JP2021088526A - Method for producing (meth)acrylate - Google Patents

Abstract

To provide a production method for efficiently producing (meth)acrylate having a condensed ring or crosslinked ring structure including a γ-butyrolactone structure in a short process.SOLUTION: A method for producing (meth)acrylate represented by the following formula (1) interchanges esters between a compound represented by the following formula (2) and (meth)acrylate. R1, R2, R3 and R4 each independently is a hydrogen atom, a methyl group or an ethyl group, A1 and A2 are hydrogen atoms or A1 and A2 form -O-, -CH2- or -CH2CH2-, either X1 or X2 is a hydrogen atom and the other is a (meth)acryloyloxy group, one of Z1 and Z2 is a hydrogen atom and the other is R5-C(=O)-O-, and R5 is a hydrogen atom or an alkyl group.SELECTED DRAWING: None

Description

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

A (meth) acrylic acid ester having a condensed ring or crosslinked ring structure containing a γ-butyrolactone structure can be used as a raw material monomer for constituent resins such as paints, adhesives, adhesives, ink resins, resists, molding materials, and optical materials. It is useful.
In Patent Document 1, a lower carboxylic acid ester having a condensed ring or a crosslinked ring structure containing a γ-butyrolactone structure is hydrolyzed, and the obtained alcohol is (meth) acrylic esterized to obtain the above (meth) acrylic acid ester. How to get it is described.

JP-A-2002-234882

However, the method of Patent Document 1 has a long process, and the yield of (meth) acrylic acid ester is not yet sufficient.
An object of the present invention is to provide a production method capable of producing a (meth) acrylic acid ester having a condensed ring or a crosslinked ring structure containing a γ-butyrolactone structure in a short process in a high yield.

The present invention is as follows.
A method for producing a (meth) acrylic acid ester represented by the following formula (1), in which a compound represented by the following formula (2) is transesterified with a (meth) acrylic acid ester.

However, R ¹ , R ² , R ³ and R ⁴ are independently hydrogen atoms, methyl groups or ethyl groups, respectively.
Or A ¹ and ^{A 2} are both hydrogen atom, or -O between ^{A 1} and ^{A 2} -, - CH ₂ - or _-CH 2 CH ₂ - forms a,
One of X ¹ and X ² is a hydrogen atom, and the other is a (meth) acryloyloxy group.
One of Z ¹ and Z ² is a hydrogen atom, the other is R ^5- C (= O) -O-, and R ⁵ is a hydrogen atom or an alkyl group.

According to the present invention, a (meth) acrylic acid ester having a condensed ring or a crosslinked ring structure containing a γ-butyrolactone structure can be produced in a short step in good yield.

In the present invention, "(meth) acrylic acid ester" means an acrylic acid ester or a methacrylic acid ester. "(Meta) acryloyloxy group" means an acryloyloxy group or a methylenedioxy group, and _{is represented by CH 2} = CR-C (= O) -O-. R is a hydrogen atom or a methyl group.
"~" Indicating a numerical range means that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.

In the production method of the present invention, the compound represented by the following formula (2) (hereinafter, also referred to as “compound (2)”) and the (meth) acrylic acid ester are transesterified. As a result, a (meth) acrylic acid ester represented by the following formula (1) (hereinafter, also referred to as “(meth) acrylic acid ester (1)”) can be obtained.

ただし、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４はそれぞれ独立に水素原子、メチル基又はエチル基であり、
Ａ^１及びＡ^２は共に水素原子であるか、又はＡ^１とＡ^２とで−Ｏ−、−ＣＨ_２−又は−ＣＨ_２ＣＨ_２−を形成しており、
Ｘ^１及びＸ^２はいずれか一方が水素原子であり、他方が（メタ）アクリロイルオキシ基であり、
Ｚ^１及びＺ^２はいずれか一方が水素原子であり、他方がＲ^５−Ｃ（＝Ｏ）−Ｏ−であり、Ｒ^５は水素原子又はアルキル基である。

However, R ¹ , R ² , R ³ and R ⁴ are independently hydrogen atoms, methyl groups or ethyl groups, respectively.
Or A ¹ and ^{A 2} are both hydrogen atom, or -O between ^{A 1} and ^{A 2} -, - CH ₂ - or _-CH 2 CH ₂ - forms a,
One of X ¹ and X ² is a hydrogen atom, and the other is a (meth) acryloyloxy group.
One of Z ¹ and Z ² is a hydrogen atom, the other is R ^5- C (= O) -O-, and R ⁵ is a hydrogen atom or an alkyl group.

More specifically, when the (meth) acrylic acid ester to be transesterified with the compound (2) (hereinafter, also referred to as “raw material (meth) acrylic acid ester”) is represented by the following formula (3), the compound ( by an ester interchange between 2) as a raw material (meth) acrylic acid esters, (meth) acrylic acid ester (1) and ^{R 5 -C (= O) -O} -R 6 is produced.
CH ₂ = CR-C (= O) -OR ⁶ (3)
However, R is a hydrogen atom or a methyl group, and R ⁶ is an arbitrary substituent.

In the formula (1), R ¹ , R ² , R ³ and R ⁴ are independently hydrogen atoms, methyl groups or ethyl groups, and hydrogen atoms or methyl groups are preferable. Of R ¹ , R ² , R ³ and R ⁴ , the number of methyl groups or ethyl groups may be any of 0 to 4, but 0 to 2 is preferable.
Or A ¹ and ^{A 2} are both hydrogen atoms, or ^{A 1} and ^{A 2} and by -O -, - CH ₂ - or _-CH 2 CH ₂ - are formed. A ¹ and ^{A 2,} -O between ^{A 1} and ^{A ₂} -, - CH ² - or _-CH 2 CH ₂ - is preferable to form a, -CH ₂ between ^{A 1} and ^{A 2} - of It is particularly preferable that it is formed.
One of X ¹ and X ² is a hydrogen atom, and the other is a (meth) acryloyloxy group. Either X ^{1 or} X ² may be (meth) acryloyloxy.
Specific examples of the (meth) acrylic acid ester (1) include those described in Patent Document 1 described above.

^{R 1,} R ^2, R ³ in the formula ^(2), R 4, ^{A 1} and ^{A 2} each, ^{R 1,} R ^2, R ³ in the formula ^(1), and R 4, ^{A 1} and ^{A 2} It is the same.
One of Z ¹ and Z ² is a hydrogen atom, and the other is R ^5- C (= O) -O-. When ^{X 1} in formula (1) is a (meth) acryloyloxy groups ^{Z 1} is ^R 5 -C (= O) -O-, and if ^{X 2} is (meth) acryloyloxy group Z ^{2 R} 5 -C (= O) is -O-.
R ⁵ is a hydrogen atom or an alkyl group. The carbon number of the alkyl group of R ⁵ is, for example, 1-3. The R ^5, from the viewpoint of the transesterification reaction tends to proceeds, preferably a hydrogen atom or a methyl group, a hydrogen atom is particularly preferred.

In the transesterification reaction, the compound (2) may be used alone or in combination of two or more. For example, ^{a mixture of a compound in which Z 1} is R ^5- C (= O) -O- and a compound in which Z ² is R ^5- C (= O) -O- may be used.
Compound (2) can be produced by the method described in Patent Document 1 described above.

In formula (3), R is a hydrogen atom or a methyl group.
R ⁶ is an arbitrary substituent. Examples of R ⁶ include an alkyl group having 1 to 3 carbon atoms and an alkenyl group having 2 to 3 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and a vinyl group. Of these, a methyl group or a vinyl group is preferable in terms of high reactivity, and an isopropyl group is preferable in terms of a small amount of by-products.

In the transesterification reaction, only one kind of raw material (meth) acrylic acid ester may be used, or two or more kinds may be used in combination. For example, methyl (meth) acrylate and vinyl (meth) acrylate may be used in combination.
When two or more kinds of raw material (meth) acrylic acid esters are used, two or more kinds of raw material (meth) acrylic acid esters may be mixed in advance and reacted with compound (2), or two or more kinds of raw materials (meth) acrylic acid esters may be used. ) Acrylic acid ester may be sequentially reacted with compound (2).

The ratio of the raw material (meth) acrylic acid ester to 1 mol of the compound (2) is preferably 2 to 15 mol, more preferably 3 to 10 mol. When the ratio of the raw material (meth) acrylic acid ester is equal to or higher than the lower limit, the reaction is likely to proceed sufficiently, and when the ratio is lower than the upper limit, the raw material (meth) unreacted from the reaction product after the transesterification reaction The time required to remove the acrylic ester is shorter.

The transesterification reaction is typically carried out in the presence of a catalyst.
The catalyst is not particularly limited as long as it allows the transesterification reaction to proceed, but for example, tetraalkoxytitaniums such as tetrabutoxytitanium, tetraisopropoxytitanium, and tetramethoxytitanium, and dialkyls such as dibutyltin oxide and dioctyltin oxide. Examples thereof include tin oxides, aluminum alkoxylates, and alkali metal alkoxylates. Only one kind of these catalysts may be used, or two or more kinds of these catalysts may be used in combination.

As the catalyst, tetrabutoxytitanium, tetraisopropoxytitanium, and tetramethoxytitanium are preferable in terms of reactivity, and dibutyltin oxide, dioctyltin oxide, and tetramethoxytitanium are preferable in terms of low by-products. Tetramethoxytitanium is more preferable in terms of excellent reactivity and few side reactions, and tetraisopropoxytitanium is more preferable in terms of excellent reactivity.

The entire amount of the catalyst may be charged at one time, or may be added in several portions. When two or more kinds of catalysts are used, the whole amount may be charged at one time, or any of the catalysts may be added at an arbitrary timing.
The amount of the catalyst used is preferably 0.005 to 0.2 mol, more preferably 0.01 to 0.1 mol, based on 1 mol of the compound (2). When the amount of the catalyst used is equal to or higher than the lower limit, the reaction is likely to proceed. If the amount of the catalyst used is not more than the upper limit, by-products are unlikely to be produced. In addition, the catalyst can be easily removed after the reaction.

The reaction temperature of the transesterification reaction is preferably 50 to 150 ° C, more preferably 80 to 130 ° C. When the reaction temperature is at least the lower limit value, the transesterification reaction is likely to proceed sufficiently, and when it is at least the upper limit value, the formation of by-products is likely to be suppressed.

The reaction time of the transesterification reaction varies depending on the batch size, catalyst and reaction temperature, but is preferably 1 to 15 hours, more preferably 2 to 12 hours. When the reaction time is at least the lower limit value, the transesterification reaction is likely to proceed sufficiently, and when it is at least the upper limit value, the formation of by-products is likely to be suppressed.

During the transesterification reaction, if there is a large amount of water in the system, the catalytic activity decreases and by-products increase. Therefore, before starting the transesterification reaction, the water content in the system is removed as necessary. To do. The amount of water in the system at the start of the transesterification reaction is preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, and even more preferably 200 ppm mass or less.

The method for removing water in the system is not particularly limited, and examples thereof include a method of azeotropically boiling with a high boiling point solvent such as toluene or methyl methacrylate using an apparatus such as a Dean-Stark trap or a decanter. Since the operation is simple, a method in which compound (2) is dissolved in toluene or methyl methacrylate, and toluene or methyl methacrylate is heated to reflux using a Dean-Stark trap or decanter, and water is removed from the reaction system. Is preferable.

The transesterification reaction is preferably carried out in the presence of a polymerization inhibitor from the viewpoint of suppressing the polymerization of the (meth) acrylic acid ester or the like. It is also effective to carry out the reaction while blowing air or oxygen.
The polymerization inhibitor is not particularly limited as long as it suppresses polymerization, but is hydroquinone, 4-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, p-benzoquinone, 2,5-diphenyl-p-. Examples thereof include benzoquinone, phenothiazine, N-nitrosodiphenylamine, copper salt, metallic copper, 2,2,6,6-tetramethylpiperidin-1-oxyl and the like.

The transesterification reaction may be carried out in the presence of a solvent. The solvent is not particularly limited, and examples thereof include toluene, heptane, hexane and the like.

After the transesterification reaction is completed, the reaction solution is concentrated and purified to recover the (meth) acrylic acid ester (1).
After the transesterification reaction is completed, the reaction solution may be concentrated as it is and purified, but in this case, the catalyst may remain after purification. Therefore, it is preferable to purify after removing the catalyst in the reaction solution.

Examples of the method for removing the catalyst include the following methods.
-A method of washing the reaction solution with water or an alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, or sodium hydrogen carbonate.
-A method in which alkaline powder such as sodium carbonate, sodium hydrogen carbonate, magnesium oxide, etc. is added to the reaction solution, stirred, and then the neutralized salt is filtered.
-A method in which water and an acid such as hydrochloric acid or sulfuric acid are added to the reaction solution to dissolve the catalyst.
Of these methods, the method of adding water and an acid to the reaction solution to dissolve the catalyst is preferable because the process is simple and the yield is good.

Tetraalkoxytitaniums, which are widely used as catalysts, generate a large amount of insoluble matter when they come into contact with water, and it is difficult to dissolve this insoluble matter. On the other hand, tetraalkoxytitaniums generate insoluble matter even when they are brought into contact with an acid, but since this insoluble matter is a water-soluble salt, it dissolves when water is added. Therefore, in order to dissolve the tetraalkoxytitaniums, it is preferable to add water after adding the acid to the reaction solution. The acid to be added at this time is not particularly limited, but a strong acid such as sulfuric acid, nitric acid, or hydrochloric acid is preferable from the viewpoint that the amount used can be reduced, and sulfuric acid is particularly preferable from the viewpoint of easy handling.

If necessary, the reaction solution is diluted with an organic solvent before the catalyst is dissolved. Examples of the organic solvent used for dilution include toluene, benzene, hexane, cyclohexane, ethyl acetate, diethyl ether, diisopropyl ether and the like. Among these, toluene, ethyl acetate and diethyl ether are preferable from the viewpoint of high extraction efficiency and the amount of solvent used can be reduced, and toluene and ethyl acetate are more preferable from the viewpoint of more excellent yield.
After dissolving the catalyst, the reaction solution is concentrated if necessary.

Examples of the purification method include column chromatography and distillation. Vacuum distillation such as simple distillation and thin film distillation is preferable from the viewpoint that impurities such as solvent and trace metal can be reduced.
When purification is performed, polymerization may occur, so it is preferable to coexist with a polymerization inhibitor. The polymerization inhibitor is not particularly limited as long as it suppresses polymerization, and the same ones used in the transesterification reaction can be used. Purification while blowing air or oxygen is also effective in suppressing polymerization.

Conventionally, an alcohol has been obtained by hydrolyzing the compound (2), and the alcohol has been converted into a (meth) acrylic ester to obtain a (meth) acrylic acid ester (1). Since the process is long, the operation is complicated, and the overall yield is low due to the loss in each process. In addition, ring opening of the lactone ring may occur during hydrolysis, and the ring opening of the lactone ring causes a further decrease in yield.
On the other hand, in the production method of the present invention, the (meth) acrylic acid ester (1) can be synthesized from the compound (2) in one step of transesterification. Moreover, the yield of this step itself is also high. In addition, ring opening of the lactone ring is less likely to occur as compared with the conventional method. Therefore, the (meth) acrylic acid ester (1) can be produced in a short process with good yield.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. "%" Means mass%.
The products in each of the following examples were identified by ^{1 1} H-NMR.

(Example 1)
In a flask equipped with a stirrer, thermometer, Dean-Stark tube, and condenser, 8-formyloxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decane-3-one and 9-formyloxy- 4- ^{Oxatricyclo [5.2.1.0 2,6} ] Mixture with decane-3-one 60.2 g (0.31 mol), methyl methacrylate 122.6 g (1.22 mol), 4-methoxyphenol 62 mg (0.50 mmol), 60.1 g of toluene and 2.6 g (0.0092 mol) of titanium tetraisopropoxide were added, and the mixture was refluxed for 8 hours while extracting the distillate containing methanol. Then, 10.2 g (0.10 mol) of sulfuric acid, 30.4 g of toluene and 60.1 g of water were added for washing, followed by washing with 5% aqueous sodium hydrogen carbonate and water in that order, and then the solvent was distilled off. This was distilled and purified, and the transparent liquid 8-methacryloyloxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decane-3-one and 9-methacryloyloxy-4-oxatricyclo [5] were distilled and purified. 2.1.0 ^2,6 ] A mixture with decane-3-one was obtained in an amount of 55.7 g (0.24 mol, 77% yield).

(Comparative Example 1)
^{8-formyloxy-4-oxatricyclo [5.2.1.0 2,6} ] decane-3-one and 9-formyloxy-4-oxatri in a flask equipped with a stirrer, a thermometer and a condenser. 35.3 g (0.18 mol) of a mixture with cyclo [5.2.1.0 ^2,6 ] decane-3-one and 100 mL of methanol were added. To this, 100 g of a 10% potassium hydroxide aqueous solution was added, and the mixture was stirred at room temperature for 12 hours for alkaline hydrolysis, and methanol was distilled off. Subsequently, the residue was extracted with ethyl acetate, the organic layers were combined, washed with water, dried over sodium sulfate, and the solvent was distilled off. This was purified by silica gel column chromatography, and the clear liquid 8-hydroxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decane-3-one and 9-hydroxy-4-oxatricyclo [5.2.1.0 ^2,6 ] 26.1 g (0.16 mol, yield 86%) of a mixture with decane-3-one was obtained.
Then, in a flask equipped with a stirrer, two dropping funnels, a thermometer and a condenser, 8-hydroxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decan-3-one and 9-hydroxy- 16.8 g (0.10 mol) of a mixture with 4-oxatricyclo [5.2.1.0 ^2,6 ] decan-3-one and 80 mL of dry dichloromethane were added. 13.2 g (0.13 mol) of triethylamine was charged in one of the dropping funnels, and 12.5 g (0.12 mol) of methacrylic acid chloride was charged in the other. The inside of the flask was replaced with nitrogen, and the inside of the system was about -5 ° C. I made it. Then, while stirring the inside of the flask, triethylamine and methacrylic acid chloride were added dropwise over 1 hour while adjusting so that triethylamine was slightly excessive with respect to the methacrylic acid chloride. After completion of the dropping, 0.3 g (0.002 mol) of dimethylaminopyridine was added, and the system was allowed to return to room temperature, and stirring was continued for 24 hours. Then, 100 mL of methanol was carefully added to the reaction solution, washed successively with water and saturated aqueous sodium hydrogen carbonate, dried over magnesium sulfate, and the solvent was distilled off. This was purified by silica gel column chromatography, and the clear liquid 8-methacryloyloxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decane-3-one and 9-methacryloyloxy-4-oxa A mixture with tricyclo [5.2.1.0 ^2,6 ] decane-3-one was obtained in an amount of 18.4 g (0.078 mol, yield 78%).
From the above, the total yield was (86/100) × (78/100) × 100 ≈67%.

According to the production method of the present invention, the (meth) acrylic acid ester (1) can be produced in a short process with good yield.
The obtained (meth) acrylic acid ester (1) is useful as a raw material monomer for constituent resins such as paints, adhesives, adhesives, ink resins, resists, molding materials, and optical materials.

Claims (1)

A method for producing a (meth) acrylic acid ester represented by the following formula (1), in which a compound represented by the following formula (2) is transesterified with a (meth) acrylic acid ester.

However, R ¹ , R ² , R ³ and R ⁴ are independently hydrogen atoms, methyl groups or ethyl groups, respectively.
Or A ¹ and ^{A 2} are both hydrogen atom, or -O between ^{A 1} and ^{A 2} -, - CH ₂ - or _-CH 2 CH ₂ - forms a,
One of X ¹ and X ² is a hydrogen atom, and the other is a (meth) acryloyloxy group.
One of Z ¹ and Z ² is a hydrogen atom, the other is R ^5- C (= O) -O-, and R ⁵ is a hydrogen atom or an alkyl group.