JP2002088018A - Method for producing (meth) acrylate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for easily producing a high-purity (meth) acrylate of a secondary or tertiary alcohol with a high yield. SOLUTION: In the method for producing a (meth) acrylate by reacting a (meth) acrylic anhydride with a secondary or tertiary alcohol, the acidity (pKa) in water at 25 ° C is 10 or less. A method for producing a (meth) acrylic ester, wherein a reaction is carried out at a reaction temperature of 80 ° C. or lower in the presence of a basic compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to secondary or tertiary
The present invention relates to a method for producing a (meth) acrylate of a secondary alcohol. The present invention particularly relates to (meth) acrylates of lactone alcohols and (meth) acrylates of adamantyl alcohols, which are useful as constituent monomers of semiconductor resists, paints, adhesives, pressure-sensitive adhesives, resins for inks and the like. It relates to a manufacturing method.

[0002]

2. Description of the Related Art (Meth) acrylic acid esters can be synthesized by an addition reaction of an alkene and (meth) acrylic acid using an acid catalyst, a dehydration reaction of alcohol and (meth) acrylic acid using a condensing agent or an acid catalyst, Esterification reaction of alcohol and (meth) acrylic anhydride using a base catalyst, transesterification reaction of alcohol with (meth) acrylic acid ester, esterification reaction with (meth) acrylic acid chloride and the like are known. .

However, sterically bulky monomers such as (meth) acrylates of secondary or tertiary alcohols are decomposable by acids and bases. Therefore, in an addition reaction, a dehydration reaction, or a transesterification reaction using an acid catalyst or a base catalyst, a product is decomposed, and it is difficult to obtain a target compound in a high yield. In particular, β-hydroxy-γ-butyrolactone or β-methyl-β-hydroxy-γ-butyrolactone, which is a lactone alcohol, is unstable under any acidic or alkaline condition and easily changes to a dehydrated compound. For this reason, as described in JPN. J. Appl. Phys. 1996, 35 (4B) L528-530, it is synthesized by an esterification reaction with (meth) acrylic acid chloride.

[0004]

However, in the case of the esterification reaction using (meth) acrylic acid chloride, although the ester can be synthesized quantitatively, since a large amount of acidic gas is generated, the apparatus is corroded. There is a problem that an expensive apparatus having resistance is required. Further, (meth) acrylic acid chloride has high reaction activity, and a large amount of by-products derived from (meth) acrylic acid chloride are generated during the reaction, so that a high-purity target product cannot be obtained. Therefore, when high purity is required, it is necessary to devise a complicated purification operation after the reaction or to carry out the reaction at an extremely low temperature in order to enhance the selectivity. However, these contrivances have problems such as a decrease in yield due to the purification operation, an increase in cost due to the treatment of waste liquid, and an increase in cost due to cooling for performing the reaction at an extremely low temperature.

[0005] On the other hand, the esterification reaction with (meth) acrylic anhydride has a lower reaction activity than the method using (meth) acrylic acid chloride, so it is necessary to carry out the reaction at a high temperature. However, since the (meth) acrylic acid ester of a secondary or tertiary alcohol is thermally unstable, when the reaction is performed at a high temperature, a decomposition product is easily generated, and the yield and purity are reduced. There is. Further, since (meth) acrylic anhydride is rich in polymerizability, if unreacted (meth) acrylic anhydride is contained in the product of the target compound, the polymerization of the target compound easily proceeds and the purity decreases. There is a problem.

Accordingly, it is an object of the present invention to provide highly pure (meth) acrylates of secondary or tertiary alcohols,
In particular, it is an object of the present invention to provide a method for easily producing a lactone alcohol represented by the formula (1) and an adamantyl alcohol represented by the formula (2) in a high yield.

[0007]

Embedded image (In the formula, R ¹ is hydrogen or an alkyl group, and n and m each independently represent the number of 0 or 1 methylene group.)

[0008]

Embedded image (In the formula, R ² represents an alkyl group.)

[0009]

SUMMARY OF THE INVENTION The present invention relates to a method for producing a (meth) acrylic ester by reacting a (meth) acrylic anhydride with a secondary or tertiary alcohol. A method for producing a (meth) acrylic acid ester, wherein a basic compound having an acidity (pKa) of 10 or less coexists and a reaction is performed at a reaction temperature of 80 ° C. or less.

The present invention is particularly suitable when the secondary or tertiary alcohol is a lactone alcohol represented by the above formula (1) and an adamantyl alcohol represented by the above formula (2).

In the present invention, it is preferable that unreacted (meth) acrylic anhydride is decomposed with alcohol after the reaction.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The secondary or tertiary alcohol used in the production method of the present invention refers to an alcohol in which two or three carbons are bonded to the first carbon to which a hydroxyl group is bonded. As the secondary or tertiary alcohol, specifically, adamantanol, 2-methyl-2-
Adamantanol, 2-ethyl-2-adamantanol, isobornyl alcohol, cyclohexanol, mevalonolactone, β-methyl-β-hydroxy-γ-butyrolactone, β-ethyl-β-hydroxy-γ-butyrolactone, β-hydroxy- γ-butyrolactone, α
-Hydroxy-γ-butyrolactone, α-methyl-α-
Hydroxy-γ-butyrolactone, isopropanol,
2-butanol, t-butanol and the like. The (meth) acrylic acid ester of the alcohol exemplified here is important as a raw material monomer of the resist resin, and a high-purity one is required. In particular, the above formula (1)
And adamantyl alcohols represented by the above formula (2) are preferred. In particular,
R ¹ is hydrogen or an alkyl group having 1 to 5 carbon atoms,
Lactone alcohols represented by the above formula (1) wherein at least one of n and m is 1 and adamantyl alcohols represented by the above formula (2) wherein R ² is an alkyl group having 1 to 5 carbon atoms are preferred.

A representative compound of the lactone alcohol represented by the above formula (1) is β-hydroxy-γ-
As a method for producing butyrolactone, for example,
Halopropane-1,2-diol, epichlorohydrin or 2,3-epoxy-1-propanol can be produced by a method of cyanation by reaction with hydrocyanic acid or hydrocyanic acid, followed by hydrolysis and cyclization. .

Further, β-methyl-β, which is a typical compound as a lactone alcohol represented by the above formula (1),
As a method for producing -hydroxy-γ-butyrolactone, for example, 3-halo-2-methylpropane-1,2
Diols can be prepared by a method of cyanating and subsequently cyclizing after hydrolysis.

The (meth) acrylic anhydride used in the production method of the present invention is acrylic anhydride and methacrylic anhydride. When used in the reaction, these commercially available products may be used as they are, or they can be easily produced by known methods. Examples of the method for producing (meth) acrylic anhydride include a method for producing a (meth) acrylic acid halide and (meth) acrylic acid by a condensation reaction, a method for producing from acetic anhydride and (meth) acrylic acid, and the like. Can be

The molar ratio of the secondary or tertiary alcohol to the (meth) acrylic anhydride at the time of the reaction depends on the conditions such as the type of the starting alcohol, the catalyst and the reaction temperature, and cannot be unconditionally determined. However, it is usually 1: 0.5 to 5, preferably 1: 0.8 to 2. When the starting alcohol is the lactone alcohol represented by the above formula (1), the mixing molar ratio is usually 1: 0.8 to 2, preferably 1: 0.9.
１．２1.2. Further, the raw material alcohol is represented by the formula (2)
The mixing molar ratio in the case of the adamantyl alcohols represented by is usually 1: 0.8 to 2, preferably 1: 0.9 to 0.9.
1.2.

In the reaction, the secondary or tertiary alcohol and the (meth) acrylic anhydride may be mixed in their entirety at the beginning of the reaction, or one of them may be mixed by a method such as dropping over time. You may.

In the reaction, a reaction solvent is not essential, but in order to control the reaction temperature, it is more advantageous to use a solvent such as methyl ethyl ketone or methylene chloride.
The amount of the reaction solvent used cannot be unconditionally determined depending on the type of alcohol and various conditions. For example, when the alcohol is a lactone alcohol represented by the formula (1), the amount of the reaction solvent is based on the lactone alcohol represented by the formula (1). 1 to 10 by weight
A double amount is preferred, and a 1.5 to 5 times amount is particularly preferred.

In the production method of the present invention, the reaction is carried out at 80 ° C.
It is important to carry out the following, preferably 40 to 8
0 ° C. The lower the reaction temperature, the lower the decomposition product of the secondary or tertiary alcohol, so that the reaction yield of the target product increases, and the higher the reaction temperature, the higher the reaction rate.

In the reaction, a base having an acidity (pKa) in water at 25 ° C. of 10 or less, preferably 8 to 10 is coexisted. When a basic compound having a pKa of more than 10 is used, the decomposition reaction of the target (meth) acrylate of a secondary or tertiary alcohol proceeds, and the yield is significantly reduced.

As the basic compound having a pKa of 10 or less, for example, pyridine (pKa = 5.42), 2,6-
Dimethylpyridine (pKa = 6.90), triethylenetetramine (pKa = 3.25, 6.56, 9.08,
9.74), triethanolamine (pKa = 7.7)
6), piperazine (pKa = 5.59, 9.71) and the like.

The amount of the basic compound used depends on the type of the secondary or tertiary alcohol to be subjected to the reaction and cannot be specified unconditionally. And usually 0.01 to 10 mol, preferably 0.05 to 5 mol. When the raw material alcohol is the lactone alcohol represented by the formula (1), it is usually 0.1 to 3 mol, preferably 0.5 to 1. mol based on 1 mol of the lactone alcohol represented by the formula (1). 5 moles. When the raw material alcohol is an adamantyl alcohol represented by the formula (2), the adamantyl alcohol represented by the formula (2) is usually 0.1 to 3 mol, preferably 0.5 to 3 mol per mol of the adamantyl alcohol. 1.5 mol.

The reaction time is not particularly limited, but the target product is obtained as much as possible in consideration of the production ratio of the target product (meth) acrylate and the decomposition product of the secondary or tertiary alcohol. It is preferable that the setting is made such that If the reaction time is too long, the decomposition of the (meth) acrylate may occur more than the formation of the (meth) acrylate.

In the reaction, a polymerization inhibitor such as hydroquinone and hydroquinone monomethyl ether and oxygen are preferably present.

The reaction solution containing the (meth) acrylate obtained by the reaction can be separated and purified as appropriate.
Examples of the purification method include distillation, washing, and extraction. Further, in addition to such a purification method, an alcohol treatment for easily removing unreacted (meth) acrylic anhydride by decomposing it with an alcohol into a (meth) acrylic ester and (meth) acrylic acid of the alcohol. Is preferably performed. In particular, it is preferable to use a lower alcohol such as methanol or ethanol as the alcohol because the (meth) acrylate of the lower alcohol can be easily removed from the reaction system by an operation such as distillation. The reaction solution to which the alcohol is added is preferably kept at 10 to 100 ° C, particularly preferably at 20 to 60 ° C. The holding time is preferably 0.1 to 5.0.
Time, particularly preferably 0.5 to 3.0 hours. The amount of the alcohol to be added is preferably 1 to 100 mol, particularly preferably 3 to 20 mol, per 1 mol of the remaining (meth) acrylic anhydride.

The alcohol treatment for reducing the acid anhydride may be carried out on the product obtained by separating the (meth) acrylic acid ester from the reaction solution. However, in this case, since the purification treatment is often required, the alcohol treatment is carried out. Is preferably performed on the reaction solution after the reaction because the purification treatment is simplified.

As a method for obtaining a (meth) acrylic ester with high purity from the (meth) acrylic ester or the reaction solution after the alcohol treatment, for example, washing with an acid and / or washing with an alkali, under reduced pressure Examples include distillation of a solvent and the like, separation and purification by column chromatography, and the like.

[0028]

EXAMPLES The present invention will be described in detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. The analysis in the examples was performed by gas chromatography (hereinafter, referred to as GC).

The purity was calculated from the GC peak area by the following equation. Purity (%) = (A / B) × 100 where A represents the peak area of the target product, and B represents the sum of all peak areas. The reaction yield and the actual yield were calculated by the following equations. Reaction yield (%) = (C / D) × 100 where C is the number of moles of the target product calculated from the GC peak area, and D is the secondary or primary material which is the raw material calculated from the GC peak area. Represents the number of moles of tertiary alcohol. Actual yield (%) = (E / F) × 100 where E is the number of moles of the target product calculated by multiplying the weight of the target product containing impurities by the purity and dividing by the molecular weight of the target product. , F represents the number of moles of a secondary or tertiary alcohol as a reference raw material.

Reference Example Synthesis of β-hydroxy-γ-butyrolactone 1-chloropropane-2,3 was placed in a glass flask equipped with a stirrer, a dropping funnel, a thermometer, a Dimroth condenser, and an alkali trap (aqueous sodium hydroxide solution). -250 g (2.26 mol) of diol and 220 ml of water were added and 5
122 g of sodium cyanide while maintaining at 0 to 60 ° C
(2.49 mol) of the aqueous solution was added dropwise over 2 hours.
After further heating and stirring for 2 hours, sodium hydroxide 1
An aqueous solution obtained by adding 120 ml of water to 33 g (2.83 mol) was added dropwise, and the mixture was heated to reflux at an internal temperature of 90 ° C to 100 ° C. Approximately 1 hour later, there appeared to be foaming likely to be ammonia gas. 3
After heating for 0 hours, the mixture was allowed to cool, and further cooled with ice.
g (3.25 mol) was added dropwise. The reaction solution was concentrated by an evaporator, and a large amount of salt was precipitated when water was distilled off. Here, 1 L of acetone and 1 g of anhydrous magnesium sulfate were added.
Then, the filtrate was concentrated, and 240 g of crude β-hydroxy-γ-butyrolactone was obtained. This is purified by silica gel column chromatography, and β
190.6 g of -hydroxy-γ-butyrolactone (1.
87 mol). The purity of the obtained β-hydroxy-γ-butyrolactone is 98%, and the actual yield is 81% (1-
Chloropropane-2,3-diol).

Example 1 53.2 g (0.51 mol) of 98% pure β-hydroxy-γ-butyrolactone obtained by the method of Reference Example in a 1 L glass flask equipped with a stirrer, a thermometer and a Dimroth cooling tube. , 94% pure A
124.7 g of methacrylic anhydride manufactured by ldrich
(0.76 mol), pyridine (pKa = 5.42) 6
3.0 g (0.80 mol), 0.01 g of hydroquinone as a polymerization inhibitor and 381 g of methyl ethyl ketone as a solvent were charged and immersed in a 50 ° C. oil bath while introducing 5 ml of air per minute while stirring. Reaction temperature of 45-5
The reaction was carried out for 15 hours while maintaining the temperature at 0 ° C. When the reaction solution was analyzed by GC, 97% of the raw material β-hydroxy-γ-butyrolactone was consumed.
The reaction yield of methacryloyloxy-γ-butyrolactone was 87.5%. Subsequently, 62.7 g (2.00 mol) of methanol was added to the reaction solution kept at 48 ° C., and the mixture was stirred for 3 hours. After concentrating the obtained reaction solution, it was purified by silica gel column chromatography, and 55.2 g of β-methacryloyloxy-γ-butyrolactone was obtained.
(0.32 mol) was obtained.

The obtained β-methacryloyloxy-γ-
The purity of butyrolactone is 98%, the acid anhydride is less than the limit of quantification (100 ppm), and the actual yield is 62.3%.
(Based on β-hydroxy-γ-butyrolactone).

Example 2 In Example 1, 2,6-dimethylpyridine (pKa = 6.9) was used instead of pyridine.
0) The reaction was started in exactly the same manner except that 80 g was used. The reaction solution 10 hours after the start of the reaction was analyzed by GC to find that the starting material β-hydroxy-γ
95% of -butyrolactone is consumed and the reaction yield of β-methacryloyloxy-γ-butyrolactone is 8
It was 3.2%.

Comparative Example 1 In Example 1, the reaction was started at a reaction temperature of 82 to 85 ° C., which is the reflux temperature of methyl ethyl ketone. GC analysis of the reaction solution after 6 hours from the start of the reaction revealed that 99% of the raw material β-hydroxy-γ-butyrolactone was consumed,
The reaction yield of -methacryloyloxy-γ-butyrolactone was 53.6%. At this time, β-hydroxy-
Remarkable formation of a dehydrated product of γ-butyrolactone was observed.

As described above, it has been found that when the reaction temperature exceeds 80 ° C., the reaction rate is increased, but the yield is remarkably reduced because the decomposition of the starting alcohol proceeds predominantly in the reaction.

Comparative Example 2 In Example 1, triethylamine (pKa = 1.72) 8 was used instead of pyridine.
The reaction was started in exactly the same manner except that 1.8 g was used. The reaction solution 6 hours after the start of the reaction is referred to as G
C analysis revealed that 99% of the raw material β-hydroxy-γ-butyrolactone was consumed, and the reaction yield of β-methacryloyloxy-γ-butyrolactone was 2.1.
%Met. At this time, remarkable generation of a dehydrated product of β-hydroxy-γ-butyrolactone was observed.

As described above, it was found that when a strong basic compound having a pKa of more than 10 was used, the decomposition of the starting alcohol proceeded predominantly in the reaction, so that the yield was significantly reduced.

[0038]

According to the method of the present invention, a (meth) acrylic acid ester of a high-purity secondary or tertiary alcohol can be easily produced at a high yield. Particularly, high-purity lactone alcohols represented by the above formula (1) and adamantyl alcohols represented by the above formula (2), which are useful as constituent monomers such as semiconductor resists, paints, adhesives, pressure-sensitive adhesives and ink resins. Can be easily produced in high yield.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor: Motomu Ohkita 20-1 Miyukicho, Otake City, Hiroshima Prefecture F-term in Central Research Laboratory, Mitsubishi Rayon Co., Ltd. 4C037 FA10 4H006 AA02 AC48 AD30 BA51 BA80 BC10 BJ30 KA06 4H039 CA66 CD10 CD30

Claims (4)

[Claims] 1. A method for producing a (meth) acrylate by reacting a (meth) acrylic anhydride with a secondary or tertiary alcohol, wherein the acidity (pKa) in water at 25 ° C. is 10 or less. Wherein the reaction is carried out at a reaction temperature of 80 ° C. or lower. 2. The secondary or tertiary alcohol is a lactone alcohol represented by the formula (1).
The method for producing the (meth) acrylic ester according to the above. Embedded image (In the formula, R ¹ is hydrogen or an alkyl group, and n and m each independently represent the number of 0 or 1 methylene group.) 3. The method for producing a (meth) acrylate according to claim 1, wherein the secondary or tertiary alcohol is an adamantyl alcohol represented by the formula (2). Embedded image (In the formula, R ² represents an alkyl group.) 4. The method for producing (meth) acrylic acid according to claim 1, wherein unreacted (meth) acrylic anhydride is decomposed with alcohol after the reaction.