JP2018020993A - Method for producing dioxolane (meth)acrylate, dioxolane (meth)acrylate and composition of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide dioxolane (meth)acrylate having high transparency and high purity.SOLUTION: A method for producing dioxolane (meth)acrylate includes reacting 1,3-dioxolane-4-yl-methanol derivative and (meth)alkyl acrylate in the presence of a transesterification catalyst and an N-oxyl-based compound that is a polymerization inhibitor and has a molecular weight of 300 or more, and distilling the reactant by adding the polymerization inhibitor thereto or in the presence of a polymerization inhibitor different from the N-oxyl-based compound.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a dioxolane (meth) acrylic acid ester.

  Dioxolane (meth) acrylic acid esters are suitably used for producing optical materials such as lenses. Methods for producing dioxolane (meth) acrylic acid esters are disclosed in, for example, the following patent documents.

  In Patent Document 1, zirconium tetraacetylacetonate (hereinafter referred to as Zr-ACAC) is used as a transesterification catalyst, reacted with methyl methacrylate and glycerol carbonate, and then distilled and purified with a rotary evaporator. How to do is described.

  Patent Document 2 discloses a production method in which a (1,3-dioxolan-4-yl) methanol derivative and a (meth) acrylic acid lower alkyl ester are reacted in the presence of a transesterification catalyst and a specific polymerization inhibitor. Is described.

International Publication WO2005 / 058862 (International publication on June 30, 2005) JP 2004-59435 A (published on February 26, 2004)

  However, the performance required for optical materials has been advanced, and a novel production method capable of producing dioxolane (meth) acrylic acid ester having high transparency and high purity is useful.

  In this regard, the production method described in Patent Document 1 does not disclose any means for solving the problem that the dioxolane (meth) acrylic acid ester is colored due to the polymerization inhibitor. Further, in the production method described in Patent Document 1, dioxolane (meth) acrylic acid ester is purified by a rotary evaporator, but its purity is as low as 91%.

  Patent Document 2 discloses that at least one polymerization inhibitor selected from the group consisting of N-oxyl compounds, phenol compounds, copper compounds, amino compounds, and hydroxylamine compounds is used as the polymerization inhibitor. However, it does not disclose any means for solving the problem that the dioxolane (meth) acrylic acid ester is colored due to these polymerization inhibitors. In the method for purifying dioxolane (meth) acrylate disclosed in Patent Document 2, the purity of dioxolane (meth) acrylate may be lowered.

  The invention of the present application has been made in view of the above problems, and its main purpose is to provide a novel production method capable of producing a dioxolane (meth) acrylic acid ester having high transparency and high purity. There is to do.

  As a result of intensive studies to achieve the above object, the present inventors have completed the present invention.

In order to solve the above problems, a method for producing a dioxolane (meth) acrylic acid ester according to an embodiment of the present invention comprises:
In the presence of a transesterification catalyst and an N-oxyl compound having a molecular weight of 300 or more, which is a polymerization inhibitor,
1,3-dioxolan-4-yl-methanol derivative represented by the following formula (1);
(Meth) acrylic acid alkyl ester having an alkyl chain having 1 to 4 carbon atoms;
By reacting
The production | generation process which produces | generates the dioxolane (meth) acrylic acid ester represented by following formula (2),
A distillation step of distilling the dioxolane (meth) acrylic acid ester in addition to the polymerization inhibitor (N-oxyl compound) or in the presence of a polymerization inhibitor different from the N-oxyl compound; ,
It is characterized by including.

（式（１）中、Ｒ^１及びＲ^２は、それぞれ独立して、水素原子、直鎖状若しくは分岐状である炭素数１〜１８のアルキル基、環状である炭素数３〜１８のアルキル基、又は、フェニル基であってもよく、Ｒ^１とＲ^２とは、互いに結合して環を形成していてもよい。）

(In Formula (1), R ¹ and R ² are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, or a cyclic alkyl group having 3 to 18 carbon atoms. Or a phenyl group, and R ¹ and R ² may be bonded to each other to form a ring.)

（式（２）中、Ｒ^１及びＲ^２は、それぞれ独立して、水素原子、直鎖状若しくは分岐状である炭素数１〜１８のアルキル基、環状である炭素数３〜１８のアルキル基、又は、フェニル基であってもよく、Ｒ^１とＲ^２とは互いに結合して環を形成していてもよく、Ｒ^３は、水素原子又はメチル基である。）

(In Formula (2), R ¹ and R ² are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, or a cyclic alkyl group having 3 to 18 carbon atoms. Or a phenyl group, R ¹ and R ² may be bonded to each other to form a ring, and R ³ is a hydrogen atom or a methyl group.)

  According to the method for producing a dioxolane (meth) acrylic acid ester according to the present invention, it is possible to produce a dioxolane (meth) acrylic acid ester having high transparency and high purity.

<Method for producing dioxolane (meth) acrylate>
Below, the manufacturing method of the dioxolane (meth) acrylic acid ester which concerns on one Embodiment of this invention is demonstrated in detail.

  The production method of a dioxolane (meth) acrylic acid ester according to the present embodiment includes a production step of producing a dioxolane (meth) acrylic acid ester using an N-oxyl-based compound as a polymerization inhibitor, and the presence of the polymerization inhibitor. And a distillation step of distilling the dioxolane (meth) acrylic acid ester produced in the production step.

[1] Generation Step In the generation step, (1,3-dioxolan-4-yl) methanol derivative and (meth) acrylic acid alkyl ester are esterified in the presence of a transesterification catalyst and an N-oxyl compound. Exchange reaction.

式（１）中、Ｒ^１及びＲ^２は、それぞれ独立して、水素原子、直鎖若しくは分岐状である炭素数１〜１８のアルキル基、環状の炭素数３〜１８のアルキル基、又はフェニル基であってもよく、Ｒ^１とＲ^２とは、互いに結合して環を形成していてもよい。 [1-1] (1,3-Dioxolan-4-yl) methanol derivative In the present specification, “(1,3-dioxolan-4-yl) methanol derivative” is represented by the following formula (1). It means a compound having a structure.

In formula (1), R ¹ and R ² are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, a cyclic alkyl group having 3 to 18 carbon atoms, or phenyl. It may be a group, and R ¹ and R ² may be bonded to each other to form a ring.

  Among the (1,3-dioxolan-4-yl) methanol derivatives represented by the above formula (1), although not limited thereto, more specifically, for example, (1,3-dioxolane-4 -Yl) methanol, (2,2-dimethyl-1,3-dioxolan-4-yl) methanol, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methanol, (2-methyl- 2-isobutyl-1,3-dioxolan-4-yl) methanol, 1,4-dioxaspiro [4.5] decane-2-methanol, (2-ethyl-2-propyl-1,3-dioxolan-4-yl) ) Methanol, (2,2-dipropyl-1,3-dioxolan-4-yl) methanol, (2-butyl-2-ethyl-1,3-dioxolan-4-yl) methanol, (2-butyl-2) Propyl-1,3-dioxolan-4-yl) methanol, (2,2-dibutyl-1,3-dioxolan-4-yl) methanol, (2-hexyl-2-propyl-1,3-dioxolane-4- Yl) methanol, (2,2-dipentyl-1,3-dioxolan-4-yl) methanol, (2-methyl-2-propyl-1,3-dioxolan-4-yl) methanol, (2- (1- Ethylpropyl) -2-methyl-1,3-dioxolan-4-yl) methanol, (2- (2,2-dimethylpropyl) -1,3-dioxolan-4-yl) methanol, (2-methyl-2) -Heptyl-1,3-dioxolan-4-yl) methanol, (2-ethyl-2-heptyl-1,3-dioxolan-4-yl) methanol, (2-ethyl-2-isobuty (L-1,3-dioxolan-4-yl) methanol and the like. Among these, for example, (2,2-dimethyl-1,3-dioxolan-4-yl) methanol, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methanol, (2-methyl 2-isobutyl-1,3-dioxolan-4-yl) methanol, 1,4-dioxaspiro [4.5] decane-2-methanol and the like are more preferable.

[1-1-1] Method for Producing (1,3-Dioxolan-4-yl) methanol Derivative In the production method according to the present embodiment, (1,3-dioxolan-4-yl) methanol derivative is a commercially available product. May be used, and may be produced and used by a known method. As a known method, for example, a method of producing by dehydrating glycerin and ketones in the presence of a nonpolar solvent and an acid catalyst can be mentioned.

  As an example, a method for producing 1,4-dioxaspiro [4.5] decane-2-methanol is shown below. Using a reflux apparatus equipped with an Oldershaw distillation column and Dean Stark, in a four-necked flask with a side tube, 1.0 mol of glycerin, 1.25 mol of cyclohexanone, 0.7 mol of hexane, 0.005 A reaction solution is prepared by charging molar p-toluenesulfonic acid. The charged reaction solution is heated to the boiling point of the solution while stirring. Water generated by the dehydration reaction is removed as an azeotrope with hexane to the outside of the reaction system, and hexane is returned to the flask. The reaction is completed when the water production rate by the dehydration reaction reaches 70 to 80%. A 25% by weight aqueous sodium hydroxide solution is added to the reaction solution to adjust the pH to 12 or higher. Thereafter, the reaction solution to which the aqueous sodium hydroxide solution has been added is transferred to a separating funnel and allowed to stand, and the lower layer (aqueous layer) containing glycerin and p-toluenesulfonic acid is removed. On the other hand, the upper layer (organic layer) is heated under an internal temperature of 100 to 110 ° C. under a reduced pressure condition of 0.5 kPa or less, thereby distilling off hexane and cyclohexanone. Thereby, 1,4-dioxaspiro [4.5] decane-2-methanol can be obtained.

[1-2] (Meth) acrylic acid alkyl ester In the present specification, “(meth) acrylic acid” means both “acrylic acid” and “methacrylic acid”. Therefore, in this specification, (meth) acrylic acid ester means both ester of acrylic acid and ester of methacrylic acid, (meth) acrylic acid alkyl ester means acrylic acid alkyl ester, and Both methacrylic acid alkyl esters are meant.

  The (meth) acrylic acid alkyl ester used in the production step has an alkyl chain with a carbon number in the range of 1 or more and 4 or less. In addition, such (meth) acrylic acid alkyl ester may use what is marketed, and may synthesize | combine by a well-known method. Examples of the (meth) acrylic acid alkyl ester include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, (n-propyl) (meth) acrylate, isopropyl (meth) acrylate, n- (meth) acrylate. Examples thereof include butyl, isobutyl (meth) acrylate, and tert-butyl (meth) acrylate. Among these, methyl (meth) acrylate is more preferably used.

  In the production step, the amount of (meth) acrylic acid alkyl ester used is not particularly limited, but for example, 1 mol per 1 mol of (1,3-dioxolan-4-yl) methanol derivative. It is preferably in the range of 10 mol or less, more preferably in the range of 2 mol or more and 8 mol or less, and most preferably in the range of 3 mol or more and 7 mol or less. By using the amount of (meth) acrylic acid alkyl ester in the range of 1 mol or more and 10 mol or less with respect to 1 mol of (1,3-dioxolan-4-yl) methanol derivative, (1,3 -Dioxolan-4-yl) methanol derivative and (meth) acrylic acid alkyl ester can be sufficiently reacted, and the purity and yield of dioxolane (meth) acrylic acid ester can be suitably increased. Moreover, in the production | generation process, the reaction temperature in a production | generation process is made from using 1 mol or more of (meth) acrylic-acid alkylesters with respect to 1 mol of (1,3-dioxolan-4-yl) methanol derivatives. It can hold suitably. From the viewpoint that the reaction rate cannot be effectively increased, the amount of (meth) acrylic acid alkyl ester used per 1 mol of (1,3-dioxolan-4-yl) methanol derivative is 10 mol or less. possible.

[1-3] Transesterification Catalyst In the production method according to this embodiment, it is preferable to use a transesterification catalyst other than a chelate complex as the transesterification catalyst in the production step. Thereby, it can prevent that the hue of dioxolane (meth) acrylic acid ester deteriorates.

  For example, Patent Document 1 (International Publication WO2005 / 058862) describes using zirconium tetraacetylacetonate (hereinafter referred to as Zr-ACAC) as a transesterification catalyst. However, chelate complexes such as Zr-ACAC generate acetylacetone as a decomposition product during the transesterification reaction. A bidentate ligand such as acetylacetone constitutes a reaction vessel, a distillation column and piping for producing dioxolane (meth) acrylate, for example, nickel and cobalt constituting iron, stainless steel (SUS) and the like. It forms a chelate complex with etc. and develops color. Thereby, dioxolane (meth) acrylic acid ester has a problem that the distillate is colored.

  If the transesterification catalyst is other than the chelate complex, a known transesterification catalyst can be used. Examples of the transesterification catalyst include a tin compound, a titanium compound, a zirconium compound, an alkali metal alcoholate, and an alkaline earth metal alcoholate.

  Examples of the tin compound include dibutyltin oxide, dioctyltin oxide, didodecyltin oxide, dibutyltin dilaurate, dibutyltin malate, dibutyltin diacetate, dibutyltin bis (2-ethylhexyl mercaptoacetate), dibutyltin bis (isooctyl mercaptoacetate). ) And the like. Among these tin compounds, it is preferable to use at least one tin compound selected from the group consisting of dibutyltin oxide, dioctyltin oxide, and didodecyltin oxide from the viewpoint of allowing the transesterification reaction to proceed efficiently in a shorter time. preferable. By using these tin compounds as transesterification catalysts, it is possible to avoid the decomposition products from corroding iron, stainless steel (SUS), and the like. Therefore, the transesterification reaction can be performed using a general-purpose reaction tank formed of iron, stainless steel, or the like.

  Examples of the titanium compound include tetraethyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetramethoxy titanate, and tetraethoxy titanate. Examples of the zirconium compound include tetraisopropyl zirconate and tetrabutyl. Zirconate etc. can be mentioned. Examples of the alkali metal alcoholate include sodium methylate, sodium ethylate, lithium methylate, and lithium ethylate. Examples of the alkaline earth metal alcoholate include calcium methylate, calcium ethylate, and magnesium. Examples thereof include methylate and magnesium ethylate. Other examples of the transesterification catalyst include aluminum alcoholates such as aluminum methylate and aluminum ethylate, and alkali metal hydroxides such as lithium hydroxide.

  The usage-amount of the transesterification catalyst used for transesterification is not limited, It can select suitably according to the raw material used for reaction, the kind of transesterification catalyst, reaction conditions, etc. For example, the amount of the transesterification catalyst used relative to 1 mol of (1,3-dioxolan-4-yl) methanol derivative is preferably within the range of 0.0005 mol or more and 0.5 mol or less. It is more preferably in the range of 001 mol or more and 0.3 mol or less, and most preferably in the range of 0.002 mol or more and 0.2 mol or less.

  If the amount of the transesterification catalyst used per 1 mol of (1,3-dioxolan-4-yl) methanol derivative is 0.0005 mol or more, a sufficient reaction rate can be obtained, and 0.5 mol or less. If so, it is possible to prevent the catalyst from remaining or mixed in the dioxolane (meth) acrylic acid ester in the subsequent distillation step.

[1-4] Polymerization inhibitor in the production step In the production step, the polymerization inhibitor is used to prevent thermal polymerization of the (meth) acrylic acid alkyl ester and the dioxolane (meth) acrylic acid ester. Here, in the manufacturing method according to the present embodiment, an N-oxyl compound having a molecular weight of 300 or more is used as a polymerization inhibitor.

  As such N-oxyl compounds having a molecular weight of 300 or more, for example, [4,4 ′-(phthaloyldioxy) bis (2,2,6,6-tetramethylpiperidine)]-1,1′diyl Bisoxyl (molecular weight 474.590) and the like can be mentioned.

  Other N-oxyl compounds include, for example, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl (molecular weight 172.24), 4-benzoyloxy-2,2,6,6. -Tetramethylpiperidine-N-oxyl (molecular weight 276.35) and the like can be mentioned, but such N-oxyl compounds have a molecular weight of less than 300. These N-oxyl compounds having a low molecular weight, like N-oxyl compounds having a molecular weight of 300 or more, have the ability to suppress high thermal polymerization, but their molecular weight and dioxolane (meth) acrylate ester The difference from the molecular weight is reduced. That is, the dioxolane (meth) acrylic acid ester produced by the production method according to this embodiment has a molecular weight of about 200, for example, (2,2-dimethyl-1,3-dioxolan-4-yl). The molecular weight of methacrylol (2,2-dimethyl-1,3-dioxolan-4-yl) methyl produced from methyl acrylate is 186.21. Therefore, when an N-oxyl compound having a molecular weight of less than 300 is used, when dioxolane (meth) acrylate is distilled, the N-oxyl compound and dioxolane (meth) acrylate are both Evaporate or scatter. The appearance of the N-oxyl compound has a dark color such as brown or yellowish red. For this reason, when an N-oxyl compound having a low molecular weight is used, the hue of the dioxolane (meth) acrylic acid ester is deteriorated by mixing the N-oxyl compound having a low molecular weight in the subsequent distillation step.

  On the other hand, when an N-oxyl compound having a molecular weight of 300 or more is used as a polymerization inhibitor in the production step, an N-oxyl compound having a molecular weight of 300 or more is distilled when dioxolane (meth) acrylate is distilled. Can be prevented from evaporating or scattering together with the dioxolane (meth) acrylic acid ester. Therefore, it can prevent that the hue of distilled dioxolane (meth) acrylic acid ester deteriorates.

  Further, from another viewpoint, the N-oxyl-based compound used in the production step is, for example, dissolved in 1,4-dioxaspiro [4.5] decan-2-ylmethyl methacrylate, at a temperature of 90 ° C. , N-oxyl compounds that do not substantially evaporate under reduced pressure conditions higher than 60 Pa.

  The N-oxyl compound has a higher effect of suppressing thermal polymerization than a quinone polymerization inhibitor and a phenol polymerization inhibitor. For this reason, in the transesterification reaction, by using an N-oxyl-based compound having a molecular weight of 300 or more, the (meth) acrylic acid alkyl ester and the dioxolane (meth) acrylic acid ester are more preferably suppressed from thermal polymerization. Can do.

  The amount of the polymerization inhibitor used in the transesterification reaction is within the range of 20 ppm or more and 2000 ppm or less with respect to the theoretical production amount of dioxolane (meth) acrylate from the viewpoint of sufficiently suppressing thermal polymerization during the reaction. Preferably, it is within a range of 30 ppm or more and 1500 ppm or less, and most preferably within a range of 50 ppm or more and 1000 ppm or less. When the amount of the polymerization inhibitor used in the transesterification reaction is 20 ppm or more, polymerization of (meth) acrylic acid and dioxolane (meth) acrylic acid ester during the transesterification reaction can be suitably prevented. Moreover, if the usage-amount of a polymerization inhibitor is 2000 ppm or less, it can prevent suitably mixing with the fraction after distillation. The theoretical production amount may be calculated from the charged amount of (1,3-dioxolan-4-yl) methanol derivative and methyl (meth) acrylate based on a known method.

[1-5] Conditions for Transesterification Reaction The temperature of the transesterification reaction in the production step is not particularly limited. For example, (meth) acrylic acid alkyl ester and dioxolane (meth) acrylic acid ester are thermally polymerized. Is preferably in the range of 80 ° C. or higher and 150 ° C. or lower, more preferably in the range of 85 ° C. or higher and 140 ° C. or lower, from the viewpoint of suitably suppressing the transesterification and the transesterification reaction. Preferably, it is in the range of 90 ° C. or higher and 130 ° C. or lower. If the reaction temperature in the transesterification reaction is 80 ° C. or higher, the reaction rate of the reaction can be suitably increased, and if it is 150 ° C. or lower, (meth) acrylic acid alkyl ester and dioxolane (meth) acrylic are used. The acid ester can be suitably prevented from thermal polymerization.

  In the production step, a transesterification reaction may be performed using a reaction solvent. A nonpolar solvent is preferably used as the reaction solvent. The nonpolar solvent is not particularly limited, and examples thereof include hydrocarbon solvents and aromatic solvents. Examples of the hydrocarbon solvents include n-hexane, n-heptane, and cyclohexane. Can be mentioned. In addition, examples of the aromatic solvent include toluene, xylene, and benzene. These reaction solvents may be used alone or in combination of two or more.

  In the production step, as the transesterification proceeds, an alkyl alcohol having 1 to 4 carbon atoms, that is, a lower alcohol is by-produced. By removing the by-produced lower alcohol as an azeotrope with (meth) acrylic acid alkyl ester from the reaction system, the reaction proceeds favorably, and the yield of dioxolane (meth) acrylic acid ester is increased. preferable. The method for extracting the lower alcohol out of the reaction system is not particularly limited, and may be extracted batchwise or continuously.

  From the viewpoint of increasing the purity and yield of the dioxolane (meth) acrylic acid ester, the transesterification reaction preferably has an end point when the azeotrope of the lower alcohol and the (meth) acrylic acid alkyl ester stops distilling. .

式（２）中、Ｒ^１及びＲ^２は、それぞれ独立して、水素原子、直鎖状若しくは分岐状である炭素数１〜１８のアルキル基、環状である炭素数３〜１８のアルキル基、又は、フェニル基であってもよく、Ｒ^１とＲ^２とは、互いに結合して環を形成していてもよく、Ｒ^３は水素原子又はメチル基である。 In the production step, after the transesterification reaction is completed, the (meth) acrylic acid alkyl ester charged excessively with respect to the (1,3-dioxolan-4-yl) methanol derivative is removed from the system under reduced pressure conditions. By removing, a crude product of dioxolane (meth) acrylate represented by the following formula (2) can be obtained.

In formula (2), R ¹ and R ² are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, a cyclic alkyl group having 3 to 18 carbon atoms, Alternatively, it may be a phenyl group, R ¹ and R ² may be bonded to each other to form a ring, and R ³ is a hydrogen atom or a methyl group.

  In the present specification, the dioxolane (meth) acrylic acid ester means a dioxolane (meth) acrylic acid ester represented by the formula (2) unless otherwise specified.

  In addition, the dioxolane (meth) acrylic acid ester produced | generated at the production | generation process is a crude product, and contains the transesterification catalyst, the polymerization inhibitor, etc. which were used in the production | generation process.

[2] Distillation step In the distillation step, the crude product of dioxolane (meth) acrylic acid ester produced in the production step is distilled. Thereby, the polymerization inhibitor and the transesterification catalyst used in the production step are removed from the crude product of dioxolane (meth) acrylate.

  In the distillation step, an N-oxyl compound having a molecular weight of 300 or more, which is a polymerization inhibitor used in the production step, is added to the crude product of dioxolane (meth) acrylic ester, or the polymerization inhibitor and Is distilled in the presence of another polymerization inhibitor. These polymerization inhibitors may be added to the crude product of dioxolane (meth) acrylate obtained in the production step before the distillation step. Further, for example, these polymerization inhibitors may be added to the reaction solution of dioxolane (meth) acrylic acid ester during the production step. Thereby, in the distillation process, these polymerization inhibitors contained in the crude product can be used.

  Thereby, it can prevent suitably that dioxolane (meth) acrylic acid ester heat-polymerizes due to the heat | fever added in a distillation process. For this reason, the dioxolane (meth) acrylic acid ester can be distilled under a reduced pressure condition and a heating condition more preferable than when distillation is carried out without adding a polymerization inhibitor.

[2-1] Polymerization inhibitor in distillation step When a polymerization inhibitor different from the polymerization inhibitor used in the production step is used as the polymerization inhibitor used in the distillation step, a polymerization inhibitor described below is used. use.

  Another polymerization inhibitor introduced in the distillation step preferably has a vapor pressure at 85 ° C. of 0.9 kPa or more. When the vapor pressure at 85 ° C. is 0.9 kPa or more, it is possible to prevent thermal polymerization of dioxolane (meth) acrylate in the gas phase in the distillation step. For this reason, the yield of dioxolane (meth) acrylic acid ester can be raised. Moreover, in a distillation process, when another polymerization inhibitor evaporates or disperses, it mixes with the refinement | purification thing of dioxolane (meth) acrylic acid ester, and can improve the storage stability of the said refinement | purification thing.

  Examples of the polymerization inhibitor whose vapor pressure at 85 ° C. is 0.9 kPa or more include a quinone polymerization inhibitor and a phenol polymerization inhibitor. Examples of quinone-based polymerization inhibitors include 1,4-benzoquinone and 1,2-benzoquinone, and derivatives of these benzoquinones. Examples of such derivatives include hydroquinone and hydroquinone monomethyl ether. More preferably, hydroquinone monomethyl ether can be mentioned. Moreover, as a phenol type polymerization inhibitor, Preferably, 6-tert- butyl- 2, 4- xylenol etc. can be mentioned, for example. These polymerization inhibitors can be used alone or in combination of two or more. These quinone-based and phenol-based polymerization inhibitors may be added alone or in advance of two or more before the ester exchange reaction in the production step, and dioxolane (meth) may be added immediately before the distillation step. You may throw into the crude product of an acrylic ester.

  The quinone-based polymerization inhibitor and the phenol-based polymerization inhibitor have, for example, white to pale yellow appearance and are lighter in color than N-oxyl compounds. For this reason, even if these quinone-based and phenol-based polymerization inhibitors are contained in the purified product of dioxolane (meth) acrylic acid ester in the distillation step, the hue is hardly deteriorated. In addition, these quinone-based and phenol-based polymerization inhibitors are less effective in suppressing thermal polymerization than the N-oxyl-based compounds, but are excellent in sustainability of the effects. Therefore, the storage stability of the dioxolane (meth) acrylic acid ester obtained by performing the distillation process can be more suitably maintained.

  The blending amount of the polymerization inhibitor used in the distillation process is based on the dioxolane (meth) acrylate to be distilled from the viewpoint of sufficiently suppressing the polymerization of the vaporized dioxolane (meth) acrylate in the distillation process. The concentration is preferably in the range of 20 ppm or more and 1000 ppm or less, more preferably in the range of 30 ppm or more and 500 ppm or less, and most preferably in the range of 40 or more and 300 ppm or less. . By setting the blending amount of the polymerization inhibitor in the distillation step to 20 ppm or more, it is possible to prevent the dioxolane (meth) acrylate from being thermally polymerized. Moreover, it can prevent suitably that the refinement | purification product of dioxolane (meth) acrylic acid ester is colored by making the compounding quantity of a polymerization inhibitor into 1000 ppm or less. In addition, when the polymerization inhibitor is excessively contained, it is possible to prevent the occurrence of polymerization inhibition when the purified product of dioxolane (meth) acrylate is used for the intended purpose.

  The apparatus used in the distillation step is not particularly limited as long as the dioxolane (meth) acrylic acid ester can be sufficiently purified. However, thin-film distillation using a thin-film evaporator can produce dioxolane (meth) acrylic in a high yield. The acid ester is preferred because it can be distilled. A thin film evaporator refers to an apparatus in which a sample is introduced from above by a vertical evaporator type distillation apparatus incorporating a wiper, the wiper is operated at high speed rotation, a thin film is formed by centrifugal stress, and continuous distillation is performed.

  The distillation of the crude product of dioxolane (meth) acrylate is preferably performed under reduced pressure. Thereby, in a distillation process, the boiling point of dioxolane (meth) acrylic acid ester is reduced, and the distillation temperature in a distillation process is reduced. For this reason, it can prevent suitably that dioxolane (meth) acrylic acid ester heat-polymerizes in a distillation process. The pressure reduction conditions in the distillation step can be appropriately selected depending on the (1,3-dioxolan-4-yl) methanol derivative, the type of polymerization inhibitor, and the like, but are preferably 60 Pa or less, and 50 Pa or less. More preferably. By setting the decompression condition of the distillation step to 60 Pa or less, dioxolane (meth) acrylic acid ester can be rapidly distilled, and a decrease in yield can be prevented. In addition, even if the dioxolane (meth) acrylic acid ester is distilled under the pressure reduction conditions of 60 Pa or less by using the N-oxyl type | system | group compound whose molecular weight is 300 or more, the manufacturing method in this embodiment is the said N-oxyl. There exists an effect that coloring by a system compound can be prevented. This effect is also one of the advantages of the manufacturing method according to this embodiment. In addition, since the distillation step can be performed under a low pressure condition of 60 Pa or less, the distillation temperature can be set low.

  The distillation temperature in the distillation step is not particularly limited, but is preferably in the range of 80 ° C. or higher and 120 ° C. or lower, and more preferably in the range of 85 ° C. or higher and 115 ° C. or lower. Most preferably, it is in the range of 90 ° C. or higher and 110 ° C. or lower. If distillation temperature is 80 degreeC or more, dioxolane (meth) acrylic acid ester can be distilled, and dioxolane (meth) acrylic acid ester can be refine | purified suitably. Further, when the distillation temperature is 120 ° C. or lower, it is possible to suitably prevent the dioxolane (meth) acrylic ester from being thermally polymerized. Moreover, the content of the transesterification catalyst in the dioxolane (meth) acrylic acid ester is reduced to 20 ppm or less by performing the distillation step at a distillation temperature in the range of 80 ° C. or higher and 120 ° C. or lower and a reduced pressure condition of 60 Pa or lower. be able to. In addition, if the distillation step is performed in the presence of a polymerization inhibitor having a vapor pressure of 0.9 kPa or higher at 85 ° C., the content of the polymerization inhibitor can be increased without adding a polymerization inhibitor after the distillation step. A dioxolane (meth) acrylic acid ester of 1000 ppm or less can be obtained.

  On the other hand, for example, in Patent Document 2 (Japanese Patent Application Laid-Open No. 2004-59435), dioxolane (meth) acrylate is distilled under the conditions of 135 ° C. and 0.7 kPa. Then, there exists a possibility of producing the fall of the yield by the dioxolane (meth) acrylic acid ester thermally polymerizing, and the fall of purity.

  As described above, the dioxolane (meth) acrylic acid ester produced by the production method according to this embodiment has a hue (Hazen color number, APHA) of 10 or less, and has very high transparency. The specific method for specifying the hue of dioxolane (meth) acrylic acid ester may be referred to the examples.

  Moreover, the dioxolane (meth) acrylic acid ester manufactured by the manufacturing method according to one embodiment has a high purity such that the content of the transesterification catalyst is 20 ppm or less. Moreover, it is a high purity compound whose content of the polymerization inhibitor having a vapor pressure at 85 ° C. of 0.9 kPa or more is 1000 ppm or less. In addition, since the dioxolane (meth) acrylic acid ester manufactured by the manufacturing method which concerns on one Embodiment contains the transesterification catalyst and the polymerization inhibitor, it can be a composition of a dioxolane (meth) acrylic acid ester. .

  The dioxolane (meth) acrylic acid ester obtained by the production method according to the present invention may be further washed or purified as necessary, and can be used in the next step as it is.

  The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope shown in the claims, and embodiments obtained by appropriately combining technical means disclosed in different embodiments. Is also included in the technical scope of the present invention.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these. Further, the values of various production conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-described upper limit or lower limit value. It may be a range defined by a combination of values of the following examples or values of the examples.

<Production of dioxolane (meth) acrylic acid ester>
The dioxolane (meth) acrylic acid esters of Examples 1 to 5 and Comparative Examples 1 to 4 were produced by changing the polymerization inhibitor, the transesterification catalyst, and the distillation process conditions, and the obtained dioxolane (meta) ) The acrylic ester purity and hue (APHA) were evaluated.

<Evaluation method>
The purity of dioxolane (meth) acrylic acid ester and the evaluation method of hue are as shown below.

[Evaluation of purity]
The purity of dioxolane (meth) acrylic acid ester was determined as gas chromatography purity (hereinafter referred to as GC purity) by quantitative analysis by gas chromatography.

  The specific GC purity measurement conditions are as follows. Hereinafter, unless otherwise specified in the examples, the unit “%” indicating GC purity indicates area% in gas chromatography.

(Gas chromatography analysis conditions)
Column: Restek Rtx-65 φ0.53mm × 15m
Inlet temperature: 230 ° C
Detector temperature: 280 ° C
Initial temperature: 50 ° C., initial temperature holding time: 0 minutes Temperature rising rate: 10 ° C./min Final temperature: 240 ° C., final temperature holding time: 5 minutes Detector: Hydrogen flame ionization detector Carrier gas: Nitrogen gas Injection amount: 1.0 μL
Injection mode: split

[Evaluation of Hue (APHA)]
Hue was evaluated based on APHA (based on the number of Hazen unit colors in JIS K 0071 Part 1). The APHA standard solution and the samples of each Example and Comparative Example were each injected up to the marked line of the colorimetric tube and allowed to stand on a colorimetric tube stand with a white plate. Under the diffuse daylight, the color of the sample of the example and the comparative example is identified by looking through the colorimetric tube from the upper side to the lower side, and the APHA standard solution having the closest color is identified for each, The APHA standard solution number was used as the APHA value.

  In addition, the yield is based on the yield relative to the theoretical production amount of dioxolane (meth) acrylate determined from the amount of (1,3-dioxolan-4-yl) methanol derivative and methyl (meth) acrylate used. The ratio was determined by “% by weight”.

<Example 1>
The dioxolane (meth) acrylic ester of Example 1 was prepared according to the following procedure.

  Using a reflux apparatus equipped with an Oldershaw distillation column, in a four-necked flask with a side tube, 1.0 mol of 1,4-dioxaspiro [4.5] decane-2-methanol (hereinafter referred to as DOOH), 6.0 mol of methyl methacrylate (hereinafter referred to as MMA) and 0.01 mol of dioctyltin oxide (hereinafter referred to as DOTO) were added, and [4,4 ′-(phthaloyldioxy) bis (2,2,2 6,6-tetramethylpiperidine)]-1,1′diylbisoxyl (molecular weight 474.590, hereinafter referred to as PDOX) is charged so as to be 500 ppm with respect to the theoretical production amount of dioxolane (meth) acrylate. Thus, a reaction solution was prepared. Subsequently, the reaction solution was heated to the boiling point while stirring in a dry air stream to conduct a transesterification reaction. The reaction temperature during the transesterification reaction was confirmed by using a metal-coated thermocouple so that the tip of the thermocouple was sufficiently immersed in the reaction solution. Methanol generated during the transesterification reaction was removed from the reaction system as an azeotrope with MMA, and the end point of the transesterification reaction was defined as the point at which this azeotropic compound stopped distilling. The transesterification time was 6 hours, and the temperature of the reaction solution at this time was in the range of 105 to 120 ° C.

  Next, this reaction solution was distilled under reduced pressure at 100 ° C. and 0.5 kPa, and excess MMA was distilled out of the system, whereby 1,4-dioxaspiro [4.5] decane methacrylate A crude product of 2-ylmethyl was obtained.

  Subsequently, hydroquinone monomethyl ether (hereinafter referred to as MEHQ) was added to 100 parts by mass of the crude product so that the addition amount was 80 ppm, and a thin-film distiller wiper (manufactured by Shinko Environmental Solution Co., Ltd.) was used. And purified and distilled under reduced pressure conditions of 40 Pa and temperature conditions of 90 ° C. As a result, a purified product of 1,4-dioxaspiro [4.5] decan-2-ylmethyl methacrylate was obtained. The obtained purified product of 1,4-dioxaspiro [4.5] decan-2-ylmethyl methacrylate had a GC purity of 98.0% and a yield of 89%.

<Example 2>
A purified product of 1,4-dioxaspiro [4.5] decan-2-ylmethyl methacrylate was obtained in the same manner as in Example 1 except that the amount of PDOX added was 20 ppm based on the theoretical production amount.

<Example 3>
A purified product of 1,4-dioxaspiro [4.5] decan-2-ylmethyl methacrylate was obtained in the same manner as in Example 1 except that the amount of PDOX added was 2000 ppm with respect to the theoretical production amount.

<Example 4>
A purified product of 1,4-dioxaspiro [4.5] decan-2-ylmethyl methacrylate was obtained in the same manner as in Example 1 except that the amount of MEHQ added was 20 ppm.

<Example 5>
A purified product of 1,4-dioxaspiro [4.5] decan-2-ylmethyl methacrylate was obtained in the same manner as in Example 1 except that the amount of MEHQ added was 1000 ppm.

<Comparative Example 1>
Similar to Example 1 except that 4-acetamido-2,2,6,6-tetramethylpiperidine 1-oxyl (molecular weight 213.3, hereinafter referred to as AMX) was charged to 500 ppm instead of PDOX. Thus, a purified product of 1,4-dioxaspiro [4.5] decan-2-ylmethyl methacrylate was obtained. The purified product obtained by the production method of Comparative Example 1 had a GC purity of 97.8% and a yield of 88%. In addition, the purified product of Comparative Example 1 was more colored than the purified products of Examples 1 to 5, and the hue (APHA) was 30.

<Comparative example 2>
In the same manner as in Example 1, a crude product of 1,4-dioxaspiro [4.5] decan-2-ylmethyl methacrylate was obtained. When the obtained crude product was purified and distilled under the same conditions as in Example 1 without adding MEHQ, the evaporated component was polymerized and solidified during the distillation operation, and 1,4-dioxaspiromethacrylate [4] .5] A purified product of decan-2-ylmethyl could not be obtained.

<Comparative Example 3>
Example 1 A composition product of 1,4-dioxaspiro [4.5] decan-2-ylmethyl methacrylate was produced under the same conditions, and purification distillation was not performed. The crude product of Comparative Example 4 was colored by PDOX remaining in the crude product.

<Comparative Example 4>
A crude product was obtained in the same manner as in Example 1 except that 500 ppm of 3,7-dioctylphenothiazine was added to the theoretical production amount instead of PDOX.

  Next, this crude product was purified and distilled in the same manner as in Example 1. As a result, the crude product was polymerized and solidified during the purification distillation, and 1,4-dioxaspiro [4.5] decane-2 methacrylate was obtained. -A purified product of ylmethyl could not be obtained.

Table 1 below shows the production conditions in Examples 1 to 5 and Comparative Examples 1 to 4 and the evaluation results of dioxolane (meth) acrylate.

  As shown in Table 1, the purified product of dioxolane (meth) acrylic acid ester obtained by the production methods of Examples 1 to 5 was purified of the dioxolane (meth) acrylic acid ester obtained by the production method of Comparative Example 1. Compared to the product, the hue (APHA) was as low as 10 or less.

  In addition, the dioxolane (meth) acrylic acid ester obtained by the production method of Comparative Example 2 is polymerized and solidified, and adding a polymerization inhibitor in the distillation step is effective for purifying the dioxolane (meth) acrylic acid ester. I was able to confirm that

  Moreover, from the evaluation results of Examples 1 to 5 and Comparative Examples 1 and 4, it was found that using an N-oxyl-based compound as a polymerization inhibitor in the production step would cause dioxolane (meth) acrylic ester to undergo thermal polymerization. It was confirmed that it was effective to prevent. Here, from the results of Examples 1 to 5 and Comparative Example 1, by using PDOX having a molecular weight of 300 or more as a polymerization inhibitor, it is possible to prevent deterioration of the hue of the obtained purified product. I was able to confirm.

  From the evaluation results of Examples 1 to 5 and Comparative Example 3, when PDOX was used as the polymerization inhibitor, PDOX was added to the dioxolane (meth) acrylate even when the distillation step was performed under a reduced pressure condition of 40 Pa. It was possible to prevent mixing, and to confirm that the hue of the dioxolane (meth) acrylic acid ester could be prevented from deteriorating.

  As described above, from the evaluation results of Examples 1 to 5 and Comparative Examples 1 to 4, by using PDOX in the production process, by adding a quinone polymerization inhibitor as another polymerization inhibitor in the distillation process, It was confirmed that dioxolane (meth) acrylic acid ester having a hue (APHA) as low as 10 or less can be obtained with high purity.

  The present invention can be used for the production of dioxolane (meth) acrylic acid esters.

Claims (15)

In the presence of a transesterification catalyst and an N-oxyl compound having a molecular weight of 300 or more, which is a polymerization inhibitor,
1,3-dioxolan-4-yl-methanol derivative represented by the following formula (1);
(Meth) acrylic acid alkyl ester having an alkyl chain having 1 to 4 carbon atoms;
By reacting
The production | generation process which produces | generates the dioxolane (meth) acrylic acid ester represented by following formula (2),
A distillation step in which the dioxolane (meth) acrylic acid ester is distilled with the addition of the polymerization inhibitor or in the presence of a polymerization inhibitor different from the N-oxyl compound;
The manufacturing method of dioxolane (meth) acrylic acid ester containing this.

(In Formula (1), R ¹ and R ² are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, or a cyclic alkyl group having 3 to 18 carbon atoms. Or a phenyl group, and R ¹ and R ² may be bonded to each other to form a ring.)

(In Formula (2), R ¹ and R ² are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, or a cyclic alkyl group having 3 to 18 carbon atoms. Or a phenyl group, R ¹ and R ² may be bonded to each other to form a ring, and R ³ is a hydrogen atom or a methyl group.)   The said transesterification catalyst is a manufacturing method of the dioxolane (meth) acrylic acid ester of Claim 1 which is transesterification catalysts other than a chelate complex.   The method for producing a dioxolane (meth) acrylic acid ester according to claim 1, wherein the transesterification catalyst is a tin compound.   The N-oxyl compound is [4,4 '-(phthaloyldioxy) bis (2,2,6,6-tetramethylpiperidine)]-1,1'-diylbisoxyl. 4. A process for producing a dioxolane (meth) acrylic acid ester according to any one of 3 above.   The content of the N-oxyl compound with respect to the theoretical production amount of dioxolane (meth) acrylic acid ester produced in the production step is in the range of 20 ppm or more and 2000 ppm or less. The manufacturing method of the dioxolane (meth) acrylic acid ester of description to term.   The method for producing a dioxolane (meth) acrylic acid ester according to any one of claims 1 to 5, wherein in the distillation step, distillation is performed under a reduced pressure condition of 60 Pa or less.   The method for producing a dioxolane (meth) acrylic acid ester according to any one of claims 1 to 6, wherein in the distillation step, distillation is performed under a temperature condition of 120 ° C or lower.   The said another polymerization inhibitor is a manufacturing method of the dioxolane (meth) acrylic acid ester of any one of Claims 1-7 whose vapor pressure in 85 degreeC is 0.9 kPa or more.   The said another polymerization inhibitor is at least one selected from the group which consists of hydroquinone, hydroquinone monomethyl ether, and 6-tert- butyl- 2, 4- xylenol, The any one of Claims 1-8. The manufacturing method of dioxolane (meth) acrylic acid ester of this.   The said polymerization inhibitor is mix | blended with the said distillation process so that it may become a density | concentration in the range of 20 ppm or more and 1000 ppm or less with respect to the said dioxolane (meth) acrylic acid ester produced | generated in the said production | generation process. The manufacturing method of the dioxolane (meth) acrylic acid ester of any one of 1-9.   The method for producing a dioxolane (meth) acrylic acid ester according to any one of claims 1 to 10, wherein in the distillation step, the dioxolane (meth) acrylic acid ester is distilled using a thin film evaporator.   Dioxolane (meth) acrylic acid ester having a hue (APHA) of 10 or less.   A composition of dioxolane (meth) acrylic acid ester comprising a transesterification catalyst in an amount of 20 ppm or less based on dioxolane (meth) acrylic acid ester.   The composition of dioxolane (meth) acrylic acid ester of Claim 13 whose said transesterification catalyst is a tin compound.   A composition of dioxolane (meth) acrylic acid ester containing a polymerization inhibitor having a vapor pressure at 85 ° C. of 0.9 kPa or more and 1,000 ppm or less based on dioxolane (meth) acrylic acid ester.