KR20210150141A - Manufacturing method for alkyl 3-alkoxy propionate - Google Patents

Abstract

The present invention relates to a method for manufacturing ethyl 3-ethoxypropionate, comprising the following steps: mixing an alkyl alcohol having a water content of 10 to 300 wt ppm and an ethoxide salt catalyst in a reactor; and manufacturing an alkyl 3-alkoxy propionate by slowly introducing an alkyl acrylate monomer into the reactor in a molar ratio of 0.6 to 1.0 relative to the alkyl alcohol.

Description

Method for producing alkyl 3-alkoxy propionate {Manufacturing method for alkyl 3-alkoxy propionate}

The present invention relates to a process for preparing an alkyl 3-alkoxy propionate by catalyzing an ethoxide salt to an alkyl alcohol and an alkyl acrylate monomer. More particularly, it relates to a method for preparing ethyl 3-ethoxypropionate (Ethyl 3-ethoxypropionate).

In the conventional method for preparing alkyl 3-alkoxy propionate, many salts were generated due to the use of an excessive amount of catalyst. Accordingly, in the case of the alkyl 3-alkoxy propionate prepared by the conventional manufacturing method, a neutralization process and a filter process were applied to ensure stability.

The present invention relates to a method for producing alkyl 3-alkoxy propionate, and an object of the present invention is to improve the stability and productivity of the production process of alkyl 3-alkoxy propionate.

The method for producing alkyl 3-alkoxy propionate according to an embodiment of the present invention comprises the steps of mixing an alkyl alcohol having a water content of 10 to 300 wt ppm and an ethoxide salt catalyst in a reactor, and adding an alkyl acrylate monomer to the alkyl alcohol and slowly introducing into the reactor in a molar ratio of 0.6 to 1.0 compared to preparing an alkyl 3-alkoxy propionate. Here, when the alkyl acrylate monomer is mixed with the mixture of the alkyl alcohol and the ethoxide salt, a phenol-based antioxidant is used as a reaction terminator, and the reaction formula of the alkyl alcohol and the alkyl acrylate monomer follows the reaction disclosed in Formula 1 below.

[Formula 1]

Here, R ¹ and R ² are each independently a C ₁ ~ C ₆ alkyl group, and the ethoxide catalyst is a strong alkali catalyst.

In one embodiment of the present invention, the reaction temperature after mixing the alkyl acrylate monomer in the mixture of the alkyl alcohol and the ethoxide salt may be maintained at 0 to 80 degrees.

In one embodiment of the present invention, the alkyl alcohol may be ethyl alcohol.

In one embodiment of the present invention, the catalyst may be lithium ethoxide, sodium ethoxide, potassium ethoxide, rubidium ethoxide, cesium ethoxide, beryllium ethoxide, magnesium ethoxide, or calcium ethoxide.

In one embodiment of the present invention, the catalyst may be provided in an amount of 0.001 to 0.05 wt% compared to ethyl alcohol, and in another embodiment, 0.005 to 0.02 wt% compared to ethyl alcohol.

In an embodiment of the present invention, the moisture content of the ethyl alcohol may be 10 to 150 wt ppm, and in an embodiment of the present invention, the moisture content of the alkyl acrylate monomer may be 50 to 100 wt ppm have. In addition, the total amount of water contained in the alkyl alcohol and the alkyl acrylate monomer may be 400 wt ppm or less.

The molar ratio of the alkyl alcohol to the alkyl acrylate monomer may be 0.8 to 1.0 moles of the alkyl acrylate monomer per 1 mole of the alkyl alcohol.

In one embodiment of the present invention, the phenolic antioxidant may be used as a reaction terminator after the reaction of a mixture of an alkyl alcohol and an ethoxide salt with an alkyl acrylate monomer is completed. The phenolic antioxidant may be at least one of BHA, BHT, Cyanox 1790, Cyanox 2246, Cyanox425, Irganox3314, Irganox1076, Irganox1330, and Irganox 1010.

In one embodiment of the present invention, the phenol-based antioxidant may be used in an amount of 50 ppm or more and 5,000 ppm or less based on the total weight.

The present invention improves the distillation process by using an optimal reaction catalyst, thereby minimizing salt formation and facilitating the salt removal process in the alkyl 3-alkoxy propionate production process. In addition, it provides a manufacturing process capable of producing high-purity alkyl 3-alkoxy propionate products through distillation by improving the thermal stability of the product by using a phenol-based reaction terminator.

The present invention may be subject to various modifications and may have various embodiments. However, this is not intended to limit the present invention to specific embodiments, and it should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention. In describing the present invention, if it is determined that a detailed description of a related known technology may obscure the gist of the present invention, the detailed description thereof will be omitted.

Hereinafter, the exemplary embodiments detailed in the detailed description and claims disclosed herein are not for limitation, and embodiments other than the described embodiments may be used, without departing from the spirit or scope of the technology disclosed herein. Other modifications are possible as long as

Since the description of the disclosed technology is merely an embodiment for structural or functional description, the scope of the disclosed technology should not be construed as being limited by the embodiment described in the text. That is, since the embodiment can have various changes and can have various forms, it should be understood that the scope of the disclosed technology includes equivalents capable of realizing the technical idea.

All terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the disclosed technology belongs, unless otherwise defined. Terms defined in the dictionary should be interpreted as being consistent with the meaning of the context of the related art, and cannot be interpreted as having an ideal or excessively formal meaning unless explicitly defined in the present application.

Since the organic solvent used in the semiconductor manufacturing process affects the electrical properties of the semiconductor product, it can be used only when it meets the quality standards of ultra-high purity, ultra-low acrylic acid, low moisture, and low metal content.

Alkyl 3-Alkoxy Propionate is one of the organic solvents used in the semiconductor manufacturing process.

In one embodiment of the present invention, alkyl 3-alkoxy propionate (Alkyl 3-Alkoxy Propionate) is prepared by using an ethoxide salt in an alkyl alcohol (Alkyl Alcohol) and an alkyl acrylate monomer (Alkyl Acrylate Monomer) as a catalyst can do.

Alkyl 3-alkoxy propionate synthesis reaction of the present invention can be represented by the following formula (1).

[Formula 1]

In Scheme 1, R ¹ and R ² may each independently be a C ₁ to C ₆ alkyl group, preferably R ¹ and R ² are each independently a methyl group, ethyl group, n-propyl group, or n-butyl group and, more preferably, both R ¹ and R ² may be an ethyl group.

In the above reaction scheme, the catalyst (Cat.) may be a strong alkali catalyst, for example, lithium ethoxide, sodium ethoxide, potassium ethoxide, rubidium ethoxide, cesium ethoxide, beryllium ethoxide, magnesium ethoxide, and calcium ethoxide. At least one may be selected from the group consisting of, but is not limited to the above example.

In one embodiment of the present invention, the alkyl 3-alkoxy propionate may be ethyl 3-alkoxy propionate in which the alkyl group is an ethyl group, and in particular, prepared by using an ethoxide salt in ethyl alcohol and an alkyl acrylate monomer as a catalyst can do.

For example, the starting material of the reaction of ethyl alcohol in the reaction (EtOH) and ethyl acrylate monomer (EAM; Ethyl Acrylate Monomer) The catalyst of sodium ethoxide (EtO ^- Na ⁺⁾ when added to a large catalyst anionic reactive ( EtO ⁻ ) reacts with ethyl acrylate monomer (EAM) to produce an ethyl acrylate monomer (EAM) anion.

The resulting ethyl acrylate monomer (EAM) anion is reacted with ethyl alcohol or water to produce ethyl 3-ethoxy propionate (EEP). However, the catalyst the anion (EtO ^-) of ethyl acrylate monomer (EAM) anion is reacted with the ethyl alcohol is slow, whereas rapid reaction with water wherein generating the hydroxide ion (OH ^-) produced by the negative ions react with EtOH catalyst (EtO ^- ) is produced.

Therefore, ionic substances such as a ^{catalyst anion (EtO − ) and a hydroxide ion (OH −} ) generated by the reaction of the catalyst anion with water are present at the beginning of the reaction as shown in Formula 2 below.

[Formula 2]

In addition, as the reaction proceeds, some of the hydroxide ions (OH ^- ) hydrolyze the esters of ethyl acrylate monomer (EAM) and ethyl 3-ethoxy propionate (EEP) to generate another anion, a carboxylate anion. . This hydrolysis reaction is an unwanted side reaction, in which hydroxide ions (OH ^- ) act as a catalyst for the hydrolysis reaction. Hydrolysis of nate (EEP) occurs.

However, when the alkyl 3-alkoxy propionate is prepared, if the amount of the ethoxide salt used as the reaction catalyst is too low, the reaction does not proceed properly and the reaction rate is lowered. Conversely, when the amount of the ethoxide salt used is greater than a predetermined range, the produced ethyl 3-ethoxy propionic acid ester is decomposed to cause a reverse reaction in which ethyl alcohol and an alkyl acrylate monomer are decomposed.

In this embodiment, in order to prevent such a reverse reaction, the reaction is controlled so that a forward reaction occurs without a reverse reaction by controlling the amount of the catalyst while maintaining the moisture content of the reactant at 500 wtppm or less during the reaction for preparing ethyl 3-ethoxy propionate. When the catalyst is used in excess, the amount of salt produced in the reaction increases, and since such a large amount of salt accelerates the decomposition of ethyl 3-ethoxy propionic acid ester in the purification process, it is advisable to adjust the amount of the catalyst to a certain degree. necessary. Therefore, when the amount of the ethoxide salt used as the catalyst is used in an appropriate range so that the forward reaction proceeds, it is possible to produce ethyl 3-ethoxypropionic acid ester in high yield with a small amount of catalyst used. In addition, the amount of salt produced after the reaction is small, and thus the stability of the reaction product is excellent.

The above-described alkyl 3-alkoxy propionate according to an embodiment of the present invention may be specifically prepared by the following method.

First, a first mixture is prepared by mixing an alkyl alcohol and a catalyst in a reactor.

Here, the moisture content of the alkyl alcohol may be about 10 to 300 wtppm. However, the present invention is not limited thereto, and the moisture content of the alkyl alcohol may be about 10 to 150 wt ppm.

The catalyst uses an ethoxide salt but is admixed at very low wt% relative to the alkyl alcohol, for example about 0.001 to 0.05 wt%.

Next, the alkyl acrylate monomer is prepared in a molar ratio of about 1.0 to 0.6 relative to the alkyl alcohol, and the alkyl acrylate is slowly introduced into the reactor. At this time, the reaction temperature is maintained at about 0 to 80 degrees Celsius. Here, the total moisture content of the alkyl acrylate monomer may be about 10 to 100 wt ppm. However, the present invention is not limited thereto, and the total moisture content of the alkyl acrylate monomer may be about 0 to 50 wt ppm.

The reaction of the above formula is carried out by introducing an alkyl acrylate monomer into the reactor, and as a result, ethyl 3-ethoxy propionic acid ester is produced.

Here, the total amount of water content included in the ethyl alcohol and the alkyl acrylate monomer may be maintained at about 400 wt ppm or less. For example, the total amount of water content included in the ethyl alcohol and the alkyl acrylate monomer may be about 200 wt ppm or less, but is not limited to the numerical range.

In one embodiment of the present invention, the ratio of the alkyl alcohol to the alkyl acrylate monomer may be 0.6 to 1.0 moles of the alkyl acrylate monomer per mole of ethyl alcohol. Preferably, it may be 0.8 to 1.0 moles of the alkyl acrylate monomer per 1 mole of the alkyl alcohol. However, it is not limited to the above numerical range.

As described above, by using the catalyst in an amount of 0.001 to 0.05 wt%, the reverse reaction in which the resultant alkyl 3-alkoxy propionate is decomposed into ethyl alcohol and alkyl acrylate monomer as reactants does not proceed, and salt is generated due to the addition of the catalyst. can also be minimized. To minimize such salt generation, a phenol-based reaction terminator may be added after a simple filter process without adding a neutralization process or water addition process before distillation to obtain stabilized alkyl 3-alkoxy propionate.

More specifically, the amount of the catalyst used may be 0.005 to 0.02 wt% compared to the alkyl alcohol, and the reaction temperature may be 30 degrees or more and 70 degrees or less. However, it is not limited to the above example.

The catalyst may be any one or more of lithium ethoxide, sodium ethoxide, potassium ethoxide, rubidium ethoxide, cesium ethoxide, beryllium ethoxide, magnesium ethoxide, and calcium ethoxide.

The reaction terminator is a phenolic antioxidant BHA (Butylated Hydroxyanisole), BHT (Butylated 　 Hydroxytoluene), Cyanox 1790 (1,3,5-Tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)- 1,3,5-triazinane-2,4,6-trione), Cyanox 2246 (2,2'-Methylenebis(4-methyl-6-tert-butylphenol)), Cyanox 425 (2,2'-Methylenebis(4) -ethyl-6-tert-butylphenol)), Irganox 3114, Irganox 1076 (Octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), Irganox 1330 (1,3,5-Trimethyl-2) ,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene), Irganox 1010 (Pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)) and the like can be used, and the phenol-based antioxidant may be used in an amount of 50 ppm or more and 5,000 ppm or less based on the total weight. However, it is not limited to the above numerical range.

[Experimental Examples and Comparative Examples]

In the experimental example of the present invention, an experiment for synthesizing the product ethyl 3-ethoxy propionate from ethyl acrylate and ethyl alcohol was conducted.

First, the water content of the reactants, ethyl alcohol and ethyl acrylate monomer (EAM; Ethyl acrylate monomer), was measured using a Karl-Fisher moisture analyzer.

As the reaction catalyst, sodium ethoxide (Sodium Ethoxide, CH ₃ CH ₂ O ^- Na ⁺ ) was used, and ethyl alcohol was used as a solvent, and sodium ethoxide was prepared as a 20 wt% solution.

The molar ratio of ethyl acrylate monomer (EAM): ethyl alcohol was set to be 1:1 to 1:1.5.

After completion of the reaction, 1,000 ppm of a phenolic antioxidant, Dibutyl Hydroxyl Toluene (BHT) was added to the reaction product, and then a sample was collected and analyzed by GC (Gas Chromatography).

Table 1 relates to Experimental Examples 1 to 5 and Comparative Examples 1 to 5, and in each Experimental Example and Comparative Example, experiments were conducted by changing the catalyst, ethyl alcohol, ethyl acrylate monomer (EAM), moisture and temperature, The conversion of the reactants to ethyl 3-ethoxy propionate (EEP) is also shown.

catalyst
Amount used (g) Amount of ethyl alcohol used (kg) EAM usage (kg) Total reactant moisture content (ppm) Reaction initiation temperature (℃) conversion rate
(%) Experimental Example 1 0.8 0.7 1.0 85 50 96 Experimental Example 2 1.6 0.7 1.0 120 50 97 Experimental Example 3 1.6 0.9 1.0 120 50 97 Experimental Example 4 1.6 0.7 1.0 250 50 97 Experimental Example 5 2.2 0.7 1.0 320 50 96 Comparative Example 1 1.0 0.7 1.0 670 50 75 Comparative Example 2 1.0 0.7 1.0 810 50 67 Comparative Example 3 1.6 0.7 1.0 320 50 81 Comparative Example 4 0.4 0.7 1.0 85 50 43 Comparative Example 5 5.6 0.7 1.0 120 50 75

As shown in Experimental Examples 1 to 5, the total water content of the reactants was about 400 wt ppm or less, and the amount of catalyst, ethyl alcohol, and ethyl acrylate monomer was as shown in Table 1, and the reaction was provided In this case, it can be confirmed that the conversion rate of the reactant to ethyl 3-ethoxy propionate (EEP) is maintained at 95% or more.

On the other hand, as disclosed in Comparative Examples 1 and 2, when the moisture content is increased while maintaining the amount of the catalyst as it is, the conversion rate of the reactant to ethyl 3-ethoxy propionate (EEP) is 75%, respectively. and 67%, which significantly decreased the conversion compared to the Example. This is because the reverse reaction in which the product ethyl 3-ethoxy propionate (EEP) is decomposed into the reactant ethyl alcohol and ethyl acrylate monomer (EAM) proceeds, so that the conversion rate of the reactant to ethyl 3-ethoxy propionate (EEP) is increased. appears to have been lowered.

In addition, as disclosed in Comparative Examples 3 and 4, when the total content of moisture in the reactant is provided in a number of moles greater than the amount of the catalyst used, the conversion rate of the reactant to ethyl 3-ethoxy propionate (EEP) is 81, respectively. % and 43% were significantly reduced compared to Examples, and in particular, in Comparative Example 4, the conversion rate of the reactant to ethyl 3-ethoxy propionate (EEP) was reduced to a very large value. It seems that the conversion rate is lowered because the reaction activity disappears early due to the moisture present in the reactant.

In addition, in the case of Experimental Example 2, the conversion rate of the reactant to ethyl 3-ethoxy propionate (EEP) reached 97%, but in Comparative Example 5, where only the amount of catalyst was different under the same conditions, ethyl 3-ethoxy propionate of the reactant The conversion to nate (EEP) was only 75%. It seems that the amount of catalyst used in the reactant is excessively large, and the reaction proceeds as a reverse reaction, resulting in a lower conversion rate.

As disclosed in Table 1 above, as a result of testing the manufacturing process under various conditions to proceed with the mass production of ethyl 3-ethoxy propionate (EEP), the reaction conversion rate is very sensitive to the moisture content and the amount of catalyst used. point was confirmed. In addition, when ethyl 3-ethoxy propionate (EEP) was mass-produced under the experimental conditions described in Experimental Examples 1 to 5 of the present invention, the conversion rate could be increased to 96% or more.

Claims (13)

mixing an alkyl alcohol having a water content of 10 to 300 wt ppm and an ethoxide salt catalyst in a reactor;
It comprises the step of slowly introducing an alkyl acrylate monomer into the reactor in a molar ratio of 0.6 to 1.0 relative to the alkyl alcohol to prepare an alkyl 3-alkoxy propionate,
When the alkyl acrylate monomer is mixed with the mixture of the alkyl alcohol and the ethoxide salt, a phenolic antioxidant is used as a reaction terminator, and the reaction formula of the alkyl alcohol and the alkyl acrylate monomer is alkyl 3-alkoxy propionate according to the following scheme manufacturing method.

Here, R ¹ and R ² are each independently a C ₁ ~ C ₆ alkyl group, and the ethoxide catalyst is a strong alkali catalyst. According to claim 1,
The reaction temperature after mixing the alkyl acrylate monomer to the mixture of the alkyl alcohol and the ethoxide salt is 0 to 80 degrees alkyl 3-alkoxy propionate production method. According to claim 1,
The alkyl alcohol is ethyl alcohol, alkyl 3-alkoxy propionate production method. 4. The method of claim 3,
wherein the catalyst is lithium ethoxide, sodium ethoxide, potassium ethoxide, rubidium ethoxide, cesium ethoxide, beryllium ethoxide, magnesium ethoxide, or calcium ethoxide. 5. The method of claim 4,
The catalyst is an alkyl 3-alkoxy propionate production method provided in 0.001 to 0.05 wt% relative to ethyl alcohol. 6. The method of claim 5,
The catalyst is 0.005 to 0.02 wt% of ethyl alcohol compared to alkyl 3-alkoxy propionate production method. 4. The method of claim 3,
The water content of the ethyl alcohol is 10 ~ 150 wt ppm of alkyl 3-alkoxy propionate production method. According to claim 1,
The water content of the alkyl acrylate monomer is 50 to 100 wt ppm of alkyl 3-alkoxy propionate production method. According to claim 1,
A method for producing ethyl 3-ethoxy propionate wherein the total amount of water contained in the alkyl alcohol and the alkyl acrylate monomer is 400 wt ppm or less. According to claim 1,
The molar ratio of the alkyl alcohol to the alkyl acrylate monomer is 0.8 to 1.0 mol of the alkyl acrylate monomer per 1 mol of the alkyl alcohol. According to claim 1,
The phenol-based antioxidant is used as a reaction terminator after the reaction of the mixture of the alkyl alcohol and the ethoxide salt with the alkyl acrylate monomer is completed. 12. The method of claim 11,
The phenolic antioxidant is at least one of BHA, BHT, Cyanox 1790, Cyanox 2246, Cyanox425, Irganox3314, Irganox1076, Irganox1330, and Irganox 1010. 13. The method of claim 12,
The method for producing an alkyl 3-alkoxy propionate wherein the phenolic antioxidant is used in an amount of 50 ppm or more and 5,000 ppm or less based on the total weight.