KR20220026456A - organic compounds containing 2-cyanoethyl group and preparing method thereof - Google Patents

Abstract

The present invention relates to an organic compound comprising a 2-cyanoethyl group and a preparation method thereof, and more specifically, to an organic compound comprising a high-purity 2-cyanoethyl group having a high substitution rate in a short time by suppressing a side reaction of a reactant and a preparation method thereof. According to the present invention, the organic compound containing a high-purity 2-cyanoethyl group having a high substitution rate in a short time can be prepared and a high-quality product by suppressing the side reactions of the reactant can be produced. In addition, the amount of wastewater generated by shortening a purification process can be reduced.

Description

An organic compound containing a 2-cyanoethyl group and a preparation method thereof {organic compounds containing 2-cyanoethyl group and preparing method thereof}

The present invention relates to an organic compound containing a 2-cyanoethyl group and a method for preparing the same, and more particularly, to an organic compound containing a 2-cyanoethyl group of high purity having a high substitution rate in a short time by suppressing side reactions of reactants. and to a method for manufacturing the same.

Organic compounds including 2-cyanoethyl group have high dielectric constant compared to other organic compounds due to high polarization of 2-cyanoethyl group, and thus have been used in various fields including organic EL devices. In addition, recently, it has been used as a binder additive for ceramic separators to enhance heat resistance and thermal stability of lithium secondary batteries.

Such an organic compound containing a 2-cyanoethyl group can generally be prepared by Michael addition reaction between an organic compound containing a hydroxyl group and acrylonitrile in the presence of a catalyst. However, for a smooth reaction, an excess of acrylonitrile is required compared to an organic compound containing a hydroxyl group, and the excess acrylonitrile remains unreacted after the reaction or various by-products are formed due to side reactions. Therefore, in order to remove it, it is necessary to repeat the process of refining unreacted acrylonitrile and by-products generated therefrom by precipitating it in a non-solvent including water after dissolving it in a solvent. In addition, a small amount of by-products may exist even after purification, and a large amount of malignant wastewater is generated in the purification process, resulting in high treatment costs.

In this regard, Korea Patent No. 1730671 discloses that the content of bis-cyanoethyl ether, a by-product contained in the final product, is increased by dissolving a polymer having a hydroxyl group in water and then using hot water during mixing and purification with a catalyst to increase solubility. suggests that it can be reduced. In addition, Korea Patent Application Publication No. 2020-0011016 and Korean Patent Application Publication No. 2020-0033672 disclose bis-cyanoethyl ether using a 2-cyanoethyl group-containing polymer and an extraction solvent having a specific Hansen solubility parameter distance for acetone. Disclosed is a method that can reduce the amount of wastewater generated by removing it.

However, in spite of the various technical proposals of these prior art, the technology for suppressing the side reaction of the reactant, which is an essential problem, has not been reached by removing by-products in the purification process or reducing only the production of specific by-products.

Accordingly, an object of the present invention is to provide an organic compound containing a high-purity 2-cyanoethyl group having a high substitution rate in a short time by suppressing side reactions of reactants, and a method for preparing the same.

According to one embodiment of the present invention, there is provided a method for producing an organic compound containing a 2-cyanoethyl group, OH ^- ion of a basic catalyst during cyanoethylation reaction of a mixture containing a hydroxyl group containing organic compound, acrylonitrile and a basic catalyst Provided is a method for preparing an organic compound containing a 2-cyanoethyl group in which the molar ratio (E _V ) of -OH in the hydroxyl group-containing organic compound as a reactant satisfies Equation 1 below.

[Equation 1]

(In Equation 1, E _i represents the molar ratio ([OH ^- ]/[R-OH]) of the OH ^- ion of the basic catalyst in the initial reaction to -OH in the hydroxyl group-containing organic compound, and α ≤ 0.5.)

The hydroxyl group-containing organic compound may be selected from polyvinyl alcohol, pullulan, and cellulose.

The initial molar ratio of the reaction between the OH ^- ion of the basic catalyst and the -OH in the hydroxyl group-containing organic compound as the reactant may be 0.3 to 2.

The cyanoethylation reaction may be carried out at a temperature of 20 to 40 °C.

According to another embodiment of the present invention (S1) initiating a reaction by mixing a hydroxyl group-containing organic compound, acrylonitrile and a basic catalyst; (S2) adding an acid or organic ester; And (S3) provides a method for producing an organic compound containing a 2-cyanoethyl group comprising the step of terminating the reaction.

The hydroxyl group-containing organic compound may be selected from polyvinyl alcohol, pullulan, and cellulose.

The step (S2) of adding the acid or organic esters may be performed two or more times.

The concentration of the added acid may be 6.0 mol/L or less.

According to another embodiment of the present invention, there is provided an organic compound containing a 2-cyanoethyl group containing 0.5 wt% or less of the compound represented by the following Chemical Formulas 1 to 3 present as a monomer.

[Formula 1]

[Formula 2]

[Formula 3]

(In Formula 3, M is at least one selected from alkali metals and alkaline earth metals.)

In the organic compound, a substitution rate of the 2-cyanoethyl group may be 50% or more.

The compounds represented by Formulas 1 to 3 may be generated from hydrolysis of acrylonitrile as a reactant.

According to the present invention, it is possible to prepare an organic compound containing a high-purity 2-cyanoethyl group having a high substitution rate in a short time, and to provide a high-quality product by suppressing side reactions of reactants. In addition, it is possible to reduce the amount of wastewater generated by shortening the purification process.

1 is a graph showing the change in the substitution rate over time according to the amount of the basic catalyst according to an embodiment of the present invention.
2 is a graph showing the amount of acid to control [OH ^- ]/[R-OH] of Example 1 of the present invention.
3 is a graph showing the substitution rate and [OH ^- ]/[R-OH] change with time of Comparative Example 1 of the present invention.
4 is a graph showing FT-IR spectra of Example 1 and Comparative Example 1 of the present invention.
Figure 5 shows the change according to the reaction time of Example 1 and Comparative Example 1 of the present invention.

Before describing the present invention in detail below, it is to be understood that the terminology used herein is for the purpose of describing specific embodiments only, and is not intended to limit the scope of the present invention. All technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art, unless otherwise stated.

Throughout this specification and claims, unless stated otherwise, the term comprise, comprises, comprising is meant to include the stated object, step or group of objects, and steps, and any other object. It is not used in the sense of excluding a step or a group of objects or groups of steps.

On the other hand, various embodiments and embodiments of the present invention may be combined with any other embodiments unless clearly indicated to the contrary. In particular, any feature indicated as preferred or advantageous may be combined with any other feature indicated as preferred or advantageous.

The present inventors performed various experiments on a method for preparing an organic compound containing a 2-cyanoethyl group, and tried to solve the problem of by-product generation. As a result, when the molar ratio of the hydroxyl group of the organic compound containing a hydroxyl group and the OH ^- ion of the basic catalyst is maintained at a specific value during the reaction, side reactions of the reactants are suppressed to produce an organic compound containing a 2-cyanoethyl group of high purity After confirming that it can be done and verifying the reproducibility, the present invention was completed.

An organic compound containing a 2-cyanoethyl group is generally obtained by cyanoethylation reaction of a hydroxyl group and acrylonitrile present in an organic compound containing a hydroxyl group as a reactant as shown in [Scheme 1] below. , where a basic material is used as a catalyst.

[Scheme 1]

In [Scheme 1], R-OH represents an organic compound containing a hydroxyl group, RO-CH ₂ CH ₂ CN represents an organic compound containing a 2-cyanoethyl group.

As the organic compound containing the hydroxyl group, any organic compound may be used without limitation as long as it can react with acrylonitrile for cyanoethylation. For example, the organic compound may include a polymer such as polyvinyl alcohol, a polysaccharide compound such as pullulan, cellulose, hydroxyalkyl cellulose, glycerol, or a derivative thereof. Among the exemplary organic compounds, polyvinyl alcohol is used in various fields because of its reasonable price and strong adhesion and heat resistance. In addition, polyvinyl alcohol substituted with a 2-cyanoethyl group has a high dielectric constant, film formation, and adhesion, so it is suitable for fields requiring high dielectric properties and adhesion. In addition, it is suitable for use as a dispersant or binder of a ceramic separator because it increases the dispersibility of the ceramic particles due to the interaction with the ceramic particles and has high adhesion to the original fabric of the separator.

A basic catalyst may be used in the cyanoethylation reaction, and the basic catalyst may include alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal carbonate, alkaline earth metal carbonate, aqueous ammonia, and mixtures thereof. Specifically, the alkali metal hydroxide may be lithium hydroxide, sodium hydroxide, potassium hydroxide, and the like, and the alkali metal carbonate may be sodium carbonate, potassium carbonate, or the like. The basic catalyst may be used alone or may be used in combination with a phase transfer catalyst. The phase transfer catalyst may include tetramethylammonium chloride, tetraethylammonium iodide, tetrabutylammonium bromide, or a mixture thereof.

A factor affecting the substitution rate of the 2-cyanoethyl group in the cyanoethylation reaction may be a mass ratio or molar ratio of acrylonitrile, a basic catalyst, a solvent, and water to a hydroxyl group of an organic compound containing a hydroxyl group. The degree of substitution from a hydroxyl group to a cyanoethyl ether group is different. Among them, in general, the more the basic catalyst is added, the faster the reaction rate and the higher the substitution rate, the greater the factor in the cyanoethylation reaction. However, these basic catalysts act as catalysts for side reactions of acrylonitrile in addition to the cyanoethylation reaction in the reaction process, thereby promoting the production of by-products.

The side reaction of acrylonitrile can be largely divided into a reaction for producing bis-cyanoethyl ether and a reaction for producing acrylamide and acrylic acid. Bis-cyanoethyl ether, a by-product, is as shown in [Scheme 2-1] below, acrylonitrile reacts with water to produce 3-hydroxypropionitrile, and then [Scheme 2] -2], it is finally produced by reaction with acrylonitrile. This reaction can be accelerated at high temperature or in the presence of a basic catalyst. When the bis-cyanoethyl ether produced by the above reaction is included in the organic compound containing the 2-cyanoethyl group, a large amount of wastewater may be generated during the purification process to remove it. In addition, when used in a ceramic separator, the dispersibility of the ceramic particles is reduced, thereby lowering heat resistance, and causing a side reaction with an electrolyte and an active material in the battery, which may cause battery deterioration. Such bis-cyanoethyl ether can be effectively removed using an organic ester solvent such as ethyl acetate that can selectively dissolve bis-cyanoethyl ether without reacting with the product in the termination or layer separation step after the completion of the reaction. can

[Scheme 2-1]

[Scheme 2-2]

On the other hand, as shown in [Scheme 3] below, acrylonitrile undergoes a hydrolysis reaction in the presence of an acid or base catalyst to produce acrylamide, and the produced acrylamide is again hydrolyzed due to Finally, acrylic acid is produced. The generated acrylic acid forms acrylic acid ions or acrylic acid metal salts depending on the atmosphere, which may vary depending on the type of metal ions of the basic catalyst used. For example, when sodium hydroxide is used as the basic catalyst, sodium acrylate is formed.

[Scheme 3]

In the above reaction, acrylonitrile acts as a solvent in the organic layer in addition to the reactants. In general, when the reaction is completed, the organic compound including the 2-cyanoethyl group is dissolved in the solvent of the organic layer because the solubility in the aqueous layer is lowered. In addition, an organic layer including an organic compound including a 2-cyanoethyl group is formed on the upper portion and an aqueous layer is formed on the lower portion due to the density difference. When acrylonitrile present in the organic layer is converted to acrylamide and acrylic acid or ions containing them due to the hydrolysis, the amount of solvent in the organic layer is lowered, resulting in formation of a precipitate during the reaction or phase inversion. . When a precipitation is formed or a phase inversion occurs during the reaction, the acrylonitrile is in direct contact with the basic catalyst present in the aqueous layer, so that hydrolysis is accelerated, and phase separation does not normally occur. The content of metal ions remaining in the organic compound may increase.

In addition, in the hydrolysis of acrylonitrile, the reaction rate can be lowered by reducing the amount of acrylonitrile or basic catalyst, but the reaction rate of cyanoethylation is also lowered at the same time, so that the process time may be longer than necessary.

The acrylonitrile can be used alone, but if necessary, methanol, ethanol, propyl alcohol, isopropyl alcohol, methyl ethyl ketone, acetone N-methylpyrrolidone, tetrahydrofuran, dimethyl formamide, acetonitrile, dimethyl sulfonyl alcohol A diluent solvent that does not react with acrylonitrile, such as phoside, dimethyl carbonate, ethyl methyl carbonate, or propylene carbonate, may be added alone or in combination.

As shown in [Scheme 4] below, the hydrolysis reaction may occur not only in the monomer acrylonitrile but also in the 2-cyanoethyl group present in the organic compound including the 2-cyanoethyl group. Through the hydrolysis reaction, the 2-cyanoethyl group is finally converted into an amide group or a carboxyl group. The converted amide group or carboxyl group may result in a decrease in the dielectric constant of the organic compound including the 2-cyanoethyl group. In particular, when used as a dispersant or binder of a ceramic coating separator, dispersibility and adhesion are greatly reduced, so it may be difficult to obtain satisfactory effects.

[Scheme 4]

As a result of various experiments and efforts, the present inventors surprisingly found that in the cyanoethylation reaction of the organic compound containing a hydroxyl group, the OH ^- ion of the basic catalyst first acts on the cyanoethylation reaction, ^and the excess OH- is the side reaction. It was confirmed that it acts as a catalyst. In addition, it was found that the side reaction of acrylonitrile, a monomer, due to steric hindrance reacts faster than an organic compound substituted with a cyanoethyl group, and in particular, when the organic compound is a polymer such as polyvinyl alcohol, the steric hindrance is further increased. Therefore, in the above reaction, the reaction rate occurs in the order of [Scheme 1] > [Scheme 3] >> [Scheme 4], and the higher the concentration of OH ^- ions in the basic catalyst, the faster the rate of the side reaction, resulting in excess by-products It is presumed that it could be

As a result, the higher the molar ratio [OH ^- ]/[R-OH] of the OH ^- ion of the basic catalyst and the -OH in the organic compound containing the reactant hydroxyl group, the reaction rate of cyanoethylation increases. The rate is also increased, which ultimately leads to an increase in the production of by-products.

In the present invention, in order to reduce side reactions other than the cyanoethylation reaction, [OH ^- ]/[R-OH] during the reaction is kept constant at the initial reaction ratio to prepare an organic compound containing a 2-cyanoethyl group of high purity. can In the cyanoethylation reaction, OH ⁻ of the basic catalyst acts as a catalyst, so there is no change in the amount added at the beginning of the reaction. On the other hand, in R ^- OH of the organic compound containing a hydroxyl group, -OH is substituted with a cyanoethyl group as the reaction progresses and the amount decreases. That is, [OH ^- ] required for the cyanoethylation reaction decreases as the reaction progresses, but [OH ^- ] contained in the actual reaction system is constant, so side reactions other than the cyanoethylation reaction may occur.

In the present invention, the initial stage of the reaction is the initial time of the cyanoethylation reaction, and refers to a section in which the cyanoethyl group substitution rate for the hydroxyl group of the hydroxyl group-containing organic compound is before 10%.

According to one embodiment of the present invention, during the cyanoethylation reaction of a mixture containing a hydroxyl group-containing organic compound, acrylonitrile and a basic catalyst, the molar ratio of OH ^- ions of the basic catalyst and -OH in the hydroxyl group-containing organic compound as a reactant ( E _V ) may satisfy Equation 1 below.

[Equation 1]

In Equation 1, E _i represents the molar ratio ([OH ^- ]/[R-OH]) of the OH ^- ion of the basic catalyst at the initial stage of the reaction and -OH in the hydroxyl group-containing organic compound, and α ≤ 0.5.

During the cyanoethylation reaction, the molar ratio ([OH ^- ]/[R-OH]) of the OH ^- ion of the basic catalyst and -OH in the hydroxyl group-containing organic compound satisfies the above formula, thereby reducing the side reaction of the reactant. It is possible to reduce the production of by-products by inhibiting the production of by-products, and it is possible to prepare an organic compound containing a high-purity 2-cyanoethyl group having a high substitution rate in a short time.

In this case, the initial ratio of the reaction of [OH ^- ] / [R -OH] is preferably 0.3 to 2. When the initial ratio of the reaction is less than 0.3, the cyanoethylation reaction rate is slow and the preparation time may be prolonged. When it exceeds 2, an excess of OH ^- ions may accelerate the side reaction of acrylonitrile to generate by-products, and the effect on the reaction rate may be insignificant compared to the difficulty and economic burden of removing metal cations.

According to an embodiment of the present invention, (S1) initiating a reaction by mixing a hydroxyl group-containing organic compound, acrylonitrile and a basic catalyst; (S2) adding an acid or organic ester; and (S3) terminating the reaction to prepare an organic compound containing a 2-cyanoethyl group.

[OH ^- ]/[R-OH] can be maintained by adding an acid or organic esters in the above reaction.

The acid may be used without limitation as long as it is a species capable of consuming OH ⁻ present in the reaction system by direct neutralization reaction with a basic catalyst without reacting with an organic compound containing a 2-cyanoethyl group. For example, in consideration of economical aspects and convenience of use, acetic acid, hydrochloric acid, nitric acid, or a diluted solution thereof may be used, and may be used alone or in combination of two or more. The organic esters may be used regardless of species as long as they react with OH ⁻ to generate acids and alcohols. Illustratively, the organic esters may include any one or a combination of methyl acetate, ethyl acetate, butyl acetate, and benzyl acetate.

The step of adding an acid or organic esters to maintain the [OH ^- ]/[R-OH] may be performed two or more times. Specifically, an acid or organic ester whose equivalent is calculated to check the remaining [-OH] at any one point in the reaction and consume an excess of [OH- ^] compared to the initial [OH ^- ]/[R-OH] This means that the process of adding can be repeated.

When an acid is added during the reaction to maintain the [OH ^- ]/[R-OH], the acid concentration may be 6.0 mol/L or less, preferably 0.05 mol/L to 6.0 mol/L there is. When the concentration of acid is less than 0.05 mol/L, the amount of acid solution added to maintain [OH ^- ]/[R-OH] is excessively large, so the amount of wastewater generated increases, and when it exceeds 6.0 mol/L, high Due to the concentration, diffusion in the reaction system is delayed and the balance may be disturbed.

In the cyanoethylation reaction, the reaction proceeds rapidly at the beginning, at this time [OH ^- ]/[R-OH] increases with a high width, and the greater the amount of the basic catalyst added before the reaction, the greater the desired substitution rate of the cyanoethyl group The time until reaching The reaction may be carried out for 1 to 8 hours, and more preferably, for 2 to 6 hours to obtain an organic compound containing a cyanoethyl group. If the reaction time is less than 1 hour, it may be difficult to obtain a desired substitution rate, and if it exceeds 8 hours, the effect of the increasing substitution rate may be insignificant even if the time is long, and the amount of by-products due to side reactions may increase. In addition, the reaction time of the reaction at a mass-produceable level can be adjusted to meet the purpose of the invention, which will be apparent to those skilled in the art.

In addition, the reaction may proceed at a temperature of 10 to 50 ℃, more preferably 20 to 40 ℃. When the reaction temperature is less than 10 °C, the reaction rate may be slow, and when it exceeds 50 °C, the hydrolysis reaction rate of the substituted cyanoethyl group is also increased, which may cause an adverse effect of decreasing the substitution rate.

The organic layer obtained after the cyanoethylation reaction may be added to water to obtain an organic compound containing a cyanoethyl group in a solidified form. In addition, if necessary, it may be further dissolved in acetone and then solidified again in water to further perform the purification process 1 to 4 times. At this time, water may be added to the organic layer or the organic layer may be added to excess water, but in order to effectively increase the purity, it is preferable to add the organic layer to excess water.

The organic compound containing a 2-cyanoethyl group according to an embodiment of the present invention may contain 0.5 wt% or less of the compound represented by the following Chemical Formulas 1 to 3 present as a monomer.

[Formula 1]

[Formula 2]

[Formula 3]

(In Formula 3, M is at least one selected from alkali metals and alkaline earth metals.)

Specifically, when [OH ^- ]/[R-OH] is maintained during the cyanoethylation reaction according to an embodiment of the present invention, the by-products represented by Chemical Formulas 1 to 3 are generated from the side reaction of acrylonitrile. can reduce the amount of Accordingly, the by-product may be included in an amount of 0.5 wt% or less in the finally obtained organic compound including a cyanoethyl group. When the amount of the by-product exceeds 0.5% by weight, discoloration occurs during the drying process, resulting in orange or dark yellow color, and light transmittance may decrease. In addition, when a ceramic separator is manufactured using this, dispersibility of ceramic particles may be reduced or adhesive strength may be reduced during the coating process. In addition, it may be eluted from the electrolyte in the battery to cause a side reaction, thereby reducing the lifespan of the battery. In particular, when sodium hydroxide is used as a basic catalyst, sodium hydroxide reacts with acrylic acid, a byproduct, to produce sodium acrylate. Moisture may be contained inside the battery, which may adversely affect the performance of the battery. In addition, since the aqueous layer and the organic layer are clearly separated after the reaction, even if the amount of the basic catalyst used before the reaction is increased, the amount of metal ions generated from the basic catalyst included in the aqueous layer is relatively small.

In the organic compound including the cyanoethyl group, the substitution rate of the cyanoethyl group may be 40% or more, more preferably 50% or more. When the substitution rate is less than 40%, there is solubility in water due to the remaining hydroxyl groups, and thus the yield may decrease in the process of solidification by putting it in water. In addition, since sufficient dielectric constant is not exhibited, ion conductivity may be lowered, and side reactions may occur in the battery due to the remaining hydroxyl groups, which may cause deterioration of battery performance.

Hereinafter, the present invention will be described in more detail through examples. However, this is only for illustrating the present invention, and it will be apparent to those of ordinary skill in the art that the scope of the present invention is not to be construed as being limited by these examples.

Example 1

44 g of polyvinyl alcohol was added to 500 g of distilled water and dissolved at 80° C. to prepare a polyvinyl alcohol solution, and then a solution of 40 g of sodium hydroxide dissolved in 300 g of distilled water was slowly added while stirring. Then, stirring was stopped, 290 g of acrylonitrile and 120 g of acetone were added, and the mixture was stirred at 30° C. for 6 hours to proceed with cyanoethylation. The product was collected every 10 minutes, the substitution rate was monitored, and acetic acid at a concentration of 1M (mol/L) was added so that the hydroxyl groups of the unreacted polyvinyl alcohol were equal to the sodium hydroxide added before the reaction. To terminate the reaction, acetic acid equivalent to the remaining sodium hydroxide was added, stirring was stopped to induce layer separation, and the organic layer was collected and added to water to solidify. After dissolving the solid in acetone again, adding it to water and repeating the purification process for solidification 4 times, drying was finally obtained to obtain polyvinyl alcohol containing 2-cyanoethyl group.

Example 2

Polyvinyl alcohol containing a 2-cyanoethyl group was obtained in the same manner as in Example 1, except that the cyanoethylation reaction was performed for 3 hours.

Example 3

Polyvinyl alcohol containing 2-cyanoethyl group was obtained in the same manner as in Example 1 except for adding a solution of 20 g of sodium hydroxide dissolved in 300 g of distilled water.

Example 4

Polyvinyl alcohol containing 2-cyanoethyl group was obtained in the same manner as in Example 1, except that a solution of 20 g of sodium hydroxide dissolved in 300 g of distilled water was added and the cyanoethylation reaction was performed for 3 hours.

Comparative Example 1

44 g of polyvinyl alcohol was added to 500 g of distilled water and dissolved at 80° C. to prepare a polyvinyl alcohol solution, and then a solution of 40 g of sodium hydroxide dissolved in 300 g of distilled water was slowly added while stirring. Then, stirring was stopped, 290 g of acrylonitrile and 120 g of acetone were added, and the mixture was stirred at 30° C. for 6 hours to proceed with cyanoethylation. To terminate the reaction, acetic acid equivalent to the remaining sodium hydroxide was added, stirring was stopped to induce layer separation, and the organic layer was collected and added to water to solidify. After dissolving the solid in acetone again, adding it to water and repeating the purification process for solidification 4 times, drying was finally obtained to obtain polyvinyl alcohol containing 2-cyanoethyl group.

Comparative Example 2

Polyvinyl alcohol containing a 2-cyanoethyl group was obtained in the same manner as in Comparative Example 1, except that the cyanoethylation reaction was performed for 3 hours.

Comparative Example 3

Polyvinyl alcohol containing 2-cyanoethyl group was obtained in the same manner as in Comparative Example 1 except for adding a solution of 20 g of sodium hydroxide dissolved in 300 g of distilled water.

Comparative Example 4

Polyvinyl alcohol containing 2-cyanoethyl group was obtained in the same manner as in Comparative Example 1, except that a solution of 20 g of sodium hydroxide dissolved in 300 g of distilled water was added and the cyanoethylation reaction was performed for 3 hours.

Calculation of substitution rate of cyanoethyl group

The substitution rate of the organic compound containing a cyanoethyl group obtained in Examples and Comparative Examples is a repeating unit of an organic compound containing a hydroxyl group and a repeating unit of an organic compound containing a cyanoethyl group after nitrogen quantitative analysis using the Kjeldahl method It was calculated from the molecular weight of the nitrogen content through the formula. In detail, an organic compound containing a cyanoethyl group was accurately measured to the fourth decimal place, and 98% concentrated sulfuric acid and a decomposition accelerator were added and heated until it became a complete solution. After the prepared solution was completely cooled to room temperature, water and 32% sodium hydroxide solution were added to make it basic, and then the ammonia nitrogen contained in the vapor was absorbed into the boric acid solution containing the indicator. Next, the nitrogen content was obtained by titration with 0.1N hydrochloric acid standard solution until it reached the wavelength of the existing boric acid solution, and then the substitution rate was calculated by substituting it in the formula. The results are shown in Table 1 below.

Identification of impurities

Acrylamide contained in the organic compound containing a cyanoethyl group obtained in Examples and Comparative Examples was analyzed and confirmed by GC-FID (Measuring Instrument Name: GC-2010, Manufacturer: Shimadzu). In addition, after obtaining FT-IR (measurement device name: NICOLET iS20; manufacturer: thermo scientific) spectra for acrylic acid and acrylic acid salt, the presence/absence of peaks corresponding to acrylic acid and acrylic acid salt was confirmed, and cyanoethyl group was analyzed through quantitative analysis from the area. The content of acrylic acid and acrylic acid salt contained in the organic compound containing The results are shown in Table 1 below.

In addition, in order to check whether the corresponding peak is due to a functional group chemically bonded to the organic compound containing the cyanoethyl group, the organic compound containing the cyanoethyl group containing the peak was redissolved in acetone and then added to water. After the purification process of input and solidification was further performed 3 times, the FT-IR spectrum was obtained again by drying, and the peak change was confirmed.

As shown in FIG. 4 , in the case of Example 1, there was no peak other than the peak of polyvinyl alcohol including a cyanoethyl group, and in the case of Comparative Example 1, it was confirmed that the peak of sodium acrylate appeared together. It was confirmed that the peak strength of the sodium acrylate peak was weakened every time it was repeated in the further purification process, so the functional group of sodium acrylate that was initially present was included in the functional group of polyvinyl alcohol containing a cyanoethyl group. It means that it is contained in the form of a monomer rather than being present.

Before reaction [OH ^- ]/ [-OH] [OH ^- ]
With/without adjustment After 1 hour of reaction [OH ^- ]/ [-OH] After 2 hours of reaction [OH ^- ]/ [-OH] reaction time
(h) substitution rate
(%) organic layer behavior Byproduct content acrylamide
(ppm) acrylic acid
(wt%) sodium acrylate
(wt%) Example 1 1.0 ○ 1.0 1.0 6 86.7 normal 23 - - Example 2 1.0 ○ 1.1 1.0 3 86.2 normal 16 - - Example 3 0.5 ○ 0.5 0.5 6 82.6 normal 21 - - Example 4 0.5 ○ 0.5 0.6 3 79.8 normal 8 - - Comparative Example 1 1.0 X 3.1 5.7 6 87.1 Reversal 1300 0.14 3.25 Comparative Example 2 1.0 X 3.2 5.6 3 86.4 Reversal 682 0.08 2.48 Comparative Example 3 0.5 X 1.6 2.8 6 84.0 Reversal 463 0.08 1.36 Comparative Example 4 0.5 X 1.4 2.8 3 80.6 normal 225 0.03 0.84

As shown in Table 1, in Examples in which side reactions were suppressed by maintaining the initial reaction molar ratio of [OH ^- ]/[-OH] during the cyanoethylation reaction, the content of by-products can be further reduced compared to Comparative Examples was confirmed.

Also, in Comparative Examples 1 to 3, the organic layer was converted to acrylamide, acrylic acid and sodium acrylate due to hydrolysis of acrylonitrile present in the organic layer, and the amount of the solvent in the organic layer was lowered, resulting in inversion of the organic layer and the aqueous layer.

Claims (7)

(S1) initiating a reaction by mixing an organic compound containing a hydroxyl group, acrylonitrile and a basic catalyst;
(S2) adding an acid or organic ester; and
(S3) A method for producing an organic compound containing a 2-cyanoethyl group, comprising the step of terminating the reaction.
The method according to claim 1, wherein the hydroxyl group-containing organic compound includes a 2-cyanoethyl group selected from polyvinyl alcohol, pullulan, and cellulose.
The method of claim 1, wherein the step (S2) of adding the acid or organic esters is performed twice or more.
The method according to claim 1, wherein the concentration of the added acid is 6.0 mol/L or less, and the organic compound containing 2-cyanoethyl group.
An organic compound comprising a 2-cyanoethyl group comprising 0.5 wt% or less of the compound represented by the following Chemical Formulas 1 to 3 present as a monomer.
[Formula 1]

[Formula 2]

[Formula 3]

(In Formula 3, M is at least one selected from alkali metals and alkaline earth metals.)
The organic compound according to claim 5, wherein the organic compound includes a 2-cyanoethyl group in which the substitution rate of the 2-cyanoethyl group is 50% or more.
The organic compound according to claim 5, wherein the compounds represented by Chemical Formulas 1 to 3 include a 2-cyanoethyl group generated from hydrolysis of acrylonitrile as a reactant.

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