JP5395989B2 - Purification method for 6-membered lactone (meth) acrylic acid ester - Google Patents

Description

  The present invention relates to a method for purifying a six-membered lactone (meth) acrylic ester. More specifically, the present invention relates to a method for purifying a 6-membered ring lactone (meth) acrylate and a method for producing a 6-membered lactone (meth) acrylate using the purification method. The six-membered lactone (meth) acrylic acid ester is a useful compound for raw materials such as electronics-related materials, pharmaceutical and agricultural production intermediates, paints, adhesives, pressure-sensitive adhesives, and ink resins.

  In the present specification, “(meth) acrylic acid” means acrylic acid and / or methacrylic acid.

  In general, six-membered ring lactone (meth) acrylic acid esters such as mevalolactone methacrylate are unstable to heat. Therefore, the produced six-membered ring lactone (meth) acrylic acid ester is converted into ether, ester and ester. There has been proposed a purification method for purification by recrystallization at an extremely low temperature of −78 to −40 ° C. using one or more aromatic hydrocarbon compounds and dry ice (for example, Patent Document 1). See Examples 1-7).

  However, according to the purification method, the produced 6-membered ring lactone (meth) acrylic acid ester needs to be recrystallized at an extremely low temperature of -78 to -40 ° C. The cooling energy for cooling the acid ester is great, and it takes a long time for purification, and further requires an aromatic hydrocarbon compound such as benzene, toluene and xylene.

JP 2002-293777 A

  The present invention has been made in view of the above prior art, and is a six-membered ring lactone that can efficiently purify a six-membered ring lactone (meth) acrylate without using an aromatic hydrocarbon compound ( A method for purifying a meth) acrylic acid ester and a six-membered lactone (meth) acrylic acid ester capable of efficiently producing a six-membered lactone (meth) acrylic acid ester without using an aromatic hydrocarbon compound It is an object to provide a manufacturing method.

The present invention
(1 ) Formula (I):

^(Wherein, R 1 to R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)
A six-membered lactone represented by formula (II):

(Wherein R ⁸ represents a hydrogen atom or a methyl group, and X represents a halogen atom)
(Meth) acrylic acid halide represented by the following formula in the presence of a base in a slightly polar ketone solvent having a relative dielectric constant ε of 10 to 18 at 20 ° C. ) Acrylic acid ester is dissolved in a mixed solvent of an aliphatic hydrocarbon compound and a ketone solvent, and then crystallized at a temperature of -20 to -10 ° C (III):

(Wherein R ^{1 to} R ⁸ are the same as above)
The manufacturing method of the six-membered ring lactone (meth) acrylic acid ester represented by these.

  According to the method for purifying a six-membered lactone (meth) acrylate of the present invention, the six-membered lactone (meth) acrylate can be efficiently purified without using an aromatic hydrocarbon compound. Moreover, according to the method for producing a six-membered ring lactone (meth) acrylate ester of the present invention, it is possible to efficiently produce a six-membered ring lactone (meth) acrylate ester without using an aromatic hydrocarbon compound. it can.

  In the method for producing a six-membered lactone (meth) acrylate of the present invention, the raw material for the six-membered lactone (meth) acrylate is represented by the formula (I):

^(Wherein, R 1 to R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)
(Meth) acrylic acid halide represented by the formula (II):

(Wherein R ⁸ represents a hydrogen atom or a methyl group, and X represents a halogen atom)
The (meth) acrylic acid halide represented by these is used.

In the (meth) acrylic acid halide represented by the formula (I), R ^{1 to} R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group and tertiary butyl group.

As the six-membered ring lactone represented by the formula (I), a six-membered ring that can be suitably used as a raw material for electronics-related materials, intermediates for the production of medicines and agricultural chemicals, paints, adhesives, adhesives, ink resins, etc. From the viewpoint of producing a lactone (meth) acrylic ester, a 6-membered ring lactone in which R ¹ is a methyl group or an ethyl group, and R ^{2 to} R ⁷ are all hydrogen atoms is preferable, and R ¹ is a methyl group. , R ^{2 to} R ⁷ are more preferably mevalonic lactones each being a hydrogen atom.

In the (meth) acrylic acid halide represented by the formula (II), R ⁸ represents a hydrogen atom or a methyl group, and X represents a halogen atom. Examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom, and among these, a chlorine atom is preferable from the viewpoint of reactivity and ease of handling. From these facts, the (meth) acrylic acid halide represented by the formula (II) is preferably (meth) acrylic acid chloride.

  In the method for producing a six-membered lactone (meth) acrylic acid ester of the present invention, first, a six-membered lactone represented by the formula (I) and a (meth) acrylic acid halide represented by the formula (II) are used as a base. In a slightly polar ketone solvent.

  In the method for producing a six-membered lactone (meth) acrylic acid ester of the present invention, a slightly polar ketone solvent is used. Therefore, by using a general cooling device instead of a special cooling device, the crude six A membered lactone (meth) acrylic ester can be produced.

  The amount of (meth) acrylic acid halide is such that the reaction between (meth) acrylic acid halide and six-membered ring lactone is a stoichiometric reaction, but the six-membered ring lactone is sufficiently reacted with (meth) acrylic acid halide. From a viewpoint, it is preferable that it is 1.0-1.5 mol per mol of 6-membered ring lactone, and it is more preferable that it is 1.1-1.3 mol.

  Examples of the base include trialkylamines such as trimethylamine and triethylamine, and pyridine. Among these, triethylamine is preferable because of its high reactivity.

  The amount of the base is preferably 1.0 to 2.1 mol per mol of the 6-membered ring lactone from the viewpoint of sufficiently reacting the (meth) acrylic acid halide and the 6-membered ring lactone. More preferably, it is -1.8 mol.

  The slightly polar ketone solvent as used herein means a ketone having a relative dielectric constant ε of 10 to 18 at 20 ° C. In the present invention, since a slightly polar ketone solvent is used, decomposition of the generated crude six-membered ring lactone (meth) acrylic acid ester can be suppressed.

  The slightly polar ketone solvent is selected from the group consisting of methyl isopropyl ketone, methyl isobutyl ketone, methyl isopentyl ketone and diethyl ketone from the viewpoint of sufficiently suppressing the decomposition of the generated crude six-membered ring lactone (meth) acrylate. At least one of them is preferred.

  The amount of the slightly polar ketone solvent is preferably 200 to 800 parts by weight per 100 parts by weight of the 6-membered ring lactone from the viewpoint of sufficiently suppressing the decomposition of the generated crude 6-membered ring lactone (meth) acrylate. More preferably, it is 300 to 500 parts by weight.

  The atmosphere when the (meth) acrylic acid halide and the six-membered ring lactone are reacted is not particularly limited, and may be an inert gas atmosphere such as nitrogen gas, or the air.

  The reaction between the six-membered ring lactone and the (meth) acrylic acid halide may be performed by adding a base to a solution in which the six-membered ring lactone and the (meth) acrylic acid halide are dissolved in a slightly polar ketone solvent, You may carry out by adding (meth) acrylic acid halide to the solution which melt | dissolved the 6-membered ring lactone and the base in the micropolar ketone solvent.

  In the reaction, if necessary, a polymerization inhibitor such as 4-acetamino-2,2,6,6-tetramethylpiperidine-N-oxyl may be added in an appropriate amount to the slightly polar ketone solvent.

  The reaction temperature of the 6-membered ring lactone and the (meth) acrylic acid halide is −15 to 0 ° C. from the viewpoint of production efficiency and the thermal stability of the resulting crude 6-membered ring lactone (meth) acrylate. Is preferred.

  By reacting the six-membered lactone and the (meth) acrylic acid halide as described above, the formula (III):

(Wherein R ^{1 to} R ⁸ are the same as above)
A crude six-membered lactone (meth) acrylic acid ester represented by In addition, the production | generation of a crude 6-membered ring lactone (meth) acrylic acid ester can be easily confirmed by gas chromatography (GC), liquid chromatography (LC), etc.

  The obtained crude 6-membered ring lactone (meth) acrylic acid ester may be purified to some extent in advance, for example, by silica gel column chromatography, vacuum distillation or the like.

  Next, after using a mixed solvent of an aliphatic hydrocarbon compound and a ketone solvent as a solvent and dissolving the crude six-membered lactone (meth) acrylic acid ester in the mixed solvent, -20 to -10 ° C. The crude 6-membered ring lactone (meth) acrylic acid ester is purified by crystallization at the following temperature.

  In the present invention, one major feature is that a mixed solvent of an aliphatic hydrocarbon compound and a ketone solvent is used as a solvent when purifying a crude six-membered ring lactone (meth) acrylate. There are features. In the present invention, when a crude six-membered ring lactone (meth) acrylic ester is purified in this way, a mixed solvent of an aliphatic hydrocarbon compound and a ketone solvent is used. Even without cooling to a very low temperature, the crude 6-membered lactone (meth) acrylic acid ester can be purified efficiently.

  Among the aliphatic hydrocarbon compounds, an aliphatic hydrocarbon compound having 5 to 12 carbon atoms is preferable from the viewpoint of efficiently purifying a crude 6-membered ring lactone (meth) acrylate, and an aliphatic hydrocarbon having 5 to 8 carbon atoms. A group hydrocarbon compound is more preferable, and n-hexane is more preferable.

  Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl isopentyl ketone, diethyl ketone, propylene glycol monomethyl acetate, and propylene glycol monoethyl acetate. Acetone, methyl isopropyl ketone, methyl isobutyl ketone, methyl isopentyl ketone, diethyl ketone and propylene glycol monomethyl acetate are preferable from the viewpoint of efficiently purifying the membered lactone (meth) acrylic acid ester, and acetone, methyl isobutyl ketone and propylene glycol are preferred. Monomethyl acetate is more preferable, and methyl isobutyl ketone is more preferable.

  The weight ratio of the aliphatic hydrocarbon compound to the ketone solvent (aliphatic hydrocarbon compound / ketone solvent) is an efficiency of the crude six-membered lactone (meth) acrylate at a temperature of -20 to -10 ° C. From the viewpoint of well purifying, it is preferably 25/75 or more, more preferably 30/70 or more, and further preferably 35/65 or more, from the viewpoint of increasing the purity of the six-membered lactone (meth) acrylate to be purified. , Preferably 90/10 or less, more preferably 85/15 or less, and still more preferably 70/30 or less.

  The amount of the mixed solvent varies depending on the crystallization temperature (crystallization temperature) of the 6-membered ring lactone (meth) acrylic acid ester and cannot be determined unconditionally, but is usually a crude 6-membered ring lactone (meth) acrylic. Preferably it is 80-700 weight part per 100 weight part of acid ester, More preferably, it is 100-650 weight part.

  The temperature at which the crude 6-membered ring lactone (meth) acrylate is dissolved in the mixed solvent may be any temperature that does not cause decomposition or polymerization of the crude 6-membered ring lactone (meth) acrylate, Preferably it is -5-10 degreeC, More preferably, it is 0-5 degreeC.

  Next, the 6-membered lactone (meth) acrylate is crystallized (crystallized) from a solution in which the crude 6-membered lactone (meth) acrylate is dissolved in a mixed solvent.

  The temperature at which the 6-membered lactone (meth) acrylate is crystallized (crystallized) from a solution in which the crude 6-membered lactone (meth) acrylate is dissolved in a mixed solvent is selected from the viewpoints of improving purification efficiency and From the viewpoint of the thermal stability of the crude 6-membered ring lactone (meth) acrylic acid ester, it is preferably −20 to −10 ° C., more preferably −15 to −10 ° C.

  Crystallization of the purified six-membered ring lactone (meth) acrylic acid ester may be performed while standing or may be performed with stirring. When crystallizing (crystallizing) the purified 6-membered lactone (meth) acrylate ester, an appropriate amount of the seed crystal of the purified 6-membered lactone (meth) acrylate ester is crude 6-membered lactone (meth) acrylic. It is preferable to immerse in a solution in which the acid ester is dissolved in a mixed solvent. When the seed crystal of 6-membered ring lactone (meth) acrylate purified in this way is used, white 6-membered ring lactone (meth) acrylate can be easily crystallized (crystallized). it can.

  When crystallizing (crystallizing) a six-membered lactone (meth) acrylate purified using a seed crystal from a solution in which a crude six-membered lactone (meth) acrylate is dissolved in a mixed solvent, the purity is From the viewpoint of efficiently crystallizing (crystallizing) a high six-membered ring lactone (meth) acrylate ester, a crude six-membered ring lactone (meth) acrylate ester is a mixed solvent of an aliphatic hydrocarbon compound and a ketone solvent. After being immersed in a seed crystal of a six-membered ring lactone (meth) acrylate ester in a solution obtained at −5 to 10 ° C., this solution is preferably −20 to −10 ° C., more preferably It is desirable to cool to -15 to -10 ° C.

  Crystals of the six-membered lactone (meth) acrylic acid ester purified as described above can be recovered by a separation operation such as filtration. At that time, in order to prevent the crystals from dissolving in the mixed solvent, the separation operation is performed in as short a time as possible, and a purified six-membered lactone (meth) acrylate ester is used by using a separator as necessary. It is preferable to cool the crystals.

  The purified crystals of the six-membered lactone (meth) acrylic acid ester can be washed if necessary. The solvent used for washing is preferably the mixed solvent. The temperature at the time of washing was purified from a solution in which a crude 6-membered lactone (meth) acrylate was dissolved in a mixed solvent from the viewpoint of preventing dissolution of the crystals of the 6-membered lactone (meth) acrylate. The temperature is the same as when crystallizing (crystallizing) the six-membered lactone (meth) acrylic acid ester, that is, preferably -20 to -10 ° C, more preferably -15 to -10 ° C. The amount of the solvent at the time of washing is not particularly limited, but is usually about 100 to 500 parts by weight per 100 parts by weight of crystals of the six-membered lactone (meth) acrylic acid ester.

The thus refined six-membered lactone (meth) acrylic acid ester is suitably used as a raw material for, for example, electronics-related materials, pharmaceutical and agricultural production intermediates, paints, adhesives, pressure-sensitive adhesives, and ink resins. Among the six-membered ring lactone (meth) acrylic acid esters, in the formula (III), R ¹ is a methyl group or an ethyl group, and R ^{2 to} R ⁷ are hydrogen atoms. Esters, preferably mevalonic lactone (meth) acrylates in which R ¹ is a methyl group and R ^{2 to} R ⁷ are all hydrogen atoms, are particularly attracting attention in electronics-related materials, and are next-generation LSI ( Large-scale integrated circuit) A useful compound expected as a raw material for high-grade resist resins.

  Next, the present invention will be described in more detail based on examples, but the present invention is not limited to such examples.

Example 1
In a 5 L glass reaction vessel equipped with a sample inlet, a condenser, a thermometer and a stirrer, 300 g (2.31 mol) of mevalonic lactone, 396 g (3.92 mol) of triethylamine, 1200 g of methyl isobutyl ketone and 4-acetamino-2,2,6,6-tetramethylpiperidine-N-oxyl 0.06 g (0.3 mmol) was charged, and the solution was cooled to −10 ° C. while blowing dry nitrogen gas into the resulting solution. .

  Blowing of dry nitrogen gas was stopped, and 289 g (2.77 mol) of methacrylic acid chloride was dropped into the reaction vessel at a temperature of −10 ° C. over about 3 hours using a pump. After stirring at the same temperature for 2 hours, a 10% aqueous formic acid solution was added to the reaction vessel from the dropping funnel while maintaining the temperature at -10 ° C or lower. At that time, the pH of the solution in the reaction vessel was 5.

  The organic layer from which the aqueous layer was separated was washed with 40% aqueous formic acid solution, and after separating the aqueous layer, pyridine was added to adjust the pH to 3-4, and the mixture was stirred at room temperature for 4 hours. After confirming the disappearance of the peak of methacrylic anhydride by gas chromatography, it was washed 5 times with pure water, 5 times with 5% aqueous sodium hydrogen carbonate solution and 3 times with 20% brine. To this was added 0.06 g (0.3 mmol) of 4-acetamino-2,2,6,6-tetramethylpiperidine-N-oxyl and 0.15 g (1.2 mmol) of 4-methoxyphenol, and methyl isobutyl ketone. Was distilled off at 40 to 50 ° C. under reduced pressure of 0.5 to 10 kPa to obtain 289 g of crude mevalonic lactone methacrylate (yield 63.1%, purity 91.2 area%).

  After mixing 62.2 g of the crude mevalonic lactone methacrylate obtained above and 375 mL of the mixed solvent shown in Table 1 in a 500 mL three-necked flask equipped with a thermometer and a stirrer, the temperature of the obtained solution The solution was cooled to 0 ° C., and the insoluble material was filtered off to obtain a filtrate.

  Into a 500 mL three-necked flask equipped with a thermometer and a stirrer, the filtrate obtained above was charged, and a seed crystal of purified mevalonic lactone methacrylate was added in an appropriate amount, and the liquid temperature was −10 ° C. The mevalonic lactone methacrylate crystal | crystallization was obtained by crystallizing mevalonic lactone methacrylate from a filtrate by agitating for 3 hours, keeping it at the same temperature.

  Next, the crystals obtained using filter paper are collected and washed with the mixed solvent at a temperature of −10 ° C., and then the mixed solvent is distilled off at a temperature of 40-50 ° C. under a reduced pressure of 0.5-10 kPa. As a result, purified mevalonic lactone methacrylate was recovered. The measurement results of the purity of this mevalonic lactone methacrylate are shown in Table 1. The purity of mevalonic lactone methacrylate was measured by gel permeation chromatography (GPC).

  The specific measurement conditions for gel permeation chromatography (GPC) are as follows.

Gel permeation chromatograph: manufactured by Tosoh Corporation, product number: HLC-8020
Column: manufactured by Tosoh Corporation, product number: TSKgel G4000HXL and G3000HXL, G2000HXL, G1000HXL are connected in series. Eluent: tetrahydrofuran, flow rate 1.0 mL / min
-Column temperature: 40 ° C
Detection method: The refractive index (RI) is measured using a refraction detector (RI), and the area% is calculated to determine the purity of mevalonic lactone methacrylate.

Example 2
In a 1 L glass reaction vessel equipped with a sample inlet, a condenser, a thermometer, and a stirrer, 60 g (0.46 mol) of mevalonic lactone, 79.3 g (0.78 mol) of triethylamine, methyl isopropyl ketone 240 g and 4-acetamino-2,2,6,6-tetramethylpiperidine-N-oxyl 0.012 g (0.06 mmol) were charged, and the resulting solution was cooled to −10 ° C.

  Into this reaction vessel, 57.8 g (0.55 mol) of methacrylic acid chloride was dropped at a temperature of −10 ° C. over about 1.5 hours using a pump. After stirring at the same temperature for 4.5 hours, a 10% aqueous formic acid solution was added to this solution from the dropping funnel while maintaining the temperature at -10 ° C or lower. At this time, the pH of the solution was 5. After separating the aqueous layer, the organic layer was washed with 40% aqueous formic acid solution, and after separating the aqueous layer, pyridine was added and stirred at room temperature for 4 hours. After confirming the disappearance of the peak of methacrylic anhydride by gas chromatography, it was washed 5 times with pure water, 5 times with 5% aqueous sodium hydrogen carbonate solution and 3 times with 20% brine. To this was added 0.012 g (0.06 mmol) of 4-acetamino-2,2,6,6-tetramethylpiperidine-N-oxyl and 0.03 g (0.24 mmol) of 4-methoxyphenol, and methyl isopropyl ketone. Was distilled off under reduced pressure of 0.5 to 10 kPa at a temperature of 40 to 50 ° C. to obtain 53 g of crude mevalonic lactone methacrylate (yield 57.6%, purity 87.8 area%).

  Next, purified mevalonic lactone methacrylate was obtained by purifying crude mevalonic lactone methacrylate in the same manner as in Example 1 using 375 mL of the mixed solvent shown in Table 1. Table 1 shows the measurement results of the purity of the obtained mevalonic lactone methacrylate.

Example 3
In Example 2, instead of methyl isopropyl ketone, 240 g of diethyl ketone was used, and 48 g of crude mevalonic lactone methacrylate was obtained in the same manner as in Example 2 except that the stirring time after dropping was changed to 5 hours ( Yield 52.1%, purity 87.7 area%).

  Next, purified mevalonic lactone methacrylate was obtained by purifying crude mevalonic lactone methacrylate in the same manner as in Example 1 using 375 mL of the mixed solvent shown in Table 1. Table 1 shows the measurement results of the purity of the obtained mevalonic lactone methacrylate.

Example 4
In Example 2, 42 g of crude mevalonic lactone methacrylate was obtained in the same manner as in Example 2 except that 240 g of methyl isopentyl ketone was used instead of methyl isopropyl ketone (yield 45.6%, purity 86). .6 area%).

  Next, purified mevalonic lactone methacrylate was obtained by purifying crude mevalonic lactone methacrylate in the same manner as in Example 1 using 375 mL of the mixed solvent shown in Table 1. Table 1 shows the measurement results of the purity of the obtained mevalonic lactone methacrylate.

Example 5
In Example 2, 240 g of methyl isobutyl ketone was used instead of 240 g of methyl isopropyl ketone, and 57.8 g (0.55 mol) of methacrylic acid chloride was charged into a glass reaction vessel instead of 79.3 g of triethylamine. Except that the solution was cooled to 0 ° C. and 79.3 g (0.78 mol) of triethylamine was added dropwise over 2.5 hours instead of 57.8 g of methacrylic acid chloride, followed by stirring at the same temperature for 5 hours. In the same manner as in Example 2, 42 g of crude mevalonic lactone methacrylate was obtained (yield 45.9%, purity 77.5 area%).

  Next, purified mevalonic lactone methacrylate was obtained by purifying crude mevalonic lactone methacrylate in the same manner as in Example 1 using 375 mL of the mixed solvent shown in Table 1. Table 1 shows the measurement results of the purity of the obtained mevalonic lactone methacrylate.

Examples 6-9
Crude mevalonic lactone methacrylate was obtained in the same manner as in Example 1 (yield 63.1%, purity 91.2 area%).

  Next, purified mevalonic lactone methacrylate was obtained by purifying 62.2 g of crude mevalonic lactone methacrylate in the same manner as in Example 1 using 375 mL of the mixed solvent shown in Table 1. Table 1 shows the measurement results of the purity of the obtained mevalonic lactone methacrylate.

Comparative Example 1
After mixing 62.2 g of crude mevalonic lactone methacrylate (purity 91.2%) obtained in the same manner as in Example 1 and 375 g of butanol in a 500 mL three-necked flask equipped with a thermometer and a stirrer. The resulting solution was cooled to 0 ° C., and insoluble matters were filtered off to obtain a filtrate.

  Next, the filtrate obtained above is charged into a 500 mL three-necked flask equipped with a thermometer and a stirrer, seed crystals are added, and the mixture is stirred for 3 hours while maintaining the liquid temperature at −10 ° C. In this way, an attempt was made to produce mevalonic lactone methacrylate crystals, but no mevalonic lactone methacrylate crystals could be produced.

Comparative Example 2
In Example 1, an attempt was made to prepare mevalonic lactone methacrylate in the same manner as in Example 1 except that 375 mL of diisopropyl ether was used instead of 375 mL of the mixed solvent shown in Table 1, but mevalonic lactone methacrylate was prepared. Of crystals could not be produced.

Comparative Example 3
In Example 1, mevalonic lactone methacrylate was prepared in the same manner as in Example 1 except that 375 mL of toluene was used instead of 375 mL of the mixed solvent shown in Table 1. Crystals could not be produced.

Comparative Example 4
In Example 1, mevalonic lactone methacrylate was prepared in the same manner as in Example 1 except that 375 mL of ethyl acetate was used instead of 375 mL of the mixed solvent shown in Table 1. Of crystals could not be produced.

In Table 1, each abbreviation means the following.
MIBK: methyl isobutyl ketone PGMAc: propylene glycol monomethyl ether acetate MEK: methyl ethyl ketone MLVMA: mevalonic lactone methacrylate

  From the above results, in each example, since a mixed solvent in which an aliphatic hydrocarbon compound and a ketone solvent are used in combination is used as a solvent, crystallization is performed at a temperature of -20 to -10 ° C. Thus, it can be seen that purified mevalonic lactone methacrylate can be obtained efficiently. In particular, the weight ratio of aliphatic hydrocarbon compound to ketone solvent (aliphatic hydrocarbon compound / ketone solvent) is in the range of about 30/70 to 85/15, especially about 30/70 to 70/30. It can be seen that when methyl isobutyl ketone is used as the aliphatic hydrocarbon compound, the purity of mevalonic lactone methacrylate is increased.

Claims (6)

Formula (I):
^(Wherein, R 1 to R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)
A six-membered lactone represented by formula (II):
(Wherein R ⁸ represents a hydrogen atom or a methyl group, and X represents a halogen atom)
(Meth) acrylic acid halide represented by the following formula in the presence of a base in a slightly polar ketone solvent having a relative dielectric constant ε of 10 to 18 at 20 ° C. ) Acrylic acid ester is dissolved in a mixed solvent of an aliphatic hydrocarbon compound and a ketone solvent, and then crystallized at a temperature of -20 to -10 ° C (III):
(Wherein R ^{1 to} R ⁸ are the same as above)
The manufacturing method of the six-membered ring lactone (meth) acrylic acid ester represented by these. Temperature of the mixed solvent when the crude is dissolved six-membered ring lactone (meth) acrylic acid ester in a mixed solvent, production of six-membered ring lactone (meth) acrylic acid esters according to claim 1 which is -5～10 ° C. Method. The six-membered lactone (meth) acrylic acid according to claim 1 or 2 , wherein the slightly polar ketone solvent is at least one selected from the group consisting of methyl isopropyl ketone, methyl isobutyl ketone, methyl isopentyl ketone and diethyl ketone. Ester production method. The six-membered member according to any one of claims 1 to 3 , wherein a weight ratio of the aliphatic hydrocarbon compound to the ketone solvent (aliphatic hydrocarbon compound / ketone solvent) is 25/75 to 90/10. A method for producing a cyclic lactone (meth) acrylic ester. The crude 6-membered ring lactone (meth) acrylate is dissolved in a mixed solvent at a temperature of -5 to 10 ° C., and the seed crystal of the 6-membered ring lactone (meth) acrylate is immersed in the resulting solution. The method for producing a six-membered ring lactone (meth) acrylate ester according to any one of claims 1 to 4 , wherein the solution is cooled to a temperature of -20 to -10 ° C. The method for producing a six-membered lactone (meth) acrylate ester according to any one of claims 1 to 5 , wherein the aliphatic hydrocarbon compound is an aliphatic hydrocarbon compound having 5 to 12 carbon atoms.