JP5289490B2 - Method for producing (meth) acrylic acid ester having ether group - Google Patents

Description

The present invention relates to a method for producing a (meth) acrylic acid ester having an ether group. More specifically, the present invention relates to a method for producing (meth) acrylic acid having an ether group that can be easily polymerized by heat, ultraviolet light, radiation, electron beam, radical polymerization initiator, acid, or the like.

(Meth) acrylic acid ester having an ether group is known to be useful as a polymer monomer because it can be easily polymerized by heat, ultraviolet rays, radiation, electron beam, radical polymerization initiator, acid, etc. Various manufacturing methods are being studied. As one of the reaction processes, a process for producing a (meth) acrylic acid ester having an ether group by reacting a (meth) acrylic acid ester with a hydroxyl group-containing ether compound is known. In such a reaction process, since both the reaction raw material and the target product have a (meth) acryloyl group that is a polymerizable double bond, they are easily polymerized by light, heat, etc. It is important to prevent The following methods are conventionally known as methods aimed at preventing the polymerization of a compound having a polymerizable double bond such as a (meth) acryloyl group.

It is disclosed that an N-nitrosamine is added to an acrylic ester or a methacrylic ester to prevent the acrylic ester or the methacrylate ester from popcorn polymerization (for example, see Patent Document 1). In the process of producing a polymerizable ethylenically unsaturated organic compound, a distillation step for purifying and recovering the reaction product is performed by a phenolic polymerization inhibitor and a liquid phase polymerization inhibitor containing a soluble manganese compound or a soluble cerium compound. And in the presence of a liquid-vapor phase polymerization inhibitor system in combination with a vapor phase polymerization inhibitor selected from the group consisting of nitric oxide and N-phenyl-N-nitrosohydroxylamine ammonium salt. (For example, refer to Patent Document 2). Further, ethylene and a radical polymerizable monomer copolymerizable with ethylene are polymerized at a pressure of 500 to 3000 Kg / cm ² or more and a temperature of 100 ° C. to 300 ° C. in the presence of a polymerization initiator to produce an ethylene copolymer. In this method, a method for producing an ethylene copolymer in which a polymerization inhibitor is injected into the system after the polymerization reaction region and before the entrance of the first separator is disclosed, in which a phosphite ester system is used as a polymerization inhibitor The use of at least one compound selected from a compound, a nitrosamine compound, and a phenol compound is disclosed (for example, see Patent Document 3). Furthermore, as a polymerization inhibitor, an N-oxyl compound is used in combination with at least one selected from the group consisting of manganese salt compounds, copper salt compounds, 2,2,6,6-tetramethylpiperidine compounds, and nitroso compounds. In addition, a method for preventing polymerization of (meth) acrylic acid esters using acids is disclosed (for example, see Patent Document 4).

JP 49-125315 A (page 1-2) JP-A-64-44243 (page 1-2) Japanese Patent Laid-Open No. 7-10910 (page 1-2) Japanese Patent No. 3990580 (first page)

As described above, various methods for preventing polymerization of a compound having a polymerizable double bond such as a (meth) acryloyl group have been studied, and use of various polymerization inhibitors has been attempted.
However, in the production of the (meth) acrylic acid ester having an ether group, not only the polymerization of the (meth) acryloyl group, but also a peroxide derived from the ether group, this peroxide is also a cause of the polymerization. Become. For this reason, in order to effectively prevent the polymerization of this compound, it is also important to suppress the formation of peroxide, but the conventional method for preventing the polymerization of a compound having a polymerizable double bond as described above In this case, it is difficult to effectively suppress the polymerization, and both the polymerization of the polymerizable double bond of the (meth) acryloyl group and the generation of the peroxide derived from the ether group are sufficiently suppressed, and the (meth) acryloyl group and There has been a demand for a production method that can be suitably used for the production of a compound having both ether groups.

The present invention has been made in view of the above-described situation, and sufficiently suppresses both polymerization of a (meth) acryloyl group and generation of a peroxide derived from an ether group, and a (meth) acryl having an ether group. It aims at providing the manufacturing method of the (meth) acrylic acid ester which has an ether group which can be used suitably for manufacture of acid ester.

The present inventor has made various studies on a method for producing a (meth) acrylic acid ester having an ether group by reacting a (meth) acrylic acid ester with a hydroxyl group-containing ether compound to prevent polymerization in the gas phase part of the reaction system. N-nitrosophenylhydroxylamine salt that plays the role of, a primary antioxidant that acts as a radical chain inhibitor in the liquid phase part of the reaction system, and a secondary antioxidant that acts as a peroxide decomposer in the liquid phase part of the reaction system Focused on the system used. First of all, N-nitrosophenylhydroxylamine salt itself does not have a polymerization-preventing effect, but it is decomposed by contact with heat or acid during the reaction, and the decomposition product nitrosobenzene is particularly effective for preventing polymerization. I found out that it has an effect. Furthermore, when triphenylphosphine, which is a representative secondary antioxidant, is used as a secondary antioxidant, the above-mentioned decomposition product, nitrosobenzene, reacts quickly with the secondary antioxidant. Therefore, it has been newly found that the effect of preventing polymerization in the reaction gas phase is lost over time. And for this newly discovered problem, the present inventors use a phosphite and / or thioether as a secondary antioxidant, because the reaction between the secondary antioxidant and nitrosobenzene is slow, The secondary antioxidant exhibits the polymerization preventing effect in the reaction system gas phase part by nitrosobenzene while maintaining its peroxide resolution, and as a result, the reaction system gas phase part over a long period of time and It has been found that both the prevention of polymerization in the liquid phase part and the suppression of the formation of peroxide can be sufficiently realized, and the inventors have arrived at the present invention by conceiving that the above problems can be solved brilliantly.

That is, the present invention is a method for producing a (meth) acrylic acid ester having an ether group from a reaction raw material containing a (meth) acrylic acid ester and a hydroxyl group-containing ether compound, wherein the production method comprises the reaction raw material, N-nitrosophenylhydroxylamine salt, phosphite and / or thioether, and the step of reacting in the presence of a primary antioxidant, the N-nitrosophenylhydroxylamine salt is represented by the following general formula (1);

(In the formula, M represents a metal atom or an ammonium group. N represents a positive number equal to the valence of M. The dotted line connecting M and the oxygen atom is that M is coordinated to the oxygen atom. (Meth) acrylic acid ester having an ether group represented by:
The present invention is described in detail below.

In the method for producing an (meth) acrylic acid ester having an ether group according to the present invention, a reaction raw material containing a (meth) acrylic acid ester and a hydroxyl group-containing ether compound is converted into an N-nitrosophenylhydroxylamine salt, a phosphorous acid ester and / or Thioether and a step of reacting in the presence of a primary antioxidant, comprising (meth) acrylic acid ester, hydroxyl group-containing ether compound, N-nitrosophenylhydroxylamine salt, phosphorous ester and / or thioether, and Each of the primary antioxidants may be used alone or in combination of two or more. Moreover, the manufacturing method of this invention may contain the other process, as long as the said reaction process is included. Furthermore, in the production method of the present invention, (meth) acrylic acid ester, hydroxyl group-containing ether compound, N-nitrosophenylhydroxylamine salt, phosphite ester and / or thioether, and primary antioxidant are used. As long as it may be performed including other components, it is preferable that a transesterification catalyst is further included as described later. That is, a form in which the reaction step is further performed in the presence of a transesterification catalyst is also a preferred embodiment of the present invention.
In the present specification, (meth) acrylic acid ester refers to acrylic acid ester and / or methacrylic acid ester, and (meth) acryloyl group refers to acryloyl group and / or methacryloyl group.

The above reaction step is performed in the presence of N-nitrosophenylhydroxylamine salt, phosphite and / or thioether, and primary antioxidant, but as long as the effects of the present invention are exhibited, (meth) At any point when the reaction raw material containing the acrylate ester and the hydroxyl group-containing ether compound reacts, N-nitrosophenylhydroxylamine salt, phosphite ester and / or thioether, and primary antioxidant are present in the reaction system. It only needs to be a condition for coexistence. Preferably, the reaction is performed for a long time under the condition in which N-nitrosophenylhydroxylamine salt, phosphite and / or thioether, and primary antioxidant coexist. -Most preferably, the reaction is carried out in the presence of a nitrosophenylhydroxylamine salt, a phosphite and / or thioether and a primary antioxidant.

The N-nitrosophenylhydroxylamine salt, phosphite and / or thioether, and primary antioxidant may be charged all at once in the reactor before starting the reaction, or sequentially added while performing the reaction. However, it is preferable to charge the reactor in a batch before starting the reaction. Thereby, the polymerization reaction in the reaction step can be more effectively suppressed.
In addition, (meth) acrylic acid ester and hydroxyl group-containing ether compound may be charged into the reactor at the same time before starting the reaction, or partly charged before starting the reaction, and the rest is reacted. However, you may add sequentially.

The N-nitrosophenylhydroxylamine salt has the following general formula (1);

(In the formula, M represents a metal atom or an ammonium group. N represents a positive number equal to the valence of M. The dotted line connecting M and the oxygen atom is that M is coordinated to the oxygen atom. It is a compound represented by.
M in the general formula (1) represents a metal atom or an ammonium group, and examples of the metal atom include aluminum, copper, iron (III), tin, zinc, magnesium, titanium, cobalt, nickel, zirconium, and vanadium ( V), niobium, tantalum, phosphorus, bismuth (III) and the like. Among these, M is preferably an aluminum, zinc, tin, phosphorus, iron (III), or ammonium group, more preferably an aluminum, zinc, tin, or ammonium group, and even more preferably an aluminum or ammonium group. It is.

The phosphite and / or thioether decomposes the peroxide produced in the liquid phase part of the reaction system in the reaction step of the present invention for synthesizing the (meth) acrylic acid ester having an ether group. It acts as a secondary antioxidant that suppresses the polymerization reaction involving phosphite, and may be used as any form of phosphite ester, thioether, and a mixture of phosphite ester and thioether. An acid ester is preferred. That is, a form in which the phosphite and / or thioether is a phosphite is also a preferred embodiment of the present invention.

The phosphite is represented by the following general formula (3):

(In the formula, R ⁴ and R ⁵ are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. R ³ is the same or different and represents a hydrocarbon group having 1 to 18 carbon atoms. M represents an integer of 0 to 3. X is the same or different and represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and when m is 0 or 1, a phosphorus atom is an oxygen atom. And a plurality of groups containing a benzene ring bonded via each other may be linked to each other via X. When they are linked to each other via X, X represents an alkylene group having 1 to 3 carbon atoms. It is preferable that it has the structure represented. Since the phosphite has such a structure, it is difficult to react with nitrosobenzene, which is a decomposition product of N-nitrosophenylhydroxylamine salt, while exhibiting its peroxide resolution more fully. The effect of preventing polymerization in the vapor phase of the reaction system by benzene can be more sufficiently exhibited.

R ⁴ and R ⁵ in the general formula (3) represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and among them, a hydrogen atom, a methyl group, and a tert-butyl group are preferable. Further, ^{R 3} in the general formula (3) is a hydrocarbon group having 1 to 18 carbon atoms, among them, preferably a hydrocarbon group having 8 to 18 carbon atoms.
Examples of the hydrocarbon group include linear or branched alkyl groups, cyclic alkyl groups, linear or branched alkenyl groups, cyclic alkenyl groups, linear or branched alkynyl groups, and cyclic alkynyl groups. Among them, among these, a linear or branched alkyl group is preferable.

X in the general formula (3) represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Among them, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferable, and a hydrogen atom is particularly preferable. It is.
When m is 0 or 1, a plurality of groups containing a benzene ring bonded to a phosphorus atom via an oxygen atom may be connected to each other via X. That is, a benzene ring in one group including a benzene ring bonded to a phosphorus atom via an oxygen atom is bonded to a benzene ring in another group including a benzene ring bonded to a phosphorus atom via an oxygen atom via X. It may be in the form. Thus, when the several group containing the benzene ring couple | bonded with a phosphorus atom through an oxygen atom connects with each other through X, X represents a C1-C3 alkylene group. X in the case where a plurality of groups containing the benzene ring are connected to each other through X is preferably a methylene group.

Specific examples of the phosphite ester include triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl). ) Octyl phosphite, diphenyl mono (tridecyl) phosphite, diphenyl monodecyl phosphite, cyclic neopentatetrayl bis (octadecyl phosphite), trioleyl phosphite and the like. Among these, triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, diphenyl mono (tridecyl) ) Phosphite, diphenyl monodecyl phosphite are preferred, triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) Octyl phosphite is more preferred. Particularly preferred are triphenyl phosphite and tris (2,4-di-tert-butylphenyl) phosphite.

Specific examples of the thioether include dilauryl 3,3′-thiodipropionate, distearyl 3,3′-thiodipropionate, didodecyl 3,3′-thiodipropionate, and 3,3′-thio. Examples include dioctadecyl dipropionate and pentaerythritol tetrakis (β-laurylthiopropionic acid). Among these, dilauryl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, didodecyl 3,3'-thiodipropionate, dioctadecyl 3,3'-thiodipropionate Preferably, dilauryl 3,3′-thiodipropionate and distearyl 3,3′-thiodipropionate are more preferable. Particularly preferred is dilauryl 3,3′-thiodipropionate.

As the primary antioxidant, the peroxy radical generated in the liquid phase part of the reaction system in the reaction step of the present invention for synthesizing the (meth) acrylic acid ester having an ether group is captured and decomposed to form a peroxy radical. It is not particularly limited as long as it can suppress the related radical polymerization reaction, and examples thereof include hydroquinone, methoxyhydroquinone, hydroquinone monomethyl ether, benzoquinone, p-tert-butylcatechol, 2,6-di-tert-butylphenol, 2 , 4-di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,4,6-tri-tert-butylphenol, 3,5-di-tert-butyl-4-hydroxytoluene, , 1,3-Tris (2-methyl-4-hydroxy-5 Phenol antioxidants such as tert-butylphenyl) butane; Aromatic amine antioxidants such as alkylated diphenylamine, N, N′-diphenyl-p-phenylenediamine, and phenothiazine; 4-hydroxy-2,2,6 , 6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1,4-dihydroxy-2,2,6,6-tetramethylpiperidine, 1-hydroxy-4-benzoyloxy Cyclic amine antioxidants such as -2,2,6,6-tetramethylpiperidine; copper dithiocarbamate antioxidants such as copper dimethyldithiocarbamate, copper diethyldithiocarbamate, copper dibutyldithiocarbamate; 2,2,6 , 6-Tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2, 6,6-tetramethylpiperidine-N-oxyl, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N -N-oxyl antioxidants such as esters of oxyl; Among these, phenolic antioxidants and aromatic amine antioxidants are preferable as the primary antioxidant. Thus, the form in which the primary antioxidant is a phenol-based antioxidant and / or an aromatic amine-based antioxidant is also a preferred embodiment of the present invention.
More preferably, the primary antioxidant is hydroquinone, hydroquinone monomethyl ether, 3,5-di-tert-butyl-4-hydroxytoluene, 1,1,3-tris (2-methyl-4-hydroxy-5-tert). -Butylphenyl) butane and phenothiazine, more preferably hydroquinone, hydroquinone monomethyl ether, 3,5-di-tert-butyl-4-hydroxytoluene, 1,1,3-tris (2-methyl-4-hydroxy) -5-tert-butylphenyl) butane, phenothiazine. Particularly preferably, hydroquinone, hydroquinone monomethyl ether, 3,5-di-tert-butyl-4-hydroxytoluene, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, It is phenothiazine.

The amount of N-nitrosophenylhydroxylamine salt used in the reaction step of the present invention is 0.0002 to 5% by mass relative to 100% by mass of the hydroxyl group-containing ether compound as the reaction raw material. It is preferable. The use amount of the N-nitrosophenylhydroxylamine salt is preferably in such a range from the viewpoint of yield, suppression of polymerization in the gas phase of the reaction system, and economical efficiency. More preferably, it is 0.001-1 mass%, More preferably, it is 0.002-0.5 mass%, Most preferably, it is 0.01-0.2 mass%.

In the reaction step of the present invention, the amount of phosphite and / or thioether used is 0.0002 to 5% by mass relative to 100% by mass of the hydroxyl group-containing ether compound as the reaction raw material. Preferably there is. The use amount of the phosphite and / or thioether is preferably in such a range from the viewpoint of yield, suppression of polymerization in the liquid phase part of the reaction system, and economical efficiency. More preferably, it is 0.001-3 mass%, More preferably, it is 0.005-1 mass%, Most preferably, it is 0.01-0.5 mass%.

The amount of the primary antioxidant used in the reaction step of the present invention is preferably 0.0002 to 5% by mass relative to 100% by mass of the hydroxyl group-containing ether compound as the reaction raw material. . The amount of the primary antioxidant used is preferably in such a range from the viewpoint of yield, suppression of polymerization in the liquid phase part of the reaction system, and economical efficiency. More preferably, it is 0.001-3 mass%, More preferably, it is 0.005-1 mass%, Most preferably, it is 0.01-0.5 mass%.

The (meth) acrylic acid ester used as a reaction raw material in the present invention is not particularly limited as long as it can react with a hydroxyl group-containing ether compound to produce a (meth) acrylic acid ester having an ether group. 4);

(Wherein R ¹ represents a hydrogen atom or a methyl group, and R ⁶ represents an organic residue).
The organic residue represented by R ⁶ in the general formula (4) is not particularly limited, for example, 1-8C straight, branched or cyclic alkyl group, 6 carbon atoms Examples thereof include 10 optionally substituted aromatic groups. Among these, a C1-C4 alkyl group is preferable.

Examples of the (meth) acrylic acid ester represented by the general formula (4) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, ( Examples include (meth) acrylic acid lower alkyl esters such as butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, and t-butyl (meth) acrylate. Among these, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate are preferable.

The hydroxyl group-containing ether compound used as a reaction raw material in the present invention is particularly limited as long as it contains a hydroxyl group and can react with a (meth) acrylic acid ester to produce a (meth) acrylic acid ester having an ether group. For example, a hydroxyl group-containing ether compound having an alkoxy group at the molecular end, the following general formula (5);

(Wherein R ² represents an organic residue), a hydroxyl group-containing vinyl ether compound represented by the formula, a hydroxyl group-containing ether compound having a Group 15 element in the molecule, and a hydroxyl group-containing ether having a Group 16 element in the molecule. Examples thereof include a compound and a hydroxyl group-containing ether compound having a Group 17 element in the molecule. Among these, the form in which the hydroxyl group-containing ether compound is a hydroxyl group-containing vinyl ether compound represented by the general formula (5) is also a preferred embodiment of the present invention.

Examples of the hydroxyl group-containing ether compound having an alkoxy group at the molecular end include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, and dipropylene. Glycol monomethyl ether, tripropylene glycol monobutyl ether, polypropylene glycol monoethyl ether, phenoxyethanol, phenoxypropanol, 1,4-cyclohexanedimethanol monomethyl ether, 1,3-cyclohexanedimethanol monomethyl ether, 1,2-cyclohexanedimethanol monomethyl ether , P-ki Lenglycol monomethyl ether, m-xylene glycol monomethyl ether, o-xylene glycol monomethyl ether, glycidol, oxetanyl methanol, tetrahydrofurfuryl alcohol, tetrahydropyranyl alcohol, 2- (2-chloroethoxy) ethanol, 2- (2-amino Monofunctional hydroxyl group-containing ether compounds such as ethoxy) ethanol and 2- (2-dimethylaminoethoxy) ethanol; ethylene oxide modified trimethylolpropane, ethylene oxide modified pentaerythritol, ethylene oxide modified dipentaerythritol, ethylene oxide modified glycerin, ethylene oxide Modified bisphenol A, ethylene oxide modified bisphenol F, ethylene oxide modified bisphenol , Ethylene oxide modified monosaccharide, propylene oxide modified pentaerythritol, propylene oxide modified dipentaerythritol, propylene oxide modified glycerin, propylene oxide modified bisphenol A, propylene oxide modified bisphenol F, propylene oxide modified bisphenol S, propylene oxide modified monosaccharide, etc. Examples thereof include polyfunctional hydroxyl group-containing ether compounds.

In the hydroxyl group-containing vinyl ether compound represented by the general formula (5), the organic residue represented by R ² in the general formula (5) is not particularly limited, but for example, a linear chain having 2 to 20 carbon atoms. -Like, branched or cyclic alkylene group, C2-C20 alkylene group having an oxygen atom by an ether bond and / or ester bond in the structure, C6-C11 aromatic optionally substituted Groups and the like. Among these, a C2-C6 alkylene group and a C4-C10 alkylene group which has an oxygen atom by an ether bond in a structure are preferable.

Examples of the hydroxyl group-containing vinyl ether compound represented by the general formula (5) include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3 -Hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxyisobutyl vinyl ether, 2-hydroxyisobutyl vinyl ether, 1-methyl-3-hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl vinyl ether, 1-hydroxymethylpropyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, 1,6-hexanediol monovinyl ether, 1,4-cyclohexyl Dimethanol monovinyl ether, 1,3-cyclohexanedimethanol monovinyl ether, 1,2-cyclohexanedimethanol monovinyl ether, p-xylene glycol monovinyl ether, m-xylene glycol monovinyl ether, o-xylene glycol monovinyl ether, diethylene glycol monovinyl ether, Triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, pentaethylene glycol monovinyl ether, oligoethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, dipropylene glycol monovinyl ether, tripropylene glycol monovinyl ether, tetrapropylene glycol monovinyl ether, pentap Propylene glycol monomethyl ether, oligo propylene glycol monomethyl ether, polypropylene glycol monovinyl ether, ethylene glycol - propylene glycol copolymer monobutyl ether.

Among these, the hydroxyl group-containing ether compound includes diethylene glycol monomethyl ether, ethylene oxide-modified trimethylolpropane, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl vinyl ether, 4-hydroxy Butyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, 1,6-hexanediol monovinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, and dipropylene glycol monovinyl ether are preferred. More preferred are diethylene glycol monomethyl ether, ethylene oxide-modified trimethylolpropane, and diethylene glycol monovinyl ether, and still more preferred are diethylene glycol monomethyl ether, ethylene oxide-modified trimethylolpropane, and diethylene glycol monovinyl ether.

The mixing ratio of the (meth) acrylic acid ester and the hydroxyl group-containing ether compound in the reaction step of the present invention can be appropriately set depending on the combination of the types of the (meth) acrylic acid ester and the hydroxyl group-containing ether compound. ) The molar ratio of the acrylate ester to the hydroxyl group-containing ether compound is preferably 20/1 to 1/5. A blending ratio in such a range is preferable in terms of yield and economy. More preferably, it is 15/1-1/3, More preferably, it is 10/1-1/2. Particularly preferably, it is 5/1 to 1/1. This molar ratio represents the ratio in the total amount of raw materials including sequential charging.

The reaction in the reaction step is a transesterification reaction between a (meth) acrylic acid ester and a hydroxyl group-containing ether compound, and the transesterification reaction is preferably performed in the presence of a transesterification catalyst.
Although it does not specifically limit as said transesterification catalyst, For example, oxides, such as calcium oxide, barium oxide, lead oxide, zinc oxide, a zirconium oxide; Potassium hydroxide, sodium hydroxide, lithium hydroxide, calcium hydroxide, water Hydroxides such as thallium oxide, tin hydroxide, lead hydroxide, nickel hydroxide; halides such as lithium chloride, calcium chloride, tin chloride, lead chloride, zirconium chloride, nickel chloride; potassium carbonate, rubidium carbonate, cesium carbonate Carbonates such as lead carbonate, zinc carbonate, nickel carbonate; bicarbonates such as potassium bicarbonate, rubidium bicarbonate, cesium bicarbonate; sodium phosphate, potassium phosphate, rubidium phosphate, lead phosphate, zinc phosphate , Phosphates such as nickel phosphate; lithium nitrate, calcium nitrate, lead nitrate, nitrate nitrate Nitrates such as nickel nitrate; carboxylates such as lithium acetate, calcium acetate, lead acetate, zinc acetate, nickel acetate; sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, potassium t-butoxide, calcium methoxy Alkoxy compounds such as lithium, calcium ethoxide, barium methoxide, barium ethoxide, tetraethoxy titanium, tetrabutoxy titanium, tetra (2-ethylhexanoxy) titanium; lithium acetylacetonate, zirconia acetylacetonate, zinc acetylacetate Acetylacetonate complexes such as nato, dibutoxytin acetylacetonate, dibutoxytitanium acetylacetonate; tetramethylammonium methoxide, tetramethylammonium t-butoxide Quaternary ammonium alkoxides such as trimethylbenzylammonium ethoxide; dialkyltin compounds such as dimethyltin oxide, methylbutyltin oxide, dibutyltin oxide and dioctyltin oxide; distanoxanes such as bis (dibutyltin acetate) oxide and bis (dibutyltin laurate) oxide; Examples include dialkyltin dicarboxylates such as dibutyltin diacetate and dibutyltin dilaurate. These may be used alone or in combination of two or more.

Among these transesterification catalysts, potassium carbonate, cesium carbonate, tetraethoxy titanium, tetrabutoxy titanium, tetra (2-ethylhexanoxy) titanium, zirconia acetylacetonate, dibutyltin oxide, dioctyltin oxide, bis (dibutyltin acetate) It is preferable to use oxide, bis (dibutyltin laurate) oxide, dibutyltin diacetate, or dibutyltin dilaurate. More preferred are dibutyltin oxide and dibutyltin dilaurate.

Although the usage-amount of the said transesterification catalyst is not specifically limited, It can set suitably, For example, it is preferable that it is the range of 0.0001-20 mol% with respect to 100 mol% of hydroxyl-containing ether compounds. It is preferable in terms of yield and economy that the amount of the transesterification catalyst used is in such a range. More preferably, it is 0.0003-15 mol%, More preferably, it is 0.0005-10 mol%, Most preferably, it is 0.001-5 mol%.

It is preferable to perform the said reaction process in the atmosphere whose molecular oxygen concentration of the reaction system gaseous-phase part is 0.001-21 volume%. By setting the molecular oxygen concentration in the gas phase of the reaction system in such a range, the polymerization reaction during the reaction step can be more effectively prevented, and the target product has an ether group (meth). Acrylic esters can be produced in high yield. More preferably, the molecular oxygen concentration in the gas phase of the reaction system is 0.005 to 15% by volume, and more preferably 0.01 to 10% by volume.

As a method of adjusting the molecular oxygen concentration in the reaction system gas phase part to the above-mentioned preferable range, (a) a reaction vessel in which a gas containing molecular oxygen such as molecular oxygen or air is reacting (a vapor exists) And (b) a gas containing molecular oxygen such as molecular oxygen or air and an inert gas such as nitrogen and argon during the reaction ( A method of adjusting the molecular oxygen concentration in the gas phase of the reaction system by supplying it to a reaction vessel in which steam exists), (c) a gas containing molecular oxygen such as molecular oxygen or air, and inert such as nitrogen and argon Examples include a method in which a gas is mixed in advance and supplied to a reaction vessel during the reaction (where steam is present) to adjust the molecular oxygen concentration in the gas phase of the reaction system.
In addition, as a method of supplying molecular oxygen and / or a mixed gas containing molecular oxygen to the reaction system, it may be supplied continuously or intermittently to one or both of the liquid phase part and the gas phase part in the reaction system. That's fine.

In addition, since the reaction in the reaction step of the present invention is a transesterification reaction, alcohol is by-produced by the progress of the reaction. It is preferable to remove the by-product alcohol out of the reaction system.
Examples of the method for removing the by-product alcohol include a method of performing a reaction under reduced pressure, a method of performing a reaction using an azeotropic solvent, and a method of performing a reaction in the presence of an adsorbent. Among these, a method of performing the reaction under reduced pressure and a method of performing the reaction using an azeotropic solvent are preferable.

The azeotropic solvent is not particularly limited as long as it does not inhibit the transesterification reaction. For example, ethers such as diethyl ether, diisopropyl ether and dibutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; pentane Aliphatic hydrocarbons such as hexane, heptane and cyclohexane; halogenated hydrocarbons such as chloroform, methylene chloride, 1,2-dichloroethane and chlorobenzene; These azeotropic solvents may be used alone or in combination of two or more. Moreover, the (meth) acrylic acid ester used excessively can also be used as an azeotropic solvent.

Although there is no restriction | limiting in particular as the usage-amount of the said azeotropic solvent, For example, it is preferable to set it as 0-300 mass% of the mass of the hydroxyl-containing ether compound which is a reaction raw material. It is preferable that the amount of the azeotropic solvent used is in such a range in terms of yield and economy. More preferably, it is 1-200 mass%, More preferably, it is 2-150 mass%, Most preferably, it is 3-100 mass%.

The reaction temperature in the reaction step is not particularly limited, but is preferably equal to or higher than the boiling point or azeotropic temperature of the by-produced alcohol, specifically, preferably 40 ° C. or higher, more preferably 50 ° C. or higher. 60 ° C. or higher is more preferable. Moreover, it is preferable to set it as 180 degrees C or less, 170 degrees C is more preferable, and 160 degrees C or less is still more preferable. The reaction pressure is not particularly limited, and may be normal pressure, pressurization, or reduced pressure. Moreover, what is necessary is just to set reaction time suitably so that reaction in the said reaction process may be completed.

In the production method of the present invention, after the reaction step, the synthesized (meth) acrylic acid ester having an ether group can be purified and separated from the reaction solution.
A method for performing the purification step is not particularly limited. For example, raw material recovery operation, catalyst recovery operation, neutralization operation, filtration operation, decantation operation, extraction operation, water washing operation, evaporation operation, distillation operation, column chromatograph The method by operation etc. is mentioned. Each of the above operations can be performed alone or in combination of two or more. Of these, purification by distillation is particularly preferred.

In the production method of the present invention, a (meth) acrylic acid ester having an ether group is produced by the reaction of a reaction raw material containing a (meth) acrylic acid ester and a hydroxyl group-containing ether compound. A (meth) acrylic acid ester having an ether group is a compound synthesized by a transesterification reaction between a (meth) acrylic acid ester and a hydroxyl group-containing ether compound. Therefore, the (meth) acrylic acid ester having an ether group is a compound synthesized by a transesterification reaction of a compound selected from the above-described (meth) acrylic acid ester and the above-described hydroxyl group-containing ether compound.
In particular, when (meth) acrylic acid ester is a compound represented by general formula (4) and the hydroxyl group-containing ether compound is a hydroxyl group-containing vinyl ether compound represented by formula (5), the resulting ether group (Meth) acrylic acid ester having the following general formula (2):

(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ² represents an organic residue.). Thus, the form in which the (meth) acrylic acid ester having an ether group is a vinyl ether group-containing (meth) acrylic acid ester represented by the general formula (2) is also a preferred embodiment of the present invention. It is.
Incidentally, ^{R 1} in the general formula (2) is the same as ^{R 1} in the general formula (4), ^{R 2} in the general formula (2) is the same as ^{R 2} in the general formula (5).

Specific examples of the vinyl ether group-containing (meth) acrylic acid ester represented by the above general formula (2) include 2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, (meth ) 1-methyl-2-vinyloxyethyl acrylate, 2-vinyloxypropyl (meth) acrylate, 4-vinyloxybutyl (meth) acrylate, 1-methyl-3-vinyloxypropyl (meth) acrylate, (meth) acryl 1-vinyloxymethylpropyl acid, 2-methyl-3-vinyloxypropyl (meth) acrylate, 1,1-dimethyl-2-vinyloxyethyl (meth) acrylate, 3-vinyloxybutyl (meth) acrylate, (meth) 1-methyl-2-vinyloxypropyl acrylate, 2-vinyloxybutyl (meth) acrylate, ( T) 4-vinyloxycyclohexyl acrylate, 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxymethylcyclohexylmethyl (meth) acrylate, 3-vinyloxymethylcyclohexylmethyl (meth) acrylate, (meth) 2-vinyloxymethylcyclohexylmethyl acrylate, p-vinyloxymethylphenylmethyl (meth) acrylate, m-vinyloxymethylphenylmethyl (meth) acrylate, o-vinyloxymethylphenylmethyl (meth) acrylate, ( 2- (vinyloxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxy) propyl (meth) acrylate, 2- (meth) acrylic acid 2- ( Vinyloxyethoxy) isopropyl, (meth) acryl 2- (vinyloxyisopropoxy) propyl acid, 2- (vinyloxyisopropoxy) isopropyl (meth) acrylate, 2- (vinyloxyethoxyethoxy) ethyl (meth) acrylate, 2- (vinyl) (meth) acrylate Loxyethoxyisopropoxy) ethyl, 2- (vinyloxyisopropoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxy) (meth) acrylate Ethoxyethoxy) propyl, (meth) acrylic acid 2- (vinyloxyethoxyisopropoxy) propyl, (meth) acrylic acid 2- (vinyloxyisopropoxyethoxy) propyl, (meth) acrylic acid 2- (vinyloxyisopropoxyiso) Propoxy) propyl, (meth) acrylic acid 2- (Vinyloxyethoxyethoxy) isopropyl, (meth) acrylic acid 2- (vinyloxyethoxyisopropoxy) isopropyl, (meth) acrylic acid 2- (vinyloxyisopropoxyethoxy) isopropyl, (meth) acrylic acid 2- (vinyloxy) Isopropoxyisopropoxy) isopropyl, 2- (vinyloxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (isopropoxy) (meth) acrylate Ethoxy) ethyl, (meth) acrylic acid 2- (isopropoxyethoxyethoxyethoxy) ethyl, (meth) acrylic acid 2- (isopropoxyethoxyethoxyethoxy) ethyl, (meth) acrylic acid 2- (isopropoxyethoxyethoxyethoxyethoxy) ) Ethyl, (meth) Polyethylene glycol monovinyl ether acrylate, and (meth) acrylic acid polypropylene glycol monovinyl ether.

The method for producing a (meth) acrylic acid ester having an ether group according to the present invention has the above-described configuration, and sufficiently suppresses both polymerization of a (meth) acryloyl group and generation of a peroxide derived from the ether group. Therefore, it can be suitably used as a method for producing a (meth) acrylic acid ester having an ether group.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

Example 1
453 g of diethylene glycol monovinyl ether (hereinafter also referred to as “DEGV”) is placed in a glass 2 L round bottom flask (reactor) equipped with an Oldershaw type rectification column, a stirrer, a thermometer, a gas introduction tube and a liquid introduction line. , 620 g of methyl acrylate (hereinafter also referred to as “AM”), 1.1 g of phenothiazine (hereinafter also referred to as “PTz”) as the primary antioxidant, and Tris (2,4- 1.1 g of di-t-butylphenyl) phosphite (hereinafter also referred to as “DBPP”), 0.32 g of N-nitrosophenylhydroxylamine ammonium salt (hereinafter also referred to as “NPNH”), and dibutyl as a catalyst 2.1 g of tin oxide (hereinafter also referred to as “DBTO”) was charged, and 7% oxygen / nitrogen balance set from the gas introduction pipe Gas was immersed reactor in an oil bath at liquid phase bubbling 120 ° C. at 15 mL / min, temperature was started to increase in the total reflux condition.
As the reaction proceeds, by-product methanol is concentrated at the top of the column, and after the column top temperature reaches 63 ° C., the azeotropic boiling point of methyl acrylate and methanol, at a reflux ratio of 8, 50 g / h. Distillation started at an extraction speed of. Methyl acrylate was fed from the liquid sequential charging line at the same rate as the distillation rate. The time of the start of distillation was defined as a reaction time of 0 hours (at the start of the reaction), and the reaction was performed for 8 hours. In order to prevent polymerization inside the tower by (meth) acrylic acid ester, an AM solution of 1% by mass PTZ was added from the top of the tower at a rate of 5 g / h.
After completion of the reaction, no polymer was visually observed in the gas phase portion of the reactor. In order to confirm the polymer formation in the reaction solution, the polymer concentration in the reaction solution was measured by the polymer analysis method shown below.

(Polymer analysis)
For polymer analysis, high-speed gel permeation chromatograph with a differential refraction detector (product name “HLC-8320GPC” manufactured by Tosoh Corporation), data acquisition / analysis PC, data acquisition / analysis software (product manufactured by Tosoh Corporation, product) The name “EcoSEC-WS”). Detailed settings for the gel permeation chromatograph are as follows.
Column: TSKgel Super H2000 x 2 (Tosoh Corporation, 6.0 mm ID x 15 cm)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (Wako Pure Chemical Industries, special reagent grade, containing stabilizer)
Eluent flow rate: 0.6 mL / min (pump discharge side pressure: 7.0 MPa)
Analytical sample: About 1 part by weight of the reaction solution was diluted with about 1000 parts by weight of tetrahydrofuran as an eluent, and then filtered using a PTFE membrane filter (trade name “13HP045CN” manufactured by ADVANTEC). 10 μL was injected.

(Polymer concentration)
The polymer concentration was calculated as the percentage of the peak area where the mass number in terms of polystyrene was 1000 Da or more out of the total area of the positive peak detected by the differential refraction detector.

In addition, as a simple method for determining the presence or absence of polymer formation in the reaction liquid, when about 1 volume part of n-hexane, which is a poor solvent for the polymer, is added to 1 volume part of the reaction liquid, the turbidity is completely visible. Was not. Hereinafter, the polymer confirmation test in which n-hexane is added to the reaction solution is also referred to as “n-hexane test”. Table 1 shows the types of compounds used in the reaction, the state of occurrence of the polymer in the gas phase, the polymer concentration by gel permeation chromatography (liquid phase polymer concentration), and the results of the n-hexane test.

Table 1 shows the yield of the product obtained by the above reaction. The method for analyzing the product and the method for calculating the yield are as follows.
(Product analysis)
The analysis of the product was performed using a gas chromatograph with a flame ionization detector (manufactured by Shimadzu Corporation, product name “GC-2014”) and a data acquisition / analysis PC, data acquisition / analysis software (manufactured by Shimadzu Corporation) Trade name “GCsolution”). Detailed settings for the gas chromatograph are as follows.
Column: DB-1 (trade name, manufactured by Agilent J & W, inner diameter: 0.53 mm, film thickness: 1.50 μm, length: 30 m)
Vaporization chamber temperature: 250 ° C
Detector temperature: 280 ° C
Split ratio: 10
Column temperature setting: Hold at initial 40 ° C. for 5 minutes, raise temperature to 200 ° C. at 5 ° C./min, increase to 280 ° C. at 10 ° C./min after reaching 200 ° C., hold gas pressure for 5 minutes after reaching 280 ° C. : Hydrogen 50 kPa, air 65 kPa, helium (carrier) 26 kPa
Total flow rate: 60 mL / min
Analytical sample: 1 part by weight of anisole as an internal standard substance and 100 parts by weight of acetone as a diluent were added to 10 parts by weight of the reaction solution and mixed well, and 0.2 μL of this was injected into a gas chromatograph with a microsyringe.

(Yield calculation)
Yield calculation is based on the chromatogram obtained by the above gas chromatography by quantitatively determining the raw alcohol, raw ester, product and by-product by the internal standard method. Of these, the molar ratio of the product to the charged raw alcohol Was the yield.

(Examples 2-32)
The reaction was carried out in the same manner as in Example 1 except that the type of compound used in the reaction and the amount used were changed to those described in Tables 1 to 4.
After completion of the reaction, in the same manner as in Example 1, the occurrence of the polymer in the gas phase was visually confirmed, the polymer concentration was measured by gel permeation chromatography, the n-hexane test, and the yield were measured. Tables 1 to 4 show the types and amounts used of the compounds used in the reaction, the state of polymer generation in the gas phase, the liquid phase polymer concentration, the n-hexane test, and the yield results.
When methyl methacrylate (hereinafter also referred to as “MMA”) was used as the raw material ester, the column top temperature at the start of distillation was 64 ° C., and the oil bath temperature was 135 ° C.

(Comparative Examples 1-4)
The reaction was carried out in the same manner as in Example 1 except that the kind of compound used for the reaction and the amount used were changed to those shown in Table 5.
After completion of the reaction, in the same manner as in Example 1, the occurrence of the polymer in the gas phase was visually confirmed, the polymer concentration was measured by gel permeation chromatography, the n-hexane test, and the yield were measured. Table 5 shows the types and amounts of compounds used in the reaction, the state of polymer generation in the gas phase, the liquid phase polymer concentration, the n-hexane test, and the yield results.

Abbreviations in Tables 1 to 5 are as follows.
DEGV: Diethylene glycol monovinyl ether TMP5EO: ethylene oxide (EO) modified trimethylolpropane (EO average 5 mol adduct)
DEGM: diethylene glycol monomethyl ether AM: methyl acrylate MMA: methyl methacrylate PTz: phenothiazine MEHQ: hydroquinone monomethyl ether BHT: 3,5-di-tert-butyl-4-hydroxytoluene TPB: 1,1,3-tris (2 -Methyl-4-hydroxy-5-tert-butylphenyl) butane DBPP: tris (2,4-di-tert-butylphenyl) phosphite TPP: triphenylphosphite BPOP: 2,2-methylenebis (4,6- Di-tert-butylphenyl) octyl phosphite TDPL: dilauryl 3,3′-thiodipropionate Ph3P: triphenylphosphine NPHN: N-nitrosophenylhydroxylamine ammonium salt NPHA: N-nitrosofeni Hydroxylamine aluminum salt DBTO: Dibutyltin oxide DBTL: Dibutyltin dilaurate Total amount: Total amount of raw material ester and the amount fed from the liquid sequential charging line Gas phase part polymer: Generation of polymer in the gas phase part In the gas phase polymer column, when the time when the distillation starts from the top of the rectification column is 0 hour (reference), the gas phase part of the reactor (flask wall, stirring shaft, gas introduction pipe, etc.) The elapsed time until the polymer is visually recognized is shown. “None” means that no polymer was observed in the gas phase portion of the reactor even after the reaction was completed. In addition, “after 2 hours” and “after 4 hours” mean that the polymer is introduced into the gas phase part of the reactor at “after 2 hours” and “after 4 hours”, respectively, from the time when distillation starts (reaction start time). It shows that it was visually recognized.
In addition, when the polymer was visually recognized in the gas phase part of the reactor, the reaction was stopped at that time.

The following was found from the results of Examples and Comparative Examples.
When producing a (meth) acrylic acid ester having an ether group from a reaction raw material containing a (meth) acrylic acid ester and a hydroxyl group-containing ether compound, the reaction is represented by N-nitrosophenylhydroxyl represented by the general formula (1). By carrying out in the presence of an amine salt, phosphite and / or thioether, and a primary antioxidant, both the polymerization of the (meth) acryloyl group and the generation of the peroxide derived from the ether group are sufficiently performed. It was demonstrated that it can be suppressed.
On the other hand, when the reaction is carried out in the presence of the N-nitrosophenylhydroxylamine salt represented by the general formula (1) and the phosphite and / or thioether without using the primary antioxidant Or when the reaction is carried out in the presence of the N-nitrosophenylhydroxylamine salt represented by the general formula (1) and the primary antioxidant without using a secondary antioxidant, n- Cloudiness was observed by the hexane test, and polymerization in the liquid phase was confirmed (Comparative Examples 1-2).
Further, when the reaction is carried out in the presence of a phosphite and / or thioether and a primary antioxidant without using the N-nitrosophenylhydroxylamine salt represented by the general formula (1), Within 4 hours from the start of the reaction, the generation of a polymer was confirmed in the gas phase (Comparative Example 3), the N-nitrosophenylhydroxylamine salt represented by the general formula (1), the secondary antioxidant, and the primary oxidation The reaction is carried out in the presence of an inhibitor, but when a secondary antioxidant that is not a phosphite and / or thioether is used, the generation of polymer in the gas phase is suppressed by the end of the reaction. (Comparative Example 4).
In the above examples, (meth) acrylic acid ester, hydroxyl group-containing ether compound, N-nitrosophenylhydroxylamine salt represented by general formula (1), phosphite and / or thioether, and primary oxidation Although what has a specific structure is used as an inhibitor, when producing a (meth) acrylic acid ester having an ether group from a reaction raw material containing a (meth) acrylic acid ester and a hydroxyl group-containing ether compound, By carrying out the reaction in the presence of an N-nitrosophenylhydroxylamine salt represented by the formula (1), a phosphite and / or thioether, and a primary antioxidant, polymerization of a (meth) acryloyl group, The mechanism that suppresses both the generation of peroxides derived from ether groups is N-nitroso represented by the general formula (1). E sulfonyl hydroxylamine salt, phosphorous acid esters and / or thioether, and, in the case of using a primary antioxidant are all similar.
Therefore, from the results of the above-mentioned examples and comparative examples, the present invention can be applied in various technical forms of the present invention and in various forms disclosed in the present specification, and advantageous effects can be exhibited. I can say that.

Claims (4)

A method for producing a (meth) acrylic acid ester having an ether group from a reaction raw material containing a (meth) acrylic acid ester and a hydroxyl group-containing ether compound,
The production method includes a step of reacting the reaction raw material in the presence of an N-nitrosophenylhydroxylamine salt, a phosphite and / or a thioether, and a primary antioxidant,
The N-nitrosophenylhydroxylamine salt has the following general formula (1);

(In the formula, M represents a metal atom or an ammonium group. N represents a positive number equal to the valence of M. The dotted line connecting M and the oxygen atom is that M is coordinated to the oxygen atom. A method for producing a (meth) acrylic acid ester having an ether group, characterized in that The method for producing a (meth) acrylic acid ester having an ether group according to claim 1, wherein the phosphite ester and / or thioether is a phosphite ester. The method for producing a (meth) acrylic acid ester having an ether group according to claim 1 or 2, wherein the primary antioxidant is a phenol-based antioxidant and / or an aromatic amine-based antioxidant. . The (meth) acrylic acid ester having an ether group is represented by the following general formula (2);

(Wherein R ¹ represents a hydrogen atom or a methyl group; R ² represents an organic residue), and is a vinyl ether group-containing (meth) acrylic acid ester. The manufacturing method of the (meth) acrylic acid ester which has an ether group in any one of -3.