KR20200131065A - Method for producing Alkyl 3-Alkoxypropionate Using Continuous Type Process - Google Patents

Abstract

The present invention relates to a method for producing an alkyl 3-alkoxy propionate, and more particularly, to a method for producing ethyl 3-ethoxypropionate in a continuous manner. The present invention provides a method for producing an alkyl 3-alkoxy propionate, capable of producing an alkyl 3-alkoxy propionate for semiconductors on a large scale in an organic synthesis method by using a continuous reaction. The method for producing an alkyl 3-alkoxy propionate according to the present invention can produce an alkyl 3-alkoxy propionate for semiconductors at a high conversion rate by using a continuous method in a large-scale production process.

Description

Method for producing alkyl 3-alkoxypropionate using continuous reaction process {Method for producing Alkyl 3-Alkoxypropionate Using Continuous Type Process}

The present invention relates to a method for preparing an alkyl 3-alkoxypropionate, and more particularly, to a method for producing ethyl 3-ethoxypropionate in a continuous manner.

Since the organic solvent used in the semiconductor manufacturing process should not adversely affect the electrical properties of the semiconductor product, it must meet the strict quality standards of ultra-high purity, ultra-low acrylic acid, ultra-low acid value, low moisture, and ultra-low metal content and low particles.

EEP (Ethyl 3-Ethoxypropionate), which is used as a thinner in the semiconductor manufacturing process, must also meet the strict quality standards of ultra-high purity, ultra-low acrylic acid, ultra-low acid value, low moisture, ultra-low metal content, and low particles.

EEP can be synthesized in small quantities on a laboratory scale using ethanol (Ethanol, EtOH) and ethyl acrylate monomer (EAM) as raw materials under a strong acid catalyst (see US5081285) or under a strong alkali catalyst (see JP1978586).

In the case of manufacturing EEP using a strong acid catalyst (see US5081285), the yield is very low (about 47 wt%) and a large amount of diethyl ether, a by-product produced from the solvent by the strong acid catalyst, may be included. It is not suitable as an EEP manufacturing method.

In the case of producing EEP using a strong alkali catalyst (see JP1978586), since it reacts simply by mixing raw materials EtOH and EAM at a scale of 0.5 liters or less on a laboratory scale, it is particularly suitable for inventive reactions that may be a problem in the case of mass scale reactions of 10 kiloliters or more. It is impossible to apply it in large-scale production processes as there are no countermeasures for the problem and interruption of the reaction during the reaction.

EEP, which is used in large quantities in the semiconductor manufacturing process, uses ethanol (EtOH) and ethyl acrylate monomer (EAM) as raw materials according to the following Scheme 1, and sodium ethoxide as a catalyst. It can be prepared by reacting.

[Scheme 1]

This EEP synthesis reaction is an exothermic reaction as an addition reaction where two molecules react to produce a target substance and no other products. In more detail, this synthesis reaction starts only by heating the reaction mixture in the presence of a catalyst, and when the reaction proceeds to generate the target substance, EEP, two single bonds within the EEP molecule instead of one of the double bonds of the EAM molecule. Is generated, and extra energy is generated to generate heat.

Therefore, since these synthetic reactions use low-boiling reactants (EtOH boiling point 78°C, EAM boiling point 99°C), heat generation must be efficiently controlled. In particular, in large-scale reactions of 10 kiloliters or more, cooling efficiency is lowered than in small-scale reactions. Can be much more difficult to control.

In addition, this EEP synthesis reaction is possible in the presence of a strong alkali catalyst, in the presence of a strong alkali catalyst, a reverse reaction from the reaction product to EtOH and EAM is also possible. If the speed is the same as ), there is a problem that the net reaction stops and the reaction rate decreases.

And when the conversion rate of EAM to EEP conversion (wtEEPx100/(wtEEP+wtEAM)) is low, the reaction mixture at the end of the reaction is purified by fractional distillation into EEP for semiconductors, as the acid value (Acid Value, amount of acetic acid). Conversion) and acrylic acid (Acrylic Acid) content may increase.

In the case of performing the purification process using fractional distillation separated by the difference in boiling point by heating the reaction mixture at the end of the reaction, esters such as EEP are hydrolyzed by moisture present in the reaction mixture. Often, the acid value increases. In general, in the case of industrial or electronic use, an acid value of less than about 150wtppm is satisfactory, but in the case of a semiconductor solvent, since acid may affect the electrical properties of the semiconductor, the EEP must satisfy a very low acid value standard of less than 20wtppm.

In particular, in the case of EEP manufacturing, since it is produced by hydrolysis of EAM (Ethyl Acrylate Monomer) and is a relatively strong acid, acrylic acid must be less than 0.5wtppm, which is a very small amount, a special technique is required for purification. In addition, the semiconductor solvent must meet the quality standards of 20wtppt or less of individual metals and of 0.1μm or more and 200/milliliter of particles.

On the other hand, conventional reaction devices for general chemical or physical reactions are largely divided into a continuous type (flow type, flow type, continuous type) reactor and a batch type (batch type, batch type, batch type) reactor. In the process of flowing the reactant by inflow, the reaction proceeds and the product is discharged through the outlet. In the latter case, the reactant is introduced into the reactor and the reaction is carried out in the reactor in a stopped state, and the product is recovered. In addition, there is a semi-batch type reactor in which raw materials are initially added and other raw materials are added as the reaction proceeds.

Continuous reactors that have been used in the past provide the advantage of quick product recovery, but lack a means to control the size of the reaction product. In the case of a batch reaction, the reaction efficiency decreases and takes a long time. Likewise, it does not provide a means to control the size of the reaction product.

Therefore, there has been a need for a method for synthesizing alkyl 3-alkoxypropionate using a continuous reaction process.

US Patent Publication US5,081,285 (1992.01.14) Korean Patent Publication No. 1997-0000138 (1997.01.04) Korean Patent Registration 10-1038232 (2011.05.25)

In one aspect, the problem to be solved by the present invention is to provide a method of manufacturing an EEP that can be purified to an excellent quality level that can be used in a semiconductor manufacturing process in a mass scale using a continuous method.

In another aspect, another problem to be solved by the present invention is to provide a method of manufacturing EEP with a high conversion rate of 97 wt% or more using a continuous method.

In one embodiment, the present invention is a batch reaction process step for obtaining a batch reaction process product by performing a batch reaction process in a reaction system, the batch reaction process product obtained in the batch reaction process step 2 Injecting the two or more reaction systems into each of the two or more reaction systems, wherein the two or more reaction systems are connected in series with each other forming a closed circuit by a connection line, but are mutually blocked by a valve provided on the connection line, and in series A continuous reactant for a continuous reaction process is continuously injected into the first reaction system arranged at the front of the connected two or more reaction systems, and each reaction system is connected while forming a closed circuit through a connection line by opening the valve. Alkyl 3-alkoxypropionate using a continuous reaction process, including a continuous reaction process step in which the reaction process is performed in the state and the outlet of the reaction system disposed at the most terminal is opened to perform a continuous reaction process It provides a method of manufacturing.

In another embodiment, the present invention forms a closed circuit by a connection line and is connected in series with each other, and a reactant is added to each of two or more reaction systems mutually blocked by a valve provided on the connection line, and in each reaction system. A batch-type reaction process step for obtaining a batch-type reaction process product by performing a batch-type reaction process at, and a continuous reaction process for a continuous reaction process in the first reaction system arranged at the front of the two or more reaction systems connected in series. Reactants are continuously added and the valves are opened so that each reaction system forms a closed circuit through the connection line, and the reaction process is carried out in a connected state, and the final product is discharged by opening the outlet of the reaction system disposed at the far end. It provides a method for producing an alkyl 3-alkoxypropionate using a continuous reaction process, including a continuous reaction process step of performing a continuous reaction process.

In another embodiment, the batch reaction process step according to one embodiment of the present invention is represented by the following scheme,

Here, R ¹ and R ² are each independently an alkyl group of C ₁ to C ₆ , the catalyst (Cat.) is a strong alkali catalyst, and the batch reaction process step 1) a mixture of alkyl alcohol and catalyst 1a in a reaction vessel Preparing; 2) adding water to the 1a mixture so that the water content is 600 ~ 1,000 wtppm to form the 2a mixture, wherein the water content is based on the total weight of the 2a mixture; 3) heating the 2a mixture to 30 to 70°C; 4) forming a 3a mixture by dropwise adding an alkyl acrylate to the 2a mixture so that the mole ratio of alkyl acrylate:alkyl alcohol is 1:1 to 1:3; 5) maintaining the 3a mixture at 50 to 70°C; 6) analyzing the reaction conversion rate at the end of the reaction of the 3a mixture; And 7) if the reaction conversion rate is 97 wt% or more, the reaction is terminated, and when the reaction conversion rate is less than 97 wt%, adding water to the mixture 3a so that the content of water is 50 to 200 wtppm, wherein the water content is zero. 3a Based on the total weight after adding water to the mixture; comprising, a method for producing an alkyl 3-alkoxypropionate using a continuous reaction process is provided.

In another embodiment, the continuous reactant according to one embodiment of the present invention is a mixture 2b produced by adding water to a mixture of alkyl alcohol and a catalyst 1b so that the content of water is 600 to 1,000 wtppm (wherein The water content is based on the total weight of the 2b mixture), and the molar ratio of alkyl acrylate:alkyl alcohol to the alkyl alcohol added to the 2b mixture is 1:1 to 1:3 There is provided a method for producing an alkyl 3-alkoxypropionate using a continuous reaction process, comprising an alkyl acrylate.

In another embodiment, the catalyst according to one embodiment of the present invention is lithium ethoxide, sodium ethoxide, potassium ethoxide, rubidium ethoxide, cesium ethoxide, beryllium ethoxide, magnesium ethoxide, and calcium ethoxide. There is provided a method for producing an alkyl 3-alkoxypropionate using a continuous reaction process, selected from the group consisting of one or more.

In another embodiment, R ¹ and R ² are each independently a methyl group, an ethyl group, an n-propyl group, or an n-butyl group, a method for preparing an alkyl 3-alkoxypropionate using a continuous reaction process is provided. .

The method for preparing alkyl 3-alkoxypropionate according to the present invention can produce alkyl 3-alkoxypropionate for semiconductors at a high conversion rate using a continuous method in a large-scale production process.

1 is a schematic diagram showing a reaction system used in a batch reaction process.
2 is a schematic diagram showing a reaction system for performing a continuous reaction process using two or more reaction systems according to an embodiment of the present invention.
3 is a schematic diagram showing a reaction system for performing a continuous reaction process using a reaction system of one unit.

In general, the chemical reaction is carried out as a batch reaction in which the reaction continues until the purpose is achieved once the raw material is added, and a semi-batch reaction in which the raw material is initially added and other raw materials are added as the reaction proceeds. However, in the case of a batch-type or semi-batch-type reaction, there is a problem that the reaction efficiency is low and it takes a long time.

In addition, the chemical reaction may be carried out as a continuous reaction in which raw materials are continuously supplied and products are discharged. In the case of a continuous reaction, the product recovery rate is fast.

Therefore, in order to solve the above problems in the production of alkyl 3-alkoxypropionate, the present inventors have used a continuous reaction as follows through a variety of long-term studies to organically synthesize alkyl 3-alkoxypropionate for semiconductors on a large scale. Invented a method for preparing an alkyl 3-alkoxypropionate capable of preparing an ate.

Hereinafter, a method of preparing an alkyl 3-alkoxypropionate using a batch type (including a semi-batch type) reaction process according to one aspect of the present invention will be described, and then, a continuous reaction process is used. A method of preparing the alkyl 3-alkoxypropionate will be described.

A general alkyl 3-alkoxypropionate synthesis reaction can be represented by Scheme 2 below.

[Scheme 2]

In the above reaction formula, R ¹ and R ² may each independently be a C ₁ to C ₆ alkyl group, and preferably R ¹ and R ² may be independently a methyl group, an ethyl group, an n-propyl group, or an n-butyl group. And, most preferably, both of 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. One or more may be selected from the group consisting of, but is not limited thereto.

A batch reaction process for synthesizing an alkyl 3-alkoxypropionate according to one aspect of the present invention may comprise the following steps:

1) preparing a mixture of alkyl alcohol and catalyst 1a in a reaction vessel;

2) adding water to the 1a mixture so that the water content is 600 ~ 1,000 wtppm to form the 2a mixture, wherein the water content is based on the total weight of the 2a mixture;

3) heating the second a mixture to 30 ~ 70 ℃;

4) forming a 3a mixture by adding an alkyl acrylate dropwise to the 2a mixture so that the molar ratio of alkyl acrylate:alkyl alcohol is 1:1 to 1:3; And

5) maintaining the 3a mixture at 50 to 70°C.

The batch reaction process for synthesizing the alkyl 3-alkoxypropionate may further include the following steps:

6) analyzing the reaction conversion rate at the end of the reaction of the 3a mixture; And

7) If the reaction conversion rate is 97 wt% or more, the reaction is terminated, and if the reaction conversion rate is less than 97 wt%, adding water to the mixture 3a so that the content of water is 50 ~ 200 wtppm, wherein the content of water is 3a Based on the total weight after adding water to the mixture.

The batch reaction process for synthesizing the alkyl 3-alkoxypropionate according to the prior art can be carried out in one closed batch reaction system as shown in FIG. 1. That is, as shown in FIG. 1, the reactant 11 can be put into one batch-type reaction system 10 and the reaction process for obtaining the product 13 can be carried out. As the reaction proceeds, the additional reactant 12 can be added if necessary. You can put in more.

However, the batch reaction process for synthesizing alkyl 3-alkoxypropionate according to one embodiment of the present invention is performed in the first reaction system 20 and the second reaction system 30 as shown in FIG. Each can be performed. At this time, the first reaction system 20 and the second reaction system 30 are connected while forming a closed circuit by the connection line 50, but are mutually blocked by the valve 61.

Specifically, as shown in FIG. 2, the reaction system for synthesizing alkyl 3-alkoxypropionate according to one embodiment of the present invention includes a first reaction system 20 and a second reaction system 30. Including, the first reaction system 20 and the second reaction system 30 may be connected while forming a closed circuit by a connection line 50, the valve 60 provided on the connection line 50 It may be mutually blocked or opened by.

As described above, the batch reaction process for synthesizing an alkyl 3-alkoxypropionate according to one embodiment of the present invention is as shown in FIG. 2, the first reaction system 20 and the second reaction system 30 ) Can be performed within each. That is, reactants 21 and 31 may be added to each of the first reaction system 20 and the second reaction system 30 to perform a reaction process for obtaining a product. As the reaction proceeds, additional reactants 22 and 32 may be added if necessary. At this time, the first reaction system 20 and the second reaction system 30 are connected while forming a closed circuit by the connection line 50 but are mutually blocked by the valve 61. On the other hand, the second reaction system 30 may be provided with an outlet for discharging the final product, and the outlet is blocked by a valve 62 during the batch reaction process.

Hereinafter, each step of the method for preparing an alkyl 3-alkoxypropionate by a batch reaction process according to the present invention will be described in detail.

In general, in the case of the manufacturing process by organic synthesis, the final yield (Yield) is preferably 90wt% or more, and according to the research of the present inventors, in order to purify the alkyl 3-alkoxypropionate satisfying the quality characteristics for semiconductors, A high conversion rate of 97wt% or more is required during the reaction, which is higher than the yield standard.

First, in order to synthesize alkyl 3-alkoxypropionate organically, in the case of reacting an alkyl alcohol and an alkyl acrylate in the presence of a catalyst, the moisture content is as low as 400 wtppm or less or too high as 0.12 wt% or more, it directly affects the yield. A problem in which the reaction stops at a low conversion rate of 70 to 80 wt% from an alkyl acrylate to an alkyl 3-alkoxypropionate may occur.

This phenomenon in which the reaction is stopped is a phenomenon in which the rate of the reverse reaction in which the product alkyl 3-alkoxypropionate is decomposed into the reactant alkyl alcohol and alkyl acrylate in the presence of a catalyst increases, and the reverse reaction becomes the same as the forward reaction in which a product is generated from the reactant. Because.

As a result of the inventors' research to solve this problem, the method for preparing alkyl 3-alkoxypropionate using a batch reaction process according to one aspect of the present invention is 1) a mixture of alkyl alcohol and catalyst in a reaction vessel Preparing, 2) adding water to the 1a mixture so that the content of water is 600 ~ 1,000 wtppm to generate the 2a mixture. Here, the content of water is based on the total weight of the second mixture to which water is added. That is, the conversion rate can be increased by adding water to the mixture of alkyl alcohol and catalyst, which is a reactant and solvent, before the start of the reaction, and adjusting the water content to be 600 ~ 1,000 wtppm. If the water content is out of the range of 600 to 1,000 wtppm, the conversion rate from the reactant alkyl acrylate to the product alkyl 3-alkoxypropionate may cause a problem in which the reaction stops at a low conversion rate of 70 to 80 wt%.

The catalyst used in the method for preparing an alkyl 3-alkoxypropionate according to one embodiment of the present invention may be a strong alkali catalyst, for example, lithium ethoxide, sodium ethoxide, potassium ethoxide, rubidium ethoxide, cesium ethoxide. Side, beryllium ethoxide, magnesium ethoxide, and may be one or more selected from the group consisting of calcium ethoxide, but is not limited thereto. The catalyst to be added may be added in an amount sufficient to act as a catalyst.

On the other hand, in order to organically synthesize alkyl 3-alkoxypropionate on a large scale, heat generation may be a problem when the reactants of alkyl alcohol and alkyl acrylate are reacted in the presence of a catalyst. This exothermic problem can be a big problem when the reaction scale is a large amount of 10 kiloliters or more. In order to solve such an exothermic problem, the inventors varied the amount of reactants and catalysts used, mixing sequence, feed rate of raw materials, reaction temperature, etc., and varied research results. As a result, the ratio of the amount of reactants used was determined by 1.0 to 3.0 moles of the reactant alkyl acrylate. It was found that this problem can be solved by using (mole) an excess of alkyl alcohol as a solvent and reactant.

Therefore, before the start of the reaction, the mixture of alkyl alcohol, catalyst and water is heated to 30 to 70°C, and then the alkyl acrylate is gradually added dropwise. The alkyl acrylate can be added continuously or semi-continuously and should be at a rate sufficient to convert the alkyl acrylate to the desired alkoxypropionate product by the desired conversion. On the other hand, if the operation is performed at a temperature outside this range, the reaction rate and/or yield are deteriorated due to the conversion rate at which the alkyl acrylate is converted into a product or decomposition of the alkyl alcohol reactant. As the alkyl acrylate is added to the mixture of alkyl alcohol, catalyst and water, the reaction starts and an exothermic phenomenon occurs. Therefore, the temperature inside the reaction system can be controlled to 50 to 70°C by the dropwise addition rate of the alkyl acrylate and appropriate cooling. By controlling the temperature in this range, it is possible to solve the exothermic problem of the reaction, which may be a problem on a large scale.

Therefore, as described above, a method for preparing an alkyl 3-alkoxypropionate using a batch reaction process according to an aspect of the present invention includes the steps of 1) preparing a mixture of alkyl alcohol and catalyst 1a in a reaction vessel, 2) water In addition to the step of generating a mixture 2a by adding water to the mixture 1a so that the content is 600 ~ 1,000 wtppm, 3) heating the mixture 2a to 30 ~ 70 ℃, 4) the mixture 2a To form a 3a mixture by dropwise adding an alkyl acrylate so that the molar ratio of the alkyl acrylate: alkyl alcohol is 1:1 to 1:3, and 5) maintaining the 3a mixture at 50 to 70°C It may include the step of.

On the other hand, as a result of analyzing the conversion rate after the reaction is terminated, the reaction may be stopped at a conversion rate of 90 to 95 wt%. This problem is that if a considerable amount of catalyst is present during the reaction process, but the moisture content in the reaction mixture is too low to 50 wtppm or less at a conversion rate of 90 to 95 wt%, the reaction is stopped due to insufficient regeneration of the catalyst essential for the catalytic reaction during the catalyst role and regeneration process. It is judged to be. Here, the moisture content is based on the total weight of the reaction mixture, which is measured as a conversion rate of 90 to 95 wt%. When the conversion rate is low as 90 to 95 wt% when the reaction mixture is analyzed after the dropwise addition of alkyl acrylate is complete, the conversion rate was analyzed. When the water content of the sample, which is a reaction mixture, is analyzed, the moisture content is less than 50 wtppm.

In order to solve this problem, it was found that if a large amount of 0.12 wt% or more was added to the alkyl alcohol including the catalyst before the start of the reaction, a considerable amount of the catalyst was destroyed by a large amount of moisture and the conversion rate was lowered, so that it could not be a solution.

As a result of research in order to solve the problem of stopping at the conversion rate of 90 to 95 wt%, it was determined that the catalyst was not smoothly regenerated in the middle of the forward reaction as described above, so that the water content after adding additional moisture was 50 to 200 wtppm. If the reaction is continued after additional addition to the reaction mixture or a small amount of catalyst is added, the reaction can be completed with a conversion rate of 97wt% or more.

Accordingly, a method for preparing an alkyl 3-alkoxypropionate using a batch reaction process according to another aspect of the present invention includes the steps of: 6) analyzing the reaction conversion rate at the end of the reaction of the mixture 3a, and 7) the reaction conversion rate is 97 wt. % Or more, the reaction is terminated, and if the reaction conversion rate is less than 97wt%, additional water is added to the mixture 3a so that the content of water is 50 to 200 wtppm based on the weight of the total reaction mixture after adding additional moisture. Can include.

Hereinafter, a method for preparing an alkyl 3-alkoxypropionate using a continuous reaction process according to another aspect of the present invention will be described.

As described above and as shown in FIG. 2, the first reaction system 20 and the second reaction system 20 are connected while forming a closed circuit by the connection line 50, but are blocked from each other by the valve 61. 30) After each batch-type reaction process is performed to complete the production of the batch-type reaction process product, while maintaining the reaction conditions, the continuous reactant 41 is continuously introduced into the first reaction system 20, and the valve ( 61) is opened to perform a continuous reaction process step in which the first reaction system 20 and the second reaction system 30 are connected to each other while forming a closed circuit by the connection line 50. At this time, the continuous reactant 41 is continuously introduced into the first reaction system 20, while the valve 61 is opened to connect the first reaction system 20 and the second reaction system 30 to the connection line 50. The mixture of the batch-type reaction process product and the continuous reactant 41 in the first reaction system 20 is connected to the second reaction system 30 while the reaction process is performed in the first reaction system 20. It moves through the connection line 50.

In the continuous reaction process for synthesizing an alkyl 3-alkoxypropionate according to an embodiment of the present invention, the continuous reactant 41 has a water content of 600 to 1,000 in the first b mixture of an alkyl alcohol and a catalyst. 2b mixture produced by adding water to a weight ppm (wherein the content of water is based on the total weight of the 2b mixture), and alkyl acrylate: mole of alkyl alcohol with respect to the alkyl alcohol added to the 2b mixture ( mole) ratio of 1:1 to 1:3. That is, when the continuous reactant 41 is added to the first reaction system 20, the mole ratio of the second b mixture and the alkyl acrylate (alkyl acrylate: alkyl alcohol to the alkyl alcohol added to the 2 b mixture) is It means adding an alkyl acrylate of 1:1 to 1:3) at the same time.

On the other hand, the second reaction system 30 by using a metering pump (not shown) so that the level of the reaction mixture in the first reaction system 20 is kept constant while the continuous reactant 41 is introduced into the first reaction system 20. ) To discharge and move the reaction mixture in the first reaction system 20. In addition, the final product generated in the second reaction system 30 is opened to the outlet by opening the pump 62 using a metering pump (not shown) so that the level of the reaction mixture in the second reaction system 30 is kept constant. Discharge.

The method for preparing alkyl 3-alkoxypropionate using a continuous reaction process according to one embodiment of the present invention comprises the first reaction system 20 and the first reaction system 20 connected while forming a closed circuit through the connection line 50 as described above. It is characterized in that at least two reaction systems of two reaction systems 30 are used.

As shown in FIG. 3, when only one reaction system is used in the continuous reaction process, it is difficult to achieve a conversion ratio of 97 wt% or more even if the residence time is increased. That is, in the reaction system 120 in which a batch reaction process product having a conversion rate of 97 wt% or more is present as the batch reaction process is completed, the continuous reactant 141 (e.g., 600 ~ 1,000 wtppm) When a mixture of an alkyl alcohol with a controlled moisture content and a mixture of a catalyst, and an alkyl acrylate) are added, a condition that can increase the conversion rate by 97 wt% or more is formed similar to that in the batch reaction process, but a continuous reaction product (e.g., alkyl alcohol Since the mixture of the catalyst and the alkyl acrylate) is continuously added to the reaction system 120, it is determined that the conversion rate cannot increase by more than 97 wt%.

However, in the case of using two or more reaction systems, in the first and second reaction systems in which the batch-type reaction process is completed and the product of the batch-type reaction process having a conversion rate of 97 wt% or more exists, continuous reactants (e.g., 600 ~ 1,000 wtppm) A mixture of an alkyl alcohol and a catalyst with a controlled moisture content, and an alkyl acrylate) are added only to the first reaction system. In this case, since the continuous reactant is continuously added to the first reaction system, moisture is added, which may correspond to the moisture control step of the batch-type reaction process, while the continuous reactant is not directly added to the second reaction system. Since the reaction mixture is supplied from the first reaction system, unlike the first reaction system, the second reaction system is supplied with a reaction mixture that has already undergone a certain amount of reaction in the first reaction system, so that a conversion rate of 97 wt% or more can be achieved when the final product is generated. It is judged to be there.

When the batch-type reaction process and the continuous reaction process according to the present invention are compared and described, in the batch-type reaction process, the conversion rate is increased to 90-95 wt% in the step of a) adding the initial reactant and moisture to proceed with the reaction, Since the reaction is stopped after that, it undergoes a two-step process of achieving a conversion rate of 97 wt% or more by adding water again and reacting.

On the other hand, in the continuous reaction process according to the present invention, such a batch reaction process is performed in advance in the first reaction system and the second reaction system, respectively, and in the presence of the batch reaction process product, the continuous reactant in the first reaction system The reaction is carried out by adding, which can be said to correspond to the step of adding moisture in step b) in the batch reaction process. Thereafter, the reaction proceeds in a second reaction system connected to the first reaction system, which can be said to correspond to the reaction step after the addition of water in step b) in the batch reaction process. The present invention can achieve a conversion rate of 97 wt% or more in a continuous manner by a two-step reaction process in the first and second reaction systems.

Example

Reaction process 1. Pre-batch reaction process

In the reaction system, the pre-batch reaction process was performed according to the following procedure.

① 1.50kg of EtOH added to the 5L reactor

② To the EtOH, a strong alkali catalyst 20wt% sodium ethoxide EtOH solution (a solution in which the catalyst is dissolved in EtOH) 35g is added and stirred to achieve a uniform concentration, followed by mixing.

③ ② Analyze the moisture content of the mixture, add an appropriate amount of moisture to the mixture, stir and mix, and adjust the moisture content of the mixture to 600~1,000 wtppm.

④ Heating to 60℃ while stirring the above ③ mixture

⑤ Add 1.97kg of EAM to the ④ mixture gradually dropwise for 60 minutes (inject to reduce droplets)

⑥ After completion of the EAM dropwise addition, a small amount of the reaction mixture was collected and analyzed by GC to calculate the conversion rate. At this time, the conversion rate was 90-95 wt%, and the moisture content was also analyzed. At this time, the moisture content was less than 50 wtppm.

⑦ Adjust the moisture content of the mixture to 50~200 wtppm after stirring and mixing by adding moisture to the above ⑥ mixture

⑧ Stir for 60 minutes so that the ⑦ mixture result is further reacted

⑨ The conversion rate was 97 wt% or more as a result of collecting a small amount of the ⑧ mixture and performing GC analysis.

Reaction process 2. Continuous reaction process

<Example 1>

As shown in FIG. 2, 4 to 4.5 L of the batch-type reaction process product produced in the reaction process 1 were prepared in each of the first reaction system (5 L reactor) and the second reaction system (10 L reactor). At this time, the first reaction system (5 L reactor) and the second reaction system (10 L reactor) are blocked by the valve 61, and the outlet of the second reaction system (10 L reactor) is connected to the valve 62. Blocked by

Next, add 2.2wt% sodium ethoxide EtOH solution of 2.2wt% based on the weight of EtOH to EtOH, add moisture, and adjust the moisture to 920 wtppm. To prepare a continuous reaction product.

Meanwhile, the temperature of the reaction mixture (ie, batch-type reaction process product) in the first reaction system (5 L reactor) and the second reaction system (10 L reactor) was maintained at 60°C using a liquid circulation device.

Thereafter, the previously prepared continuous reactants, that is, EtOH and EAM containing a catalyst in which the moisture content is controlled, are introduced into the first reaction system (5 L reactor), EtOH is at a rate of 21.3 g (27 mL)/min, and EAM is At a rate of 30.1 g (32 mL)/min, it was continuously and continuously added simultaneously to the first reaction system (5 L reactor).

After that, the valve 51 is opened so that the first reaction system (5 L reactor) and the second reaction system (10 L reactor) are connected to each other through the connection line 50, and are prepared using a metering pump (not shown). The reaction mixture is discharged so that the level of the reaction mixture in the first reaction system (5 L reactor) is kept constant, and the discharged reaction mixture is introduced into the second reaction system (10 L reactor) through the connection line 50. In addition, in order to maintain the level of the reaction mixture in the second reaction system (10 L reactor), the final product generated in the second reaction system (10 L reactor) was discharged through the outlet using a metering pump (not shown).

Meanwhile, the conversion rate of the reaction mixture discharged from each reaction system over time was measured using GC analysis.

Here, the residence time (minutes) of the reaction mixture in each reaction system is the volume of the reaction mixture in the reaction system (mL) / input amount (mL/minute). And the input flow rate (mL) is the accumulated amount (mL) + the production amount (mL, the reaction system discharge), where the accumulated amount is 0 mL, so the input flow rate and the production amount are the same.

As described above, the moisture content was controlled and the catalyst-containing EtOH and EAM were each controlled at a rate of 21.3 g (27 mL)/min, and at a rate of 30.1 g (32 mL)/min, and continuously continuously transferred to the first reaction system. In this case, the volume of the reaction mixture in each reaction system is 4.48L, the residence time of the reaction mixture is 76 minutes, and the product output per hour is 3.54L.

In the reaction process performed according to Example 1, the results of measuring the conversion rate of the reaction mixture (i.e., product) discharged from the first reaction system (5 L reactor) and the second reaction system (10 L reactor) over time are shown in the table below. It was shown in 1 and Table 2, respectively.

Reaction time 60 minutes 90 minutes 120 minutes 150 minutes 180 minutes 210 minutes 240 minutes 270 minutes 300 minutes Conversion rate,% 95.5 94.5 92.8 96.2 95.7 92.0 96.7 95.7 95.9

Reaction time 60 minutes 90 minutes 120 minutes 150 minutes 180 minutes 210 minutes 240 minutes 270 minutes 300 minutes Conversion rate,% 97.8 97.5 97.8 97.6 97.3 97.8 97.8 97.3 97.3

As can be seen in Table 2 above, since the conversion rate of the final product discharged from the second reaction system (10 L reactor) 1 hour after the start of the reaction is continuously achieved above 97wt%, continuous synthesis of EEP for semiconductors using two reactors Since it is possible stably and there is no problem in maintaining 60℃ in terms of conversion rate and reaction temperature, it can be applied to mass-scale continuous production.

<Example 2>

An EEP reaction mixture was prepared in the same manner as in Example 1, and the residence time in each reaction system was 62 minutes, the moisture content in EtOH including the catalyst solution of 2.2 wt% relative to the weight of EtOH was 920 wtppm, and the EtOH flow rate 30.0 g (38 mL)/ Minute, EAM flow rate 39.5g (42mL)/min, the volume of the reaction mixture in the reaction system was 4.96L, and the product output per hour was 4.80L.

In the reaction process carried out according to Example 2, the results of measuring the conversion rate of the reaction mixture (i.e., product) discharged from the first reaction system (5 L reactor) and the second reaction system (10 L reactor) over time are shown in the table below. It is shown in 3 and Table 4 respectively.

Reaction time 30 minutes 60 minutes 90 minutes 150 minutes 180 minutes Conversion rate,% 96.5 96.8 96.8 96.4 96.4

Reaction time 30 minutes 60 minutes 120 minutes 150 minutes 180 minutes Conversion rate,% 96.5 96.8 97.4 97.9 98.0

As can be seen in Table 4 above, since the conversion rate of the final product discharged from the second reaction system (10 L reactor) 2 hours after the start of the reaction is continuously achieved above 97wt%, continuous synthesis of EEP for semiconductors using 2 reactors Since it is possible stably and there is no problem in maintaining 60℃ in terms of conversion rate and reaction temperature, it can be applied to mass-scale continuous production.

<Example 3>

An EEP reaction mixture was prepared in the same manner as in Example 1, and the residence time in each reaction system was 40 minutes, the moisture content in EtOH including the catalyst solution of 2.2 wt% relative to the weight of EtOH was 900 wtppm, and the EtOH flow rate 30.0 g (38 mL). /Min, EAM flow rate 39.5g (42mL)/min, the volume of the reaction mixture in the reaction system was 4.48L, and the product produced per hour was 4.80L.

In the reaction process performed according to Example 3, the results of measuring the conversion rate of the reaction mixture (i.e., product) discharged from the first reaction system (5 L reactor) and the second reaction system (10 L reactor) over time are shown in the table below. It is shown in 3 and Table 4 respectively.

Reaction time 40 minutes 60 minutes 100 minutes 140 minutes 180 minutes Conversion rate,% 89.6 93.4 94.8 94.9 95.0

Reaction time 40 minutes 60 minutes 100 minutes 140 minutes 180 minutes Conversion rate,% 87.8 90.4 95.7 97.5 97.1

As can be seen in Table 6 above, since the conversion rate of the final product discharged from the second reaction system (10 L reactor) 140 minutes after the start of the reaction is continuously achieved above 97wt%, continuous synthesis of EEP for semiconductors using two reactors Since it is possible stably and there is no problem in maintaining 60℃ in terms of conversion rate and reaction temperature, it can be applied to mass-scale continuous production.

<Example 4>

An EEP reaction mixture was prepared in the same manner as in Example 1, and the residence time in each reaction system was 40 minutes, the moisture content in EtOH including the catalyst solution of 1.8 wt% relative to the weight of EtOH was 900 wtppm, and the EtOH flow rate 30.0 g (38 mL). /Min, EAM flow rate 39.5g (42mL)/min, the volume of the reaction mixture in the reaction system was 3.20L, and the product produced per hour was 4.80L.

In the reaction process performed according to Example 4, the result of measuring the conversion rate of the reaction mixture (i.e., product) discharged from the first reaction system (5 L reactor) and the second reaction system (10 L reactor) over time is shown in the table below. It is shown in 3 and Table 4 respectively.

Reaction time 40 minutes 80 minutes 120 minutes 160 minutes 200 minutes 240 minutes 280 minutes 320 minutes 360 minutes Conversion rate,% 74.9 85.5 88.1 92.5 83.7 88.7 93.9 93.6 93.1

Reaction time 40 minutes 80 minutes 120 minutes 160 minutes 200 minutes 240 minutes 280 minutes 320 minutes 360 minutes Conversion rate,% 89.8 85.2 88.1 93.5 94.3 91.8 95.4 97.1 97.0

As can be seen in Table 8 above, since the conversion rate of the final product discharged from the second reaction system (10 L reactor) after 320 minutes of the start of the reaction is continuously achieved above 97wt%, continuous synthesis of EEP for semiconductors using two reactors Since it is possible stably and there is no problem in maintaining 60℃ in terms of conversion rate and reaction temperature, it can be applied to mass-scale continuous production.

On the other hand, even if the residence time of the reaction mixture in the reactor was shortened from 76 minutes (Example 1) to 40 minutes and the amount of catalyst was reduced to 1.8 wt% compared to EtOH, the reaction could be completed.

Comparative example

As shown in FIG. 3, 4 to 4.5 L of the batch-type reaction process product produced in the reaction process 1 were prepared in a reaction system (5 L reactor).

Next, add 2.2 wt% sodium ethoxide EtOH solution of 2.2 wt% to the weight of EtOH to EtOH, add moisture to adjust the moisture to 750 wtppm, and add about 5 kg to the EtOH raw vessel, and also add about 5 kg EAM to the EAM vessel. To prepare a continuous reaction product

On the other hand, the temperature of the reaction mixture (ie, batch reaction process product) inside the reaction system (5 L reactor) was maintained at 60°C using a liquid circulation device or the like.

Thereafter, the previously prepared continuous reactants, that is, EtOH and EAM containing a catalyst with controlled moisture content, are added to the reaction system (5 L reactor), EtOH at a rate of 16.6 g (21 mL)/min, and EAM at a rate of 20.7 g. It was continuously added to the reaction system (5 L reactor) at the same time and continuously by controlling at a rate of (22 mL)/min.

Thereafter, the final product was discharged through the outlet so that the level of the reaction mixture in the reaction system (5 L reactor) was kept constant using a metering pump (not shown).

Meanwhile, the conversion rate of the reaction mixture discharged from each reaction system over time was measured using GC analysis.

Here, the residence time (minutes) of the reaction mixture in each reaction system is the volume of the reaction mixture in the reaction system (mL) / input amount (mL/minute). And the input flow rate (mL) is the accumulated amount (mL) + the production amount (mL, the reaction system discharge), where the accumulated amount is 0 mL, so the input flow rate and the production amount are the same.

As described above, the moisture content was controlled and the catalyst-containing EtOH and EAM were each adjusted at a rate of 16.6 g (21 mL)/min, and at a rate of 20.7 g (22 mL)/min, and continuously added to the reaction system. In this case, the volume of the reaction mixture in each reaction system is 3.89L, the residence time of the reaction mixture is 90 minutes, and the product yield per hour is 2.58L.

Table 9 shows the results of measuring the conversion rate of the reaction mixture (ie, product) discharged from the reaction system (5 L reactor) over time in the reaction process performed according to the comparative example.

Reaction time Initial reactor 60 minutes 100 minutes 130 minutes 160 minutes 200 minutes 240 minutes Conversion rate,% 97.9 88.6 94.1 91.6 94.3 94.5 94.3

As can be seen from Table 9 above, since the conversion rate cannot achieve more than 97wt% even after a long reaction, continuous synthesis of EEP for semiconductor using one reactor is inappropriate.

Claims (6)

A batch reaction process step for obtaining a batch reaction process product by performing a batch reaction process in the reaction system;
Injecting the batch-type reaction process product obtained in the batch-type reaction process step into each of two or more reaction systems, wherein the two or more reaction systems are connected in series with each other forming a closed circuit by a connection line, wherein the connection line They are mutually blocked by a valve provided on the top; And
A continuous reactant for a continuous reaction process is continuously injected into the first reaction system arranged at the front of the two or more reaction systems connected in series, and the valve is opened so that each reaction system forms a closed circuit through the connection line. A continuous reaction process step of performing a continuous reaction process by opening the outlet of the reaction system disposed at the far end of the reaction process while being connected to the reaction process;
Containing, a method for producing an alkyl 3-alkoxypropionate using a continuous reaction process. Placed by putting reactants into each of two or more reaction systems that are connected in series while forming a closed circuit by a connection line and blocked from each other by a valve provided on the connection line, and perform a batch reaction process within each reaction system. A batch reaction process step to obtain a formula reaction process product; And
A continuous reactant for a continuous reaction process is continuously injected into the first reaction system arranged at the front of the two or more reaction systems connected in series, and the valve is opened so that each reaction system forms a closed circuit through the connection line. A continuous reaction process step of performing a continuous reaction process by allowing the reaction process to be performed in a connected state and discharging the final product by opening the outlet of the reaction system disposed at the far end;
Containing, a method for producing an alkyl 3-alkoxypropionate using a continuous reaction process. The method of claim 1 or 2, wherein the batch reaction process step is represented by the following reaction formula,

here
R ¹ and R ² are each independently a C ₁ ~ C ₆ alkyl group,
Catalyst (Cat.) is a strong alkali catalyst,
The batch reaction process step is a method for producing an alkyl 3-alkoxypropionate using a continuous reaction process comprising the following steps:
1) preparing a mixture of alkyl alcohol and catalyst 1a in a reaction vessel;
2) adding water to the 1a mixture so that the water content is 600 ~ 1,000 wtppm to form the 2a mixture, wherein the water content is based on the total weight of the 2a mixture;
3) heating the second a mixture to 30 ~ 70 ℃;
4) forming a 3a mixture by adding an alkyl acrylate dropwise to the 2a mixture so that the molar ratio of alkyl acrylate:alkyl alcohol is 1:1 to 1:3;
5) maintaining the 3a mixture at 50 to 70°C;
6) analyzing the reaction conversion rate at the end of the reaction of the 3a mixture; And
7) If the reaction conversion rate is 97 wt% or more, the reaction is terminated, and if the reaction conversion rate is less than 97 wt%, adding water to the mixture 3a so that the content of water is 50 ~ 200 wtppm, wherein the content of water is 3a Based on the total weight after adding water to the mixture. The method of claim 3, wherein the continuous reactant comprises a mixture of 2b produced by adding water to a mixture of alkyl alcohol and a catalyst having a water content of 600 to 1,000 wtppm (wherein the content of water is the entire 2b mixture Based on the weight), the alkyl acrylate to the alkyl alcohol added to the 2b mixture: a molar ratio of the alkyl alcohol is 1:1 to 1:3, including an alkyl acrylate added A method for producing an alkyl 3-alkoxypropionate using the formula reaction process. The method of claim 3, wherein the catalyst is at least one selected from the group consisting of lithium ethoxide, sodium ethoxide, potassium ethoxide, rubidium ethoxide, cesium ethoxide, beryllium ethoxide, magnesium ethoxide and calcium ethoxide A method for producing an alkyl 3-alkoxypropionate using a continuous reaction process. The method of claim 3, wherein R ¹ and R ² are each independently a methyl group, an ethyl group, an n-propyl group, or an n-butyl group. The method of producing an alkyl 3-alkoxypropionate using a continuous reaction process.

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