylic ester having the cyclic skeleton Disclosed is a method for producing a (meth) acrylic ester having a cyclic skeleton containing:

 In the formulas (lb), (lc), (Id), and (le), n is preferably 0.

In the above-mentioned production method, an alcohol having a cyclic skeleton represented by the formula (la), (lb), (lc), (Id) or (le) is reacted with (meth) acrylic acid or a reactive derivative thereof. The reaction product may be washed with at least one washing solution selected from water, an aqueous alkali solution and an aqueous salt solution, and then subjected to molecular distillation. Also, a reaction product of an alcohol having a cyclic skeleton represented by the formula (la), (lb), (lc), (Id) or (le) with (meth) acrylic acid or a reactive derivative thereof. Is preferably subjected to an adsorption treatment using at least one adsorbent selected from activated carbon, a chelating resin, a chelating fiber and a zeta potential membrane, followed by molecular distillation. The molecular distillation can be performed, for example, under the conditions of a pressure of 0.0001 to 0.5 mmHg (0.013 33 to 68 Pa) and a temperature of 10 to 100 ° C. BRIEF DESCRIPTION OF THE FIGURES

 FIG. 1 is a manufacturing process diagram showing an example of the method of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION

 The process for producing a (meth) acrylic acid ester having a cyclic skeleton according to the present invention comprises the step of preparing a cyclic skeleton represented by the above formula (la), (lb), (lc), (Id) or (le). The reaction product of the alcohol and the (meth) acrylic acid or a reactive derivative thereof is subjected to molecular distillation to obtain a compound represented by the formula (2a) or (2a) corresponding to the alcohol.

The method includes at least a step of distilling out the (meth) atalylic ester having a cyclic skeleton represented by 2b), (2c), (2d) or (2e).

1 represented by the formula used as a reaction raw material (la) - In Adamantano Ichiru such, the two R ^a, may be the same group, it may also be a different group les. X is a hydrogen atom, a hydroxyl group or a (meth) acryloyloxy group.

 As typical 1-adamantanols represented by the formula (la), for example,

, 1—adamantanol, 3,5-dimethyl 1—adamantanol, 1,3-adamantanediol, 5,7—dimethyl-1,3,3-adamantanediol, 3- (meth) acryloyl Examples include noroxy-1 -adamantano, 3- (meth) atalyloyloxy-5,7-dimethyl-11-adamantanol.

The 1-adamantanol represented by the formula (la) is obtained by converting a corresponding adamantane having no or one hydroxy group into an N-hydroxy imide such as N-hydroxyphthalimide. System catalyst and necessary Depending on the reaction, metal compounds such as vanadium compounds (for example, vanadium acetyl acetate, vanadyl acetyl acetate, etc.) and cobalt compounds (for example, cobalt acetate, cobalt acetyl acetate, etc.) It can be obtained by oxidizing with oxygen in the presence to introduce a hydroxyl group at the bridgehead of the adamantane ring. In this method, the amount of the N-hydroxyimide catalyst used is, for example, from 0.000 to 0.01, preferably 0.00 to 0.1, per mole of adamantane. It is about 0.3 mol. The amount of the metal compound promoter used is, for example, about 0.001 to 0.5 mol, preferably about 0.005 to 0.1 mol, per 1 mol of the adamantane. The oxidation reaction is carried out at normal pressure or under pressure in an organic solvent such as an organic acid such as acetic acid, nitriles such as acetonitrile and benzonitrile, and a halogenated hydrocarbon such as triphenylenomethylbenzene. [For example, about 5 to 40 atm (0.505 to 4.04 MPa)], for example, at a temperature of about 40 to 150 ° C, preferably about 60 to 120 ° C. The above 1-adamantanol is obtained by brominating adamantane with bromine and then treating with hydrochloric acid to form adamantane monool, or reacting the adamantane monool with sulfuric acid. It can also be obtained by using adamantanediol (Japanese Patent Publication No. Hei 7-19860). However, the above-mentioned method using an N-hydroxyimide-based catalyst has been proposed because it does not use halogen, which is a problem when used as a resist polymer, and can be easily produced under mild conditions. preferable.

Among the 1-adamantanols represented by the formula (la), a compound in which X is a (meth) acryloyloxy group is a compound in which X is a hydroxyl group according to the esterification method described later. (Meta) It can be obtained by reacting with acrylic acid or its reactive derivative. In the adamantane methanols represented by the formula (lb), the number of methyl groups bonded to the ring is about 0 to 3. Methyl groups are often attached to the bridgehead carbon atom.

 Representative examples of adamantane methanols represented by the formula (lb) include, for example, α, adimethytinol 1-adamantanemethanol, hi, a, 3-trimethinolane 1-adamantane methanol a, a, 3, 5—tetramethyl-1-adamantanemethanol.

 The adamantane methanol represented by the formula (lb) is composed of, for example, an adamantane compound having a hydrogen atom at a bridgehead, (a) biacetyl, (b) oxygen, and (c) a metal compound. It can be obtained by reacting a acylating agent to give a corresponding acetyl-adamantane derivative and reacting the acetyl-adamantane derivative with methylmagnesium halide (Grignard reagent).

 As the metal compound (c), for example, a cobalt compound such as cobalt acetyl acetate is preferably used. The amount of the biacetyl (a) used is 1 mol or more (for example, 1 to 50 mol), and preferably about 1.5 to 20 mol, per 1 mol of the adamantane compound having a hydrogen atom at the tachibana head position. Oxygen is often used in excess with respect to the adamantane compound. The amount of the metal compound (c) to be used is, for example, about 0.001 to 1 mol, and preferably about 0.001 to 0.7 mol, per 1 mol of the adamantane compound. The acylation reaction is carried out in a suitable solvent such as acetic acid at a temperature of about 40 to 150 ° C. The reaction of the acetyl-adamantane derivative with methylmagnesium halide can be carried out under general Grignard reaction conditions.

In the 2-adamantanols represented by the formula (lc), n is usually about 0 to 3, preferably about 0 to 2. n methyl groups Often attached to a carbon atom.

 Representative examples of 2-adamantanol represented by the formula (lc) include, for example, 2-methyl-2-adamantanol, 2,5-dimethyl-2-adamantanol, 2,5, 7 — Trimethyl-2 — adamantanol.

 The 2-adamantanol represented by the formula (lc) 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 3-hydroxy γ-petit mouth lactones represented by the above formula (Id), η is usually about 0 to 5, preferably about 0 to 3.

As typical examples of β-hydroxy-γ-butyl lactones represented by the formula (Id), 3—hydroxy-γ-butyrolactone, —hydroxy-, di-methylinole-γ Butyrolataton, / 3-Hydroxy-1-γ, γ-Dimethyl-1-γ-butyrolataton, / 3-Hydroxy-h, α, / 3 — Trimethylinyl-7-Butyrolactone,] 3—Hydroxy / 3 , Y, γ-trimethinoley γ-butyrolactone; 3-hydroxy α, α, β, γ, γ-pentamethyl- _γ -petit mouth rataton.

In the α-hydroxy- ₁₇ -petit mouth lactones represented by the above formula (le), η is usually about 0 to 5, preferably about 0 to 3.

As representative examples of the hydroxy-γ-petit mouth ratatones represented by the formula (le), for example, α-hydroxy- _l -butyrolactone, α-hydroxy-ct-methinole γ-butyrolactone, a—hydroxy-1 / 3, β-dimethyl-γ-butyrolactone, hi-hydroxy α, β, -trimethinole γ-butyrolactone, ct-hydroxyl "/ ,, γ— Dimethinoley γ — pu, tyrolactone, a — Hydroxy α, γ, γ — Trimethinole γ — Buty Russia lactone, ct- human Dorokishi one | 3, β 'γ, γ- Te Toramechinore one γ- Breakfast Ciro Rata tons, α- human Dorokishi one shed, β, β, y, γ- Pentamechinore one _γ - Buchiro lactone And the like.

 As the reactive derivative of the (meth) acrylic acid in the present invention, a derivative capable of producing a corresponding ester by reacting with alcohol, for example, a (meth) acrylate such as (meth) acrylic acid chloride Atyl acid halide; acid anhydrides such as (meth) acrylic anhydride; methyl (meth) acrylate, ethyl (meth) acrylate, vinyl (meth) acrylate, (meth) acrylic acid 2 — (Meth) acrylic acid esters such as propenyl and the like (for example, alkyl esters, alkenyl esters and the like).

 The reaction (esterification) between the alcohol having a cyclic skeleton such as the adamantanols and the (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 Halogenated hydrocarbons such as 1,2-dichloroethane, black mouth benzene, and trifluoromethylbenzene; Estenoles such as ethyl acetate and butynole acetate; And other solvents such as sopropynole ether, dibutynole ether, aniso monoole and the like, and mixed solvents thereof. As the solvent, a solvent azeotropic with water by-produced and capable of being separated from water (a solvent capable of azeotropic dehydration), for example, toluene is preferable.

Examples of the catalyst used in the esterification reaction include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and heteropoly acids (for example, kytungstic acid, chemimolybdic acid, lintungstic acid, linmolybdic acid, etc.). Benzenesulfonate, ρ-toluenesolenoate, naphthalenesolenoate, methansolenate Examples include sulfonic acids such as sulfonic acid, trifluoromethanesulfonic acid, ethanesulfonic acid, and sulfonic acid-based strongly acidic ion exchange resins. These can be used alone or in combination 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 to the system, or to supply oxygen to the system. Oxygen can be used after being diluted with an inert gas such as nitrogen.

 The esterification reaction between the alcohol having a cyclic skeleton such as the adamantanols and (meth) acrylic acid is carried out under normal pressure or reduced pressure, for example, 50 to 150. It is performed at a temperature of about C. The amount of (meth) acrylic acid used may be 1 mol or more per mol of the hydroxyl group to be esterified, but may be 1.1 mol or more (for example, 1.1 to 10 mol). Many. In order to increase the conversion of the raw materials, the reaction is preferably carried out while distilling off by-product water out of the system.

On the other hand, the reaction between an alcohol having a cyclic skeleton such as adamantanols and a reactive derivative of (meth) acrylic acid is carried out in the presence of a base or a transesterification catalyst depending on the type of the reactive derivative. be able to. For example, when (meth) acrylic acid halide or an acid anhydride is used as a reactive derivative of (meth) acrylic acid, for example, in the presence of a base (acid scavenger) such as triethylamine or pyridine, The reaction is carried out in the solvent at a temperature of about 0 to 100 ° C. When (meth) acrylic acid ester is used as the reactive derivative of (meth) acrylic acid, a conventional transesterification catalyst or alkenyl (meth) acrylic acid is used as the reactive derivative. In the case of using a catalyst, especially the presence of a catalyst of a Group 3 element compound of the periodic table (for example, a samarium compound such as samarium acetate, trifluoromethanesnolephonate, or a samarium complex) is present. The reaction is carried out at a temperature of about 0 to 150 ° C., for example, in the solvent described above. The reaction of an alcohol having a cyclic skeleton, such as the above adamantanols, with (meth) atalylic acid or a reactive derivative thereof results in the formation of the corresponding formula.

(Meth) acrylic ester having a cyclic skeleton such as adamantyl (meth) atalylate represented by (2a), (2b), (2c), (2d) or (2e) is formed . In the formula (2a), Y represents a hydrogen atom, a hydroxyl group or a (meth) acryloyloxy group. Compounds in which Y is a hydroxyl group (monoester) or compounds in which (meth) acryloyloxy is a compound (diester) are compounds in which X in the formula (la) is a hydroxyl (diol) Is produced by reacting with a (meth) acrylic acid or a reactive derivative thereof. The monoester or diester can be selectively obtained by appropriately adjusting the amount of (meth) acrylic acid or a reactive derivative thereof, the reaction temperature, the reaction time, and the like. The diester compound is obtained by reacting a compound of the adamantanol represented by the formula (la) wherein X is a (meth) acryloyloxy group with (meth) acrylic acid or a reactive derivative thereof. It can also be obtained by having As a component that reacts with an alcohol having a cyclic skeleton such as adamantanols, a halogen that deteriorates performance when used as a resin for a resist or the like is not included in the reaction product. Therefore, (meth) acrylic acid is preferred.

Representative examples of 1-adamantyl (meth) acrylates represented by the formula (2a) include, for example, 1-acryloyloxydamantane, 1-methacryloyloxydamantane, 1-Cryroyloxy-1,3,5-dimethyladamantane, 1—Methacryloyloxy-1,3,5-dimethylthioadamantane, 1 Atari Mouth inoleoxy-3—Hydroxy 5,7 Dimethinorea damantane, 1—Hydroxy 1 3 — methacryloyloxy — 5,7 — dimethyl adamantane, 1, 3 — bisacryloyloxy Examples include 5,7-dimethyladamantane and 1,3-bismethacryloyloxy 5,7-dimethyladamantane. These compounds are liquid at room temperature.

 As a typical example of the (meth) acrylic acid ester having an adamantylmethyl group represented by the above formula (2b), for example, 1— (1—acryloyloxy-1-1-methylethyl) Adamantane, 1— (1-acryloyloxy-1-methylethyl) 1-3-methyladamantane, 1— (1—acrylonioleoxy-1—methinoleetinole) 1,3,5-dimethinorea damantane, 1— (1-methacrylic 1- (1 -methacryloyloxy 1 -methylethyl) 13 -methyl adamantane, 1 _ (1 -methacryloirenoxy-1 -methinoleethinole) -3,5-dimethyla Damantane and the like.

 Representative examples of the 2-adamantyl (meth) acrylates represented by the above formula (2c) include, for example, 2-acryloyloxy-1,2-methyladamantane, and 2-acryloyloxy 2 , 5-dimethyl adamantane, 2-acryloyloxy 2, 5, 7-trimethyl adamantane, 2-metharyloyloxy 1-2-methyl adamantane, 2- methacryloyloxy 1-2, 5-dimethinoreadamantane, 2-methacrylonioleoxy-2, 5, 7-trimethyladamantane and the like.

As typical examples of the (meth) acrylic acid ester having a γ-butyrolactone ring represented by the above formula (2d), for example, / 3—acryloyloxy-y-butyrolataton, 3 one Atta Li Roiruokishi a, alpha-dimethyl one gamma - butyrolactone tons, - § click Li Roinoreokishi gamma, .gamma. Jimechinore gamma - butyrolactone tons, J3- Ata Li port Lee Noreokishi one _alpha, a, 3 - Application Benefits Mechinore - gamma —Butyrolactone, / 3 —acryloyloxy-1] 3, γ, trimethyltinone γ-butyrolactone, / 3—acryloyloxy, hi, β, γ , Γ-pentamethinole γ-butyrolactone,] 3-methacryloylonoxy-γ-butyrolactone,] 3-methacryloynoleoxy-, HI-dimethinole-γ-butyrolactone, / 3-methacryloyl-norexoxy-γ , y —Dimethinole — γ —butyrolactone, 0 —methacrylinoleoxy-α,, / 3 —trimethylinole γ —butyrolactone,] 3—methacrylinoleoxy j3, y, y —trimethylinole γ _ Butyrolataton, / 3-methacryloylonoleoxy-α, a, β, γ, <y-pentamethinole-γ-butyrolactone, etc. having a γ _ petit-mouth lactone ring represented by the formula (2e) Representative examples of (meth) acrylate esters include, for example, α-acryloyloxy-γ-butyrolactone, α- Noreoxy mono-α-methinole γ-butyrolactone, polyacryloxyl] 3, | 3_dimethyl-"/-butyrolactone, c-acrylyl-norreoxy mono-, β, / 3-trimethyl-γ- Butyrolactone, polyacryloinoleoxy-gamma-dimethinole-γ _ butyrolactone, hyacryloinoleoxy-α, y, γ-trimethylolone γ-butyrolactone, ct-acryl Leunorreoxy-1 / 3, β, y, γ — tetramethinole — γ — butyrolactone, β-β, γ, Ί-pentamethyl-γ —butyrolactone, α — methacrylic Royloxy peroxylactone, ct—methacrylic acid / norethoxy-methine! / — Butyrolataton, _α— methacryloynorreoxy—, _dimethyl- _γ Butyl lorataton, α-methacryloyl oleoxy-ct, β, / 3—trimethylinone γ-butyrolactone, hi methacrylonioroxy 1 !, γ—dimethinole γ-butyrolactone, α—methacryloyl Noreoxy-, 7, γ-trimethylino- _γ -Ptyloractone, Hi-methacryloynorreoxy-13, β, γ, γ-Tetramethyl-1-γ-butyrolactone, α-Methacryloyloxy α, β, β, γ, γ-pentamethyl-γ-butyrolataton It is.

 [Washing process (A)]

 The reaction product (reaction mixture) thus obtained may be subjected to the molecular distillation process as it is, but before that, it is washed with at least one washing solution selected from water, an aqueous alkali solution and an aqueous salt solution. Preferably, it is subjected to a washing step of washing. 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 are removed. It can be removed efficiently.

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

 Examples of the salt aqueous solution include alkali metal such as sodium chloride, potassium chloride, magnesium chloride, calcium chloride, sodium sulfate, and magnesium sulfate, or alkaline earth metal. An aqueous solution of metal haptic compounds or sulfates may, for example, be mentioned.

Washing may be performed using any one of water, an aqueous alkali solution, and an aqueous salt solution, but it is preferable to use a combination of at least two cleaning solutions. The number of washings may be one or more for each washing solution. The amount of the cleaning liquid used is, for example, about 100 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 treatment. The temperature at the time of washing is, for example, about 10 to 50 ° C. If the washing temperature is too high, (meth) acrylic acid esters having a cyclic skeleton such as hydroxyadamantyl (meth) acrylates may polymerize. There is.

 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 separating property.

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

 [Adsorption treatment process (B)]

A reaction product of an alcohol having a cyclic skeleton such as adamantanols and (meth) acrylic acid or a reactive derivative thereof undergoes the washing step (A) or goes through the washing step. Without being applied, it may be subjected to the adsorption treatment step (B). In the adsorption treatment step (B), the reaction mixture or the washing treatment liquid obtained above is subjected to solvent substitution (exchange) as necessary, and then subjected to adsorption treatment. The adsorption treatment is not particularly limited as long as it can remove impurities in the reaction product, but at least one selected from activated carbon, chelating resin, chelating fiber and zeta potential membrane is used. Treatment using a type of adsorbent is preferred. The adsorption treatment may be performed by combining two or more treatment methods. The solvent replacement can be carried out, for example, by distilling off the reaction solvent in the reaction mixture or the washing solution obtained in the washing step (A), and adding a solvent used for the adsorption treatment. The distillation of the reaction solvent varies depending on the type of the solvent, but, for example, a pressure of about 5 to 100 mmHg (666 to 13300 Pa) and a pressure of about 10 to 50 ° C. It is performed at a temperature of about If the temperature is too high, there is a risk that (meth) acrylate esters having a cyclic skeleton such as adamantyl (meth) acrylates will be polymerized. In the solvent replacement, the reaction solvent does not necessarily need to be completely distilled off, but may be concentrated, for example, by 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 gas activated carbon and chemical activated carbon can be used. The origin of activated carbon is also not particularly limited, and activated carbon obtained from plant-based materials such as wood, sawdust, fruit husk, and fruit husk charcoal; minerals such as peat, lignite, lignite, coatas, coal pitch, and oil pitch Activated carbon obtained from raw materials; any of activated carbon obtained from synthetic resin raw materials such as phenolic resin and acrylic resin can be used. The shape of the activated carbon is also not particularly limited, and may be any of powder, granule, fiber, and the like. The specific surface area of the activated carbon is, for example, about 10 to 300 m ² Z g. The liquid to be subjected to the activated carbon treatment is not particularly limited as long as it is a solution. From the viewpoint of the effect of removing impurities, for example, an alcohol such as methanol or ethanol is preferable as the solvent of the liquid to be treated. The concentration of the (meth) acrylic acid ester having a cyclic skeleton in the liquid to be subjected to the activated carbon treatment can be appropriately selected within a range that does not impair the treatment efficiency, workability, and the like. weight. / ₀ , preferably about 5 to 30 weight. / ₀ or so. When an alcohol such as methanol is used as the activated carbon treatment solvent, the amount of the alcohol used is, for example, 200 to 100 parts by weight of (meth) acrylic acid ester having a cyclic skeleton. It is about 1000 parts by weight. The amount of activated carbon used can also be appropriately selected in consideration of treatment efficiency, workability, etc., for example, based on 100 parts by weight of a (meth) acrylic acid ester having a cyclic skeleton contained in the liquid to be treated. 5 to 100 parts by weight, 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 processing temperature is too high, (meth) acrylic acid esters having a cyclic skeleton such as adamantyl (meth) acrylate may be polymerized. For the activated carbon treatment, known methods such as a batch type, a continuous type, a fixed bed type, and a fluidized bed type can be adopted. Efficient removal of mainly colored components by activated carbon treatment Thus, a (meth) acrylic 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 has a functional group capable of forming a chelate with a metal, and a typical example thereof is iminodiacetic acid type. And chelating resins such as polyamine type. The exchange capacity of the chelating resin is not particularly limited, but for example, a resin having a capacity of about 0.1 to 2 mol Z1 is used.

 The liquid to be treated to be subjected to the chelating resin treatment is not particularly limited as long as it is a solution. However, from the viewpoint of the effect of removing impurities, for example, the solvent of the liquid to be treated may be a metal oxide or a solvent. Preference is given to phenolic resins such as ethanol, esters such as ethyl acetate and butyl alcohol. 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, and the like, but is generally 1 to 50 weight. %, Preferably about 5 to 30% by weight. The amount of the chelating resin to be used can be appropriately selected in consideration of the processing efficiency, workability, and the like. It is about 0.000 mol.

 The processing temperature in the chelate resin processing is, for example, about 10 to 50 ° C. If the treatment temperature is too high, a (meth) acrylic ester having a cyclic skeleton such as adamantyl (meth) acrylate may be polymerized. Known methods such as a batch type, a continuous type, a fixed bed type, and a fluidized bed type can be used for the chelating resin treatment. By the chelating resin treatment, mainly trace metal components (eg, Fe, A1, etc.) can be efficiently removed.

The chelate fiber used for the chelate fiber treatment is not particularly limited as long as a chelate functional group is immobilized on a natural fiber by a chemical bond, and a typical example thereof is cellulose. Chelate fiber based on Brand name “Kires Toffeibar”, manufactured by Kiresto Co., Ltd.).

 The liquid to be treated to be subjected to the chelate fiber treatment is not particularly limited as long as it is a solution. However, from the viewpoint of the effect of removing impurities, for example, the solvent of the liquid to be treated may be methanol or ethanol. Isopropyl alcohols such as isopropinoleanol and octanol; esters such as ethyl acetate and butynole acetate; aromatic hydrocarbons such as toluene; aliphatic hydrocarbons such as hexane and heptane; methylene chloride; Halogenated hydrocarbons such as 1,2-dichloroethane; ethers such as tetrahydrofuran are preferred. The concentration of the (meth) acrylic ester having a cyclic skeleton in the liquid to be treated to be treated with the chelate fiber can be appropriately selected within a range that does not impair the treatment efficiency, workability, and the like. It is about 0% by weight, preferably about 5 to 30% by weight. The amount of chelating fiber used can also be appropriately selected in consideration of processing efficiency, workability, and the like.

 The processing temperature in the chelate fiber processing is, for example, about 10 to 50 ° C. If the treatment temperature is too high, a (meth) acrylic ester having a cyclic skeleton such as adamantyl (meth) acrylate may be polymerized. Known methods such as a batch type, a continuous type, a fixed bed type, and a fluidized bed type can be used for the chelate fiber treatment. By chelating fiber treatment, trace metal components (eg, Fe, A1, etc.) can be efficiently removed.

 The zeta potential membrane treatment is performed by passing the liquid to be treated through the zeta potential membrane. The zeta potential membrane used in 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. Plus "etc. can be used. Examples of the material of the zeta potential membrane include resin, cellulose, perlite, silica earth, and glass fiber.

The solvent of the liquid to be treated for the zeta potential membrane treatment is not particularly limited. As typical examples, there may be mentioned, for example, alcohols such as methanol and ethanol; ethenole acetates such as ethynole acetate and butynole acetate; and aromatic hydrocarbons such as toluene and xylene. The concentration of the (meth) acrylic acid ester having a cyclic skeleton in the liquid to be subjected to the zeta potential membrane treatment can be appropriately selected within a range that does not impair the treatment efficiency, workability, and the like. weight. / ₀ , preferably about 5 to 30% by weight.

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

 The processing temperature in the zeta potential membrane processing is, for example, about 10 to 50 ° C. If the treatment temperature is too high, (meth) acrylic esters having a cyclic skeleton such as adamantyl (meth) acrylates may be polymerized. By zeta potential membrane treatment, mainly trace metal components (eg, Fe, A1, etc.) can be efficiently removed.

 [Molecular distillation process (C)]

 The reaction product of an alcohol having a cyclic skeleton, such as adamantanols, with (meth) acrylic acid or a reactive derivative thereof has gone through the washing step (A) and / or the adsorption step (B). After or without going through the above-mentioned steps, usually after desolvation, it is subjected to the molecular distillation step (C).

 Desolvation varies depending on the type of solvent. For example, the temperature is 10 to 100 ° C (preferably 10 to 50.C), the pressure is 5 to 300 mmHg (665 to 39). 900 Pa]) [preferably 5 to 100 mmHg (666 to 13300 Pa)].

In the molecular distillation step (C), a (meth) acrylate ester having a cyclic skeleton such as adamantyl (meth) acrylates is distilled out by molecular distillation. Molecular distillation is a conventional molecular distillation device, such as a pot-type molecular distillation device. T / JP 0/07315

 20

It can be performed using a falling film molecular distillation apparatus, a centrifugal molecular distillation apparatus, or the like. Among them, a centrifugal molecular distillation apparatus is particularly preferable because it can form an extremely thin liquid film and can instantaneously heat and evaporate a sample.

 The operating conditions for 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 about 10 to 80 ° C., more preferably about 10 to 65 ° C., and particularly preferably about 10 to 50 ° C. The pressure is, for example, 0.001 to 0.5 mmHg (0.013 3 to 66.5 Pa), preferably 0.00001 to 0.2 mmHg (0 0.13 to 26.6 Pa), more preferably about 0.001 to 0.1 ImmHg (0.013 to 13.3 Pa), and especially about 0. A level of about 0.01 to 0.05 mmHg (0.13 to 6.65 Pa) is preferred.

 If the operating temperature is too high, the (meth) acrylic acid ester having a cyclic skeleton such as adamantyl (meth) acrylate is polymerized, thereby lowering the purification yield and discoloring the product. The purity tends to decrease. Therefore, the present invention relates to a (meth) acrylic acid ester adamantyl (meta) which is liquid at ordinary temperature or has a cyclic skeleton having a melting point of 100 ° C. or less, particularly 50 ° C. or less. This is useful for the production of acrylics.

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

FIG. 1 is a manufacturing process diagram showing an example of the manufacturing method of the present invention. In this example, an alcohol having a cyclic skeleton (such as adamantanol) as a raw material, (meth) acrylic acid, a reaction solvent, a catalyst (acid catalyst), and a polymerization inhibitor, if necessary, are added to a reactor 1 (Reaction step). It also suppresses polymerization For this reason, air diluted with nitrogen may be supplied to the liquid in the reactor 1 for bubbling. 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 solution of water, an aqueous alkali solution and an aqueous salt solution (washing step). The washed organic layer usually contains a (meth) acrylate ester having a cyclic skeleton formed by the reaction (eg, adamantyl (meth) acrylate) and a reaction solvent. On the other hand, the water layer after washing contains unreacted raw materials and catalyst. Unreacted raw materials can be collected and reused by a conventional method. The organic layer after washing 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 forced, a (meth) acrylic acid ester having a desired cyclic skeleton (such as adamantyl (meta) acrylates) having an intended cyclic skeleton from the top of the tower (Such as the molecular distillation process). High boiling components such as polymerization inhibitors are discharged from the bottom of the column. Industrial applicability

 ADVANTAGE OF THE INVENTION According to this invention, (meta) acrylate (adamantyl (meta) acrylates, etc.) which has a high quality and has a high-quality cyclic skeleton with little impurity content is efficiently manufactured. it can. In addition, (meta) acrylate esters having a cyclic skeleton that is liquid at ordinary temperature (such as adamantyl (meta) acrylates) can be efficiently obtained with high purity. Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. JP 07315

 22 Example 1

 According to the manufacturing process diagram in Fig. 1, 1-methacryloyloxy-1,3-dimethyladamantane was manufactured.

 In a glass reactor 1 with an internal volume of 10 L, 3,5-dimethyl-1 -adamantanol 1200 g, methacrylic acid 1147 g, sulfuric acid 20.2 g, methquinone 1. 2 g and 5 211 g of toluene were added, and an oxygen-nitrogen mixed gas having an oxygen concentration of 5 mol% was supplied into the solution at a flow rate of 31 1 min. The temperature of the liquid was raised to 110 ° C., water produced as a by-product in the reaction was distilled off by azeotropic distillation with toluene, and the reaction was carried out for about 7.5 hours while returning only toluene to the reactor. As a result of analyzing the reaction solution by gas chromatography, 1-methacryloyloxy 3,5-dimethyladamantane was produced in an amount of 1400 g.

 The reaction solution was transferred to a glass washing tank 2 equipped with a stirrer, and 800 g of hexane was added. Then, under the condition of a temperature of 40 ° C., 30000 g of 10 wt. /. Washing was performed twice with an aqueous solution of sodium carbonate and three times with 300 g of water, for a total of five washes. By this washing operation, unreacted 3,5-dimethyl-1-adamantanol, methacrylic acid and sulfuric acid are removed, and as an organic layer, 1-methacrylic inoleoxy-3,5-dimethinoreadamantane is removed. A toluene-hexane solution was obtained.

 The organic layer was concentrated using a 10-liter glass evaporator 13 having an internal volume of 10 [L O mmHg (133 0 Pa), 35 ° C], to obtain 1091 g of a concentrated solution. Was. The concentrated solution was subjected to a pressure of 0.02 mmHg (2.66 Pa) using a glass centrifugal molecular distillation apparatus 4 (manufactured by Nippon Sharyo Co., Ltd., trade name: “MS-150”). ) And molecular distillation under the condition of a temperature of 40 ° C. to obtain 104 g of 1-methacryloylonoleoxy-1,3,5-dimethyladamantane (purity: 98.1%).

Example 2 According to the manufacturing process diagram in Fig. 1, 11-methacryloyloxy-adamantane (= 1-adamantyl methacrylate) was manufactured.

 In a glass reactor 1 with an inner volume of 10 L, 1-adamantanol 1100 g, methacrylic acid 1245 g, sulfuric acid 21.2 g, metoquinone 1.lg and toluene 4 Add 7 7 4 g, and oxygen concentration 5 mol in the solution. /. Was supplied at a flow rate of 31 Z. The temperature of the solution was raised to 110 ° C, water produced as a by-product in the reaction was distilled off by azeotropic distillation with toluene, and the reaction was carried out for about 6 hours while returning only toluene to the reactor. . As a result of analyzing the reaction solution by gas chromatography, 1-methacryloyloxydamantane was found to be produced in an amount of 133 g.

 The reaction solution was transferred to a glass washing tank 2 equipped with a stirrer, and toluene was added thereto, and then 774 g of toluene was added. 0 g 10 weight. /. Batch washing was performed three times, once with sodium carbonate aqueous solution. 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 to obtain [10 mmHg (1330 Pa), 35 ° C], and 2968 g of a concentrated solution was obtained. . The concentrated solution is desolvated using a glass centrifugal molecular distillation apparatus 4 (manufactured by Nippon Sharyo Co., Ltd., trade name “MS-150”), and then the glass centrifugal molecular distillation apparatus 4 is used again. (Manufactured by Nippon Sharyo Co., Ltd., trade name: “MS-150”) and molecular distillation under the conditions of pressure 0.03 mmHg (3.99 Pa) and temperature 40 ° C As a result, 984 g of 1-methacryloyloxyadamantane (purity: 98.0%) was obtained.

 Example 3

According to the manufacturing process diagram in Fig. 1, acrylic acid 1-1 (adamantane 1-yl) ) 1-Methylethyl ester [= 1 — (1 -acryloyloxy 1 -methylethyl) adamantane] was produced.

 In a glass reactor 1 having an internal volume of 10 L, 2- (adamantane-1-yl) -11-prononone-12-onole (= α, α-dimethinoreadamantane methanol) 60.4 g, 400 g of tetrahydrofuran and 1093 g of trietinoreamine were added, and 364 g of acrylic acid mouthride was added dropwise under a nitrogen atmosphere in 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. The reaction mixture was analyzed by liquid chromatography to find that 499 g of acrylic acid-111 (adamantane-11-yl) -111-methylethyl ester was produced.

 This reaction solution was transferred to a washing tank 2 equipped with a stirrer, and once under water at a temperature of 40 ° C, once with water, once with a 10% by weight aqueous sodium carbonate solution, and further with 10% by weight sodium chloride. Each batch was washed three times with an aqueous solution of lithium. 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- (adamantane-111)-1-butane-1-ol and acrylic acid trihydrate are removed, and the ata- lyte is removed as an organic layer. Linoleic acid 111 (adamantane) was obtained as a solution of 111-methylethylester in tetrahydrofuran.

 This organic layer was concentrated using a glass evaporator 3 having an inner volume of 10 L [50 mmHg (6664 Pa), 60 ° C] to obtain 1491 g of a concentrated solution. .

 To the obtained concentrated solution, 3973 g of methanol was added to precipitate a polymer. The slurry was separated by filtration and further concentrated [200 mmHg (266658 Pa)] to 60. C], 799 g of a concentrated solution was obtained.

The concentrated solution was centrifuged using a glass centrifugal molecular distillation apparatus 4 (manufactured by Nippon Sharyo Co., Ltd., trade name: “MS-150”) to obtain a pressure of 0.07 mmHg (0 Fifteen

 twenty five

93 P a), molecular distillation at a temperature of 58 ° C, and 452 g of acrylic acid 1-(adamantan 1-yl) 1-1-methylethynoleester (purity 95). 0%).

 Example 4

 According to the manufacturing process diagram in Fig. 1, 5-methoxyl trahydrodrofuran 13-inoleestenole (= β-metacrylo-inoleoxy-1γ-butyrolactone) was produced.

 In a glass reactor 1 having an internal volume of 10 L, 4-hydroxy-2-hydrofuran-1-2-one (= | 3 — hydroxy γ -butyrolactone) 40.2 g, phenothiazine 0.405 g, Add 496 g of triethylamine and 4.9 g of N, N-dimethylformamide, and in a nitrogen atmosphere, add 496 g of methacryloyl chloride and 1 N, N-dimethylformamide. 964 g of the mixture was added dropwise over 2 hours. After aging for 1 hour, the reaction was terminated. During this time, the temperature of the liquid was controlled to 13 ° C. or lower.

 To the resulting reaction solution, 160 g of water was added, acid chloride was quenched, and 513 g of toluene were further added. This solution was transferred to a washing tank 2 equipped with a stirrer, and washed three times with water at a temperature of 40 ° C. In each case, 100 parts by weight of the cleaning liquid was used with respect to 100 parts by weight of the liquid to be cleaned. As a result of this quench and washing operation, unreacted 4-hydroxydihydrofuran-1-one and methacrylic acid chloride are removed, and as an organic layer, methacryloleic acid 5-oxotetrahydrofuran is removed. An N, N-dimethylformamide / toluene solution of 13-yl ester was obtained. Analysis of this solution by liquid chromatography revealed that 254.4 g of methacrylic acid 5-year-old oxote trahydrofuran-1-furyl ester was produced.

This solution 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. Was. After filtration, the solid was rinsed with 8688 g of toluene, and the obtained filtrate was further concentrated to obtain 89.9 g of a crude concentrated liquid.

 The obtained crude concentrated solution was further concentrated by WFE (Wiped Film Evapolator), and the concentrated solution of 200 mmHg (26665 Pa) at 60 ° C and 5772 g was concentrated. Obtained. The concentrated solution was centrifuged using a glass centrifugal molecular distillation apparatus 4 (manufactured by Nippon Sharyo Co., Ltd., trade name: “MS—: 150”), and the pressure was 0, 34 mmHg (45.3 P). a), molecular distillation was carried out at a temperature of 90 ° C. to obtain 133.1 g of methacryloleic acid 5-oxotetrahydrofuran-13-inoleester (purity: 98.6%).

 Example 5

 According to the manufacturing process diagram in FIG. 1, methacrylic acid 2-methyladamantan-2-yl ester (= 2-methacryloyloxy-12-methyladamantane) was manufactured.

 In a glass reactor 1 with an internal volume of 10 L, 2-methyladamantan-2-ol (= 2-methyl-2-adamantanol) 5 13.3 g, toluene 3746 4 g and 3.2 g of lyethylamine was added, and a mixed solution of 420 g and 144 g of methacrylic acid chloride was dropped under a nitrogen atmosphere in 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. Analysis of the reaction mixture by liquid chromatography revealed that 74.1 g of 2-methyladamantane-2-ylester methacrylate was produced.

The reaction solution was transferred to a washing tank 2 equipped with a stirrer, and once under water at a temperature of 40 ° C, once with water, twice with a 15% by weight aqueous solution of sodium carbonate, and 10% by weight. Each batch was washed four times with a sodium chloride aqueous solution once in total. 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-methyladamantane-2-ol Then, the methacrylic acid mouthride was removed, and as a organic layer, a tonolene solution of methacrylic acid 2-methinorea damantane-2-inoreestenole was obtained.

 The organic layer was concentrated using a glass evaporator 13 having an inner volume of 10 L [50 mmHg (6664 Pa), 80 ° C], to obtain 9554 g of a concentrated solution. .

 Using a glass centrifugal molecular distillation apparatus 4 (manufactured by Nippon Sharyo Co., Ltd., trade name “MS-150”), the concentrated solution was subjected to a pressure of 0.15 mmHg (20 Pa), A molecular distillation was carried out at a temperature of 72 ° C. to obtain 491.9 g of 2-methyl adamantan-1-yl methacrylate (purity: 98.2%). Example 6

According to the manufacturing process diagram in Fig. 1, 5,5-dimethyl-2-oxotetrahydrofurofuran-3-yl methacrylate (= _{α- methacryloyloxy} , _γ- dimethyl- _γ- butyrolactone) was produced. .

 In a glass reactor 1 with an inner volume of 10 L, 3-hydroxy-1,5,5-dimethylinohydrofuran-2-one (= α-hydroxyγ, γ-dimethyl-1-γ-butyrolactone) 5 1 0 g, toluene 425 g, and triethylamine 525 g, and a mixture of methacrylic acid mouth glass 528 g and toluene 182 1 g in a nitrogen atmosphere for 1 hour. It was dropped. 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. Analysis of the reaction solution by gas chromatography revealed that 7,34 g of 5,5-dimethyl-2-oxotetrahydrofuran-1-yl methacrylate was produced.

The reaction solution was transferred to a washing tank 2 equipped with a stirrer, and once under water at a temperature of 40 ° C., once with water, once with a 10% by weight aqueous sodium carbonate solution, and again with 10 weight. /. The batch washing was performed three times, once with a sodium chloride aqueous solution. Any Also in this case, 100 parts by weight of the washing liquid was used with respect to 100 parts by weight of the liquid to be washed. By this washing operation, unreacted 3-hydroxy-5,5-dimethyldihydrofuran-12-one and methacrylic acid chloride are removed, and as an organic layer, 5,5-dimethyl methacrylate is prepared. A toluene solution of 1-oxo-tetrahydrofuran-3-yl ester was obtained.

 The organic layer was concentrated using a glass evaporator 3 having an internal volume of 10 L [45 mmHg (5998 Pa), 50 ° C]. Subsequently, the concentrated solution was subjected to a pressure of 0.03 mmH g (using a 10-liter glass centrifugal molecular distillation apparatus 4 (manufactured by Nippon Sharyo Co., Ltd., trade name: “MS-150”)). 4.0 Pa), temperature 60. The mixture was subjected to batch distillation under the conditions of C to obtain 409.5 g of 5,5-dimethyl-2-oxotetrahydrofuran-1,3-inoleestenomethacrylate (purity: 95.2%).

Claims

δ Blue range 1. The following formula (la) (lb) (lc) (Id) or (le)

 (la) (lb) (lc) (Id)

(le) [In the formula (la), R "represents a hydrogen atom or a methyl group, and X represents a hydrogen atom, a hydroxyl group or a (meth) acryloyloxy group. In the formula (lb) (le) And the number n of methyl groups bonded to the ring is an integer of 0. 5) and an alcohol having a cyclic skeleton represented by the formula (1) and (meth) acrylic acid or a reactive derivative thereof, respectively, (2a) (2b) (2c) (2d) or (2e) ) ノ n

 (2a) (2b) (2c) (2d)

 (2e) [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 the same as above. A method for producing a (meth) acrylic acid ester having a cyclic skeleton represented by the following formula (la), (lb), (lc), (Id) or (le) Subjecting the reaction product of the alcohol having a cyclic skeleton to (meth) acrylic acid or a reactive derivative thereof to molecular distillation to distill the (meth) acrylic ester having the cyclic skeleton A method for producing a (meth) acrylic ester having a cyclic skeleton containing 2. The method for producing a (meth) acrylic acid ester having a cyclic skeleton according to claim 1, wherein in the formulas (lb), (lc), (Id), and (le), n is 0. . 3. A reaction product of an alcohol having a cyclic skeleton represented by the formula (la), (lb), (lc), (Id) or (le) with (meth) acrylic acid or a reactive derivative thereof. 3. A (meth) acyl having a cyclic skeleton according to claim 1 or 2, which is subjected to molecular distillation after washing with at least one kind of washing solution selected from water, an aqueous alkali solution and an aqueous salt solution. A method for producing a lylic acid ester.  4. A reaction product of an alcohol having a cyclic skeleton represented by the formula (la), (lb), (lc), (Id) or (le) with (meth) acrylic acid or a reactive derivative thereof. Is subjected to an adsorption treatment using at least one adsorbent selected from activated carbon, a chelating resin, a chelating fiber and a zeta potential membrane, followed by molecular distillation. 3. A process for producing a (meth) acrylic ester having a cyclic skeleton according to claim 2.  5. Molecular distillation under the conditions of pressure 0.00001 to 0.5 mmHg (0.013 3 to 68 Pa) and temperature of 10 to 100 ° C. 5. A method for producing a (meth) acrylic acid ester having a cyclic skeleton according to any one of items 4 to 4.