Method for producing methylene lactone-based compound

Abstract

The present invention provides a method for producing a methylene lactone-based compound, the method being capable of efficiently producing the methylene lactone-based compound. The present invention relates to a method for producing a methylene lactone-based compound, the method being characterized by involving a step in which a specific γ-butyrolactone-based compound and a specific aldehyde compound are reacted in the presence of an oxide or hydroxide of a metal including an element in group 2 of the periodic table.

Description

Method for producing methylene lactone compounds

[0001] The present invention relates to a method for producing a methylene lactone compound, and more particularly to a method for efficiently producing a methylene lactone compound.

[0002] Methylene lactone and its derivatives are useful as raw monomer materials for polymers used in resists and films for optical devices and electric / electronic devices, and have become increasingly important in recent years.

[0003] Various methods are known for producing methylene lactone compounds. For example, Non-Patent Document 1 describes a method for producing α-alkylidene-γ-butyrolactone by reacting α-acetyl-γ-butyrolactone with formaldehyde.

[0004] Tetrahedron, 60, (2004), 2337-2349

[0005] However, conventional production methods have had problems such as the production of a large amount of by-products, resulting in a low yield of the target methylene lactone compound, and problems such as a low reaction concentration and a low yield per batch. In view of the above-mentioned current situation, an object of the present invention is to provide a production method for a methylene lactone compound that can efficiently produce the target methylene lactone compound.

[0006] In order to solve the above-mentioned problems, the present inventors have conducted extensive research into methods for producing methylene lactone compounds and have found that by reacting a specific γ-butyrolactone compound with an aldehyde compound in the presence of a specific compound, methylene lactone compounds can be produced in high yield with minimal production of by-products. They have also found that by reacting a specific γ-butyrolactone compound with a base and then reacting it with a specific aldehyde compound, methylene lactone compounds can be produced in higher yield with minimal production of by-products, leading to the completion of the present invention.

[0007] That is, the present invention provides the following aspects of the invention: <1> A compound represented by the following formula (1):

[0008]

[0009] (Wherein, X is -R １ Or -OR ２ R is a group represented by the formula: １ and R ２ and R are the same or different and represent a hydrogen atom or a hydrocarbon group which may have a substituent. ３ CHO (2) (wherein, R ３ represents a hydrogen atom or a hydrocarbon group which may have a substituent.) or an aldehyde compound containing paraformaldehyde, in the presence of an oxide or hydroxide of a metal consisting of an element of Group 2 of the periodic table. <2> A method for producing a methylene lactone compound according to <1> above, wherein the metal consisting of an element of Group 2 of the periodic table is calcium, magnesium, or strontium. <3> A method for producing a methylene lactone compound according to the following formula (1):

[0010]

[0011] (Wherein, X is -R １ Or -OR ２ R is a group represented by the formula: １ and R ２ and R are the same or different and represent a hydrogen atom or a hydrocarbon group which may have a substituent.) A step (1) of reacting a γ-butyrolactone compound represented by the following formula (2): R ３ CHO (2) (wherein, R ３represents a hydrogen atom or an optionally substituted hydrocarbon group.) or an aldehyde compound containing paraformaldehyde. <4> A method for producing a methylene lactone compound according to <3> above, wherein the step (1) is carried out in the presence of a solvent, and the solvent contains an ester solvent. <5> A method for producing a methylene lactone compound according to <3> or <4> above, wherein the base is an oxide or hydroxide of a metal consisting of an element of Group 2 of the periodic table. <6> A method for producing a methylene lactone compound according to the following formula (2):

[0012]

[0013] (In the formula, R ３ represents a hydrogen atom or a hydrocarbon group which may have a substituent, and the compound includes a methylene lactone compound represented by the following formulas (3) to (5):

[0014]

[0015] (In the formula, R ３ represents a hydrogen atom or a hydrocarbon group which may have a substituent.), is 0.1 to 10 mass% based on 100 mass% of the methylene lactone compound.

[0016] The method for producing a methylene lactone compound of the present invention can economically produce a methylene lactone compound in high yield with little by-product formation and in high batch yield.

[0017] The present invention will be described in detail below. Note that a combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

[0018] 1. Method for Producing Methylene Lactone Compounds The present invention relates to a method for producing methylene lactone compounds, which allows for efficient production of methylene lactone compounds. The first invention relates to a method for producing methylene lactone compounds, which comprises a step of reacting a γ-butyrolactone compound represented by the general formula (1) above with a compound represented by the formula (2) above or an aldehyde compound containing paraformaldehyde in the presence of an oxide or hydroxide of a metal of Group 2 of the periodic table. The second invention relates to a method for producing methylene lactone compounds, which comprises a step (1) of reacting a γ-butyrolactone compound represented by the general formula (1) above with a base, and a step (2) of reacting the reaction product obtained in step (1) with a compound represented by the formula (2) above or an aldehyde compound containing paraformaldehyde. In this specification, the "first invention" and the "second invention" may be collectively referred to as the "present invention."

[0019] <First Method for Producing Methylene Lactone Compounds> The first method for producing methylene lactone compounds of the present invention comprises the step of reacting a γ-butyrolactone compound represented by formula (1) above with an aldehyde compound containing either a compound represented by formula (2) above or paraformaldehyde in the presence of an oxide or hydroxide of a metal of Group 2 of the periodic table. By reacting a specific γ-butyrolactone compound with a specific aldehyde compound in the presence of an oxide or hydroxide of a metal of Group 2 of the periodic table, it is possible to suppress the production of by-products and produce methylene lactone compounds in high yields. This is presumably because the oxide or hydroxide of the metal of Group 2 of the periodic table has an appropriate basicity, allowing the formation of a salt with the γ-butyrolactone compound, the reaction with the specific aldehyde compound, and the subsequent decarboxylation or decarboxylation reaction to proceed smoothly.

[0020] (A) γ-Butyrolactone Compound The γ-butyrolactone compound of the present invention is a compound represented by the above formula (1). In formula (1), X is -R １ Or -OR ２ R is a group represented by the formula: １ and R２ are the same or different and represent a hydrogen atom or an optionally substituted hydrocarbon group.

[0021] R １ and R ２ The hydrocarbon group represented by the formula (I) may be saturated or unsaturated, and may be linear or cyclic. The hydrocarbon group is preferably an alkyl group, an alkenyl group, an aryl group, or an aralkyl group.

[0022] R １ and R ２ The alkyl group represented by the formula (I) may be linear or branched, but is preferably linear in that it reduces steric hindrance. The number of carbon atoms in the alkyl group is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 4.

[0023] R １ and R ２ Examples of the alkenyl group represented by the formula (I) include a vinyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, a pentenyl group, a hexenyl group, etc. The number of carbon atoms in the alkenyl group is preferably 2 to 8, more preferably 2 to 6, and even more preferably 2 to 5.

[0024] R １ and R ２ Examples of the aryl group represented by the formula (I) include a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, etc. The number of carbon atoms in the aryl group is preferably 6 to 14, more preferably 6 to 12, and even more preferably 6 to 10.

[0025] R １ and R ２ Examples of the aralkyl group represented by the formula (I) include a benzyl group, a phenethyl group, a phenylpropyl group, etc. The number of carbon atoms in the aralkyl group is preferably 1 to 9, more preferably 1 to 8, and even more preferably 1 to 7.

[0026] Among them, R １ and R ２ The hydrocarbon group represented by the formula (I) is preferably an alkyl group or an aralkyl group, more preferably an alkyl group.

[0027] R １ and R ２ Examples of the substituent that the hydrocarbon group represented by the formula (I) may have include a halogen atom, a hydroxy group, an ether group, an ester group, an amide group, a nitrile group, an amino group, an imino group, and a nitro group.

[0028] Among them, R １ R is preferably an alkyl group which may have a substituent or an aralkyl group, more preferably an alkyl group which may have a substituent, and even more preferably an alkyl group. ２ As the alkyl group, an optionally substituted alkyl group or an aralkyl group is preferable, an optionally substituted alkyl group is more preferable, and an alkyl group is even more preferable.

[0029] As X, -R is preferred because it is easy to abstract the proton at the α-position of the lactone ring. １ are preferred, a hydrocarbon group which may have a substituent is more preferred, an alkyl group or aralkyl group which may have a substituent is even more preferred, and an alkyl group is even more preferred.

[0030] (B) Aldehyde Compound The aldehyde compound in the present invention includes a compound represented by the above formula (2) or paraformaldehyde. ３ represents a hydrogen atom or a hydrocarbon group which may have a substituent. ３ The hydrocarbon group represented by the formula (I) may be saturated or unsaturated, and may be linear or cyclic, but is preferably an alkyl group, an alkenyl group, an aryl group, or an aralkyl group.

[0031] R ３ The alkyl group, alkenyl group, aryl group, and aralkyl group represented by the above-mentioned R １ and R ２ Examples of the alkyl group, alkenyl group, aryl group, and aralkyl group are each represented by the following formula:

[0032] R ３ The number of carbon atoms in the alkyl group represented by R is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 4. ３The number of carbon atoms in the alkenyl group represented by R is preferably 2 to 8, more preferably 2 to 6, and even more preferably 2 to 5. ３ The number of carbon atoms in the aryl group represented by R is preferably 6 to 14, more preferably 6 to 12, and even more preferably 6 to 10. ３ The aralkyl group represented by the formula (I) preferably has 1 to 9 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 7 carbon atoms.

[0033] R ３ Examples of the substituent that the hydrocarbon group represented by the formula (I) may have include a halogen atom, a hydroxy group, an ether group, an ester group, an amide group, a nitrile group, an amino group, an imino group, and a nitro group.

[0034] Among them, R ３ is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.

[0035] Specific examples of the compound represented by the above formula (2) include formaldehyde, acetaldehyde, propionaldehyde, pivalaldehyde, butyraldehyde, pentanal, diphenylacetaldehyde, ethylbutyraldehyde, benzaldehyde, and naphthaldehyde.

[0036] The paraformaldehyde is a compound represented by the following formula (3): HO(CH ２ O) ｎ H (3) (wherein n represents an integer of 8 to 100.)

[0037] Among these, formaldehyde, acetaldehyde, and paraformaldehyde are preferred, and formaldehyde and paraformaldehyde are more preferred. The aldehyde compounds may be used alone or in combination of two or more.

[0038] (C) Oxide or hydroxide of metal consisting of element of Group 2 of the periodic table Examples of the element of Group 2 of the periodic table include magnesium, calcium, strontium, barium, and radium. Among them, calcium, magnesium, and strontium are preferred, and calcium is more preferred, in that the basicity of the oxide or hydroxide is appropriate.

[0039] Specific examples of the oxides or hydroxides of metals consisting of Group 2 elements of the periodic table include magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, strontium oxide, strontium hydroxide, barium oxide, and barium hydroxide. Among these, calcium oxide, calcium hydroxide, magnesium oxide, and strontium oxide are preferred in terms of increasing the yield of the methylene lactone compound, calcium oxide and calcium hydroxide are more preferred, and calcium oxide is even more preferred. The oxides or hydroxides of metals consisting of Group 2 elements of the periodic table may be used alone or in combination of two or more.

[0040] In the first production method of the present invention, the γ-butyrolactone compound (hereinafter also referred to as compound (A)) and the aldehyde compound (hereinafter also referred to as compound (B)) are reacted in the presence of the oxide or hydroxide of a metal consisting of an element of Group 2 of the periodic table (hereinafter also referred to as compound (C)).

[0041] The reaction can be carried out by mixing the compound (A), compound (B) and compound (C) in a reaction vessel and heating the mixture.

[0042] In the above reaction, the amount of compound (B) used is not particularly limited, but is preferably 50 to 500 mol, more preferably 75 to 400 mol, and even more preferably 100 to 250 mol relative to 100 mol of compound (A) used.

[0043] The amount of compound (C) used is not particularly limited, but when an inorganic base is used, it is preferable to change the amount depending on the valence of the metal. For example, in the case of an inorganic base containing a metal element of Group 2 of the periodic table, the amount is preferably 25 to 500 mol, more preferably 40 to 400 mol, and even more preferably 50 to 250 mol, relative to 100 mol of compound (A) used.

[0044] The temperature of the reaction solution is not particularly limited, and will change during the reaction because it is an exothermic reaction. However, the temperature is preferably 10 to 120°C, more preferably 30 to 100°C, even more preferably 40 to 80°C, and particularly preferably 50 to 80°C, from the viewpoint of achieving a sufficient reaction rate while suppressing polymerization of the produced monomers.

[0045] The reaction time is not particularly limited and depends on the temperature of the reaction solution, but is preferably 1 to 96 hours, more preferably 1 to 48 hours, and even more preferably 2 to 24 hours, from the viewpoint that the product is not consumed by decomposition or polymerization while achieving full conversion.

[0046] The reaction may be carried out in air or in an inert gas atmosphere such as nitrogen gas, argon gas, helium gas or a mixture thereof, but an inert gas atmosphere is preferred in that polymerization is suppressed.

[0047] In the above reaction, it is preferable to use a solvent, in order to facilitate dispersion and stirring of the reaction suspension. Examples of the solvent include aromatic hydrocarbon solvents such as toluene, xylene, and benzene; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; halogenated hydrocarbon solvents such as chlorobenzene, dichloromethane, chloroform, and 1,2-dichloroethane; nitrile solvents such as acetonitrile, propionitrile, and valeronitrile; ester solvents such as methyl acetate, ethyl acetate, isopropyl acetate, and butyl acetate; amide solvents such as dimethylformamide (DMF), dimethylacetamide, and N-methylpyrrolidone; and ether solvents such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane (DME), 1,4-dioxane, tetrahydrofuran (THF), tetrahydropyran (THP), anisole, diethylene glycol dimethyl ether (diglyme), diethylene glycol ethyl ether (carbitol), and cyclopentyl methyl ether (CPME). Among these, aromatic hydrocarbon solvents, ester solvents, and ether solvents are preferred from the viewpoint of further improving the yield of methylene lactone compounds, with ester solvents and ether solvents being more preferred, ester solvents being particularly preferred, and acetate ester solvents being most preferred. Furthermore, from the viewpoint of facilitating the reaction at a high concentration, it is preferred to include at least one of ketone solvents, nitrile solvents, ester solvents, amide solvents, and ether solvents, more preferred to include at least one of amide solvents, ether solvents, and ester solvents, even more preferred to include at least one of ether solvents and ester solvents, particularly preferred to include an ester solvent, and most preferred to include an acetate ester solvent. The above solvents may be used alone or in combination of two or more.

[0048] In the reaction, the content of the preferred solvent relative to the total solvent (when two or more preferred solvents are used, the total content of these solvents) is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, even more preferably 90 to 100% by mass, still more preferably 95 to 100% by mass, and particularly preferably 98 to 100% by mass, relative to 100% by mass of the solvent.

[0049] When a solvent is used in the reaction, the amount of the solvent used is not particularly limited, but is preferably 30 to 5,000 parts by mass, more preferably 50 to 2,000 parts by mass, and even more preferably 100 to 1,000 parts by mass relative to 100 parts by mass of the compound (A) used.

[0050] In the above reaction, in addition to the above-mentioned components, commonly used additives such as a catalyst, a moisture absorbent, a polymerization inhibitor, etc. The additives may be appropriately selected from known additives as needed.

[0051] The method for producing a methylene lactone compound of the first aspect of the present invention may include, in addition to the reaction step, known steps that are usually carried out in methods for producing methylene lactone compounds, such as a solid-liquid separation step, a concentration step, and a purification step.

[0052] <Second Method for Producing Methylene Lactone Compound> The second method for producing a methylene lactone compound of the present invention is characterized by comprising: a step (1) of reacting a γ-butyrolactone compound represented by the above general formula (1) with a base; and a step (2) of reacting the reaction product obtained in the step (1) with a compound represented by the above formula (2) or an aldehyde compound including paraformaldehyde.

[0053] The reason why the second method for producing a methylene lactone compound can suppress the generation of by-products and produce a methylene lactone compound in high yield is presumably because, in step (1), an enolate of the γ-butyrolactone compound is formed by reacting the γ-butyrolactone compound with a base, and since no active protons derived from the γ-butyrolactone compound are present in the system, the progress of side reactions is suppressed, and the reaction with the aldehyde compound and the subsequent decarboxylation reaction or decarboxylation reaction are more likely to proceed.

[0054] In the production method of the second invention, the γ-butyrolactone compound represented by the above formula (1) and the compound represented by the above formula (2) may be the same as those in the production method of the first invention described above.

[0055] <Step (1)> In step (1), a γ-butyrolactone compound represented by the above formula (1) is reacted with a base. Examples of the γ-butyrolactone compound represented by the above formula (1) include the same γ-butyrolactone compounds as those in the above-mentioned first production method of the present invention.

[0056] The base includes organic bases and inorganic bases, such as pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, and 1,8-diazabicyclo[5,4,0]-7-undecene.

[0057] Examples of the inorganic base include carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium hydrogencarbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, and cesium hydrogencarbonate; hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; and oxides such as calcium oxide, lithium oxide, magnesium oxide, and strontium oxide. Among these, oxides or hydroxides of metals consisting of elements in Group 2 of the periodic table are preferred, oxides of metals consisting of elements in Group 2 of the periodic table are more preferred, calcium oxide, magnesium oxide, and strontium oxide are even more preferred, and calcium oxide is even more preferred.

[0058] Among these, the base is preferably an inorganic base, and more preferably an oxide or hydroxide of a metal consisting of an element of Group 2 of the periodic table, in that it facilitates the reaction with the aldehyde compound and the subsequent decarboxylation or decarboxylation reaction in the subsequent step (2). Only one type of base may be used, or two or more types may be used.

[0059] The reaction of the γ-butyrolactone compound with the base can be carried out by mixing the γ-butyrolactone compound with the base in a reaction vessel and heating the mixture.

[0060] The amount of the base used in the reaction is preferably changed depending on the valence of the metal, for example, when an inorganic base is used as the base. For example, in the case of an inorganic base containing a metal element of Group 2 of the periodic table, the amount is preferably 25 to 500 mol, more preferably 40 to 400 mol, and even more preferably 50 to 250 mol, relative to 100 mol of the γ-butyrolactone compound.

[0061] The reaction temperature will change during the reaction because it is an exothermic reaction, but in order to achieve an appropriate reaction rate, it is preferably 10 to 120°C, more preferably 15 to 100°C, and even more preferably 20 to 80°C. Furthermore, it is even more preferably 30 to 80°C, and particularly preferably 40 to 80°C. From the viewpoint of easily suppressing an increase in viscosity of the reaction solution as the reaction proceeds, the reaction temperature is preferably 30°C or higher, and more preferably 40°C or higher.

[0062] The reaction time is not particularly limited and depends on the reaction temperature, but is preferably 1 to 96 hours, more preferably 1 to 48 hours, and even more preferably 1 to 24 hours.

[0063] The reaction may be carried out in the air or in an inert gas atmosphere such as nitrogen gas, argon gas, or helium gas. However, an inert gas atmosphere is preferred in order to avoid the influence of water and carbon dioxide in the air.

[0064] The reaction is preferably carried out in the presence of a solvent. Examples of the solvent include the same solvents as those used in the production method of the first aspect of the present invention. The solvent may be used alone or in combination of two or more.

[0065] The amount of the solvent used is not particularly limited, but from the viewpoint of facilitating dispersion and stirring of the reaction suspension, it is preferably 30 to 5,000 parts by mass, more preferably 50 to 2,000 parts by mass, and even more preferably 100 to 1,000 parts by mass relative to 100 parts by mass of the γ-butyrolactone compound.

[0066] Among these, the solvent is preferably an ester solvent, and more preferably an acetate solvent, in terms of improving the yield of the methylene lactone compound. The enolate of the γ-butyrolactone compound has high dispersibility in ester solvents. Therefore, when an ester solvent is used as the reaction solvent in step (1), a larger amount of the enolate of the γ-butyrolactone compound can be contained in the solvent, thereby enabling a larger amount of the target product to be obtained with the same amount of reaction solvent. Furthermore, from the viewpoint of facilitating the reaction at a high concentration, the solvent preferably includes one or more of a ketone solvent, a nitrile solvent, an ester solvent, an amide solvent, or an ether solvent, more preferably one or more of a nitrile solvent, an amide solvent, an ether solvent, or an ester solvent, even more preferably one or more of an ether solvent or an ester solvent, even more preferably an ester solvent, and particularly preferably an acetate solvent.

[0067] The amount of the ester solvent used is preferably 10 to 1,000 parts by mass, more preferably 20 to 750 parts by mass, and even more preferably 30 to 500 parts by mass, relative to 100 parts by mass of the γ-butyrolactone compound, in terms of improving the yield of the methylene lactone compound. From the viewpoint of facilitating the reaction at a high concentration, the content of the preferred solvent (when two or more preferred solvents are used, the total content of these solvents) relative to 100% by mass of the solvent used in the reaction is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, even more preferably 90 to 100% by mass, still more preferably 95 to 100% by mass, and particularly preferably 98 to 100% by mass.

[0068] <Step (2)> In step (2), the reaction product obtained in step (1) is reacted with an aldehyde compound including the compound represented by formula (2) or paraformaldehyde. The reaction in step (2) can be carried out by mixing the reaction product obtained in step (1) with the aldehyde compound and heating the mixture.

[0069] Examples of the compound represented by the formula (2) or the aldehyde compound containing paraformaldehyde include the same aldehyde compounds as those in the above-mentioned first production method of the present invention.

[0070] The amount of the aldehyde compound used in step (2) is preferably 25 to 500 mol, more preferably 40 to 400 mol, and even more preferably 50 to 250 mol, relative to 100 mol of the compound (A) used in step (1).

[0071] The temperature of the reaction liquid in the reaction of step (2) is an exothermic reaction and therefore changes during the reaction. However, the temperature is preferably 10 to 120°C, more preferably 30 to 100°C, even more preferably 40 to 80°C, and particularly preferably 50 to 80°C, from the viewpoint of achieving a sufficient reaction rate while suppressing polymerization of the produced monomer.

[0072] The reaction time in step (2) is not particularly limited and depends on the reaction temperature. However, from the viewpoint of achieving full conversion while preventing the product from being consumed by decomposition or polymerization, the reaction time is preferably 1 to 96 hours, more preferably 1 to 48 hours, and even more preferably 2 to 24 hours.

[0073] The reaction in step (2) may be carried out in an air atmosphere or in an inert gas atmosphere such as nitrogen gas, argon gas, or helium gas. However, an inert gas atmosphere is preferred in that polymerization can be effectively suppressed.

[0074] The reaction in step (2) is preferably carried out in the presence of a solvent. Examples of the solvent include the same solvents as those used in step (1). The solvent used in step (1) may be used as is, or a new solvent may be added.

[0075] In the reactions of steps (1) and (2), in addition to the above-mentioned components, commonly used additives such as a catalyst, a moisture absorbent, a polymerization inhibitor, etc. The additives may be appropriately selected from known additives as needed.

[0076] The method for producing a methylene lactone compound of the second aspect of the present invention may include, in addition to the reaction step described above, known steps that are usually carried out in methods for producing methylene lactone compounds, such as a solid-liquid separation step, a concentration step, and a purification step.

[0077] The method for producing a methylene lactone compound of the present invention can efficiently produce a methylene lactone compound with a small amount of by-products and a high yield.

[0078] In the production method of the present invention, the reaction yield of the by-product is preferably 50% or less, more preferably 30% or less, and even more preferably 25% or less. The reaction yield of the by-product can be determined by the method described in the examples below.

[0079] In the production method of the present invention, the reaction yield of the methylene lactone compound is preferably 21% or more, more preferably 30% or more, and even more preferably 40% or more. The reaction yield can be determined by the method described in the examples below.

[0080] 2. Methylene lactone compound-containing composition The present invention also provides a methylene lactone compound-containing composition comprising a compound represented by the following formula (2):

[0081]

[0082] (In the formula, R ３ represents a hydrogen atom or a hydrocarbon group which may have a substituent, and the compound includes a methylene lactone compound represented by the following formulas (3) to (5):

[0083]

[0084] (In the formula, R ３ represents a hydrogen atom or a hydrocarbon group which may have a substituent.) is 0.1 to 10 mass% relative to 100 mass% of the methylene lactone compound.

[0085] The methylene lactone compound represented by formula (1) has a high refractive index and is therefore suitable for use as an optical material. For example, lenses and the like can be produced from polymers containing the methylene lactone compound as a raw material. When used as a material for lenses and the like, polymers containing the methylene lactone compound as a raw material are required to have excellent moldability. By preparing a composition containing the methylene lactone compound represented by formula (1) and the compounds represented by formulas (3) to (5) in a total content of 0.1 to 10 mass% relative to 100 mass% of the methylene lactone compound, the glass transition temperature of the polymer containing the methylene lactone compound as a raw material can be lowered, making it more suitable for optical materials and the like. The total content of the compounds represented by formulas (3) to (5) is preferably 0.5 to 5 mass% relative to 100 mass% of the methylene lactone compound. More preferably, it is 1.0 to 2.0 mass%.

[0086] Furthermore, the methylene lactone compound-containing composition may contain a compound represented by the following formula (6) in a proportion of 0.1 to 20% by mass relative to 100% by mass of the methylene lactone compound represented by formula (1). The compound represented by formula (6) is a compound that may be produced as a by-product when a methylene lactone compound is produced using the method for producing a methylene lactone compound of the present invention. The content of the compound represented by formula (6) is preferably 1 to 5% by mass relative to 100% by mass of the methylene lactone compound represented by formula (1). It is more preferably 2 to 3% by mass.

[0087]

[0088] The methylene lactone compound-containing composition may further contain compounds represented by the following formulas (7) to (13), but the total content of these compounds is preferably 5% by mass or less, more preferably 1% by mass or less, and even more preferably 0.1% by mass or less, based on 100% by mass of the methylene lactone compound represented by formula (1).

[0089]

[0090] The content ratio of the compounds represented by the above formulas (2) to (13) in the methylene lactone compound-containing composition of the present invention can be measured by gas chromatography, liquid chromatography, or nuclear magnetic resonance (NMR) measurement under the conditions described in the Examples.

[0091] Although there are no particular limitations on the method for producing the methylene lactone compound-containing composition of the present invention, it is preferable to use the method for producing a methylene lactone compound of the present invention. The method for producing a methylene lactone compound of the present invention is a production method that produces fewer by-products than the conventional production methods described above. By using the method for producing a methylene lactone compound of the present invention, it is possible to obtain a composition in which the total content of compounds represented by formulas (3) to (5) is 0.1 to 10 mass% based on 100 mass% of the methylene lactone compound. When using the method for producing a methylene lactone compound of the present invention, it is preferable to perform a purification step after the reaction step. Although there are no particular limitations on the method for performing the purification step, distillation is preferred. More preferably, precision distillation is used. Precision distillation can be used to reduce the total content of compounds represented by formulas (7) to (13) to 5 mass% or less based on 100 mass% of the methylene lactone compound represented by formula (1).

[0092] As described above, polymers obtained by polymerizing a monomer component containing the methylene lactone compound-containing composition of the present invention can be suitably used as optical materials, etc., such as for use as lens materials.

[0093] When the methylene lactone compound-containing composition of the present invention is used as a raw material for a polymer, the content of the methylene lactone compound-containing composition in the monomer component is not particularly limited, but is preferably 5 to 50 mass %, more preferably 10 to 40 mass %, relative to 100 mass % of the monomer component.

[0094] When the monomer component serving as the raw material for the polymer contains a monomer other than the methylene lactone compound-containing composition of the present invention, examples of the other monomer include (meth)acrylic acid and salts thereof, and alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, and isopropyl (meth)acrylate, and one or more of these may be used.

[0095] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0096] Comparative Example 1: Paraformaldehyde (FUJIFILM Wako Pure Chemical Industries, Ltd., 20 mmol, 601 mg), potassium carbonate (FUJIFILM Wako Pure Chemical Industries, Ltd., 99.5% purity, 10 mmol, 1.38 g), mesitylene (Tokyo Chemical Industry Co., Ltd., 10 mmol, 1.20 g), and THF (FUJIFILM Wako Pure Chemical Industries, Ltd., 6.4 g) were added to a Schlenk flask and stirred at 500 rpm using a magnetic stirrer. α-acetyl-γ-butyrolactone (Tokyo Chemical Industry Co., Ltd., 10 mmol, 1.28 g) was added to the resulting suspension. The Schlenk flask was heated and stirred in a synthesis reactor (aluminum block, Chemist Plaza Chemi Chemi-300, Shibata Scientific Co., Ltd.) at a jacket temperature of 60°C for 24 hours, yielding a reaction solution in a suspension state. 50 μl of the resulting reaction solution was collected, deuterated chloroform (Fujifilm Wako Pure Chemical Industries, 1 ml) was added, and the mixture was filtered through Celite, and the filtrate was subjected to NMR measurement. The NMR measurement conditions were as follows: １ H-NMR Measurement> Apparatus: Varian VNMRS Frequency: 600 MHz Measurement time (acquisition time): 3.4 seconds Number of accumulations: 16 External reference material: tetramethylsilane

[0097] In the spectrum obtained by the measurement, the area of ​​the triplet peak derived from one of the two protons of the vinyl group of methylene lactone, observed at a chemical shift of 6.26 ppm, was defined as the "target product peak area," and the area of ​​the singlet peak derived from the three protons of mesitylene, observed at a chemical shift of around 6.8 ppm, was defined as the "internal standard peak area." The reaction yield (molar yield) of methylene lactone was calculated using the following formula: Reaction yield (%) of methylene lactone = [(target product peak area) / (internal standard peak area / 3)] x 100

[0098] Similarly, the area of ​​the doublet peak derived from one of the protons on the acetal carbon of the by-product, observed at a chemical shift of 5.28 to 5.29 ppm, was defined as the "by-product peak area," and the reaction yield (molar yield) of the by-product was calculated using the following formula: Reaction yield of by-product (%) = [(by-product peak area) / (internal standard peak area / 3)] × 100

[0099]

[0100] Comparative Example 2 The reaction and NMR measurement were carried out in the same manner as in Comparative Example 1, except that toluene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.9%, 6.4 g) was used instead of THF, and the reaction yields of methylene lactone and by-products were calculated.

[0101] Comparative Example 3 The reaction and NMR measurement were carried out in the same manner as in Comparative Example 2, except that sodium carbonate (manufactured by Nacalai Tesque, Inc., purity 99.0%, 10 mmol, 1.06 g) was used instead of potassium carbonate, and the reaction yields of methylene lactone and by-products were calculated.

[0102] Comparative Example 4 The reaction and NMR measurement were carried out in the same manner as in Comparative Example 2, except that sodium hydrogen carbonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.0%, 20 mmol, 1.68 g) was used instead of potassium carbonate, and the reaction yields of methylene lactone and by-products were calculated.

[0103] Comparative Example 5 Reaction and NMR measurement were carried out in the same manner as in Comparative Example 2, except that sodium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 93%, 20 mmol, 800 mg) was used instead of potassium carbonate, and the reaction yields of methylene lactone and by-products were calculated.

[0104] Comparative Example 6 Reaction and NMR measurement were carried out in the same manner as in Comparative Example 2, except that potassium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 85.0%, 20 mmol, 1.12 g) was used instead of potassium carbonate, and the reaction yields of methylene lactone and by-products were calculated.

[0105] Comparative Example 7 The reaction and NMR measurement were carried out in the same manner as in Comparative Example 2, except that sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd., purity 60%, 20 mmol, 480 mg) was used instead of potassium carbonate, and the reaction yields of methylene lactone and by-products were calculated.

[0106] Comparative Example 8 The reaction and NMR measurement were carried out in the same manner as in Comparative Example 2, except that calcium carbonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.5%, 10 mmol, 1.00 g) was used instead of potassium carbonate, and the reaction yields of methylene lactone and by-products were calculated.

[0107] Example 1 Reaction and NMR measurement were carried out in the same manner as in Comparative Example 2, except that calcium oxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.9%, 10 mmol, 561 mg) was used instead of potassium carbonate, and the reaction yields of methylene lactone and by-products were calculated.

[0108] Example 2 The reaction and NMR measurement were carried out in the same manner as in Example 1, except that Glyme (ethylene glycol dimethyl ether, 6.4 g) was used instead of toluene, and the reaction yields of methylene lactone and by-products were calculated.

[0109] Example 3 The reaction and NMR measurement were carried out in the same manner as in Example 1, except that butyl acetate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.0%, 6.4 g) was used instead of toluene, and the reaction yields of methylene lactone and by-products were calculated.

[0110] Example 4 The reaction and NMR measurement were carried out in the same manner as in Example 2, except that calcium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 96%, 10 mmol, 741 mg) was used instead of calcium oxide, and the reaction yields of methylene lactone and by-products were calculated.

[0111] Example 5 The reaction and NMR measurement were carried out in the same manner as in Example 2, except that strontium oxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.5%, 10 mmol, 1036 mg) was used instead of calcium oxide, and the reaction yields of methylene lactone and by-products were calculated.

[0112] Example 6 Calcium oxide (Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.9%, 10 mmol, 561 mg), mesitylene (Tokyo Chemical Industry Co., Ltd., 10 mmol, 1.20 g), and toluene (Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.9%, 6.4 g) were added to a Schlenk flask and stirred at 500 rpm using a magnetic stirrer in a synthesis reactor (aluminum block). α-acetyl-γ-butyrolactone (Tokyo Chemical Industry Co., Ltd., 10 mmol, 1.28 g) was added thereto, and the mixture was heated and stirred at a jacket temperature of 60°C for 2 hours. Paraformaldehyde (Fujifilm Wako Pure Chemical Industries, Ltd., 20 mmol, 601 mg) was added to the resulting suspension. The Schlenk flask was then heated and stirred in the synthesis reactor (aluminum block) at a jacket temperature of 60°C. After 24 hours, 50 μl of the reaction solution in a suspended state was sampled, deuterated chloroform (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 1 ml) was added, and the mixture was filtered through Celite using a Kiriyama funnel. The filtrate was subjected to NMR measurement, and the reaction yields of methylene lactone and by-products were calculated in the same manner as in Comparative Example 1.

[0113] Example 7: The reaction and NMR measurement were carried out in the same manner as in Example 6, except that potassium carbonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.5%, 10 mmol, 1.38 g) was used instead of calcium oxide and THF (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 6.4 g) was used instead of toluene, and the reaction yields of methylene lactone and by-products were calculated. Example 8: Magnesium oxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.9%, 30 mmol, 1.21 g), mesitylene (manufactured by Tokyo Chemical Industry Co., Ltd., 10 mmol, 1.20 g), and toluene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.9%, 6.4 g) were added to a Schlenk flask and stirred at 500 rpm with a magnetic stirrer in a synthesis reaction apparatus (aluminum block). To this was added α-acetyl-γ-butyrolactone (Tokyo Chemical Industry Co., Ltd., 10 mmol, 1.28 g), and the mixture was heated and stirred at a jacket temperature of 100°C for 4 hours. To the resulting suspension was added paraformaldehyde (Fujifilm Wako Pure Chemical Industries, Ltd., 20 mmol, 601 mg). The Schlenk flask was then placed in a synthesis reactor (aluminum block) and heated and stirred at a jacket temperature of 60°C. After 24 hours, 50 μl of the reaction solution in the suspension state was sampled, and deuterated chloroform (Fujifilm Wako Pure Chemical Industries, Ltd., 1 ml) was added. The mixture was filtered through Celite using a Kiriyama funnel. The filtrate was subjected to NMR analysis, and the reaction yields of methylene lactone and by-products were calculated in the same manner as in Comparative Example 1.

[0114] The results of Comparative Examples 1 to 8 and Examples 1 to 8 are summarized in Table 1 below.

[0115]

[0116] Comparisons of Examples 1 to 5 with Comparative Examples 1 to 8 and comparisons of Example 7 with Example 8 reveal that when α-acetyl-γ-butyrolactone, which is a γ-butyrolactone-based compound, paraformaldehyde, which is an aldehyde compound, and a base are simultaneously added and reacted, and when calcium oxide, calcium hydroxide, strontium oxide, or magnesium oxide, which are oxides or hydroxides of metals in Group 2 of the periodic table, are used, methylene lactone can be obtained in a higher yield than when other bases are used.

[0117] Furthermore, when Example 1 and Example 6, and Comparative Example 1 and Example 7 are compared, it was found that when α-acetyl-γ-butyrolactone is first reacted with a base to form an enolate, and then paraformaldehyde is added and reacted, the production of by-products can be suppressed and methylene lactone can be obtained in a high yield, regardless of which base is used, compared to when paraformaldehyde is added from the beginning.

[0118] In the above example, the solvent was used in an amount five times the weight of α-acetyl-γ-butyrolactone. Considering production costs, a higher yield per batch is desirable. Therefore, next, we investigated whether it would be possible to increase the reaction concentration under reaction conditions in which calcium oxide, which gives a high yield, is used as a base, and an enolate is first formed between α-acetyl-γ-butyrolactone and a base, and then paraformaldehyde is added to the enolate.

[0119] Example 9: Calcium oxide (Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.9%, 15 mmol, 842 mg), mesitylene (Tokyo Chemical Industry Co., Ltd., 10 mmol, 1.20 g), and ethyl acetate (Fujifilm Wako Pure Chemical Industries, Ltd., 4.2 g) were added to a Schlenk flask and stirred at 500 rpm using a magnetic stirrer in a synthesis reactor (aluminum block). α-acetyl-γ-butyrolactone (Tokyo Chemical Industry Co., Ltd., 10 mmol, 1.28 g) was added thereto, and the mixture was heated and stirred at a jacket temperature of 60°C for 2 hours. Paraformaldehyde (Fujifilm Wako Pure Chemical Industries, Ltd., 20 mmol, 601 mg) was added to the resulting suspension. The Schlenk flask was then heated and stirred in the synthesis reactor (aluminum block) at a jacket temperature of 60°C for 24 hours, yielding a suspended reaction solution. The reaction scheme is shown below. 50 μl of the resulting reaction solution was sampled, deuterated chloroform (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 1 ml) was added, and the mixture was filtered through Celite using a Kiriyama funnel. The filtrate was subjected to NMR measurement, and the reaction yields of methylene lactone and by-products were calculated in the same manner as in Comparative Example 1.

[0120]

[0121] Example 10 The reaction and NMR measurement were carried out in the same manner as in Example 9, except that butyl acetate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 2.6 g) was used instead of ethyl acetate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 4.2 g), and the reaction yields of methylene lactone and by-products were calculated.

[0122] The results of Examples 9-10 are shown in Table 2 below.

[0123]

[0124] The results of Example 9 revealed that when ethyl acetate was used as a solvent, the yield was not impaired and the reaction proceeded without any problems even when an attempt was made to increase the concentration by reducing the amount of solvent to 3.3 times the amount of α-acetyl-γ-butyrolactone. Furthermore, the results of Example 10 revealed that an even higher concentration could be achieved by using butyl acetate as a solvent.

[0125] (Examples 11-12) 1. Analysis of Product The solution obtained by the reaction in Example 3 was filtered under reduced pressure using a Kiriyama funnel, and the filtrate was concentrated at 50°C and 30 Torr using an evaporator (Tokyo Rikakikai Co., Ltd.) to obtain a concentrated solution (1). 150 mg of the obtained concentrated solution (1) was sampled, and diethylene glycol dimethyl ether (Tokyo Chemical Industry Co., Ltd., 100 mg) was added as an internal standard and acetonitrile (Fujifilm Wako Pure Chemical Industries, Ltd., 1.5 g) was added as a dilution solvent to prepare a solution, which was then measured by gas chromatography (GC). The GC measurement conditions were as follows. Note that hereinafter, diethylene glycol dimethyl ether will be abbreviated as DGDE. <Gas chromatography (GC) analysis> Apparatus name: GC-2010 plus manufactured by Shimadzu Corporation Column: InertCap 35 manufactured by GL Sciences Inc. Vaporization chamber temperature: 280.0°C Carrier gas: He Detector: Flame ionization detector (FID) Column temperature: 40.0°C Temperature program: After holding the initial temperature at 40.0°C for 5 minutes, the temperature was increased to 280°C at 10°C / min and held at 280°C for 11 minutes (total 40 minutes)

[0126] Liquid chromatography (LC) measurements were also performed under the instrument environment described below. Measurements were performed using the following two methods, Methods 1 and 2. <Liquid chromatography (LC) measurement conditions> Instrument name: LC-20A manufactured by Shimadzu Corporation; Column: TSKgel ODS-100Z manufactured by Tosoh Corporation; Particle size: 5 μm; Column length: 25 cm; Flow rate: 1.0000 mL / min; Oven temperature: 40°C; Detector: PDA; Mobile phase A: 0.1 wt% aqueous phosphoric acid containing 10 vol% methanol; Mobile phase B: acetonitrile. <LC measurement method 1> 150 mg of the resulting concentrated liquid (1) was collected, and heptylbenzene (Tokyo Chemical Industry Co., Ltd., 20 mg) and acetonitrile (Fujifilm Wako Pure Chemical Industries, Ltd., 1.5 g) were added as internal standards to prepare a solution, which was then subjected to LC measurement. The ratio of Solution B in the mobile phase was as shown in Table 3. The detection wavelength was 254 nm.

[0127]

[0128] <LC Measurement Method 2> 20 mg of the obtained concentrated solution (1) was collected, and heptylbenzene (Tokyo Chemical Industry Co., Ltd., 20 mg) and acetonitrile (Fujifilm Wako Pure Chemical Industries, Ltd., 2.0 g) were added as internal standards to prepare a solution, which was then subjected to LC measurement. The LC measurement environment was the same as in Measurement Method 1, except that the ratio of Solution B in the mobile phase during measurement was changed as shown in Table 4. The detection wavelength was 211 nm.

[0129]

[0130] In addition, 20 mg of the obtained concentrated solution (1) was collected, and anisole (Tokyo Chemical Industry Co., Ltd., 20 mg) and deuterated chloroform (Fujifilm Wako Pure Chemical Industries, Ltd., 1.5 g) were added as internal standards to prepare a solution. １ H-NMR measurement was carried out. １ The H-NMR measurement conditions are as follows: １ H-NMR Measurement> Apparatus: Varian VNMRS Frequency: 600 MHz Measurement time (acquisition time): 3.4 seconds Number of accumulations: 16 External reference material: tetramethylsilane

[0131] The obtained concentrate (1) was analyzed by GC, LC, １As a result of H-NMR analysis, it was found that the following components were contained in the following proportions.

[0132]

[0133] The retention times of the components detected and quantified by GC measurement are shown in Table 5.

[0134]

[0135] The composition ratios of methylene lactone and by-products 6 to 8 were calculated from the ratio of the peaks attributable to each component detected by GC measurement to the DGDE area using the following formula: Composition of each component (wt%) = (amount of concentrated solution used (mg)) / [(peak area of ​​each component) / (internal standard peak area)] / X × (amount of DGDE used (mg)) × 100. The values ​​in Table 6 were used as coefficients X for each component. This coefficient X was determined based on the calibration curves created for each component. The composition ratios of by-products 2, 3, and 5 were calculated using the following formula: Composition of each component (wt%) = [(peak area of ​​each component) / (methylene lactone area)] × (methylene lactone concentration (wt%))

[0136]

[0137] For By-Product 1 and By-Product 4, the composition was calculated from the ratio of the peak area assigned to each component detected by LC measurement to the heptylbenzene area using the following formula: Composition of each component (wt %) = (amount of concentrated solution used (mg)) / [(peak area of ​​each component) / (peak area of ​​internal standard)] / Y × (amount of DGDE used (mg)) × 100. The values ​​in Table 7 were used as coefficient Y for each component. Note that this coefficient Y was determined based on the calibration curves prepared for each component.

[0138]

[0139] Regarding the combined concentration of by-products 9 to 11, １In the spectrum obtained by H-NMR measurement, the area of ​​the double doublet peak attributed to the two protons on the acetal carbon observed at a chemical shift of 5.30 to 5.20 ppm was defined as the "combined peak area of ​​by-products 9 to 11," and the area of ​​the multiplet peak attributed to the three protons of anisole observed at a chemical shift of around 7.08 to 6.74 ppm was defined as the "internal standard peak area," and the combined composition of by-products 9 to 11 (wt %) was calculated using the following formula: Combined composition of by-products 9 to 11 (wt %) = (amount of concentrated solution used (mg)) / [(combined peak area of ​​by-products 9 to 11 / 2) / (internal standard peak area / 3) × (amount of anisole used (mg)) / (molecular weight of anisole) × (average molecular weight of by-products 9 to 11)] × 100

[0140] 2. Purification and Analysis of Product (A-1) Distillation Purification: Simple Distillation The obtained concentrated liquid (1) was subjected to simple distillation at 15 Torr and 130°C using a glass distillation apparatus equipped with an empty column, thereby obtaining a composition (1) of Example 11 containing methylene lactone as a main component and containing each component at the following concentrations:

[0141] (A-2) Analysis after distillation purification (simple distillation) 150 mg of composition (1) obtained by the simple distillation was sampled, and 100 mg of DGDE (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as an internal standard, and 1.5 g of acetonitrile (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added as a dilution solvent to prepare a solution, which was then subjected to GC measurement. Furthermore, LC measurement was performed on the obtained composition (1) based on the above LC measurement methods 1 and 2. Based on the results of GC and LC analysis of composition (1) obtained by simple distillation, and on the formula used to calculate the composition ratio of each component in the concentrated solution (1), it was found that each component was contained in the following proportions.

[0142]

[0143] (B-1) Distillation purification: Precision distillation When the distillation of the obtained concentrated liquid (1) was carried out under precision distillation conditions of 20 Torr and 130°C using a glass distillation apparatus equipped with a Sulzer packing as a distillation column packing, a composition (2) of Example 12 containing methylene lactone as a main component and containing each component in the following concentrations was obtained.

[0144] (B-2) Analysis after distillation purification (precise distillation) 150 mg of the obtained composition (2) was collected, and diethylene glycol dimethyl ether (Tokyo Chemical Industry Co., Ltd., 100 mg) and acetonitrile (Fujifilm Wako Pure Chemical Industries, Ltd., 1.5 g) were added as internal standards to prepare a solution, which was then subjected to GC measurement. The obtained composition (2) was also subjected to LC measurement based on the above LC measurement methods 1 and 2. Based on the results of GC and LC analysis of the composition (2) obtained by precision distillation and the formula used to calculate the composition ratio of each component in the concentrated solution (1), it was found that each component was contained in the proportion shown in the figure below.

[0145]

[0146] Example 13 One part by mass of by-product 1 was added to 100 parts by mass of composition (1) obtained in Example 11, and the mixture was stirred to prepare composition (3).

[0147] Example 14 Two parts by mass of by-product 1 were added to 100 parts by mass of composition (1) obtained in Example 11, and the mixture was stirred to prepare composition (4).

[0148] Example 15 3 parts by mass of by-product 1 was added to 100 parts by mass of composition (1) obtained in Example 11, and the mixture was stirred to prepare composition (5).

[0149] Compositions (3) to (5) obtained in Examples 13 to 15 were analyzed in the same manner as in Example 11. The content ratios of methylene lactone and by-products 1 to 3 in compositions (1), (3) to (5) obtained in Examples 11 and 13 to 15 are shown in Table 8.

[0150] Polymerization was carried out using the compositions (1) to (5) obtained in Examples 11 to 15, respectively, by the following method to prepare copolymer powder samples. <Preparation Method of Copolymer Powder Sample> <<Preparation of Polymer Powder Sample Using Composition (1)>> A reactor equipped with a stirrer, temperature sensor, condenser, and nitrogen inlet tube was prepared. 75 parts by mass of deionized water containing 0.25 parts by mass of polyoxyethylene distyrylphenyl ether ammonium sulfate (Hitenol (registered trademark) NF-08, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was charged into a separate vessel. A previously prepared mixture of 37.5 parts by mass of methyl methacrylate (MMA, manufactured by Sumitomo Chemical Co., Ltd.), 12.5 parts by mass of Composition (1) of Example 11, 0.5 parts by mass of dilauroyl peroxide (Perloyl (registered trademark) L (LPO), manufactured by NOF Corporation), and 0.05 parts by mass of n-dodecyl mercaptan (n-DM, manufactured by NOF Corporation) was then added. The mixture in the container was then stirred at 3000 rpm using a disperser (Primix Corporation; Homomixer MARK II model 2.5). 125 parts by mass of deionized water was added to the mixture and then transferred to a reactor. In the reactor, the reaction solution was heated to 65°C while continuing to stir and supply nitrogen gas. The point at which the internal temperature reached 65°C was considered to be the start of polymerization. After the liquid temperature reached the peak temperature due to self-heating, the reaction solution was heated to 75°C and stirred. Two hours after the start of polymerization, the reaction solution was further heated to 90°C and stirred for 4 hours. The polymerization reaction was thus completed. Thereafter, the reaction solution was cooled, and the resulting copolymer 1 was filtered and further subjected to a drying process at 90°C for 10 hours using a hot air dryer, followed by a heat treatment process at 150°C for 1 hour, thereby obtaining a copolymer powder sample A containing copolymer 1.

[0151] <<Preparation of polymer samples using compositions (3) to (5)>> Copolymer powder samples B to D were obtained in the same manner as in the preparation of the polymer powder sample using composition (1), except that the compositions shown below were used in the amounts (parts by mass) shown below instead of 12.5 parts by mass of composition (1) in the preparation of the polymer powder sample using composition (1). Copolymer powder sample B: 12.5 parts by mass of composition (3) used Copolymer powder sample C: 12.5 parts by mass of composition (4) used Copolymer powder sample D: 12.5 parts by mass of composition (5) used

[0152] The weight average molecular weight (Mw), number average molecular weight (Mn), and glass transition temperature (Tg) of the obtained copolymer powder samples A to D were measured. The results are shown in Table 8. The measurement methods are as follows. <Weight average molecular weight (Mw) and number average molecular weight (Mn) of copolymer> The weight average molecular weight (Mw) and number average molecular weight (Mn) of the copolymer were measured using gel permeation chromatography (GPC) in terms of polystyrene. The measurement device and measurement conditions are as follows.

[0047] Apparatus name: GPC system HLC-8220, manufactured by Tosoh Corporation Measurement side column configuration: Guard column: TSKgel guard column SuperHZ-L, manufactured by Tosoh Corporation Separation column: TSKgel SuperHZM-M, two columns connected in series, manufactured by Tosoh Corporation Reference side column configuration: Reference column: TSKgel SuperH-RC, manufactured by Tosoh Corporation Developing solvent: chloroform (special grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Developing solvent flow rate: 0.6 mL / min Standard sample: TSK standard polystyrene (PS-oligomer kit, manufactured by Tosoh Corporation) Column temperature: 40°C <Glass transition temperature (Tg) of copolymer> The glass transition temperature of the copolymer was measured in accordance with the provisions of JIS K 7121. Specifically, a differential scanning calorimeter (Rigaku Thermo plus EVO DSC-8230) was used to measure the starting point method from a DSC curve obtained by heating approximately 10 mg of a sample from room temperature to 200°C (heating rate: 20°C / min) under a nitrogen gas atmosphere. α-Alumina was used as a reference.

[0153]

[0154] As shown in Table 8, the Tg value decreased in accordance with the content of by-products 1 to 3. From this result, it was confirmed that the glass transition temperature of a polymer made from methylene lactone can be lowered by including certain by-products in methylene lactone.

Claims

1. The following formula (1): (Wherein, X is -R １ Or -OR ２ R is a group represented by the formula: １ and R ２ R are the same or different and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. ３ CHO (2) (wherein, R ３ represents a hydrogen atom or a hydrocarbon group which may have a substituent.) or an aldehyde compound containing paraformaldehyde, in the presence of an oxide or hydroxide of a metal consisting of an element of Group 2 of the periodic table.

2. The method for producing a methylene lactone compound according to claim 1, wherein the metal consisting of an element of Group 2 of the periodic table is calcium, magnesium or strontium.

3. The following formula (1): (Wherein, X is -R １ Or -OR ２ R is a group represented by the formula: １ and R ２ and R are the same or different and each represents a hydrogen atom or a hydrocarbon group which may have a substituent.) A step (1) of reacting a γ-butyrolactone compound represented by the following formula (2): R ３ CHO (2) (wherein, R ３ represents a hydrogen atom or a hydrocarbon group which may have a substituent.) or an aldehyde compound containing paraformaldehyde.

4. The method for producing a methylene lactone compound according to claim 3, characterized in that the step (1) is carried out in the presence of a solvent, and the solvent contains an ester solvent.

5. The method for producing a methylene lactone compound according to claim 3, characterized in that the base is an oxide or hydroxide of a metal consisting of an element of Group 2 of the periodic table.

6. The following formula (2): (In the formula, R ３ represents a hydrogen atom or a hydrocarbon group which may have a substituent. (In the formula, R ３ represents a hydrogen atom or a hydrocarbon group which may have a substituent.) is 0.1 to 10 mass % relative to 100 mass % of the methylene lactone compound.

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