TW201838962A - Method for producing (meth)acrylate - Google Patents

Abstract

Provided is a method for producing a high-quality (meth)acrylate that has little coloration. The present invention relates to a method for producing a (meth)acrylate comprising steps 1 through 3 which are performed in order. Step 1 A step for producing a (meth)acrylate by subjecting an alcohol and a compound having 1 (meth)acryloyl group to ester exchange in the presence of an ester exchange catalyst. Step 2 A step for removing the ester exchange catalyst in the reaction product containing the (meth)acrylate obtained in step 1. Step 3 A step for adding hydroxylamine or hydrazine to the (meth)acrylate-containing reaction product obtained in step 2.

Description

Method for producing (meth) acrylate

The present invention relates to a method for producing a (meth) acrylate, and belongs to the technical field of a method for producing a (meth) acrylate and using the (meth) acrylate. In addition, in this specification, any one or both of acryl and methacryl is represented by (meth) acryl, and either or both of acrylate and methacrylate, or both These are expressed as (meth) acrylates, and either or both of acrylic acid and methacrylic acid are expressed as (meth) acrylic acid.

(Meth) acrylate is hardened by irradiation with active energy rays such as ultraviolet rays or electron beams, or is heated by heating. Therefore, it is widely used as a main component of coatings, inks, adhesives, optical lenses, fillers, and molding materials. Components, cross-linking components, and reactive diluent components.

These (meth) acrylates are produced by the dehydration esterification reaction of an alcohol with (meth) acrylic acid in the presence of an acidic catalyst such as sulfonic acid; or in the presence of a transesterification catalyst such as an organotin compound A compound (hereinafter referred to as "monofunctional (meth) acrylate") having an alcohol and one (meth) acrylfluorenyl group is used as a raw material, and is produced by a transesterification reaction or the like.

However, it is known that (meth) acrylic acid and monofunctional (meth) acrylic acid esters used in these reactions have a vinyl group or the like in their molecules, and therefore have a very easy polymerization property, come into contact with an acid or a base, or be heated due to heating. Or light and polymerization occur repeatedly. The polymer-containing (meth) acrylate has uneven curing or turbidity, and therefore cannot be preferably used for optical lens applications where uniformity or light transmission is important. Therefore, the method of adding a polymerization inhibitor at the time of producing a (meth) acrylic acid ester is generally implemented, but it may be colored depending on the kind and amount of the polymerization inhibitor. The colored (meth) acrylate cannot be used for optical lens applications that require transparency in any case, so a method of purification by distillation or the like is implemented, but it is difficult to perform it in the case of a high boiling point (meth) acrylate. Purified by distillation.

Therefore, as a method for preventing (meth) acrylate coloration, a method of adding a basic substance such as hydrotalcite during dehydration esterification reaction (Patent Document 1), a method of adding magnesium sulfate during a transesterification reaction, etc. have been proposed. Method of dehydrating agent (Patent Document 2), method of adding an alkali metal salt to (meth) acrylate for the purpose of stabilizing (meth) acrylate over time (Patent Document 3), using metal hydrogenation complex A method of reducing a methacrylate by using an aqueous solution (Patent Document 4) and the like.

However, the methods of Patent Literature 1 and Patent Literature 2 are methods in which a basic substance or a dehydrating agent is added during the reaction, and therefore there is a problem that these components hinder the reaction during the reaction. In addition, in the method of Patent Document 3, a high-temperature treatment is required, and therefore, a thermally unstable (meth) acrylate may cause deterioration in quality (coloring). In addition, in the method of Patent Document 4, it is necessary to separate an organic phase from an aqueous phase, and therefore, in the case of a water-soluble acrylate or an acrylate that is unstable to water, there is a problem that the yield is significantly reduced. [Prior Art Literature] [Patent Literature]

[Patent Literature 1] Japanese Patent Laid-Open No. 2007-314502 [Patent Literature 2] Japanese Patent Laid-Open No. 2012-236805 [Patent Literature 3] Japanese Patent Laid-Open No. 09-067307 [Patent Literature 4] Japanese Patent Special Kaiping Publication No. 07-258160

[Problems to be Solved by the Invention] The present invention is made in view of the above-mentioned circumstances, and an object thereof is to obtain a high-quality (meth) acrylate with less coloration in the production of a (meth) acrylate. [Means for solving problems]

In order to solve the above-mentioned problems, the present inventors have made intensive studies. As a result, it was found that after a (meth) acrylic acid ester was produced by transesterifying an alcohol with a monofunctional (meth) acrylate in the presence of a transesterification catalyst, the transesterification catalyst was removed, and hydroxylamine or By this, hydrazine can obtain a (meth) acrylate with little coloring, and completed this invention. That is, this invention relates to the manufacturing method of a (meth) acrylic acid ester which includes the following 1st-3rd steps, and implements the following 1st-3rd steps in order. ○ The first step is a step of producing a (meth) acrylate by transesterifying an alcohol with a monofunctional (meth) acrylate in the presence of a transesterification catalyst. ○ The second step includes the obtained in the first step. Step of removing transesterification catalyst from the reaction product of (meth) acrylate ○ Step 3 The step of adding hydroxylamine or hydrazine to the reaction product containing (meth) acrylate obtained in Step 2 is as follows. Detailed description. [Effect of the invention]

According to the production method of the present invention, a high-quality (meth) acrylate with little coloring can be obtained. In addition, the obtained (meth) acrylic acid esters require different degrees of coloring depending on the type of the compound. According to the production method of the present invention, the target (meth) acrylic acid esters can be obtained by using the conventional (meth) acrylic acid esters. Compared with the (meth) acrylate obtained by the transesterification method, the (meth) acrylate has less coloration. Therefore, the (meth) acrylate obtained by the manufacturing method of the present invention can be used as a main component, a cross-linking component, and a reactive diluent component of a composition such as paint, ink, adhesive, optical lens, filler, and molding material. It is preferably used for various industrial applications.

The present invention relates to a method for producing a (meth) acrylate, which includes the following first to third steps, and sequentially performs the following first to third steps. ○ The first step is a step of producing a (meth) acrylate by transesterifying an alcohol with a monofunctional (meth) acrylate in the presence of a transesterification catalyst. ○ The second step includes the obtained in the first step. Step of removing transesterification catalyst from the reaction product of (meth) acrylate ○ Step 3 The step of adding hydroxylamine or hydrazine to the reaction product containing (meth) acrylate obtained in Step 2 is as follows. 1 to 3 steps, other steps and applications will be described.

1. First step The first step is a step of producing a (meth) acrylate by subjecting an alcohol to a monofunctional (meth) acrylate in an ester exchange reaction in the presence of a transesterification catalyst.

The method for producing a (meth) acrylate by a transesterification reaction may be a conventional method, and examples thereof include a method of heating and stirring an alcohol and a monofunctional (meth) acrylate in the presence of a transesterification catalyst. Wait. Hereinafter, alcohols, monofunctional (meth) acrylates, transesterification catalysts, and reaction conditions will be described.

1-1. Alcohols As long as the alcohol used as a raw material in the present invention is a compound having at least one or more alcoholic hydroxyl groups in the molecule, various compounds can be used. Examples thereof include aliphatic alcohols, alicyclic alcohols, aromatic alcohols, and polyhydric alcohols. Ether, etc. The alcohol may be a compound having other functional groups or bonds in the molecule. Examples of the functional group include a phenolic hydroxyl group, a keto group, a fluorenyl group, an aldehyde group, a thiol group, an amine group, an imino group, a cyano group, and a nitro group. Examples of the bond include an ether bond and an ester. Bond, carbonate bond, amidine bond, amidine bond, peptide bond, carbamate bond, acetal bond, hemiacetal bond and hemiketal bond.

Specific examples of the monohydric alcohol having one alcoholic hydroxyl group include monohydric alcohols having an ether bond in the molecule such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether; 2-hydroxyl Ethyl vinyl ether (also known as ethylene glycol monovinyl ether), 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, and 2-hydroxyisopropyl vinyl ether have vinyl and Ether-bonded monohydric alcohols; tricyclic [5.2.1.0 ^2.6 ] decenol (alias hydroxydicyclopentadiene), tricyclic [5.2.1.0 ^2.6 ] decanol, tricyclic [5.2.1.0 ^2.6 ] decenyl Monohydric alcohols having a cyclic structure such as oxyethanol and tricyclic [5.2.1.0 ^2.6 ] decyloxyethanol; and benzyl alcohol, phenoxyethanol, phenoxypropanol, and p-xylylene glycol monomethyl ether, etc. Alcohols having aromatic rings and the like.

Specific examples of the glycol having two alcoholic hydroxyl groups include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol; hydroquinone, bisphenol A, and bis Phenol F, bisphenol S, 4,4 '-(1-phenylethylidene) bisphenol (4,4'-(1-phenylethylidene) bisphenol) (bisphenol AP), 2,2-bis (4- Alkylene oxide adducts of compounds having phenolic hydroxyl groups, such as hydroxyphenyl) hexafluoropropane (bisphenol AF); alcohols having carbonate bonds, such as polycarbonate diols. As specific examples of the glycol, in addition to the alcohols listed in Japanese Patent Laid-Open No. 2017-39916, Japanese Patent Laid-Open No. 2017-39917, and International Publication No. 2017/033732.

Specific examples of the triol having three alcoholic hydroxyl groups include trimethylolethane, trimethylolpropane, glycerol, tris (2-hydroxyethyl) isocyanurate, triethanolamine, and These alkylene oxide adducts and the like. Specific examples of the trihydric alcohol include the alcohols listed in Japanese Patent Laid-Open No. 2017-39916, Japanese Patent Laid-Open No. 2017-39917, and International Publication No. 2017/033732 in addition to the above-mentioned.

Specific examples of the tetrahydric alcohol having four alcoholic hydroxyl groups include di-trimethylolethane, di-trimethylolpropane, diglycerol, pentaerythritol, and these alkylene oxide adducts. . Specific examples of the tetrahydric alcohol include the alcohols listed in Japanese Patent Laid-Open Publication No. 2017-39916, Japanese Patent Laid-Open Publication No. 2017-39917, and International Publication No. 2017/033732, in addition to those mentioned above.

Specific examples of the pentahydric alcohol having five alcoholic hydroxyl groups include tri-trimethylolethane, tri-trimethylolpropane, triglycerol, and bis (2-hydroxyethyl) aminotri ( Hydroxymethyl) methane, xylitol, and these alkylene oxide adducts. As specific examples of the pentavalent alcohol, in addition to the alcohols listed in Japanese Patent Laid-Open No. 2017-39916, Japanese Patent Laid-Open No. 2017-39917, and International Publication No. 2017/033732.

Specific examples of the polyol having six or more alcoholic hydroxyl groups include polytrimethylolethane, polytrimethylolpropane, polyglycerol, dipentaerythritol, D-sorbitol, and L-sorbose. Alcohols and these alkylene oxide adducts. As specific examples of the polyhydric alcohol, in addition to the alcohols listed in Japanese Patent Laid-Open No. 2017-39916, Japanese Patent Laid-Open No. 2017-39917, and International Publication No. 2017/033732.

Examples of the alkylene oxide adduct of the alcohol include ethylene oxide, propylene oxide, and butylene oxide.

In the present invention, these alcohols can be used alone or in any combination of two or more. Among these alcohols, polyhydric alcohols having three or more alcoholic hydroxyl groups are preferred. Furthermore, as the polyol having three or more alcoholic hydroxyl groups, trimethylolethane, trimethylolpropane, glycerol, an alkylene oxide adduct of glycerol, and tris (2-hydroxyethyl) are preferred. Isocyanurate, triethanolamine, bis-trimethylolethane, bis-trimethylolpropane, diglycerol, alkylene oxide adducts of diglycerol, pentaerythritol, alkylene oxide adducts of pentaerythritol, Xylitol, dipentaerythritol, alkylene oxide adduct of dipentaerythritol, D-sorbitol and polyglycerol. In addition, regarding these alcohols, when the hydrate or solvate thereof is present, the hydrate and solvate can also be used as the alcohol in the production method of the present invention.

1-2. Monofunctional (meth) acrylate Monofunctional (meth) acrylate is a compound having one (meth) acrylfluorenyl group in the molecule, and examples thereof include compounds represented by the following general formula (3).

[Chemical 1]

In the formula (3), R ⁵ represents a hydrogen atom or a methyl group. R ⁶ represents an organic group having 1 to 50 carbon atoms.

Preferred specific examples of R ⁶ in the general formula (3) include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and 2-ethylhexyl. Alkyl groups having 1 to 8 carbon atoms; alkoxyalkyl groups such as 2-methoxyethyl, 2-ethoxyethyl, and 2-methoxybutyl; and N, N-dimethylaminoethyl Groups, dialkylamino groups such as N, N-diethylaminoethyl, N, N-dimethylaminopropyl and N, N-diethylaminopropyl. As specific examples of R ⁶ in the general formula (3), in addition to the above, Japanese Patent Laid-Open No. 2017-39916, Japanese Patent Laid-Open No. 2017-39917, and International Publication No. 2017/033732 can be cited. The functional groups listed in No.

In the present invention, these monofunctional (meth) acrylates may be used alone or in any combination of two or more. Among these monofunctional (meth) acrylates, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and ( (Meth) acrylic acid alkyl esters having 1 to 8 carbons, such as 2-ethylhexyl methacrylate, and alkoxy (meth) acrylic acid, such as 2-methoxyethyl (meth) acrylate Alkyl esters, and N, N-dimethylaminoethyl (meth) acrylate. Furthermore, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, and 2-methoxyethyl acrylate which exhibit good reactivity to most alcohols and are easily available are preferred. In particular, 2-methoxyethyl acrylate which promotes dissolution of alcohol and exhibits extremely good reactivity is more preferred.

The use ratio of the alcohol to the monofunctional (meth) acrylate in the transesterification reaction of the present invention is not particularly limited, and it is preferred that the monofunctional (meth) acrylate is 0.4 mol relative to the hydroxyl group of the alcohol. ~ 10.0 moles, more preferably from 0.6 moles to 5.0 moles. By using a monofunctional (meth) acrylate of 0.4 mol or more, the production amount of the target (meth) acrylate can be increased. By setting it to 10.0 mol or less, the generation of by-products or the coloring of the reaction solution can be suppressed. , Simplify the purification steps after the reaction.

1-3. Transesterification catalyst As the transesterification catalyst in the transesterification reaction of the present invention, it is only necessary to be a user generally used in the transesterification reaction. Examples include: titanium catalysts such as tetrabutyl titanate; zirconium catalysts such as tetrabutyl zirconate; dialkyl tin dihalide, and dialkyl tin dicarboxylate ( dialkyl tin dicarboxylate), dialkyl tin dialcoholate, dibutyl tin dichloride, dioctyl tin dichloride, dibutyl tin diacetate, dibutyl tin dilaurate, dioctyl Tin-based catalysts such as tin diacetate, dioctyltin dilaurate, distannoxane, and tristannoxane; alkali-based catalysts such as lithium hydroxide; zinc acetate, zinc acrylate, and zinc acetate And other zinc-based catalysts; and sulfuric acid. These transesterification catalysts can be used alone or in any combination of two or more.

As the transesterification catalyst in the transesterification reaction of the present invention, it is particularly preferable to use the following catalyst X and catalyst Y in combination for the reason that the reaction product containing the target (meth) acrylate can be produced in high yield. Catalyst X: selected from the group consisting of a cyclic tertiary amine having an azabicyclic structure or a salt or a complex thereof (hereinafter referred to as "azabicyclic compound"), arsine or a salt or a complex thereof (hereinafter referred to as " Actinide compound "), a compound having a pyridine ring or a salt or complex thereof (hereinafter referred to as" pyridine-based compound "), and a phosphine or its salt or complex (hereinafter referred to as" phosphine-based compound ") More than one compound in the group. Catalyst Y: Zinc-containing compound. The catalyst X and the catalyst Y will be described below.

1-3-1. Catalyst X Catalyst X is one or more compounds selected from the group consisting of azabicyclic compounds, fluorene compounds, pyridine compounds, and phosphine compounds. As the catalyst X, in the compound group described above, one or more compounds selected from the group consisting of an azabicyclic compound, a fluorene compound, and a pyridine compound are preferable. These compounds are excellent in catalyst activity and can be used to produce (meth) acrylates. In addition, they form complexes with the catalyst Y described later during and after the reaction. The method is simple and convenient, and the reaction solution is easily removed from the reaction. In particular, the azabicyclic compound is more difficult to dissolve in the reaction solution because it is difficult to dissolve with the catalyst Y. Therefore, it can be more easily removed by filtration, adsorption, and the like. On the other hand, although phosphine compounds are excellent in catalytic activity, they are difficult to form complexes with catalyst Y, or are easily soluble in the reaction solution when complexes are formed. Since a part is dissolved in the reaction solution after completion of the reaction, it is difficult to remove it from the reaction solution by a simple method such as filtration or adsorption. Therefore, the phosphine compounds remain in the final product, which may cause storage stability problems such as turbidity or precipitation of the catalyst during storage, or thickening or gelation over time. .

As specific examples of the azabicyclic compound, if the compound satisfies a cyclic tertiary amine having an azabicyclic structure, a salt of the amine, or a complex of the amine, various compounds can be cited as preferable compounds. Can be listed: (Quinuclidine), 3-hydroxyl Pyridine, 3- 3-quinuclidinone, 1-azabicyclo [2.2.2] octane-3-carboxylic acid, and triethylenediamine (alias: 1,4-diazabicyclo [2.2.2] octane; Hereinafter called "DABCO"). Specific examples of the azabicyclic compound include the compounds listed in Japanese Patent Laid-Open Publication No. 2017-39916, Japanese Patent Laid-Open Publication No. 2017-39917, and International Publication No. 2017/033732, in addition to the above. .

Specific examples of the fluorene-based compound include imidazole, N-methylimidazole, N-ethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, and 1-ethylene. Imidazole, 1-allylimidazole, 1,8-diazabicyclo [5.4.0] undec-7-ene (hereinafter referred to as "DBU"), 1,5-diazabicyclo [4.3. 0] non-5-ene (hereinafter referred to as "DBN"), N-methylimidazole hydrochloride, DBU hydrochloride, DBN hydrochloride, N-methylimidazole acetate, DBU acetate, DBN acetate N-methylimidazole acrylate, DBU acrylate, DBN acrylate, and phthalimide DBU.

The main specific examples of the pyridine-based compound include pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 3-ethylpyridine, and 4-ethylpyridine. , And N, N-dimethyl-4-aminopyridine (hereinafter referred to as "DMAP") and the like. Specific examples of the pyridine-based compound include the compounds listed in Japanese Patent Laid-Open No. 2017-39916, Japanese Patent Laid-Open No. 2017-39917, and International Publication No. 2017/033732, in addition to the above.

Examples of the phosphine compound include compounds having a structure represented by the following general formula (4).

[Chemical 2]

In formula (4), R ⁷ , R ⁸ and R ⁹ refer to a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 1 to 20 carbon atoms, and 6 to 6 carbon atoms. An aryl group of 24 or a cycloalkyl group having 5 to 20 carbon atoms. R ⁷ , R ⁸ and R ⁹ may be the same or different.

Specific examples of the phosphine compound include triphenylphosphine, tris (4-methoxyphenyl) phosphine, tris (p-tolyl) phosphine, tris (m-tolyl) phosphine, and tris (4-methoxy) -3,5-dimethylphenyl) phosphine, and tricyclohexylphosphine. Specific examples of the phosphine compound include the compounds listed in Japanese Patent Laid-Open No. 2017-39916, Japanese Patent Laid-Open No. 2017-39917, and International Publication No. 2017/033732 in addition to the above.

In the present invention, these catalysts X may be used alone or in any combination of two or more. Of these catalysts X, preferably Pyridine, 3- Pyridone, 3-hydroxyl Pyridine, DABCO, N-methylimidazole, DBU, DBN, and DMAP, especially 3-hydroxy, which shows good reactivity to most polyols and is easily available Pyridine, DABCO, N-methylimidazole, DBU and DMAP.

The use ratio of the catalyst X in the first step is not particularly limited, and it is preferable to use the catalyst X of 0.0001 mol to 0.5 mol with respect to 1 mol of the hydroxyl group of the alcohol, and more preferably 0.0005 mol to 0.2 mol. ear. By using Catalyst X with 0.0001 mol or more, the amount of target (meth) acrylates can be increased. By setting it with 0.5 mol or less, the generation of by-products or the coloring of the reaction solution can be suppressed, and the reaction after the reaction is simplified. Purification steps.

1-3-2. Catalyst Y Catalyst Y is a compound containing zinc. As the catalyst Y, various compounds can be used as long as they are zinc-containing compounds. In terms of excellent reactivity, zinc organic acid and zinc diketone enolate are preferred. Examples of the organic acid zinc include zinc dibasic acids such as zinc oxalate and compounds represented by the following general formula (5).

[Chemical 3]

In formula (5), R ¹⁰ and R ¹¹ are a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 1 to 20 carbon atoms, and an aromatic group having 6 to 24 carbon atoms. Or a cycloalkyl group having 5 to 20 carbon atoms. R ¹⁰ and R ¹¹ may be the same or different. As the compound of the formula (5), preferred is a compound in which R ¹⁰ and R ¹¹ are a linear or branched alkyl or alkenyl group having 1 to 20 carbon atoms. In R ¹⁰ and R ¹¹ , the linear or branched alkyl or alkenyl group having 1 to 20 carbon atoms is a functional group having no halogen atom such as fluorine and chlorine, and the catalyst Y having the functional group can be produced in high yield. (Meth) acrylate is preferred.

Examples of the zinc diketenol include compounds represented by the following general formula (6).

[Chemical 4]

In formula (6), R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ refer to a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, and a straight group having 1 to 20 carbon atoms. A chain or branched alkenyl group, an aryl group having 6 to 24 carbon atoms, or a cycloalkyl group having 5 to 20 carbon atoms. R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ may be the same or different.

Specific examples of the zinc-containing compound represented by the general formula (5) include zinc acetate, zinc acetate dihydrate, zinc propionate, zinc octoate, zinc neodecanoate, zinc laurate, and myristic acid. Zinc, zinc stearate, zinc cyclohexanebutyrate, zinc 2-ethylhexanoate, zinc benzoate, zinc third butylbenzoate, zinc salicylate, zinc naphthenate, zinc acrylate, and methyl Zinc acrylate, etc. Furthermore, in the case of these zinc-containing compounds, in the presence of their hydrates or solvates or complexes with catalyst X, the hydrates and solvates and the complexes with catalyst X are also It can be used as the catalyst Y in the first step.

Specific examples of the zinc-containing compound represented by the general formula (6) include acetoacetone zinc, acetoacetone zinc hydrate, bis (2,6-dimethyl-3,5-heptane) Keto acid) zinc, bis (2,2,6,6-tetramethyl-3,5-heptanedione acid) zinc, and bis (5,5-dimethyl-2,4-hexadione acid) Zinc and so on. Furthermore, in the case of these zinc-containing compounds, in the presence of their hydrates or solvates or complexes with catalyst X, the hydrates and solvates and the complexes with catalyst X are also It can be used as the catalyst Y in the first step.

As the organic acid zinc and zinc diketenol in the catalyst Y, the above-mentioned compounds can be used directly, or these compounds can be generated and used in the reaction system. For example, zinc compounds such as metal zinc, zinc oxide, zinc hydroxide, zinc chloride, and zinc nitrate (hereinafter referred to as "raw material zinc compounds") are used as the raw materials, and in the case of organic acid zinc, the raw material zinc compounds and organic A method of acid reaction, a method of reacting a raw material zinc compound with acetoacetone in the case of zinc diketenol, and the like.

In the present invention, these catalysts Y can be used alone or in any combination of two or more. Among these catalysts Y, zinc acetate, zinc propionate, zinc acrylate, zinc methacrylate, and zinc acetoacetone are preferred, and acetic acid that exhibits good reactivity to most polyols and is easily available is particularly preferred. Zinc, zinc acrylate and zinc acetoacetone.

The use ratio of the catalyst Y in the first step is not particularly limited, and it is preferable to use the catalyst Y of 0.0001 to 0.5 mol with respect to 1 mol of the hydroxyl group of the alcohol, and more preferably 0.0005 to 0.2 mol. ear. By using a catalyst Y of 0.0001 mol or more, the amount of (meth) acrylic acid esters can be increased. By setting it to 0.5 mol or less, the generation of by-products or the coloring of the reaction solution can be suppressed, which simplifies the reaction after the reaction. Purification step.

The transesterification catalyst used in the first step may be added from the beginning of the reaction or may be added halfway. In addition, the desired usage amount may be added at one time, or may be added separately. In addition, when the transesterification catalyst is solid, it may be added after being dissolved by a solvent.

1.4. The method for producing a (meth) acrylate by a transesterification reaction The first step is to perform an ester exchange by heating and stirring an alcohol and a monofunctional (meth) acrylate in the presence of a transesterification catalyst. A step of reacting to produce a (meth) acrylate.

The reaction temperature in the first step is preferably 40 ° C to 180 ° C, and particularly preferably 60 ° C to 160 ° C. By setting the reaction temperature to 40 ° C or higher, the reaction speed can be accelerated. By setting the reaction temperature to 180 ° C or lower, thermal polymerization of the (meth) acrylfluorenyl group in the raw material or product can be suppressed, and the coloration of the reaction solution can be suppressed, which can be simplified. Purification step after completion of the reaction.

The reaction pressure in the first step is not particularly limited as long as a predetermined reaction temperature can be maintained, and it can be carried out under reduced pressure or under pressure. The reaction pressure is preferably 0.000001 MPa to 10 MPa (absolute pressure).

In the first step, as the transesterification reaction proceeds, a by-product monohydric alcohol derived from a monofunctional (meth) acrylate used as a raw material is produced. The monohydric alcohol can coexist in the reaction system, but the transesterification reaction can be further promoted by discharging the monohydric alcohol out of the reaction system.

In the first step, it may be carried out without using an organic solvent, and an organic solvent may be used as necessary. Specific examples of the organic solvent include n-hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, n-nonane, n-decane, benzene, toluene, xylene, ethylbenzene, Diethylbenzene, cumene, pentylbenzene, dipentylbenzene, tripentylbenzene, dodecylbenzene, di-dodecylbenzene, pentyltoluene, cumenetoluene, decahydronaphthalene And hydrocarbons such as tetrahydronaphthalene; diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, diethyl acetal, dihexyl acetal, third butyl methyl ether , Cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, trioxane, dioxane, anisole, diphenyl ether, dimethyl cyrusol, diethylene glycol diglyme, Ethers such as triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether; crown ethers such as 18-crown-6; esters such as methyl benzoate and γ-butyrolactone; acetone, methyl ethyl ketone , Ketones such as methyl isobutyl ketone, cyclohexanone, acetophenone and benzophenone; dimethyl carbonate, diethyl carbonate, ethylene glycol carbonate, propylene glycol carbonate, 1,2-butane Carbonate compounds such as alcohol carbonates; cyclobutane Isofluorenes; hydrazones such as dimethylsulfine; ureas or derivatives thereof; phosphine oxides such as tributylphosphine oxide; ionic liquids such as imidazolium, piperidinium, and pyridinium salts; silicone oils; and water Wait. Among these organic solvents, hydrocarbons, ethers, carbonate compounds, and ionic liquids are preferred. These organic solvents may be used alone, or two or more of them may be used in combination as a mixed solvent.

The use ratio of the organic solvent is preferably a ratio of 10% to 75% by weight, and more preferably a ratio of 15% to 55% by weight based on the total amount of the alcohol and the monofunctional (meth) acrylate. .

In the first step, an oxygen-containing gas can be introduced into the system for the purpose of preventing the polymerization of the (meth) acrylfluorenyl group. Specific examples of the oxygen-containing gas include air, a mixed gas of oxygen and nitrogen, and a mixed gas of oxygen and helium. Examples of the method for introducing the gas include a method of blowing into a reaction product (so-called bubbling) and the like.

In the first step, a polymerization inhibitor is preferably added to the reaction solution for the purpose of preventing polymerization of a (meth) acrylfluorenyl group. Examples of the polymerization inhibitor include organic polymerization inhibitors, inorganic polymerization inhibitors, and organic salt polymerization inhibitors. Specific examples of the organic polymerization inhibitor include hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, and 2,6-di-tert-butyl-4-methyl. Phenol compounds such as phenol, 2,4,6-tri-tert-butylphenol and 4-tert-butylcatechol; quinone compounds such as benzoquinone; phenothiazine; N-nitroso-N-benzene Ammonium hydroxylamine; and N-oxyl compounds. Examples of the N-oxyl radical compound include 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxy radical, and 2,2,6,6-tetramethylpiperidine-1. -Oxy radical, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxy radical and 4-methoxy-2,2,6,6-tetramethylpiperidine- 1-oxygen radicals, etc. Examples of the inorganic polymerization inhibitor include copper chloride, copper sulfate, and iron sulfate. Examples of the organic salt-based polymerization inhibitor include copper butyldithiocarbamate and aluminum N-nitroso-N-phenylhydroxylamine. The polymerization inhibitor may be added singly or in any combination of two or more kinds. The polymerization inhibitor may be added from the beginning of the present invention or may be added halfway. In addition, the desired usage amount may be added at one time, or may be added separately. Alternatively, it may be continuously added via a rectification column.

As the polymerization inhibitor, among the above-mentioned compounds, an N-oxyl radical compound is preferably used. The N-oxyl radical compound is preferably the compound described above. Furthermore, as the polymerization inhibitor, it is preferred to use an N-oxyl radical compound in combination with a polymerization inhibitor other than the N-oxyl radical compound. As the polymerization inhibitor other than the N-oxyl radical compound in this case, a phenolic compound and an phenothiazine are preferable, and a phenolic compound is more preferable.

The addition ratio of the polymerization inhibitor is preferably 5 ppm to 30,000 ppm by weight in the reaction solution, and more preferably 25 ppm to 10,000 ppm. By setting the ratio to 5 ppm or more, the effect of preventing polymerization can be made sufficiently. By setting the ratio to 30,000 ppm or less, it is possible to prevent coloration or prevent a decrease in the hardenability of the product. The above is the proportion of the polymerization inhibitor present in the reaction solution, but as the reaction proceeds, the monofunctional (meth) acrylate as a raw material reacts to become an alcohol, so the monofunctional (meth) acrylate is gradually supplied to In the reaction solution. At this time, the polymerization inhibitor was also added to the reaction solution at the same time. The proportion of the polymerization inhibitor used in the entire reaction is preferably 0.0005 to 3.0 parts by weight, and more preferably 0.0025 to 1.0 parts by weight based on 100 parts by weight of the total amount of the reaction solution. Furthermore, when an N-oxyl radical compound is used in combination with a polymerization inhibitor other than the N-oxyl radical compound as a polymerization inhibitor, 2 to 80% by weight of the N-oxyl radical compound is contained in a total of 100% by weight of the polymerization inhibitor. It is more preferable to exhibit the polymerization prevention effect more fully.

Regarding the reaction time in the first step, it depends on the structure of the alcohol and monofunctional (meth) acrylate used, the target (meth) acrylate, the type and amount of the transesterification catalyst, the reaction temperature, and the reaction pressure. It may be appropriately set, and is preferably 0.1 to 150 hours, and more preferably 0.5 to 80 hours.

The first step can be carried out by any of a batch method, a semi-batch method, and a continuous method. As an example of a batch method, an alcohol, a monofunctional (meth) acrylate, a transesterification catalyst, and a polymerization inhibitor are added to the reactor, and the mixture is stirred at a predetermined temperature while bubbling an oxygen-containing gas in the reaction solution. . Thereafter, as the transesterification reaction proceeds, a by-product monohydric alcohol derived from a monofunctional (meth) acrylate is produced. By extracting the monohydric alcohol from the reactor at a predetermined pressure, the production of a target (meth) acrylate can be promoted.

As described above, in the first step, it is preferable to use the catalyst X and the catalyst Y together as a catalyst manufacturing method, and the manufacturing method will be described below. The use ratio of the catalyst X to the catalyst Y is not particularly limited. It is preferable to use the catalyst X of 0.005 to 10.0 mol, and more preferably 0.05 to 5.0 mol relative to 1 mol of the catalyst Y. ear. By using 0.005 mol or more, the production amount of the target (meth) acrylate can be increased. By setting it to 10.0 mol or less, the generation of by-products or the color of the reaction solution can be suppressed, and the purification step after the reaction is simplified.

As the combination of the catalyst X and the catalyst Y used in the present invention, it is preferable that the catalyst X is an azabicyclic compound and the catalyst Y is a combination of the compound represented by the general formula (5). Preferably, a combination of the azabicyclic compound is DABCO, and the compound represented by the general formula (5) is zinc acetate and / or zinc acrylate. This combination can obtain a (meth) acrylic acid ester with good yield, and it is excellent in the color tone after completion | finish of reaction. Therefore, it can be used suitably for various industrial use which attaches importance to color tone. Furthermore, since it is a catalyst which can be obtained relatively cheaply, it is an economically advantageous manufacturing method.

The catalyst X and the catalyst Y used in the present invention may be added from the beginning of the reaction or may be added halfway. In addition, the desired usage amount may be added at one time, or may be added separately.

The reaction conditions such as the reaction temperature, the reaction pressure, the organic solvent, the polymerization inhibitor, and the reaction time need only follow the same method as described above.

2. Second Step The second step is a step of removing the transesterification catalyst (hereinafter referred to as "catalyst") in the reaction product containing the (meth) acrylate obtained in the first step. Examples of the method for removing the catalyst include operations such as solid-liquid separation, extraction, crystallization, and adsorption. These operations may be appropriately selected depending on the type of alcohol and monofunctional (meth) acrylate as raw materials, the type of catalyst, the type of (meth) acrylate obtained, reaction conditions, and the like. These operations may be used alone or in combination of two or more. For example, when pentaerythritol, tris (2-hydroxyethyl) isocyanurate, etc. are used as the raw material alcohol, the catalyst is not precipitated in the reaction product in most cases, and the catalyst can be removed only by adsorption treatment. On the other hand, in the case where dipentaerythritol, glycerol, or the like is used as a raw material alcohol, the catalyst is usually precipitated in the reaction product. It is preferable to remove the catalyst by adsorption treatment after filtration.

When the catalyst is contained in the reaction product as a solid, solid-liquid separation such as filtration and centrifugation is performed. Regarding solid-liquid separation, filtration methods include filter paper, filter cloth, cartridge filter, double-layer filter of cellulose and polyester, metal mesh filter, and metal sintered filter. Or a method of filtering under pressure to separate and remove the catalyst as a filtration residue. Examples of the centrifugal separation method include a method in which a catalyst is settled by using a decanter, a centrifugal clarifier, or the like, and then a liquid phase is separated from a precipitated component.

When the catalyst is dissolved in the reaction product, extraction and cleaning are performed using an aqueous solution containing water, acid, or alkali. Examples of the extraction include adding an acidic aqueous solution such as water, sulfuric acid, or hydrochloric acid, and / or an alkaline aqueous solution (hereinafter, referred to as a "cleaning agent") such as sodium hydroxide and potassium hydroxide, and performing a contact treatment such as stirring, and then combining the organic layer with Water layer liquid-liquid separation method to remove catalyst. In this case, the liquid amount of the cleaning agent, or the acid and alkali concentrations may be in a known range, and the cleaning treatment may be performed only once, or may be performed twice or more.

Examples of the crystallization include a method of adding a lean solvent, lowering the temperature, and concentrating under reduced pressure. As a specific method of crystallization, the catalyst can be separated by adding a lean solvent, which is a solvent with a low solubility, or stirring while reducing the temperature, etc., to separate the solid and liquid from the precipitated catalyst. Method: The solvent or monofunctional (meth) acrylate, by-product water, and by-product alcohol are distilled out of the system by concentration under reduced pressure, and the catalyst is solidified and precipitated, followed by solid-liquid separation. Method, etc. The lean solvent may be used alone, or two or more of them may be used in combination as a mixed solvent.

The use ratio of the lean solvent is not particularly limited, and it is preferably added to 5 parts by weight to 100 parts by weight, and more preferably 10 to 50 parts by weight based on 100 parts by weight of the target (meth) acrylate. If the addition ratio of the lean solvent is less than 5 parts by weight, the catalyst removal effect is insufficient, and if it is more than 100 parts by weight, separation of the solvent from the target (meth) acrylate is complicated.

Examples of the adsorption include a method of adding a solid having adsorption energy and / or ion exchange energy (hereinafter referred to as "adsorbent") to the catalyst, and performing a contact treatment such as stirring, and then performing solid-liquid separation. Examples of the adsorbent include silicates such as aluminum silicate and magnesium silicate, activated clay, acid clay, silicone, and ion exchange resins. Examples of the silicate include magnesium silicate [commercial products include, for example, Kyoward 600 (trade name) manufactured by Kyowa Chemical Industry Co., Ltd., and Mizuka Life (Mizuka Life manufactured by Mizusawa Chemical Industry Co., Ltd.) ) (Trade name), etc. The following brackets are examples of commercially available products], aluminum silicate [Kyoward 700 (trade name) manufactured by Kyowa Chemical Industry Co., Ltd., and Neobead manufactured by Mizusawa Chemical Industry Co., Ltd. ） SA (product name), etc.]; Examples of the activated clay include montmorillonite-based compounds [Galleon Earth (trade name) manufactured by Mizusawa Chemical Industry Co., Ltd., and MIZUKA -ACE) (trade name), Galleonite (trade name), etc .; Examples of acid clay include bentonite-based compounds [Benclay manufactured by Mizusawa Chemical Industry Co., Ltd.] ) (Trade name), etc.]; Examples of the ion exchange resin include Amberlyst (registered trademark) and Amberlite (registered trademark) manufactured by Dow Chemical. , DIAION (registered trademark) manufactured by Mitsubishi Chemical Corporation, DOWEX (registered trademark) manufactured by Dow Chemical, etc. These adsorbents may be used alone or in any combination of two or more.

The use ratio of the adsorbent is not particularly limited, but it is preferable to use 0.001 to 1.5 parts of the adsorbent with respect to 1 part of the target (meth) acrylate, and more preferably 0.005 to 0.8 part. The removal effect of the catalyst can be made sufficient by setting it to 0.001 parts or more, and it becomes easy to separate an adsorbent from a target (meth) acrylate by setting it to 1.5 parts or less.

The implementation temperature of the second step is not particularly limited, but is preferably -10 ° C to 140 ° C, and particularly preferably 30 ° C to 100 ° C. By setting the implementation temperature to -10 ° C or higher, solidification of the target (meth) acrylic acid ester or solvent can be suppressed, and complexity of solid-liquid separation can be suppressed. By setting the temperature to 140 ° C or lower, the target (methyl) can be prevented. Polymerization of acrylates.

The pressure for implementing the second step is not particularly limited, and it can be performed under reduced pressure or under pressure. The implementation pressure is preferably 0.000001 MPa to 10 MPa (absolute pressure).

The implementation time of the second step varies depending on the type of the (meth) acrylate, the implementation temperature, and the like, but is preferably from 0.05 hours to 80 hours, and more preferably from 0.2 hours to 40 hours.

By implementing the second step, it is preferable to remove 80% by weight or more of the catalyst used in the first step from the reaction product containing the target (meth) acrylate, and more preferably remove 90% by weight or more. If the removal of the catalyst is less than 80% by weight, the effect of the present invention on color tone may be insufficient, or the target (meth) acrylate may be polymerized during the third step or activated carbon treatment step described later.

3. Third step The third step is a step of adding hydroxylamine or hydrazine to the reaction product containing the (meth) acrylate obtained in the second step. By implementing the third step, a high-quality (meth) acrylate with reduced coloration can be obtained. As the hydroxylamine or hydrazine used in the third step, various compounds can be used.

Examples of the hydroxylamine include compounds represented by the following general formula (1).

[Chemical 5]

[In the general formula (1), R ¹ and R ² each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or a linear or branched carbon group having 1 to 20 carbon atoms. Branched alkoxy, linear or branched alkyl having 1 to 20 carbons substituted with alkoxy having 1 to 20 carbons, aryl having 6 to 12 carbons, and aralkyl having 7 to 30 carbons The base in the base. R ¹ and R ² may be the same or different.]

Specific examples of hydroxylamine include N, N-dimethylhydroxylamine, N, N-diethylhydroxylamine, N, N-dipropylhydroxylamine, N, N-dibutylhydroxylamine, and N, N-methyl Ethylhydroxylamine, N, N-ethylpropylhydroxylamine, N, N-propylbutylhydroxylamine, N, N-didecylhydroxylamine, N, N-diphenylhydroxylamine, and N, N-dibenzyl Hydroxylamine and so on. Among these compounds, preferred are N, N-diethylhydroxylamine and N, N-dibenzylhydroxylamine, which are easily available and obtain excellent color reduction effects.

Examples of the hydrazine include compounds represented by the following general formula (2). [Chemical 6]

[In the general formula (2), R ³ and R ⁴ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a fluorenyl group having 1 to 20 carbon atoms, The alkoxy group having 1 to 20 carbon atoms is a linear or branched alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms. R ³ and R ⁴ may be the same or different.]

Specific examples of hydrazine include hydrazine, hydrazine monohydrate, N-phenylhydrazine, N-ethylhydrazine, N-benzylhydrazine, N, N-dimethylhydrazine, N, N- Diethylhydrazine, N, N-dipropylhydrazine, N, N-dibutylhydrazine, N, N-methylethylhydrazine, N, N-ethylpropylhydrazine, N, N-propylbutyl Hydrazine, N, N-didecylhydrazine, N, N-diphenylhydrazine and N, N-dibenzylhydrazine. Among these compounds, hydrazine monohydrate which can be easily obtained and obtains excellent color reducing effects is preferred.

In order to make the coloring reduction effect more excellent, it is more preferable to use hydroxylamine as the hydroxylamine or hydrazine in the third step.

The use ratio of hydroxylamine or hydrazine in the third step is not particularly limited, and it is preferably 10 weight ppm to 100,000 weight ppm relative to the total amount of the reaction product containing the (meth) acrylate obtained in the second step. It is particularly preferable to use 50 ppm by weight to 50,000 ppm by weight. By using 10 ppm by weight or more, the color tone can be reduced, and by setting it to 100,000 ppm by weight or less, a decrease in the curing speed of the obtained (meth) acrylate can be suppressed.

The hydroxylamine or hydrazine used in the third step may be used in a desired amount at one time, or may be used separately. When hydroxylamine or hydrazine is added to the reaction product, stirring or shaking may be performed, and an inert gas such as nitrogen or a mixed gas of oxygen and nitrogen may be introduced.

The implementation temperature of the third step is not particularly limited, but is preferably -10 ° C to 140 ° C, and particularly preferably 20 ° C to 100 ° C. By setting the implementation temperature to -10 ° C or higher, the effect of reducing coloration can be made sufficiently. By setting the temperature to 140 ° C or lower, side reactions of hydroxylamine or hydrazine or polymerization can be prevented.

The implementation pressure of the third step is not particularly limited, and it can be performed under reduced pressure or under pressure. The implementation pressure is preferably 0.000001 MPa to 10 MPa (absolute pressure).

The implementation time of the third step varies depending on the type of the (meth) acrylate, the implementation temperature, and the like, but is preferably from 0.05 hours to 80 hours, and more preferably from 0.2 hours to 40 hours.

The third step is performed after performing the second step described above. If hydroxylamine or hydrazine is added during the implementation of the first step or the second step, there are cases in which the effect of the present invention on color tone is insufficient, or in particular, when an N-oxyl radical compound is used as a polymerization inhibitor, The reducing ability of hydroxylamine or hydrazine causes the reduction of the N-oxyl radical compound, which weakens the function as a polymerization inhibitor, and thus initiates polymerization of the (meth) acrylate.

4. Other steps The production method of the present invention is a method for producing a (meth) acrylic acid ester including the first step to the third step described above, and may include other steps as necessary. In the production method of the present invention, it is preferable that the reaction product containing the (meth) acrylate obtained in the third step is subjected to a contact treatment with activated carbon (hereinafter referred to as "activated carbon treatment step"). Thereby, a high-quality (meth) acrylate which can reduce coloring and suppress coloring for a long time can be obtained. The contact treatment can be performed by adding activated carbon to the reaction product containing (meth) acrylate and stirring or shaking, or by passing the reaction product containing (meth) acrylate to a fixed layer filled with activated carbon. Implementation.

Examples of the activated carbon used in the activated carbon treatment step include activated carbon activated by chemicals and activated carbon activated by water vapor. Activated carbon is commercially available. Specifically, as activated carbon activated by a chemical, a trade name "Taiko S" manufactured by Futamura Chemical Co., Ltd .; Osaka Gas Chemicals ( Stock) manufactured under the trade names "Carborafin", "Powerful Egret", "Purified Egret", and "Special Egret". Examples of activated carbon activated by steam include "Taige K" and "Taige P" manufactured by Nimura Chemical Co., Ltd., and "Egret C" and "Taiwan Gas" manufactured by Osaka Gas Chemical Co., Ltd. "Egret M", "Egret A" and "Egret P". The properties of the activated carbon may be any of powder, granular, crushed, and granulated materials. The added form of activated carbon may be either a dry product or a mixed product with water. The activated carbon treatment method may be a batch method or a continuous method.

The use ratio of the activated carbon in the activated carbon treatment step is not particularly limited, and it is preferably 0.01 to 50% by weight based on the total amount of the reaction product containing the (meth) acrylate obtained in the second step. Particularly preferred is the use of 0.1% to 5.0% by weight. By setting the use ratio of activated carbon to 0.01% by weight or more, the hue can be sufficiently reduced, and by setting it to 50% by weight or less, separation of the activated carbon from the target (meth) acrylate can be facilitated.

The activated carbon used in the activated carbon treatment step may be used in a desired amount at one time, or may be used separately.

The activated carbon subjected to the contact treatment with the activated carbon is preferably removed by solid-liquid separation such as filtration described above.

The implementation temperature of the activated carbon treatment step is not particularly limited, but is preferably 0 ° C to 150 ° C, and particularly preferably 20 ° C to 130 ° C. By setting the reaction temperature to 0 ° C or higher, the hue can be sufficiently reduced, and by setting to 150 ° C or lower, the polymerization of the (meth) acrylfluorenyl group can be suppressed.

The implementation pressure of the activated carbon treatment step is not particularly limited, and it can be performed under reduced pressure or under pressure. The implementation pressure is preferably 0.000001 MPa to 10 MPa (absolute pressure).

The implementation time of the activated carbon treatment step varies depending on the type of (meth) acrylate, the implementation temperature, the method of the contact treatment, and the like, but it is preferably from 0.1 to 150 hours, more preferably from 0.5 to 80 hours.

In the production method of the present invention, the third step and the activated carbon treatment step may be performed simultaneously. That is, the reaction product containing the (meth) acrylic acid ester obtained in the second step may be simultaneously subjected to a contact treatment with addition of hydroxylamine or hydrazine and activated carbon.

5. Use The (meth) acrylate obtained by the manufacturing method of this invention can be used for various uses using a conventional (meth) acrylate. For example, it can be used as the main component, cross-linking component, or reactive diluent component of the composition in optical applications such as coatings, inks, adhesives, films, sheets, and optical lenses, fillers, and molding materials. Ideal for a variety of industrial applications.

When used for the said application, the (meth) acrylate obtained by the manufacturing method of this invention mixes various components used for the said application, for example, a photoinitiator, a thermal-polymerization initiator, and coloring Agents, pigment dispersants, organic solvents, antioxidants, ultraviolet absorbers, leveling agents, silane coupling agents, surface modifiers, and polymerization inhibitors. [Example]

Hereinafter, the present invention will be described more specifically with examples and comparative examples, but the present invention is not limited to these examples. In addition, unless otherwise specified below, the expression of "%" means "weight%", and the expression of "ppm" means "weight ppm".

1. Various definitions 1) Abbreviations The abbreviations in the examples refer to the following. MCA: 2-methoxyethyl acrylate MEL: 2-methoxyethanol GLY: glycerol DPET: dipentaerythritol PET: pentaerythritol THEIC: tris (2-hydroxyethyl) isocyanurate MEHQ: hydroquinone mono Methyl ether TEMPOL: 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxy radical DEHA: N, N-diethylhydroxylamine DBHA: N, N-dibenzylhydroxylamine

2) Reaction yield The reaction yield of the transesterification reaction in Examples 1 to 11 and Comparative Examples 1 to 5 is a MEL by-product [derived from the use as a raw material] as the transesterification reaction proceeds. MCA] was quantified and calculated using the following formula (1). In addition, the quantification of MEL was performed using a high-performance liquid chromatograph with a differential refractive index detector (column: Atlantis, manufactured by Waters Corporation, Japan (Part No. (Part No.) is 186003748, the inner diameter of the column is 4.6 mm, the length of the column is 250 mm), the solvent: pure water or 10% by volume isopropyl alcohol in water), and the internal standard method is used. Reaction yield (mol%) = mole number of MEL by-produced with the progress of the transesterification reaction / (mol number of alcohol used as raw material × alcoholic hydroxyl group of alcohol molecule used as raw material Number) × 100… (1)

3) Purification yields The purification yields in the examples and comparative examples are obtained by using the weight of the purified target acrylate containing the target acrylate obtained after the reaction product after the third step is subjected to separation and purification operations such as distillation, crystallization, and filtration. Calculated using the following formula (2). Purification yield (%) = Purified product containing target acrylate (g) / (Molecular weight of acrylate produced when all alcoholic hydroxyl groups in alcohol used as raw material are acrylated × Molar number of alcohol) × 100… (2)

4) In the qualitative examples and comparative examples, it was confirmed that the target acrylate was contained in the reaction product and purification treatment. A high-performance liquid chromatography (ultraviolet, UV) detector (column: Japan Waters Corporation Limited) was used. ACQUITY UPLC BEH C18 (P / N 186002350, 2.1 mm column diameter, 50 mm column length) manufactured by the company, detection wavelength: 210 mm, solvent: 0.03% by weight trifluoroacetic acid aqueous solution and Mixed solvent of methanol).

2. Evaluation method The effects of the present invention were evaluated by measuring the purified processed products containing acrylates obtained in the examples and comparative examples, and the hue after the purified processed products were subjected to a forced degradation test.

1) Measurement of hue The color difference meter (Petroleum Color Tester OME-2000 manufactured by Nippon Denshoku Industries) was used to measure APHA and a1 values.

2) Forced degradation test 20 g of acrylate was added to a 50 ml glass container, and heated in a heating block maintained at 105 ° C. for 40 hours under atmospheric pressure. After leaving to cool, the hue was measured.

3. Examples and Comparative Examples 1) Example 1 (1) Step 1 In a 3-liter flask equipped with a stirrer, a thermometer, a gas introduction tube, a rectification column, and a cooling tube, 302.71 g (3.29 mol) of GLY was added. 2,231.76 g (17.77 moles) of MCA, 9.76 g (0.087 moles) of DABCO (triethylenediamine) as catalyst X, 36.10 g (0.17 moles) of zinc acrylate as catalyst Y, 1.60 g (685 ppm relative to the total weight of the added raw materials), 0.074 g (28 ppm relative to the total weight of the added raw materials) of TEMPOL, 5.00 g (0.28 mol) of pure water, and an oxygen-containing gas (oxygen is 5% by volume and 95% by volume of nitrogen) were bubbled in the liquid. While heating and stirring the reaction solution at a temperature in the range of 105 ° C to 130 ° C, adjust the pressure in the reaction system in the range of 20.0 × 10 ^-3 MPa to 101 × 10 ^-3 MPa (150 mmHg to 760 mmHg). A distillation column and a cooling pipe extract a mixed liquid of MEL and MCA by-produced as the transesterification reaction proceeds. In addition, an MCA having the same weight as the extract was added to the reaction system at any time. In addition, MCA including MEHQ and TEMPOL was added to the reaction system at any time via the rectification column. The MEL contained in the extraction solution extracted from the reaction system was quantified. As a result, the reaction yield reached 91% after 40 hours from the start of heating and stirring, so the heating of the reaction solution was ended, and the pressure in the reaction system was returned to normal pressure. And the extraction ends. In the first step, the ratio of MEHQ to 0.078 g and TEMPOL to 0.031 g was used with respect to the total of 100 g of the reaction solution.

(2) Second step The reaction product obtained in the first step was cooled to room temperature, and the precipitate was separated and recovered by pressure filtration. The recovered amount of this precipitate was 38.84 g. The precipitate was analyzed according to the method described in the Example of Japanese Patent Application No. 2015-46655. As a result, it was confirmed that the precipitate was DABCO as catalyst X and zinc acrylate as catalyst Y in a ratio of 1: 2 (Mole Ratio). From this result, it was confirmed that 85% of the catalyst X and the catalyst Y added in the first step were separated and recovered as precipitates.

14 g of aluminum silicate [Kyoward 700 (trade name) manufactured by Kyowa Chemical Industry Co., Ltd.] was put into the filtrate as an adsorbent, and the internal temperature was within a range of 80 ° C to 105 ° C and heated under normal pressure. The contact treatment was performed by stirring for 1 hour. After removing the catalyst dissolved in the reaction product, 27 g of calcium hydroxide was added at an internal temperature ranging from 20 ° C to 40 ° C, and the mixture was stirred at normal pressure for 1 hour. After the insoluble matter was separated by pressure filtration, the dry air was bubbled in the filtrate while the temperature was 70 ° C to 98 ° C and the pressure was 13.3 × 10 ^-6 MPa to 13.3 × 10 ^-3 MPa (0.001 mmHg Under reduced pressure distillation in the range of -100 mmHg) for 16 hours, the distillate containing unreacted MCA was separated.

(3) Step 3 The obtained kettle liquid was cooled to room temperature, and 0.16 g (200 ppm with respect to the processed product in Step 2) of DEHA was added, followed by stirring at normal pressure for 1 hour. Thereafter, 8.0 g (1.0% of the treated product in the second step) of activated carbon [Taiko S (trade name) manufactured by Nimura Chemical Co., Ltd.] was added, and the mixture was stirred at room temperature for 1 hour to perform contact treatment The solid content containing activated carbon is separated by pressure filtration. The composition analysis of the filtrate after pressure filtration was performed using a high-performance liquid chromatography equipped with a UV detector, and as a result, it was confirmed that glycerin diacrylate and glycerin triacrylate were contained as main components. The filtrate was regarded as a purified product, and the calculated purification yield was 89%. Table 1 shows the results of the measurement of the color tone and the forced degradation test using the obtained purified treatment product.

2) Example 2 to Example 7, Comparative Example 1 and Comparative Example 2 Regarding Example 2 to Example 7, in the third step, the types and amounts of hydroxylamine, hydrazine, and activated carbon were changed as shown in Table 1. Except for this, the first step to the third step were performed by the same method as in Example 1 to obtain a purified product containing the target acrylate. Regarding Comparative Example 1 and Comparative Example 2, the first step and the second step were performed by the same method as in Example 1, except that the third step was not performed to obtain a purified product containing the target acrylate. The measurement of the hue of the obtained purified processed material and the forced degradation test were performed. The results are shown in Table 1.

[Table 1]

Acrylic esters obtained by Examples 1 to 7 of the production method of the present invention have less coloration, and have less coloration after the forced deterioration test, and high-quality acrylates can be obtained. In contrast, in the acrylates obtained in Comparative Examples 1 and 2 in which the third step was not performed, the values of APHA and a1 became larger than those of the examples, and the values of APHA and a1 after the forced degradation test also became larger. Furthermore, in Comparative Example 2, it is estimated that the results of the forced deterioration test show the same tendency as Comparative Example 1, and the evaluation is omitted.

3) Example 8 and Example 9 and Comparative Example 3 (1) In the first step, 260.00 g (1.02 mole) of DPET was added in place of GLY and 1437.00 g (11.04 mole) of MCA as 6.07 g (0.054 mol) of DABCO for catalyst X, 19.86 g (0.11 mol) of zinc acetate as catalyst Y instead of zinc acrylate, and 1.18 g (766 ppm relative to the total weight of the added raw materials) of MEHQ 0.16 g (90 ppm relative to the total weight of the added raw material) of phenothiazine, 0.022 g (150 ppm relative to the total weight of the added raw material) TEMPOL, and an oxygen-containing gas was bubbled in the liquid. While heating and stirring the reaction solution at a temperature in the range of 131 ° C to 133 ° C, the pressure in the reaction system was adjusted in the range of 37.3 × 10 ^-3 MPa to 44.0 × 10 ^-3 MPa (280 mmHg to 330 mmHg). A distillation column and a cooling pipe extracted a mixed liquid of MEL and MCA that was produced as a transesterification reaction from the reaction system, and reacted in the same manner as in Example 1 for 18 hours. In the first step, the ratio of MEHQ to 0.024 g and TEMPOL to 0.0032 g was used with respect to the total 100 g of the reaction solution.

(2) Second step After removing the catalyst of the reaction product by filtration according to the same method as in Example 1, the filtrate was subjected to adsorption treatment, and then subjected to reduced pressure distillation.

(3) Step 3 DEHA was added to the obtained kettle liquid in the ratio shown in Table 2, and the mixture was stirred at 80 ° C and normal pressure for 1 hour.

Regarding Comparative Example 3, the first step and the second step were performed by the same method as in Example 8 and Example 9, but the third step was not performed to obtain a purified product containing the target acrylate.

The measurement of the hue of the obtained purified processed material and the forced degradation test were performed. These results are shown in Table 2.

4) Example 10 and Comparative Example 4 (1) The first step In Example 1, 300.00 g (2.20 mol) of PET was added instead of GLY, 2064.65 g (15.87 mol) of MCA, and catalyst X 1.94 g (0.017 mol) of DABCO, 7.17 g (0.035 mol) of zinc acrylate as catalyst Y, 0.77 g (413 ppm relative to the total weight of the added raw material) of MEHQ, 0.103 g (relative to the added raw material) (Total weight is 43 ppm) of TEMPOL, which causes oxygen-containing gas to bubble in the liquid. While heating and stirring the reaction solution at a temperature in the range of 110 ° C to 128 ° C, adjust the pressure in the reaction system in the range of 24.7 × 10 ^-3 MPa to 101.0 × 10 ^-3 MPa (185 mmHg to 760 mmHg). A distillation column and a cooling tube extract a mixed liquid of MEL and MCA by-produced from the reaction system as the transesterification reaction proceeds, and react in the same manner as in Example 1 for 15 hours. In the first step, a ratio of 0.0044 g of MEHQ and 0.0049 g of TEMPOL was used with respect to the total of 100 g of the reaction solution.

(2) Second step According to the same method as in Example 1, the reaction product was subjected to adsorption treatment to remove the catalyst, and then subjected to vacuum distillation.

(3) Step 3 DEHA was added to the obtained kettle liquid in the ratio shown in Table 2, and the mixture was stirred at 80 ° C and normal pressure for 1 hour.

Regarding Comparative Example 4, the first step and the second step were performed by the same method as in Example 10, but the third step was not performed to obtain a purified product containing the desired acrylate.

The measurement of the hue of the obtained purified processed material and the forced degradation test were performed. These results are shown in Table 2.

5) Example 11 and Comparative Example 5 (1) First step In Example 1, 679.98 g (2.60 mol) of THEIC was added instead of GLY, 1829.27 g (14.06 mol) of MCA, and catalyst X 0.35 g (0.0031 mol) of DABCO, 1.29 g (0.0062 mol) of zinc acrylate as catalyst Y, 1.25 g (572 ppm relative to the total weight of the added raw materials), 0.255 g (relative to the added raw materials) The total weight is 101 ppm) of TEMPOL, which causes oxygen-containing gas to bubble in the liquid. While heating and stirring the reaction solution at a temperature in the range of 125 ° C to 127 ° C, adjust the pressure in the reaction system in the range of 30.7 × 10 ^-3 MPa to 40.0 × 10 ^-3 MPa (230 mmHg to 300 mmHg), and then A distillation column and a cooling pipe extracted a mixed liquid of MEL and MCA by-produced from the reaction system as the transesterification reaction proceeded, and reacted in the same manner as in Example 1 for 8 hours. In the first step, a ratio of 0.0037 g of MEHQ and 0.0041 g of TEMPOL was used with respect to the total of 100 g of the reaction solution.

(2) Second step According to the same method as in Example 1, the reaction product was subjected to adsorption treatment to remove the catalyst, and then subjected to vacuum distillation.

(3) Step 3 DEHA was added to the obtained kettle liquid in the ratio shown in Table 2, and the mixture was stirred at 80 ° C and normal pressure for 1 hour.

Regarding Comparative Example 5, the first step and the second step were performed by the same method as in Example 11, but the third step was not performed to obtain a purified product containing the desired acrylate.

The measurement of the hue of the obtained purified processed material and the forced degradation test were performed. These results are shown in Table 2.

[Table 2]

Acrylic esters obtained by Examples 8 to 11 of the production method of the present invention have less coloration and further less coloration after the forced deterioration test, and high-quality acrylates can be obtained. In contrast, the values of APHA and a1 in the acrylates obtained in Comparative Examples 3 to 5 without performing the third step are larger than those corresponding to the same alcohols used in Examples 8 to 11, The values of APHA and a1 after the forced degradation test also increased.

6) Comparative Example 6 In a 3-liter flask equipped with a stirrer, a thermometer, a gas introduction tube, a rectification column, and a cooling tube, 284.50 g (3.09 mol) of GLY and 2173.65 g (16.70 mol) of MCA were added as a contact. 12.23 g (0.11 mol) of DABCO in vehicle X, 45.24 g (0.22 mol) of zinc acrylate as catalyst Y, 1.49 g (675 ppm relative to the total weight of added raw materials), MEHQ, 0.074 g (relative to Tempol, 0.47 g (186 ppm relative to the total weight of the added raw materials), DBHA, 12.69 g (0.70 mol) of pure water was added to the TEMPOL (29 ppm total weight of the added raw materials), and oxygen-containing gas (5 volumes of oxygen was used). %, Nitrogen is 95% by volume) bubbling in the liquid. While heating and stirring the reaction solution at a temperature in the range of 105 ° C to 130 ° C, adjust the pressure in the reaction system in the range of 20.0 × 10 ^-3 MPa to 101 × 10 ^-3 MPa (150 mmHg to 760 mmHg). A distillation column and a cooling pipe extracted a mixed liquid of MEL and MCA by-produced with the progress of the transesterification reaction. As a result, polymerization occurred 10 hours after the start of the reaction, and no purified product was obtained. [Industrial availability]

According to the production method of the present invention, a high-quality (meth) acrylate with little coloring can be produced. The (meth) acrylate obtained by the method of the present invention can be used as a main component, a cross-linking component, and a reaction of a composition such as a coating, an ink, an adhesive, a film, a sheet, an optical lens, a filler, and a molding material. It is preferably used in various industrial applications.

no

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Claims (15)

A method for producing a (meth) acrylate, which includes the following first to third steps, and sequentially performs the following first to third steps: ○ The first step is in the presence of a transesterification catalyst, A step of producing a (meth) acrylic acid ester by subjecting an alcohol to a compound having one (meth) acrylfluorenyl group; ○ The second step includes the (meth) acrylic acid obtained in the first step. A step of removing the transesterification catalyst from the reaction product of the ester; a third step of adding a hydroxylamine or hydrazine to the reaction product containing the (meth) acrylate obtained in the second step; The method for producing a (meth) acrylic acid ester according to item 1 of the scope of patent application, wherein the hydroxylamine used in the third step is a compound represented by the following general formula (1) or hydrazine is the following general formula ( 2) the compound represented, [In the general formula (1), R ¹ and R ² each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or a linear or branched carbon group having 1 to 20 carbon atoms. Branched alkoxy, linear or branched alkyl having 1 to 20 carbons substituted with alkoxy having 1 to 20 carbons, aryl having 6 to 12 carbons, and aralkyl having 7 to 30 carbons Radicals in radicals; R ¹ and R ² may be the same or different] [In the general formula (2), R ³ and R ⁴ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a fluorenyl group having 1 to 20 carbon atoms, 1 to 20 alkoxy-substituted linear or branched alkyl groups having 1 to 20 carbon atoms, 6 to 12 aryl groups and 7 to 30 aralkyl groups; R ³ And R ⁴ may be the same or different]. The method for manufacturing a (meth) acrylate according to item 1 or 2 of the scope of the patent application, wherein the third step further includes a step of obtaining the (meth) acrylate containing the (meth) acrylate obtained in the second step. Contact treatment of reaction products with activated carbon. The method for producing a (meth) acrylic acid ester according to item 1 or item 2 of the scope of patent application, wherein in the first step, an N-oxyl radical compound is added as a polymerization inhibitor. The method for producing a (meth) acrylic acid ester according to item 4 of the scope of the patent application, wherein the N-oxyl radical compound is selected from the group consisting of 4-hydroxy-2,2,6,6-tetramethylpiperidine- 1-oxyl radical, 2,2,6,6-tetramethylpiperidine-1-oxyl radical, 4-oxo-2,2,2,6,6-tetramethylpiperidine-1-oxyl radical One or more compounds in the group consisting of 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxy radical. The method for producing a (meth) acrylic acid ester according to item 4 of the scope of patent application, wherein in the first step, a phenolic compound or / and phenothiazine is used in combination with the N-oxyl radical compound Comes as the polymerization inhibitor. The method for producing a (meth) acrylic acid ester according to item 2 of the scope of patent application, wherein the hydroxylamine represented by the general formula (1) is selected from the group consisting of N, N-dimethylhydroxylamine, N, N-diethyl Hydroxylamine, N, N-dipropylhydroxylamine, N, N-dibutylhydroxylamine, N, N-methylethylhydroxylamine, N, N-ethylpropylhydroxylamine, N, N-propylbutylhydroxylamine One or more compounds in the group consisting of N, N-didecylhydroxylamine, N, N-diphenylhydroxylamine, and N, N-dibenzylhydroxylamine. The method for producing a (meth) acrylic acid ester according to item 7 in the scope of the patent application, wherein the hydroxylamine represented by the general formula (1) is N, N-diethylhydroxylamine or N, N-dibenzylhydroxylamine . The method for producing a (meth) acrylate according to item 2 of the scope of the patent application, wherein the hydrazine represented by the general formula (2) is a hydrazine monohydrate. The method for producing a (meth) acrylic acid ester according to item 1 or item 2 of the patent application scope, wherein the alcohol used in the first step is a polyhydric alcohol having three or more alcoholic hydroxyl groups. The method for producing a (meth) acrylic acid ester according to item 10 of the scope of the patent application, wherein the polyol having three or more alcoholic hydroxyl groups is selected from the group consisting of trimethylolethane, trimethylolpropane, Glycerin, glycerine alkylene oxide adduct, tris (2-hydroxyethyl) isocyanurate, triethanolamine, bis-trimethylolethane, bis-trimethylolpropane, diglycerol, diglycerol Group of alkylene oxide adducts, pentaerythritol, pentaerythritol adducts, xylitol, dipentaerythritol, dipentaerythritol alkylene oxide adducts, D-sorbitol and polyglycerol 1 or more compounds. The method for producing a (meth) acrylic acid ester according to item 1 or 2 of the scope of patent application, wherein the compound having one (meth) acrylfluorenyl group used in the first step is selected from the group consisting of acrylic acid One or more compounds in the group consisting of methyl ester, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, and 2-methoxyethyl acrylate. The method for producing a (meth) acrylic acid ester according to item 1 or item 2 of the scope of the patent application, wherein the transesterification catalyst used in the first step uses the following catalyst X and catalyst Y: Catalyst X: selected from the group consisting of a cyclic tertiary amine or a salt or a complex thereof having an azabicyclic structure, a hydrazone or a salt or a complex thereof, a compound having a pyridine ring or a salt or a complex thereof, and a phosphine or One or more compounds in the group consisting of salts or complexes thereof; Catalyst Y: a compound containing zinc. The method for producing a (meth) acrylic acid ester according to item 13 of the scope of the patent application, wherein the catalyst Y is an organic acid zinc and / or a zinc diketenol. The method for producing a (meth) acrylic acid ester according to item 13 of the scope of the patent application, wherein the catalyst X is triethylenediamine.