JP2010163406A - Method for producing (meth)acrylate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a lactone ring-bearing (meth)acrylate useful as e.g. a constitutive monomer for polymeric compounds for photoresists. <P>SOLUTION: The method for producing the (meth)acrylate includes conducting a reaction between 3-hydroxy-γ-butyrolactone or the like and an acid anhydride such as (meth)acrylic acid anhydride in the presence of a catalyst comprising of a compound represented by formula (1): M<SB>a</SB>X<SB>b</SB>(wherein, M is a group 4 to 12 element or the like; X is a halogen atom or SO<SB>4</SB>; and (a) and b are each an integer of ≥1). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention is a (meth) acrylic acid ester useful as a monomer of a high molecular compound for a photoresist used for microfabrication of a semiconductor, more specifically, generated from a lactone skeleton or an acid generator. The present invention relates to a method for industrially and efficiently producing a (meth) acrylic acid ester containing a cyclic skeleton having a function of being eliminated by an acid.

  As a monomer for a chemically amplified resist polymer used in a semiconductor manufacturing process, a (meth) acrylic acid ester containing a lactone ring or a tertiary ester type monomer containing a monocyclic or polycyclic non-aromatic cyclic group ( A (meth) acrylic acid ester (a monomer for forming a structural unit having a group that is eliminated by an acid and becomes alkali-soluble) is widely used.

  As a method for producing such a (meth) acrylic acid ester, a method using (meth) acrylic acid halide as an esterifying agent is known. For example, a method for producing mevalonic lactone (meth) acrylate by reacting mevalonic lactone and (meth) acryloyl halide in the presence of a base at a temperature of −15 ° C. to −5 ° C. is disclosed (patent). Reference 1). However, this method requires equipment for reaction at a low temperature. Moreover, crotonolactone is easily produced as a by-product due to β-elimination of the raw material and the target product, and the target product cannot be obtained in a high yield.

  On the other hand, a method using an acid anhydride as an esterifying agent is also known. For example, a (meth) acrylic ester is obtained by reacting a secondary or tertiary alcohol such as lactone alcohol or adamantyl alcohol with (meth) acrylic anhydride in the presence of a weakly basic compound such as pyridine. A method is disclosed (see Patent Document 2). However, in this method, the reaction rate is slow and a long time is required for the reaction, and more crotonolactone is produced as a by-product, so that the target product cannot be obtained in high yield.

  Also disclosed is a method for producing a methacrylic acid ester by reacting a lactone alcohol with methacrylic anhydride in the presence of an alkali metal inorganic salt and methacrylic acid (see Patent Document 3). However, even in this method, the reaction time is long and the yield of the target product is not sufficient.

  Furthermore, in the presence of a Lewis acid catalyst composed of a triflate such as a transition metal, an alcohol having a lactone skeleton or a tertiary alcohol containing a monocyclic or polycyclic non-aromatic cyclic group is reacted with (meth) acrylic anhydride. And a method for producing a (meth) acrylic acid ester is disclosed (see Patent Document 4). In this method, the target product can be obtained in a high yield, but it is difficult to obtain the catalyst because the catalyst is a special compound, so it cannot be said to be an industrial or general-purpose method. When sulfuric acid is used as a catalyst for this reaction, the yield is low and a large amount of by-products (for example, β-elimination products) is produced, so that it cannot be used as an industrial production method.

  In addition, the monomer of the chemically amplified resist polymer used in the semiconductor manufacturing process does not contain an oligomer or a metal as much as possible in order to obtain a fine pattern with high accuracy or to prevent trouble in the semiconductor manufacturing process. Is required.

Japanese Patent Laid-Open No. 2004-2243 Japanese Patent Laid-Open No. 2002-88018 JP 2003-261556 A JP 2007-91665 A

  Accordingly, an object of the present invention is to provide a (meth) acrylic acid ester having a lactone ring useful as a constituent monomer or the like of a polymer compound for photoresist or a (meth) acrylic acid containing a cyclic skeleton and having acid detachability. It is an object of the present invention to provide a method and a catalyst capable of industrially and efficiently producing an acid ester at a high yield and at a low cost. Another object of the present invention is to efficiently produce a (meth) acrylic acid ester having a lactone ring that contains as little oligomer or metal as possible, or a (meth) acrylic acid ester having a cyclic skeleton and having acid detachability. It is to provide a method and a catalyst.

  As a result of intensive studies to achieve the above object, the present inventors have found that an alcohol having a specific cyclic skeleton and (meth) acrylic anhydride or (meth) acrylic acid and a carboxylic acid other than (meth) acrylic acid. When an anhydride is reacted with a specific readily available compound as a catalyst, the side reaction hardly occurs, the esterification reaction proceeds rapidly, and the target (meth) acrylate ester is obtained in a very high yield. As a result, the present invention was completed.

［式中、Ｒ¹は水素原子、又はハロゲン原子を有していてもよい炭素数１〜６のアルキル基を示す。Ｒ²、Ｒ³、Ｒ⁴は、それぞれ、ハロゲン原子を有していてもよい炭素数１〜６のアルキル基を示す。Ｚ¹、Ｚ²は、それぞれ、環内にエーテル結合、エステル結合を有していてもよい単環又は多環の非芳香族性環式基を示す。Ａは連結基を示す。ｋは０又は１、ｍは０〜３の整数、ｎは０〜３の整数、ｐは１〜３の整数を示す。式（２）中のラクトン環、式（３）中の環状エーテルを構成する環、式（４）中の環Ｚ¹、式（５）中の環Ｚ²に、置換基を有していてもよい］
で表されるアルコール（Ａ）と、（メタ）アクリル酸無水物（Ｂ１）、及び（メタ）アクリル酸と（メタ）アクリル酸以外のカルボン酸との無水物（Ｂ２）から選ばれる少なくとも１種の酸無水物（Ｂ）とを反応させて、対応する（メタ）アクリル酸エステルを得ることを特徴とする（メタ）アクリル酸エステルの製造法を提供する。 That is, the present invention provides the following formula (1):
M _a X _b (1)
(In the formula, M represents an element selected from Group 4 to Group 12 elements of the periodic table, aluminum, gallium, indium, thallium, silicon, germanium, tin, lead, antimony and bismuth, and X represents a halogen atom or SO. ₄ and a and b each represent an integer of 1 or more)
In the presence of a catalyst composed of a compound represented by formula (2), (3), (4) or (5)

[Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R ² , R ³ , and R ⁴ each represent an alkyl group having 1 to 6 carbon atoms that may have a halogen atom. Z ¹ and Z ² each represents a monocyclic or polycyclic non-aromatic cyclic group which may have an ether bond or an ester bond in the ring. A represents a linking group. k is 0 or 1, m is an integer of 0 to 3, n is an integer of 0 to 3, and p is an integer of 1 to 3. The lactone ring in the formula (2), the ring constituting the cyclic ether in the formula (3), the ring Z ^{1 in} the formula (4), and the ring Z ² in the formula (5) have a substituent. It is good]
At least one selected from alcohol (A), (meth) acrylic anhydride (B1), and anhydride (B2) of (meth) acrylic acid and a carboxylic acid other than (meth) acrylic acid A method for producing a (meth) acrylic acid ester is provided, which comprises reacting the acid anhydride (B) with a corresponding (meth) acrylic acid ester.

  In this production method, the reaction between the alcohol (A) and the acid anhydride (B) is carried out in the absence of a solvent or in an organic solvent of 100 times by weight (preferably 2 times by weight or less) with respect to the alcohol (A). May be.

  The usage-amount of the catalyst comprised with the compound represented by Formula (1) is 0.00001-0.3 mol with respect to 1 mol of alcohol (A).

  In this production method, it is preferable to use a compound in which X is a chlorine atom in formula (1) as a catalyst.

［式中、Ｒ¹は水素原子、又はハロゲン原子を有していてもよい炭素数１〜６のアルキル基を示す。Ｒ²、Ｒ³、Ｒ⁴は、それぞれ、ハロゲン原子を有していてもよい炭素数１〜６のアルキル基を示す。Ｚ¹、Ｚ²は、それぞれ、環内にエーテル結合、エステル結合を有していてもよい単環又は多環の非芳香族性環式基を示す。Ａは連結基を示す。ｋは０又は１、ｍは０〜３の整数、ｎは０〜３の整数、ｐは１〜３の整数を示す。式（２）中のラクトン環、式（３）中の環状エーテルを構成する環、式（４）中の環Ｚ¹、式（５）中の環Ｚ²は、置換基を有していてもよい］
で表されるアルコール（Ａ）と、（メタ）アクリル酸無水物（Ｂ１）、及び（メタ）アクリル酸と（メタ）アクリル酸以外のカルボン酸との無水物（Ｂ２）から選ばれる少なくとも１種の酸無水物（Ｂ）とから、対応する（メタ）アクリル酸エステルを得るために用いられる（メタ）アクリル酸エステル製造用触媒を提供する。 The present invention also provides the following formula (1):
M _a X _b (1)
(In the formula, M represents an element selected from Group 4 to Group 12 elements of the periodic table, aluminum, gallium, indium, thallium, silicon, germanium, tin, lead, antimony and bismuth, and X represents a halogen atom or SO. ₄ and a and b each represent an integer of 1 or more)
And is represented by the following formula (2), (3), (4) or (5)

[Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R ² , R ³ and R ⁴ each represent an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. Z ¹ and Z ² each represents a monocyclic or polycyclic non-aromatic cyclic group which may have an ether bond or an ester bond in the ring. A represents a linking group. k is 0 or 1, m is an integer of 0 to 3, n is an integer of 0 to 3, and p is an integer of 1 to 3. The lactone ring in formula (2), the ring constituting the cyclic ether in formula (3), the ring Z ¹ in formula (4), and the ring Z ² in formula (5) have a substituent. It is good]
At least one selected from alcohol (A), (meth) acrylic anhydride (B1), and anhydride (B2) of (meth) acrylic acid and a carboxylic acid other than (meth) acrylic acid A catalyst for producing a (meth) acrylic acid ester used for obtaining a corresponding (meth) acrylic acid ester from the acid anhydride (B) is provided.

  According to the present invention, a (meth) acrylic acid ester having a lactone ring useful as a constituent monomer for a photoresist polymer compound or a (meth) acrylic acid ester having a cyclic skeleton and having acid detachability Can be produced industrially and efficiently at a high yield and at a low cost. In addition, (meth) acrylic acid esters having a lactone ring with an extremely small oligomer or metal content, and (meth) acrylic acid esters having a cyclic skeleton and having acid detachability can be produced efficiently.

  In the production method of the present invention, an alcohol (A) represented by the formula (2), (3), (4) or (5) in the presence of a catalyst composed of the compound represented by the formula (1). ), (Meth) acrylic anhydride (B1), and (meth) acrylic acid and anhydrides (B2) of carboxylic acids other than (meth) acrylic acid (B2) To give the corresponding (meth) acrylic acid ester.

[catalyst]
The catalyst in the present invention is composed of the compound represented by the formula (1). In formula (1), M represents an element selected from Group 4 to Group 12 elements of the periodic table, aluminum, gallium, indium, thallium, silicon, germanium, tin, lead, antimony and bismuth, and X represents a halogen atom. Or, SO ₄ is indicated. a and b each represent an integer of 1 or more.

  Examples of Group 4 elements in the periodic table include titanium and zirconium, Group 5 elements include vanadium, niobium, and tantalum. Group 6 elements include chromium, molybdenum, tungsten, and the like. Examples of the group element include manganese, examples of the group 8 element include iron, ruthenium, and osmium. Examples of the group 9 element include cobalt, rhodium, and iridium. Examples of the group 10 element include nickel, Examples of the group 11 element include copper, silver, and gold. Examples of the group 12 element include zinc and cadmium.

  As M, among the above, from the viewpoint of catalytic activity, from Group 4 element, Group 8 element, Group 12 element, aluminum, gallium, indium, thallium, silicon, germanium, tin, lead, antimony, and bismuth. The element selected is preferable, the element selected from titanium, zirconium, hafnium, iron, and zinc is more preferable, and zirconium and iron are particularly preferable. The valence of M is, for example, 2 to 4, and is preferably 3 or 4 from the viewpoint of catalytic activity.

Examples of the halogen atom in X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a chlorine atom and a bromine atom are more preferable. X is particularly preferably a chlorine atom or SO ₄ from the viewpoint of availability of the compound.

Typical examples of the compound represented by the formula (1) include FeCl ₃ , Fe ₂ (SO ₄ ) ₃ , ZrCl ₄ , Zr (SO ₄ ) ₂ , ZnCl ₂ , ZnSO _{4 and the} like. The compound (catalyst) represented by the formula (1) can be used alone or in combination of two or more.

  In the production method of the present invention, the amount of the compound (catalyst) represented by the formula (1) used is the alcohol (A) 1 represented by the formula (2), (3), (4) or (5). Although it is 0.00001-0.3 mol normally with respect to mol, from the point of operativity and efficiency of the metal removal at the time of reaction and refinement | purification, Preferably it is 0.001-0.2 mol, More preferably, it is 0. 0.005 to 0.03 mol. The amount of the compound (catalyst) represented by the formula (1) when no solvent is used is the alcohol (A) represented by the formula (2), (3), (4) or (5). It is 0.00001-0.3 mol normally with respect to 1 mol, Preferably it is 0.001-0.2 mol, More preferably, it is 0.002-0.03 mol. When the amount of solvent used in the reaction is small, the amount of catalyst can be small. When the amount of catalyst used can be reduced, the amount of metal remaining in the system is inevitably reduced, and the number of washings required to reduce the amount of metal as a post-treatment can be reduced, and as a result It also leads to an improvement in the recovery rate of the target compound.

[Alcohol (A)]
The alcohol (A) used in the production method of the present invention is a compound represented by the formula (2), (3), (4) or (5). In the formula, R ¹ represents a hydrogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R ² , R ³ , and R ⁴ each represent an alkyl group having 1 to 6 carbon atoms that may have a halogen atom. Z ¹ and Z ² each represents a monocyclic or polycyclic non-aromatic cyclic group which may have an ether bond or an ester bond in the ring. A represents a linking group. k is 0 or 1, m is an integer of 0 to 3, n is an integer of 0 to 3, and p is an integer of 1 to 3. The lactone ring in formula (2), the ring constituting the cyclic ether in formula (3), the ring Z ¹ in formula (4), and the ring Z ² in formula (5) have a substituent. Also good.

Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in R ¹ , R ² , R ³ and R ⁴ include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, Examples thereof include C1-C6 alkyl groups such as pentyl and hexyl groups, and C1-C6 fluoroalkyl groups in which one or more hydrogen atoms of these alkyl groups are replaced with fluorine atoms. The 1-position carbon atom of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom preferably has at least one hydrogen atom. As the alkyl group having 1 to 6 carbon atoms which may have a halogen atom, an alkyl group having 1 to 3 carbon atoms which may have a halogen atom is particularly preferable, and a methyl group or an ethyl group is particularly preferable. .

Examples of the monocyclic or polycyclic non-aromatic cyclic group which may have an ether bond or an ester bond in the ring in Z ¹ and Z ² include, for example, a cyclopentyl group, a cyclohexyl group, a norbornyl group, 7- An oxa-bicyclo [2.2.1] heptan-2-yl group, an adamantyl group, a tetrahydrofuranyl group, a tetrahydropyranyl group and the like can be mentioned. The carbon number of the monocyclic or polycyclic non-aromatic cyclic group which may have an ether bond or an ester bond in the ring in Z ¹ and Z ² is, for example, 4 to 20, preferably 4 to 16. is there.

Examples of the linking group represented by A include divalent aliphatic hydrocarbon groups such as methylene, ethylene, propylene, and trimethylene groups; cyclopentane ring, cyclohexane ring, norbornane ring, perhydronaphthalene (decalin) ring, and adamantane ring. , Tricyclo [5.2.1.0 ^2,6 ] decane ring, tetracyclo [4.4.0.1 ^2,5 . ^1,7,10 ] Divalent alicyclic hydrocarbon group corresponding to an alicyclic ring (monocyclic or bridged ring) such as dodecane ring; divalent corresponding to an aromatic hydrocarbon ring such as benzene ring or naphthalene ring And a group in which a plurality of these groups are linked via or without oxygen atom or ester group.

The lactone ring in formula (2), the ring constituting the cyclic ether in formula (3), the ring Z ¹ in formula (4), and the substituent that ring Z ² in formula (5) may have As, for example, a halogen atom such as a fluorine atom or a chlorine atom; an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or an isopropyl group; An alkoxy group having 1 to 4 carbon atoms such as a methoxy group or an ethoxy group; a hydroxyl group which may be protected with a protecting group; a carboxyl group which may be protected with a protecting group; an oxo group; a cyano group, etc. It is done. The number of substituents is about 0-5. In the formula (2), when m is 1, the α-position carbon atom among the carbon atoms constituting the lactone ring has a hydrogen atom because of the reactivity and the usefulness of the target compound. This is preferable.

  Typical examples of the compound represented by the formula (2), (3), (4) or (5) include the following compounds.

[Acid anhydride (B)]
The acid anhydride (B) used in the production method of the present invention includes (meth) acrylic anhydride (B1), and anhydride (B2) of (meth) acrylic acid and a carboxylic acid other than (meth) acrylic acid. Is at least one selected from

  The (meth) acrylic anhydride (B1) is not particularly limited, and commercially available products can be used.

  The anhydride (B2) of (meth) acrylic acid and a carboxylic acid other than (meth) acrylic acid is not particularly limited. For example, an anhydride of (meth) acrylic acid and formic acid, (meth) acrylic acid and Examples include anhydrides with acetic acid, anhydrides of (meth) acrylic acid and propionic acid, and anhydrides of (meth) acrylic acid and isobutyric acid.

  In the production method of the present invention, the amount of the acid anhydride (B) used is, for example, 1 mol of the alcohol (A) represented by the formula (2), (3), (4) or (5). 0.95 to 5 mol, preferably 1 to 3 mol, more preferably 1.05 to 1.5 mol. If the amount of the acid anhydride (B) used is too small, the yield tends to decrease, and if it is too large, the operation (such as neutralization treatment) for removing unreacted products during purification tends to be complicated.

  In the production method of the present invention, the reaction between the alcohol (A) and the acid anhydride (B) is carried out in the absence of a solvent or in an organic solvent. Examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; aliphatic hydrocarbons such as hexane and octane; alicyclic hydrocarbons such as cyclohexane; ethers such as diethyl ether, diisopropyl ether, and tetrahydrofuran. Halogenated hydrocarbons such as dichloromethane; nitriles such as acetonitrile; aprotic polar solvents such as dimethyl sulfoxide and N, N-dimethylformamide; and mixed solvents thereof. Of these, aromatic hydrocarbons, ethers, and nitriles are preferable because they are inert to the reaction, the esterification reaction proceeds smoothly, and distillation is easy. In addition, when alcohol (A) or acid anhydride (B) is a liquid, it is not necessary to use an organic solvent.

  Although there is no restriction | limiting in particular in the usage-amount of an organic solvent, Generally 0-100 weight times (for example, with respect to alcohol (A) represented by said Formula (2), (3), (4) or (5) (for example) 0.5 to 100 times by weight), preferably 0 to 10 times by weight (for example, 0.5 to 10 times by weight), and particularly preferably 0 to 2 times by weight (particularly 0.5 to 2 times by weight). As described above, when the amount of solvent is reduced, the amount of catalyst used can be reduced.

  In the production method of the present invention, a polymerization inhibitor is preferably present in the reaction system in order to suppress polymerization. The polymerization inhibitor is not particularly limited, and examples thereof include hydroquinone monomethyl ether, hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine, 4,4′-butylidene-bis (6-tert-butyl- 3-methylphenol)}, 6-tert-butyl-2,4-xylenol, and other known polymerization inhibitors (phenolic polymerization inhibitors and the like) can be used. These can be used alone or in combination of two or more. The usage-amount of a polymerization inhibitor is about 10 weight ppm-10000 weight ppm with respect to an acid anhydride (B), for example.

  When iron (III) chloride is used as a catalyst, it is not necessary to use a polymerization inhibitor such as a phenol-based polymerization inhibitor as described above, because the effect of inhibiting polymerization is obtained with iron (III) chloride alone. . When a phenolic polymerization inhibitor is used, the (meth) acrylation reaction of the phenolic polymerization inhibitor tends to occur, but when using iron (III) chloride as a catalyst, it is not necessary to use a phenolic polymerization inhibitor. Therefore, such a side reaction can be prevented. In addition, when iron (III) chloride is used as a catalyst, there is an advantage that oligomer by-product can be remarkably suppressed.

  The reaction temperature is, for example, −10 ° C. to 150 ° C., preferably 0 to 120 ° C., more preferably 40 to 100 ° C., and particularly preferably 60 to 85 ° C. If the reaction temperature is too low, the reaction rate is slowed. Conversely, if the reaction temperature is too high, side reactions such as β-elimination tend to occur.

  In order to increase the reaction rate, the reaction may be performed while removing (meth) acrylic acid or other carboxylic acid by-produced in the reaction from the system. (Meth) acrylic acid or the like can be distilled out of the system using azeotropic distillation. The reaction may be carried out by any system such as batch system, semi-batch system, and continuous system.

  After completion of the reaction, after adding water as necessary, for example, filtration, concentration, extraction, washing (water washing, acid or alkali washing, etc.), distillation, crystallization, recrystallization, column chromatography, etc. By using it, the target (meth) acrylic acid ester can be obtained. For example, from the alcohols represented by the formulas (2), (3), (4), and (5), they are represented by the following formulas (6), (7), (8), and (9), respectively ( A (meth) acrylic acid ester can be obtained. The symbols in the formula are the same as above.

  The (meth) acrylic acid ester obtained by the method of the present invention is useful as an intermediate material for fine chemicals, in addition to functional polymer monomers such as photosensitive resins.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The raw materials, products, and by-products were quantified by gas chromatography (hereinafter abbreviated as GC).

Example 1
In a glass flask equipped with a stirrer, thermometer, Dimroth cooling tank, and dropping funnel, 5.55 g of toluene, 0.12 g (0.7 mmol) of iron (III) chloride, BBMS {4,4′-butylidene-bis (6-tert-butyl-3-methylphenol)} 0.049 g, Topanol A (6-tert-butyl-2,4-xylenol) 0.049 g, 3-hydroxy-γ-butyrolactone [formula (2-1) Of compound] 1.50 g (14.7 mmol) was added and stirred at 70 ° C. The dropping funnel was charged with 2.49 g (16.2 mmol) of methacrylic anhydride and dropped into the flask in 5 minutes. After completion of the dropping, the reaction was carried out while adjusting the reaction temperature to 70 ° C. Sampling is performed during the reaction, and the sample is analyzed by GC until 3-hydroxy-γ-butyrolactone disappears, and 3-hydroxy-γ-butyrolactone methacrylate (= γ-butyrolactone-3-yl methacrylate) is obtained. Obtained. The reaction time was 3 hours after addition of methacrylic anhydride. After completion of the reaction, the content of 3-hydroxy-γ-butyrolactone methacrylate was 2.48 g, and the reaction yield was 99.5%. Crotonolactone, a reaction byproduct (β-eliminated ester), was not detected. Further, when the reaction solution was analyzed by GPC (gel permeation chromatography), no oligomer component was detected.

(Example 2)
The 3-hydroxy-γ-butyrolactone methacrylate was reacted under the same conditions as in Example 1 except that the iron (III) chloride of Example 1 was changed to 0.26 g (0.7 mmol) of zirconium sulfate tetrahydrate. Obtained. When traced by GC, 3-hydroxy-γ-butyrolactone disappeared for 3 hours after addition of methacrylic anhydride. After completion of the reaction, the content of 3-hydroxy-γ-butyrolactone methacrylate was 2.47 g, and the reaction yield was 98.7%. Crotonolactone, a reaction byproduct (β-eliminated ester), was not detected. Further, when the reaction solution was analyzed by GPC, no oligomer component was detected.

(Example 3)
The reaction was conducted under the same conditions as in Example 1 except that 5.55 g of toluene in Example 1 was changed to 5.55 g of acetonitrile to obtain 3-hydroxy-γ-butyrolactone methacrylate. When traced by GC, 3-hydroxy-γ-butyrolactone disappeared for 3 hours after addition of methacrylic anhydride. The content of 3-hydroxy-γ-butyrolactone methacrylate after completion of the reaction was 2.35 g, and the reaction yield was 98.4%. Crotonolactone, a reaction byproduct (β-eliminated ester), was not detected. Further, when the reaction solution was analyzed by GPC, no oligomer component was detected.

Example 4
The reaction was carried out under the same conditions as in Example 2 except that 5.55 g of toluene in Example 2 was changed to 5.55 g of acetonitrile to obtain 3-hydroxy-γ-butyrolactone methacrylate. When traced by GC, 3-hydroxy-γ-butyrolactone disappeared for 3 hours after addition of methacrylic anhydride. The content of 3-hydroxy-γ-butyrolactone methacrylate after completion of the reaction was 2.35 g, and the reaction yield was 94.9%. Crotonolactone, a reaction byproduct (β-eliminated ester), was not detected. Further, when the reaction solution was analyzed by GPC, no oligomer component was detected.

(Example 5)
3-hydroxy-γ-butyrolactone methacrylate was reacted under the same conditions as in Example 3 except that 5.55 g of acetonitrile in Example 3 was changed to 0.74 g and 0.12 g of iron (III) chloride was changed to 0.036 g. Got. When traced by GC, 3-hydroxy-γ-butyrolactone disappeared for 3 hours after addition of methacrylic anhydride. The content of 3-hydroxy-γ-butyrolactone methacrylate after completion of the reaction was 2.50 g, and the reaction yield was 99.9%. Crotonolactone, a reaction byproduct (β-eliminated ester), was not detected. Further, when the reaction solution was analyzed by GPC, no oligomer component was detected. The reaction solution was washed with a 7% by weight aqueous sodium hydrogen carbonate solution, washed with a 1% by weight aqueous hydrochloric acid solution, washed with water, and then purified by distillation. The content was 3500 wt ppb.

(Example 6)
A 3-hydroxy-γ-butyrolactone methacrylate was obtained by reacting under the same conditions as in Example 5 except that 0.036 g of iron (III) chloride in Example 5 was changed to 0.024 g. When traced by GC, 3-hydroxy-γ-butyrolactone disappeared for 3 hours after addition of methacrylic anhydride. The content of 3-hydroxy-γ-butyrolactone methacrylate after completion of the reaction was 2.50 g, and the reaction yield was 99.9%. Crotonolactone, a reaction byproduct (β-eliminated ester), was not detected. Further, when the reaction solution was analyzed by GPC, no oligomer component was detected. The reaction solution was washed with a 7% by weight aqueous sodium hydrogen carbonate solution, washed with a 1% by weight aqueous hydrochloric acid solution, washed with water, and then purified by distillation to obtain a solution of iron in 3-hydroxy-γ-butyrolactone methacrylate. The content was 210 weight ppb.

(Example 7)
In Example 3, BBMS {4,4′-butylidene-bis (6-tert-butyl-3-methylphenol)} and 0.049 g of Topanol A (6-tert-butyl-2,4-xylenol) were not used. Except for the above, the reaction was carried out under the same conditions as in Example 3 to obtain 3-hydroxy-γ-butyrolactone methacrylate. When traced by GC, 3-hydroxy-γ-butyrolactone disappeared for 3 hours after addition of methacrylic anhydride. The content of 3-hydroxy-γ-butyrolactone methacrylate after completion of the reaction was 2.50 g, and the reaction yield was 99.9%. Crotonolactone, a reaction byproduct (β-eliminated ester), was not detected. Further, when the reaction solution was analyzed by GPC, no oligomer component was detected. The reaction solution was washed with a 7% by weight aqueous sodium hydrogen carbonate solution, washed with a 1% by weight aqueous hydrochloric acid solution, washed with water, and then purified by distillation. The content was 3500 wt ppb.

(Comparative Example 1)
The reaction was carried out under the same conditions as in Example 1 except that the reaction temperature in Example 1 was changed to 50 ° C. and iron (III) chloride was changed to 0.14 g (1.5 mmol) of sulfuric acid to give 3-hydroxy-γ-butyrolactone methacrylate. Obtained. When traced by GC, 3-hydroxy-γ-butyrolactone was lost by 68.3% in 3 hours after addition of methacrylic anhydride. The content of 3-hydroxy-γ-butyrolactone methacrylate at the same time was 0.24 g, and the reaction yield was 9.7%. The content of crotonolactone, which is a reaction byproduct (β-eliminated ester), was 0.42 g, and the reaction yield was 16.9%.

(Comparative Example 2)
The reaction was conducted under the same conditions as in Comparative Example 1 except that the sulfuric acid in Comparative Example 1 was changed to 0.18 g (1.5 mmol) of 4-dimethylaminopyridine to obtain 3-hydroxy-γ-butyrolactone methacrylate. As monitored by GC, 3-hydroxy-γ-butyrolactone disappeared 68.3% in 5 hours after addition of methacrylic anhydride. The content of 3-hydroxy-γ-butyrolactone methacrylate at the same time was 0.95 g, and the reaction yield was 37.9%. The content of crotonolactone, which is a reaction byproduct (β-eliminated ester), was 0.32 g, and the reaction yield was 12.6%.

(Comparative Example 3)
3-Hydroxy-γ-butyrolactone methacrylate was obtained by reacting under the same conditions as in Example 3 except that iron (III) chloride in Example 3 was changed to cerium chloride (1.5 mmol). When traced by GC, 3-hydroxy-γ-butyrolactone disappeared 85.0% in 7 hours after addition of methacrylic anhydride. The content of 3-hydroxy-γ-butyrolactone methacrylate at the same time was 1.83 g, and the reaction yield was 73.7%. Crotonolactone, a reaction byproduct (β-eliminated ester), was not detected.

Claims (6)

Following formula (1)
M _a X _b (1)
(In the formula, M represents an element selected from Group 4 to Group 12 elements of the periodic table, aluminum, gallium, indium, thallium, silicon, germanium, tin, lead, antimony and bismuth, and X represents a halogen atom or SO. ₄ and a and b each represent an integer of 1 or more)
In the presence of a catalyst composed of a compound represented by formula (2), (3), (4) or (5)

[Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R ² , R ³ , and R ⁴ each represent an alkyl group having 1 to 6 carbon atoms that may have a halogen atom. Z ¹ and Z ² each represents a monocyclic or polycyclic non-aromatic cyclic group which may have an ether bond or an ester bond in the ring. A represents a linking group. k is 0 or 1, m is an integer of 0 to 3, n is an integer of 0 to 3, and p is an integer of 1 to 3. The lactone ring in formula (2), the ring constituting the cyclic ether in formula (3), the ring Z ¹ in formula (4), and the ring Z ² in formula (5) have a substituent. It is good]
At least one selected from alcohol (A), (meth) acrylic anhydride (B1), and anhydride (B2) of (meth) acrylic acid and a carboxylic acid other than (meth) acrylic acid A process for producing a (meth) acrylic acid ester, wherein the acid anhydride (B) is reacted to obtain the corresponding (meth) acrylic acid ester.   The production of a (meth) acrylic acid ester according to claim 1, wherein the reaction between the alcohol (A) and the acid anhydride (B) is carried out in the absence of a solvent or in an organic solvent not more than 100 times by weight with respect to the alcohol (A). Law.   The (meth) acrylic acid ester according to claim 1 or 2, wherein the reaction between the alcohol (A) and the acid anhydride (B) is carried out in the absence of a solvent or in an organic solvent of 2 times by weight or less with respect to the alcohol (A). Manufacturing method.   The catalyst composed of the compound represented by the formula (1) is used in an amount of 0.00001 to 0.3 mol per 1 mol of the alcohol (A). ) A process for producing acrylic esters.   The method for producing a (meth) acrylic acid ester according to any one of claims 1 to 4, wherein a compound in which X is a chlorine atom in the formula (1) is used as a catalyst. Following formula (1)
M _a X _b (1)
(In the formula, M represents an element selected from Group 4 to Group 12 elements of the periodic table, aluminum, gallium, indium, thallium, silicon, germanium, tin, lead, antimony and bismuth, and X represents a halogen atom or SO. ₄ and a and b each represent an integer of 1 or more)
And is represented by the following formula (2), (3), (4) or (5)

[Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R ² , R ³ , and R ⁴ each represent an alkyl group having 1 to 6 carbon atoms that may have a halogen atom. Z ¹ and Z ² each represents a monocyclic or polycyclic non-aromatic cyclic group which may have an ether bond or an ester bond in the ring. A represents a linking group. k is 0 or 1, m is an integer of 0 to 3, n is an integer of 0 to 3, and p is an integer of 1 to 3. The lactone ring in formula (2), the ring constituting the cyclic ether in formula (3), the ring Z ¹ in formula (4), and the ring Z ² in formula (5) have a substituent. It is good]
At least one selected from alcohol (A), (meth) acrylic anhydride (B1), and anhydride (B2) of (meth) acrylic acid and a carboxylic acid other than (meth) acrylic acid A catalyst for producing a (meth) acrylic acid ester used for obtaining a corresponding (meth) acrylic acid ester from the acid anhydride (B).