KR100749564B1 - Process for manufacturing N,N,N´,N´-tetraacetylethylenediamine - Google Patents

Abstract

The present invention relates to a method for producing tetraacetylethylenediamine, and more particularly, in the production of tetraacetylethylenediamine (TAED) by reacting diacetylethylenediamine (DAED) with acetic acid, inhibiting side reactions and promoting only forward reaction. The use of a specific catalyst minimizes the formation of colorants in the filtrate due to side reactions, thereby solving the color problem of tetraacetylethylenediamine (TAED) obtained after the cooling and crystallization process, and the reaction intermediate triacetylethylenediamine (Tri). -AED) and tetraacetylethylenediamine (TAED) to increase the reaction rate and yield by increasing the speed of the forward reaction, and because the appropriate amount of acetic acid as a reactant is used properly, such as recrystallization or purification process Tetraacetyl, a bleach activator with high yield, high purity and good color without post-treatment Ethylene relates to a process for the preparation of a diamine (TAED).

Bleach activator, diacetylethylenediamine, tetraacetylethylenediamine, catalyst

Description

Process for manufacturing N, N, N´, N´-tetraacetylethylenediamine}

The present invention relates to a method for producing tetraacetylethylenediamine, and more particularly, in the production of tetraacetylethylenediamine (TAED) by reacting diacetylethylenediamine (DAED) with acetic acid, inhibiting side reactions and promoting only forward reaction. The use of a specific catalyst minimizes the formation of colorants in the filtrate due to side reactions, thereby solving the color problem of tetraacetylethylenediamine (TAED) obtained after the cooling and crystallization process, and the reaction intermediate triacetylethylenediamine (Tri). -AED) and tetraacetylethylenediamine (TAED) to increase the reaction rate and yield by increasing the rate of the forward reaction, and after the recrystallization or purification process, such as the appropriate amount of acetic acid Tetraacetyl, a bleaching activator with high yield, high purity and good color, without treatment Alkylene relates to a process for the preparation of a diamine (TAED).

Inorganic peroxides such as sodium perborate and sodium percarbonate are used as oxidants for bleaching or disinfection because they dissolve in water to produce hydrogen peroxide. Hydrogen peroxide oxidizes and decomposes materials with double bond chromophores that make colors such as fruit juices, tea, coffee, and vegetables contaminated with fibers or clothing that are difficult to remove as surfactants or enzymes. Bleaching or disinfecting by removing microorganisms and odors from the surface.

The oxidation power of the inorganic peroxide, that is, the bleaching power, varies greatly depending on the temperature. If the use of sodium perborate is used for the bleaching of the fiber, sufficient bleaching effect can be obtained only at a temperature of about 80 ° C. or more and 60 ° C. or more for sodium percarbonate.

Since the bleaching power of these inorganic peroxides drops sharply below 60 ° C., a material called a bleach activator must be added for bleaching at low temperatures.

Such bleach activators generally include tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonate (NOBS), isononanoyloxybenzenesulfonate (ISONOBS), and the like. Diamine (TAED) is used a lot.

As a method for producing tetraacetylethylenediamine (TAED), German Patent No. 2,133,458 discloses diacetyl ethylenediamine (TAED) by distilling acetic acid as a byproduct while reacting diacetylethylenediamine (DAED) with acetic anhydride to produce tetraacetylethylenediamine (TAED). Although a method is disclosed, it has the disadvantage of using excess acetic anhydride.

U.S. Patent No. 4,354,042 discloses that in preparing tetraacetylethylenediamine (TAED), acetic acid is distilled off while reacting diacetylethylenediamine (DAED) with acetic anhydride and the resulting tetraacetylethylenediamine (TAED) A method of reusing the brown filtrate in the next reaction is disclosed, but has the disadvantage of having to recrystallize to remove the color of the resulting tetraacetylethylenediamine (TAED).

U.S. Patent No. 4,240,980 discloses a method for purifying and reusing a dark brown filtrate after filtering tetraacetylethylenediamine (TAED) produced by reacting diacetylethylenediamine (DAED) with acetic anhydride. However, the purification of the filtrate requires an additional step of filtration with a large amount of adsorbent in the hot state, followed by distillation with the filtrate from here.

International Patent WO88 / 06153 discloses a tetraacetylethylenediamine (TAED) by reacting diacetylethylenediamine (DAED) with acetic anhydride, using a solvent that does not cause azeotropy of acetic anhydride as a reactant and acetic acid as a product. A method for producing tetraacetylethylenediamine (TAED) which effectively distills only acetic acid is disclosed.

However, the above method has a problem in the manufacturing method that the dark brown solvent after the reaction is filtered using a large amount of adsorbent and a filter aid in a hot state, and the tetraacetylethylenediamine (TAED) that is filtered out is a solvent odor. There is a disadvantage that is difficult to commercialize.

International Patent WO04 / 002942 uses a solvent that can be boiled to effectively remove acetic acid, which is a byproduct, in the production of tetraacetylethylenediamine (TAED) by reacting diacetylethylenediamine (DAED) with acetic anhydride, A method of using triethanolamine tungstosilicate, tetrabutyl ammonium chloride, activated clay and the like as a catalyst is disclosed.

However, according to the above method, despite the use of excess acetic anhydride, the yield is low, and the smell of the solvent remains in the produced tetraacetylethylenediamine, which is difficult to commercialize.

That is, a major problem in preparing tetraacetylethylenediamine (TAED) by reacting diacetylethylenediamine (DAED) with acetic anhydride is a problem of improving the yield of tetraacetylethylenediamine (TAED) and improving color.

However, the problem of improving the yield of the tetraacetylethylenediamine (TAED) and the improvement of color is a compatible property, and it is difficult to achieve both the increase of yield and the improvement of color at the same time.

That is, in order to increase the yield of tetraacetylethylenediamine (TAED), it is necessary to increase the amount of acetic anhydride as a reactant and at the same time effectively remove acetic acid as a by-product. However, as the reaction proceeds, the color of the filtrate becomes dark brown by side reaction, and after completion of the reaction, crystallization occurs by cooling. During this process, the color of the filtrate enters the crystal, and the purity falls and the color becomes dark yellow. Acetylethylenediamine (TAED) is obtained.

On the other hand, in order to improve the color of the tetraacetylethylenediamine (TAED), when the reaction is terminated and cooled before the color of the filtrate becomes dark due to side reactions, a white tetraacetylethylenediamine (TAED) can be obtained but yield This is not good.

Due to this problem, the conventional patents use an excess of acetic anhydride and at the same time expect an increase in yield by using a solvent to effectively remove acetic acid, and a cooling and crystallization step to remove colored material due to side reactions. A process of purifying the filtrate using an adsorbent and a filter aid before and after or recrystallizing yellow tetraacetylethylenediamine (TAED) was presented.

However, the use of excess acetic anhydride and solvents has a problem of increasing the manufacturing cost, and the process of purifying the filtrate by using an adsorbent or recrystallization of tetraacetylethylenediamine (TAED) as well as an increase in the manufacturing cost, as well as additional steps of two or more steps This is necessary.

In addition, strong acid catalysts such as sulfuric acid and paratoluenesulfonic acid, which are generally known in the acetylation reaction, have higher yields than those without a catalyst, but have very poor color, and thus have to undergo recrystallization. There are problems such as corrosion and difficulty in handling. Catalysts such as sodium acetate and sodium carbonate, which are base catalysts, have poor yields and poor color.

Accordingly, the inventors of the present invention have made efforts to solve the problems described above. As a result, a halogenated compound of an alkali metal or an alkaline earth metal that suppresses side reactions and promotes a forward reaction is catalyzed, and in the presence thereof, diacetylethylenediamine (DAED) and When acetic acid is used as a raw material for the production of tetraacetylethylenediamine (TAED), high yield and high purity color are required without post-treatment such as recrystallization or purification due to the color of tetraacetylethylenediamine (TAED) and filtrate. Tetraacetylethylenediamine (TAED) was found to be able to produce the present invention was completed.

Accordingly, an object of the present invention is to provide a method for preparing tetraacetylethylenediamine, which is a bleaching activator which selectively promotes a forward reaction.

The present invention provides a method for producing tetraacetylethylenediamine (TAED) using ethylenediamine and acetic acid, acetic anhydride, or a mixture thereof as a reactant, wherein the alkali metal or alkaline earth metal is used as a reaction catalyst. Characterized by a method for producing tetraacetylethylenediamine (TAED) using one or a mixture of two or more selected from the group consisting of halogen salts.

Hereinafter, the present invention will be described in detail.

The present invention, in the production of tetraacetylethylenediamine (TAED) by reacting diacetylethylenediamine and acetic acid, by using a specific catalyst that suppresses side reactions and promotes only forward reactions to produce a material that makes the filtrate color by the side reactions Minimization solves the color problem of tetraacetylethylenediamine (TAED) obtained after the cooling and crystallization process, and speeds up the rate of forward reaction in which the reaction intermediates triacetylethylenediamine (Tri-AED) and tetraacetylethylenediamine (TAED) are produced. By increasing the reaction rate and yield by increasing the amount of acetic acid, which is a proper amount of reactant, tetraacetylethylenediamine, a bleaching activator of good yield and high purity color, is used without any post-treatment process such as recrystallization or purification. TAED).

Acetic acid used as a reactant in the present invention is acetic acid (acetic acid, CH ₃ COOH), acetic anhydride (CH ₃ CO) ₂ O), glacial acetic acid (CH ₃ COOH) and hydrous acetic acid (CH ₃ COOH NH ₂ O) and the like.

Hereinafter, the method for preparing tetraacetylethylenediamine (TAED) of the present invention will be described in detail step by step.

The present invention, as shown in the following scheme 1, a one-step process for preparing the intermediate diacetylethylenediamine (DAED) from the starting material ethylenediamine (ED) and tetraacetyl as the target from the diacetyl ethylenediamine (DAED) It is largely divided into a two step process for preparing acetylethylenediamine (TAED).

Scheme 1

The present invention is characterized by using a halogen compound or an oxide of a metal element as a catalyst during the preparation of such tetraacetylethylenediamine.

Such a catalyst may be used in one step of producing diacetylethylenediamine (DAED), in either step of producing triacetylethylenediamine (TAED), or in both steps 1 and 2. Such a catalyst is used in a catalytic amount, and preferably 0.01 parts by weight or more based on 100 parts by weight of ethylenediamine or diacetylethylenediamine, but preferably 0.1 to 10.0 parts by weight.

 The catalyst uses one or a mixture of two or more selected from halogen salts of alkali metals or alkaline earth metals, specifically lithium chloride, lithium bromide, lithium iodide, sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide and potassium iodide 1 type selected from the halogen salts of alkali metals (group 1A) selected from among others, and the halogen salts of alkali earth metals (group 2A) selected from magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide and calcium iodide. Or a mixture of two or more kinds.

Acetic acid may be acetic acid, acetic anhydride, or a mixture thereof as the reactant reacting with ethylenediamine used as the starting material. Preferably, acetic acid is used.

The use ratio of ethylenediamine and acetic acid in this one-step process is used 2 to 3 equivalents based on 1 equivalent of ethylenediamine. When using a mixture of acetic acid and acetic anhydride, 1-3 equivalents are used, and when using acetic anhydride, it is preferable to use 1-1.5 equivalents.

In the first step, acetyldiamine is added dropwise while maintaining acetic acid at a temperature in the range of 100 to 110 ° C., followed by reaction in the range of 100 to 170 ° C. to prepare a diacetylethylene diamine (DAED) intermediate represented by the following Formula 3.

Meanwhile, when ethylenediamine is added dropwise to acetic acid, it is added dropwise while maintaining a temperature in the range of 110 ° C. or lower, preferably 100 to 110 ° C. under a nitrogen atmosphere. Here, the reason for maintaining the temperature below 110 ° C. when dropping ethylenediamine is When ethylenediamine reacts with acetic acid, heat is generated to prevent evaporation of ethylenediamine by this heat. That is to solve this problem because there is a problem that the yield of diacetylethylenediamine (DAED) is lowered due to vaporization.

Ethylenediamine is added dropwise while maintaining the temperature below 110 ° C. to prepare diacetylethylenediamine. At this time, the reaction temperature is removed from the byproduct water at a temperature of 100 to 170 ° C., preferably 140 to 160 ° C. Carry out the reaction. At this time, when the reaction temperature for preparing the diacetylethylene diamine is less than 100 ℃ is difficult to remove the by-product water, the reaction is slow, when the temperature exceeds 170 ℃ to produce a lot of side reactions darkening color.

The diacetylethylenediamine reaction can proceed both in the absence of a catalyst or in the presence of a catalyst, and the reaction rate is faster and the reaction yield is higher when using a catalyst.

The ratio of acetic acid used as the diacetyl ethylene diamine (DAED) intermediate and the reactant in the second step is 2 to 16 equivalents to 1 equivalent of the diacetyl ethylene diamine (DAED) intermediate, 2 to 8 equivalents when using acetic anhydride 4 to 16 equivalents is preferably used when using a mixture of acetic anhydride and acetic acid (60% or more).

The two-step process consists of adding acetic acid dropwise to the diacetylethylenediamine (DAED) intermediate and then reacting for 2 to 5 hours while removing acetic acid produced in the range of 120 ~ 150 ℃.

After the dropwise addition is completed, the reaction of generating tetraacetylethylenediamine is performed, and is performed at a temperature range of 120 to 150 ° C, preferably 130 to 145 ° C. At this time, if the reaction temperature is lower than 120 ℃ reaction rate is slow, if it exceeds 150 ℃ the color becomes dark and many by-products appear.

The tetraacetylethylenediamine (TAED) production reaction under the above conditions is carried out while removing acetic acid as a byproduct for 2 to 5 hours, preferably 3 to 4 hours.

When the reaction is complete, the reaction solution is cooled to room temperature, filtered and washed to obtain tetraacetylethylenediamine (TAED).

Such a present invention will be described in more detail based on the following examples, but the present invention is not limited by the examples.

Examples 1 to 5: Preparation of tetraacetylethylenediamine (TAED) using a catalyst in a two step process

436 g of acetic acid was added to a 2 L reactor under a nitrogen atmosphere, and then 213 g of ethylenediamine was added dropwise for 1 hour while cooling. At this time, the temperature was maintained at 110 ° C or less. After the dropping of the ethylenediamine was completed, the reaction temperature was heated to 140 ℃ to reflux for 3 hours, the reaction proceeds while removing the water produced at this time for 5 hours to obtain diacetylethylenediamine (DAED) in quantitative yield.

¹ H NMR (CDCl ₃ ) δ: 6.45 (brs, 2H), 3.34 (s, 4H), 1.96 (s, 6H); ¹³ C NMR (CDCl ₃ ) δ: 171.5, 40.5, 23.5 ppm.

To 100 g of diacetylethylenediamine (DAED) prepared above, 3 g of a catalyst was added as shown in Table 1 below, and 283 g of acetic anhydride was added dropwise for 30 minutes under a nitrogen atmosphere. After the reaction temperature was heated to 140 to 145 ° C and refluxed for 3 hours, the resulting acetic acid was distilled and cooled for 4 hours, and then purified, washed and dried to obtain high purity, good color tetraacetylethylenediamine (TAED). Obtained.

¹ H NMR (CDCl ₃ ) δ: 3.73 (s, 4H), 2.44 (s, 12H); ¹³ C NMR (CDCl ₃ ) δ: 173.4, 43.3, 26.5 ppm.

Comparative Example 1: Preparation of Tetraacetylethylenediamine (TAED) without Catalyst

205 g of acetic acid was added to a 2L reactor under a nitrogen atmosphere, and then 100 g of ethylenediamine was added dropwise for 30 minutes while cooling. At this time, the temperature was maintained at 110 ° C or less. After the dropping of the ethylenediamine was completed, the reaction temperature was heated to 140 ℃ and refluxed for 3 hours, the reaction proceeds while removing the water generated at this time for 5 hours to obtain 246 g of diacetylethylenediamine (DAED), 697 g of acetic anhydride was added dropwise to diacetylethylenediamine (DAED) under a nitrogen atmosphere for 30 minutes. After the reaction temperature was heated to 140 to 145 ° C and refluxed for 3 hours, the resulting acetic acid was distilled and cooled for 4 hours to obtain tetraacetylethylenediamine (TAED) through filtration, washing and drying.

Comparative Example 2: Preparation of Tetraacetylethylenediamine (TAED) Under Known Catalysts

To 100 g of diacetylethylenediamine (DAED) used in Examples 1 to 10, 3 g of a catalyst was added as shown in Table 1 below, and 283 g of acetic anhydride was added dropwise for 30 minutes under a nitrogen atmosphere. After the reaction temperature was heated to 140 to 145 ° C and refluxed for 3 hours, the resulting acetic acid was distilled and cooled for 4 hours to obtain tetraacetylethylenediamine (TAED) through filtration, washing and drying.

Example 6 Preparation of TAED Using Catalyst in One Step Process

3 g of a catalyst and 205 g of acetic acid were added to a 2 L reactor under a nitrogen atmosphere, and then 100 g of ethylenediamine was added dropwise for 30 minutes while cooling. At this time, the temperature was maintained at 110 ° C or less. After the dropping of the ethylenediamine was completed, the reaction temperature was heated to 140 ℃ to reflux for 3 hours, the reaction proceeds while removing the water generated at this time for 5 hours to obtain 246 g of diacetylethylenediamine (DAED), Diethylethylenediamine (DAED) was added dropwise to anhydrous acetic acid 69 7g for 30 minutes in a nitrogen atmosphere. After the reaction temperature was heated to 140 to 145 ° C to reflux for 3 hours, the resulting acetic acid was distilled and cooled for 4 hours, and then filtered, washed, and dried to obtain high purity and good color tetraacetylethylenediamine (TAED). Obtained.

Examples 7 to 12 Preparation of TAED with Change in Molar Ratio of Acetic Acid or Acetic Acid Anhydride under Catalyst

Acetic acid was added to a 2L reactor under nitrogen atmosphere, and then 100 g of ethylenediamine was added dropwise for 30 minutes while cooling. At this time, the temperature was maintained at 110 ° C or less.

After the dropwise addition of the ethylenediamine, the reaction temperature was heated to 140 ° C. and refluxed for 3 hours, and then the reaction proceeded while removing the generated water for 5 hours to obtain quantitatively diacetylethylenediamine (DAED). Sodium bromide was added to ethylenediamine (DAED) under a nitrogen atmosphere as shown in Table 2, and acetic anhydride was added dropwise for 30 minutes. After the reaction temperature was heated to 140 to 145 ° C to reflux for 3 hours, the resulting acetic acid was distilled and cooled for 4 hours, and then filtered, washed, and dried to obtain high purity and good color of tetraacetylethylenediamine (TAED). ) Was obtained.

Examples 13-16: Preparation of TAED according to the change in catalyst amount in two steps

Sodium bromide was added to 100 g of diacetylethylenediamine (DAED) used in Examples 1 to 10 at a ratio as shown in the following Table 3 under a nitrogen atmosphere, and 283 g of acetic anhydride was added dropwise for 30 minutes. After the reaction temperature was heated to 140 to 145 ° C and refluxed for 3 hours, the resulting acetic acid was distilled and cooled for 4 hours to obtain respective tetraacetylethylenediamine (TAED) through filtration, washing and drying.

division Reaction catalyst Catalyst input time water(%) color yield(%) Example 1 Magnesium chloride 2 steps 99.2 2 78 Example 2 Calcium chloride 2 steps 99.2 3 75 Example 3 Sodium bromide 2 steps 99.3 3 73 Example 4 Lithium bromide 2 steps 99.6 3.5 74 Example 5 Potassium Iodine 2 steps 99.5 4 66 Comparative Example 1 No catalyst - 99.2 One 58 Comparative Example 2 Sulfuric acid 2 steps 99.2 One 64 Comparative Example 3 Paratoluenesulfonic acid 2 steps 99.1 One 65 Comparative Example 4 Sodium acetate 2 steps 99.3 2 58 Comparative Example 5 Sodium carbonate 2 steps 99.3 One 59 Example 6 Magnesium chloride Stage 1 99.3 2 78 * 3% of catalyst used in experiments with catalyst * Color; 5-very good, 4-good, 3-normal, 2-bad, 1-very bad

As shown in Table 1, it can be seen that when the catalyst is used in the two-step process or the one-step process of the present invention, high purity tetraacetyldimine can be obtained with excellent color and high yield.

This is especially true for Comparative Example 1, which does not use a catalyst at all, and strong acid catalysts such as sulfuric acid and paratoluenesulfonic acid, which are generally known in the existing acetylation reaction, when the catalyst is used, the yield is improved, but the color is very poor, such as recrystallization. It has to go through the process, there are problems such as corrosion of the production line due to the use of strong acid, difficulty in handling.

In addition, catalysts such as sodium acetate and sodium carbonate, which are base catalysts, have poor yields and poor color.

division EDA: AcOH catalyst DAED: Ac2O color yield(%) Example 3 1: 2 Sodium bromide 1: 4 3 73 Example 7 1: 3 Sodium bromide 1: 4 3 73 Example 8 1: 4 Sodium bromide 1: 4 3 73 Example 9 1: 2.05 Sodium bromide 1: 3 2.5 60 Example 10 1: 2.05 Sodium bromide 1: 6 4 75 Example 11 1: 2.05 Sodium bromide 1: 8 4.5 81 Example 12 1: 2.05 Sodium bromide 1: 9 4.5 85 Comparative Example 1 1: 2 No catalyst 1: 4 One 58 *. The catalyst used in the experiment using the catalyst was 3% *. color; 5-very good, 4-good, 3-normal, 2-bad, 1-very bad *. Catalyst injection timing in experiments using catalysts; At secondary reaction

As shown in Table 2, it can be seen that the yield and color of tetraacetylethylenediamine can be controlled by controlling the molar ratio of the reactants, and in particular, it is important to control the molar ratio of reactants such as diacetylethylenediamine and acetic acid. Can be.

division catalyst Catalyst usage (%) water color yield(%) Example 13 Sodium bromide 0.01 99.2 One 59 Example 14 Sodium bromide 0.1 99.2 One 60 Example 3 Sodium bromide 3 99.3 3 73 Example 15 Sodium bromide 10 99.4 3.5 75 Example 16 Sodium bromide 15 99.4 3.5 75 Comparative Example 1 No catalyst - 99.2 One 58 *. Catalyst dosing time for experiments using catalysts; At secondary reaction

As shown in Table 3, it can be seen that a large change in yield and color by controlling the amount of the catalyst used.

As described above, according to the present invention, when a halogen salt of an alkali metal or alkaline earth metal is used as a catalyst, when the tetraacetylethylenediamine formation reaction is performed, the formation of the fibrous material of the filtrate caused by the side reaction is suppressed, and the cooling and crystallization is performed. It solves the coloring phenomenon of tetraacetylethylenediamine (TAED), the main product obtained after the process, and speeds up the forward reaction in which triacetylethylenediamine (Tri-AED) and tetraacetylethylenediamine (TAED) are formed. The reaction rate and yield can be enhanced, and high yield, high purity, and good color tetraacetylethylenediamine (TAED) can be prepared without post-treatment such as additional refining such as separate recrystallization or decolorization.

Claims (5)

In the process for preparing tetraacetylethylenediamine (TAED) using ethylene diamine and acetic acid (acetic anhydride) or a mixture thereof as a reactant, A method for producing tetraacetylethylenediamine (TAED), characterized in that one or a mixture of two or more selected from the group consisting of halogen salts of alkali metals or alkaline earth metals is used as the reaction catalyst. The method of claim 1, The reaction catalyst is selected from the group consisting of lithium chloride, lithium bromide, lithium iodide, sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide and calcium iodide A method for producing tetraacetylethylenediamine, wherein one or more selected mixtures are used. delete The method of claim 1, Reacting ethylenediamine with acetic acid, acetic anhydride or a mixture thereof to prepare a diacetylethylenediamine (DAED) intermediate represented by the following Formula 3; A two-step process of reacting the diacetylethylenediamine (DAED) intermediate with acetic acid, acetic anhydride or a mixture thereof to produce tetraacetylethylenediamine (TAED) represented by the following formula (4), Method for producing tetraacetylethylenediamine (TAED), characterized in that consisting of.  [Formula 3]

 [Formula 4]

The reaction catalyst according to claim 4, wherein the reaction catalyst is selected from the group consisting of halogen salts of alkali metals or alkaline earth metals in the one-step process, in the two-step process, or in both the first and second steps. Method for producing tetraacetylethylenediamine (TAED), characterized in that using.