TWI435862B - Tetraacetylalkylenediamine - Google Patents

Description

Method for producing tetraethylene alkylene diamine

The invention relates to a method for producing tetraethenyl alkanediamine, which is obtained by oximation of diethyl hydrazine diamine and carboxylic acid anhydride under catalysis of an ionic liquid catalyst to form tetraethoxyalkylenediamine.

Tetraacetylethylenediamine (TAED) is a high-efficiency low-temperature oxygen bleach activator widely used in the daily chemical industry. It is also a non-toxic, environmentally-friendly and biodegradable environmentally friendly additive, and various The surfactant has good compatibility with the enzyme. Only 0.5~5.0% tetraethylamethylenediamine can make sodium perborate or sodium percarbonate exert its bleaching effect at low temperature, greatly improving the cleaning ability of detergent/detergent. In addition, tetraethylene ethylenediamine can also be used as a bleach activator for hydrogen peroxide. Therefore, it has been successfully used in bleaching systems in the textile, paper, dyeing and finishing, industrial and household cleaning sectors.

There are two main methods for the preparation of tetraethylene decyl ethylenediamine in the industry, which are a one-step method and a two-step method, which are all obtained by reacting ethyleneamine as a main raw material and reacting with a guanidine reagent. Known guanamine reagents include carboxylic acid, ruthenium chloride, acid anhydride, carboxylate, ketene, cyanuric chloride, etc., but ruthenium chloride and cyanuric chloride are not suitable for the preparation of tetraethylene sulfonate. amine. The process of using ketene as a raw material is relatively risky, and belongs to the early old process in the one-step preparation. It is directly reacted with ethylenediamine or diethyl ethanediamine and ketene in the presence of an organic solvent. Tetraethylethylenediamine. The use of ketene converts the acetic acid formed by the reaction of diethylethylenediamine with acetic anhydride into acetic anhydride, reduces the concentration of by-product acetic acid and increases the concentration of the reactant acetic anhydride, thereby effectively promoting the reaction. However, since ketene is a toxic gas at normal temperature and pressure, it is difficult to store and cannot be transported across borders, and it is inconvenient to use as a raw material, so the process method has been eliminated and is no longer used.

British Patent GB 1357595 discloses a method for synthesizing tetraethylene decyl ethylenediamine by reacting diethyldimethoxyethylenediamine, acetic anhydride and ketene at 135-147 °C. There are several patents to add an acidic catalyst to this process. For example, German Patent DE 1910300 discloses an ethylenediamine or diethyl ethanediamine, acetic anhydride and ketene as raw materials, acetone, carbon trichloride or ethyl acetate. As a solvent, tetraethylene ethanediamine was synthesized under the action of a concentrated phosphoric acid of the catalyst. This process method has many shortcomings. First, concentrated phosphoric acid is easy to corrode equipment and cannot be reused. The high cost of waste acid treatment and the reaction wastewater are easy to cause environmental problems. Second, in addition to the solvent required for the reaction itself, the purification of the product needs to be additionally A large number of solvent cleaning, this patent process cost, high energy consumption, low space-time yield. U.S. Patent Nos. 3,223,732 and 3,228,983 each use p-toluenesulfonic acid and concentrated sulfuric acid as catalysts, respectively, in low yields and additional purification of the product. U.S. Patent No. 3,539,629 uses concentrated phosphoric acid, concentrated sulfuric acid, and p-toluenesulfonic acid as catalysts, and the yield thereof is relatively low from 59 to 70.5%, and there are also problems of equipment corrosion and waste acid treatment.

Another one-step process uses ethylenediamine and acetic anhydride as starting materials. However, this process uses all expensive acetic anhydride as a deuteration reagent, resulting in high investment cost and energy loss, and less industrially. It is economical. German patent DE 2832021 uses a bubble column to continuously prepare tetraethylene ethanediamine, which is directly synthesized from acetic anhydride and ethylenediamine as a raw material. The higher reaction temperature is used, and the purity of tetraethylene sulfonium ethylenediamine is higher. It is low and needs to be purified by distillation at 250 Pa high vacuum and 165 °C. The reaction conditions and equipment are more stringent.

Nowadays, the industrial process is mostly synthesized by a two-step method. First, ethylenediamine is reacted with acetic acid to form diethylglycidyldiamine, and then deuterated with acetic anhydride to obtain tetraethylenephosphonium ethylenediamine, thereby saving acetic anhydride. The amount of use reduces the cost of raw materials for the first stage of the reaction. Some existing literatures and patents mention that the first stage process can be added with a dehydrating agent, thereby reducing the temperature of the strip water and increasing the water transport rate to effectively shorten the reaction time; the second stage process can add an acidic catalyst to promote the deuteration reaction. Conventionally, concentrated sulfuric acid, concentrated phosphoric acid, concentrated hydrochloric acid or aluminum trichloride is used as a catalyst, but there are problems of equipment corrosion and waste acid, so it is still necessary to find an alternative catalyst. In addition, at present, the biggest problem in the production of tetraethylene ethanediamine is that the reaction time is too long, which inevitably restricts the annual output of industrial production and increases the cost.

The British patent GB 1335204 is synthesized by a two-step method. The first step takes nearly 8 hours. The second step is heated to 140 ° C by adding acetic anhydride, and the yield of 77 mg after the acetic acid is distilled off for 4 hours. The reaction time is longer. Long, limit production capacity per unit time. U.S. Patent No. 4,354,042 discloses a recycling process to increase the overall yield. The yield of tetraethylene ethanediamine obtained in the first reaction is only 56%. The mother liquor after the reaction is recovered and the ethylenediamine and acetic anhydride are added again. After repeating twice, the total yield is 86%, but the process flow is long and there are many equipment units. The total time consumption of the reaction is not mentioned in the specification, and it is impossible to evaluate whether it is economical.

British Patent Publication GB 2106903 A uses a two-column reactor, the first column is reacted with ethylenediamine to a molar ratio of 1:2.25 to form diethylglycolethylenediamine, and the by-product is continuously distilled under reduced pressure during the process. Water; the second column is added with 3~4.5 times molar equivalent of acetic anhydride, reacted at 140-150 ° C for 10 hours and the acetic acid by-product is continuously distilled off during the process, in which excess acetic anhydride is distilled together with the conversion rate. At 50%, fresh acetic anhydride is additionally added to maintain the overall reaction in the ratio of diethyl ethanediamine: acetic anhydride = 1:3 to 10, and the final yield can reach 96%. 70% of the vapor is removed from the system at a reflux ratio of 3:7, wherein acetic acid can be recovered to the first step and then reacted with ethylenediamine. This patent document clearly discloses that when the removal rate of acetic acid is greater than the rate of formation, and the acetic acid content of the reaction system is less than 2.5%, the conversion rate can reach 95%. Although this process has excellent yield performance, the equipment investment is large, and the relative time is too long to meet the economic benefits of the process.

British Patent GB 2096133 B discloses a two-column continuous operation in which diisopropyl ether, butyl acetate or ethyl acetate is added as a water-carrying agent in the synthesis of the first column of ethylenediethylethylenediamine, and the catalyst is used to promote dehydration reaction. The heterogeneous catalyst may be: alumina, ruthenium alumina, phosphoric acid, and the homogeneous catalyst may be: sulfuric acid, zinc acetate or boric acid, and the catalyst is removed before the reaction liquid enters the second column. However, the investment cost of the equipment of this process is high, and it is necessary to add a water-carrying agent, and at the same time, the problem of recycling the water-retaining agent.

Chinese Patent Publication No. CN 1332153 A discloses a two-step two-step continuous process, in which a dehydrating agent of butyl acetate is added in an amount of 2 to 3 times by weight of ethylenediamine in the first step reaction; and a second step is in a catalyst of 85% concentrated sulfuric acid. In the presence of the reaction, the reaction was carried out at a temperature of 150 to 160 ° C for 6.5 hours, and acetic acid was intermittently distilled off during the process to obtain a yield of 83%. However, there are several shortcomings in this process: additional dehydrating agent is added and a distillation unit is added to separate and recover water, which increases equipment investment costs; strong acid causes equipment corrosion and subsequent treatment of waste acid; higher reaction temperature increases energy consumption, and It is easy to cause coking of the product tetraethylene ethanediamine.

Chinese patent CN 1255376 C proposes to add a solvent and a catalyst azeotroped with acetic acid in a two-step reaction, the solvent comprising one or more mixed solutions of diisobutyl ether, toluene and chlorobenzene, and the catalyst comprises triethanolamine tungstate a mixture of one or more of tetrabutylammonium chloride, activated clay and p-toluenesulfonic acid. The addition of the catalyst makes the reactants have better activity, and can lower the reaction temperature to 125 ° C, which is beneficial to improve the color of the product and reduce the energy consumption; but the reaction time is only 8 to 11 hours in the second step, and the yield is only 48 to 75. %. It is a long-term, low-yield and environmentally friendly problem caused by the addition of a large amount of highly toxic azeotrope, which is a disadvantage of this process.

In the chemical industry process, the use of acidic substances to catalyze the reaction has been applied for many years, including cracking, alkylation, isomerization, polymerization, etherification, esterification, deuteration, transesterification and other processes. At this stage, most of the acid catalysts use inorganic acids (sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, hydrofluoric acid) or halides Lewis acid (aluminum trichloride), which are mature and inexpensive. Although the above acid catalyst has been used for many years, it has the following disadvantages: production of waste water, waste acid and salt by-products, causing environmental pollution; corrosion of production equipment, improvement of equipment replacement frequency; difficulty in separation and recovery of products and catalysts, purification steps Trouble; public safety issues in transportation and storage, high added costs, etc. In view of the shortcomings of the use of inorganic acid catalyst process technology, the development of a high reactivity, shortened reaction time, reusable catalyst, increase the capacity of process equipment, reduce equipment corrosion problems, make the process more economical, is still the main future Research topics.

An ionic liquid system refers to a molten salt system which is liquid at room temperature or near room temperature and consists entirely of cations and anions. It is also called a low-temperature molten salt. It can be controlled by simply changing its composition to control the melting point, viscosity, density, Properties such as polarity, solubility, acidity, and conductivity, which make the ionic liquid a "solid" liquid that has both liquid and solid functional properties. Ionic liquids have many advantages such as high polarity, low melting point, wide liquid range, non-flammability, high thermal stability, high electrical conductivity, good electrochemical properties, environmental friendliness and almost negligible vapor pressure. They are widely used in chemistry. And in line with the demands of the development of green chemistry and received a lot of attention. In recent years, ionic liquids have gradually developed into a new catalytic reaction system, which can play various roles such as organic catalyst, cocatalyst, coordination source and reaction solvent in the reaction, showing high selectivity and good reaction. On the other hand, because ionic liquid can be operated under normal pressure, it can be used as a substitute for general volatile organic solvents, replacing volatile, toxic and flammable organic solvents, reducing environmental pollution and avoiding operator exposure. At the risk of harm, ionic liquids are considered a new green solvent.

In the past, most of the researches focused on the Lewis acid type ionic liquid of aluminum chloride. In recent years, the Br Φ nsted acid type ionic liquid has been paid more and more attention, because it has water to the former. The advantage of stability. Acidic ionic liquids have many advantages: good fluidity with liquid acid, high acid density, uniform acid strength distribution and acid loss, and non-volatile solid acid, which can change its acidity and solubility by adjusting the structure of anion and cation. Sex, which is good for catalyst design. In the catalytic system, the ionic liquid which is easy to separate and recover has the high-density reaction point of the liquid acid and the non-volatileity of the solid acid, and the structure and the acidity can be variably changed, which has great potential in the acid catalyst industrial application.

SUMMARY OF THE INVENTION The main object of the present invention is to provide a process for producing tetraethylene alkylalkanediamine which can improve the reactivity by adding an ionic liquid catalyst, effectively shorten the reaction time, and maintain good tetraethenyldiamine yield.

Another object of the present invention is to provide a process for producing tetraethenyldiamine diamine which can reduce corrosion of production equipment, reduce waste acid treatment, and meet green chemical requirements.

For the above and other purposes, the present invention is the first to use an ionic liquid catalyst to catalyze the deuteration reaction of diethylene alkyl diamine.

As a catalyst for the deuteration reaction, the aforementioned ionic liquid system is an ionic compound composed of one or more cations and one or more anions. The cation constituting the ionic liquid has a nitrogen-containing cationic structure, and optionally an ammonium compound, an imidazole compound, a pyrrole compound, a benzimidazole compound, a pyridine ( A group consisting of a pyridine compound, a bipyridine compound, a pyridazine compound, a pyrimidine compound, a cation derived from a pyrazine compound, and combinations thereof. The anion constituting the ionic liquid may be selected from F ^- , Cl ^- , Br ^- , I ^- , BF ₄ ^- , PF ₆ ^- , HSO ₄ ^- , CH ₃ SO ₃ ^- , CH ₃ SO ₄ ^- , H ₂ PO ₄ ^- a group consisting of CF ₃ COO ^- , CH ₃ COO ^- , NO ₃ ^- and combinations thereof.

The method for producing tetrakisylalkylenediamine of the present invention is carried out by oxime-reacting diethyldidecyldiamine and carboxylic anhydride under ionic liquid catalyst to form tetraethenyldiamine. Wherein the diethylene alkylene diamine-based alkylene chain has a di-decylalkylenediamine having 2 to 6 carbon atoms, and may be a carboxylic acid or a carboxylic acid anhydride and an alkyl diamine having 2 to 6 carbon atoms such as ethylene. The amine, the propylenediamine, the butanediamine, the pentamethylenediamine and the hexamethylenediamine are synthetically prepared, and the diethylaminoalkyldiamine is preferably diethylidene ethylenediamine; in addition, the carboxylic acid may be acetic acid or a carboxylic anhydride. It can be acetic anhydride or propionic anhydride. The molar ratio of the diethylaminoalkyldiamine to the carboxylic acid anhydride used in the reaction is 1:2 to 14, and the ionic liquid catalyst is added in an amount of at least 1% by weight, preferably at least 3, of the diethylaminoalkylenediamine. The weight %, more preferably 3 to 30% by weight, and the reaction temperature range is 120 to 160 ° C. The reaction solution was cooled to precipitate tetraethylene alkylenediamine, and the product was obtained by filtration (purity: about 99%). After filtration, the reaction filtrate containing the catalyst was recycled. The by-product carboxylic acid produced in the reaction process can be distilled off by a distillation apparatus and recycled for the preparation of diethylidene diamine.

According to the manufacturing method of the present invention, by adding an ionic liquid catalyst, the deuteration reaction rate can be effectively increased, the reaction time can be shortened, the yield of tetraethylene alkyldiamine can be increased, the equipment productivity can be improved, and tetraethylene alkylene can be solved. The biggest problem of long reaction time of amine is to reduce the corrosion of equipment and the problem of waste acid derivatization.

The features and effects of the present invention are further illustrated by the following specific examples, which are not intended to limit the scope of the invention.

Ionic liquid preparation

27.25 g of 1,4-butane sultone and 15.86 g of pyridine were placed in a 250 mL round bottom flask, and after stirring at 40 ° C for one day, the resulting white solid was washed several times with diethyl ether. Drying under vacuum, then slowly adding an equivalent amount of concentrated sulfuric acid dropwise, and stirring at 80 ° C for 6 hours to obtain 1-(4-sulfonic acid) ionic liquid 1-(4-sulfonic acid) Butylpyridinium hydrogen sulfate, [HSO ₃ BPy]HSO ₄ ).

Other ionic liquid types that can be used in the present invention include, but are not limited to, 1-Butyl-3-methylimidazolium hydrogen sulfate ([BMIM]HSO ₄ ), 1-B. 1-Ethyl-3-methylimidazolium hydrogen sulfate ([EMIM]HSO ₄ ), 1-butyl-3-methylimidazolium trifluoroacetate (1-Butyl-3-methylimidazolium) Trifluoroacetate, [BMIM]CF ₃ COO), Tetrabutylammonium hydrogen sulfate (TBAHS), Tetrabutylammonium dihydrogen phosphate (TBAHP).

Example 1: Preparation of Diethylene Glycol Diamine

30.05 g of ethylenediamine was added to a 1 L reactor equipped with a thermometer, a stirring device, a dropping funnel and a distillation apparatus, and 75.06 g of acetic acid was placed in a dropping funnel, and the temperature was slowly dropped into a 1/2 amount at a temperature below 80 ° C. Acetic acid, then the reaction system is heated to 80 ° C, and the remaining acetic acid is added dropwise before 110 ° C, heated to 140 ° C, slowly evaporating to 160 ° C depending on the evaporation of water, then control the constant temperature, slowly decompressing water and Excess acetic acid was used for 1 hour, and the distillation temperature was controlled to be between 100 and 105 ° C. After cooling, crystallization and purification, 67.05 g of white solid diethyl ethanediamine was obtained in a yield of 93%.

Example 2: Preparation of tetraethylenemethyldiamine - 6hr - no catalyst

72.15 g of diethylethylenediamine and 510 g of acetic anhydride were added to a 1 L reaction flask, and after heating to 140 ° C for 2 hours, the acetic acid was distilled off for 4 hours and the distillation temperature was controlled to be 110 to 125 ° C. After cooling and crystallization, the mixture was filtered under air and dried to obtain 91.36 g of tetraethylene decylethylenediamine in a yield of 80.0%.

Example 3: Preparation of tetraethylenemethyldiamine-4hr - no catalyst

60.03 g of diethylaminodiamine and 425 g of acetic anhydride were added to a 1 L reaction flask, and after heating to 140 ° C for 2 hours, the acetic acid was distilled off for 2 hours and the distillation temperature was controlled to be 110 to 125 ° C. After cooling and crystallization, the mixture was filtered under air and dried to obtain 71.35 g of tetraethylene decylethylenediamine in a yield of 75.1%.

Example 4: Preparation of tetraethylenemethyldiamine-4hr-catalyst 8.2% by weight

The procedure of Example 3 was repeated, and 4.92 g of [BMIM]HSO _{4 was added} as a catalyst, and the remaining composition addition ratio was maintained to be the same as the operation reaction conditions to obtain 76.85 g of the product tetraethylenesulfonylethylenediamine in a yield of 80.9%.

Example 5: Preparation of tetraethylenemethyldiamine-4hr-catalyst 3 wt%

The procedure of Example 3 was repeated, and 1.80 g of [BMIM]HSO _{4 was added} as a catalyst, and the remaining composition addition ratio was maintained to be the same as the operation reaction conditions to obtain 76.36 g of the product tetraethylenesulfonylethylenediamine in a yield of 80.3%.

From the comparison of the yields of tetraethylenethiodiamine in Examples 2 to 4, when the reaction time was shortened from 6 hours (Example 2) to 4 hours (Example 3), the yield decreased by 5% and only reached 75.1. %, but in Example 4, by adding an imidazole hydrogensulfate type ionic liquid [BMIM]HSO ₄ , the yield was increased by 5.8% to 80.9%, which was longer than the longer reaction time but without the addition of catalyst. 2, the yield of 80.0%) significantly promotes the progress of the deuteration reaction and effectively shortens the reaction time. Considering the economic benefit of the catalyst addition cost, the amount of catalyst used in Example 5 was reduced to 3% by weight, and the yield was slightly decreased by 0.6% compared with Example 4, but still maintained good performance of over 80%.

The effect of shortening the reaction time by the catalyst is further tested below. The following examples reduce the reaction time to 3 hr and add different amounts to react with different types of ionic liquids to test the catalyst efficacy.

Example 6: Preparation of tetraethyleneethylenediamine-3hr-catalyst-free

60.16 g of diethylethylenediamine and 426 g of acetic anhydride were added to a 1 L reaction flask, and after heating to 140 ° C for 1.5 hours, the acetic acid was distilled off for 1.5 hours and the distillation temperature was controlled to be 110 to 125 ° C. After cooling and crystallization, the mixture was suction filtered and dried to obtain 68.45 g of tetraethylene decylethylenediamine in a yield of 71.9%.

Example 7: Preparation of tetraethyleneethylenediamine-3hr-catalyst 8.2% by weight

The procedure of Example 6 was repeated, 4.94 g of [BMIM]HSO _{4 was added} as a catalyst, and the remaining composition addition ratio was maintained to be the same as the operation reaction conditions to obtain 76.41 g of the product tetraethylenesulfonylethylenediamine in a yield of 80.1%.

In Examples 6 and 7, the reaction time was compressed to half for 3 hours, the yield of the catalyst-free reaction was reduced to 71.9%, and the yield obtained by the addition of the ionic liquid of the present invention was greatly increased by 8.2%, maintained and implemented. Example 2 has a similar yield under twice the reaction time, so when the process production equipment is fixed, the annual output value of tetraethylene ethanediamine can be doubled, and the sales volume is increased.

Example 8: Preparation of tetraethylenemethyldiamine-3hr-catalyst 10% by weight

The procedure of Example 6 was repeated, 6.00 g of TBAHS was added as a catalyst, and the remaining composition addition ratio was maintained to be the same as the operation reaction conditions, and 76.03 g of the product tetraethylenesulfonylethylenediamine was obtained in a yield of 80.1%.

Example 9: Preparation of tetraethyleneethylenediamine-3hr-catalyst 10% by weight

The procedure of Example 6 was repeated, and 6.06 g of TBAHP was added as a catalyst, and the remaining composition addition ratio was maintained the same as the operation reaction conditions to obtain 76.9 g of the product tetraethylenesulfonylethylenediamine in a yield of 80.8%.

Example 10: Preparation of tetraethylenemethyldiamine-3hr-catalyst 10% by weight

The procedure of Example 6 was repeated, and 6.08 g of [BMIM]CF ₃ COO was added as a catalyst, and the remaining composition addition ratio was maintained the same as the operation reaction conditions to obtain 77.09 g of the product tetraethylenesulfonylethylenediamine in a yield of 81.2%.

Example 11: Preparation of tetraethyleneethylenediamine-3hr-catalyst 15% by weight

The procedure of Example 6 was repeated, and 9.02 g of [HSO ₃ BPy]HSO _{4 was added} as a catalyst, and the remaining composition addition ratio was maintained to be the same as the operation reaction conditions, thereby obtaining 76.05 g of the product tetraethyleneethylenediamine in a yield of 80.0%.

Other ionic liquids were used in Examples 8-11 and the reaction time was 3 hours. The cation of the ionic liquid of Example 8 was changed to quaternary ammonium, and the yield was maintained at 80% or more. The ionic liquid of Example 9 maintained the cation as a quaternary ammonium, and the anion was changed to a phosphate. As a result, the yield reached 80.8%, which was not added. Catalyst results increased by 9%. Further, in further comparison of Examples 8 and 9, when the cation is a quaternary ammonium system, the ionic liquid catalytic effect of the anion phosphate is superior to that of the sulfate. In Example 10, an ionic liquid having an anion of a trifluoroacetate type was used, and as a result, the yield was as high as 81.2%, which had an excellent catalytic effect. In Example 11, a pyridine type sulfate ion liquid was used, and the yield was maintained at 80% under the condition that the amount of the catalyst added was 15 wt%. The above examples show that the addition of different kinds of ionic liquids can also effectively promote the progress of the deuteration reaction of tetraethylene ethylenediamine, and successfully shorten the reaction time.

The effect of shortening the reaction time by the catalyst is further tested below. The following examples will reduce the reaction time to 2 hours and add different amounts of imidazole hydrogensulfate-type ionic liquids with different substituents for reaction.

Example 12: Preparation of tetraethyleneethylenediamine-2hr-catalystless

60.01 g of diethylidene ethylenediamine and 425 g of acetic anhydride were added to a 1 L reaction flask, and after heating to 140 ° C for 1 hour, the acetic acid was distilled off for 1 hour and the distillation temperature was controlled to be 110 to 125 ° C. After cooling and crystallization, the mixture was suction filtered and dried to obtain 56.44 g of tetraethylenesulfonylethylenediamine in a yield of 59.4%.

Example 13: Preparation of tetraethyleneethylenediamine-2hr-catalyst 5 wt%

The procedure of Example 12 was repeated, 3.00 g of [BMIM]HSO _{4 was added} as a catalyst, and the remaining composition addition ratio was maintained to be the same as the operation reaction conditions to obtain 70.91 g of the product tetraethyleneethylenediamine in a yield of 74.6%.

Example 14: Preparation of tetraethyleneethylenediamine-2hr-catalyst 8.2% by weight

The procedure of Example 12 was repeated, 4.92 g of [BMIM]HSO _{4 was added} as a catalyst, and the remaining composition addition ratio was maintained to be the same as the operation reaction conditions to obtain 71.93 g of the product tetraethylenesulfonylethylenediamine in a yield of 75.8%.

Example 15: Preparation of tetraethyleneethylenediamine-2hr-catalyst 15% by weight

The procedure of Example 12 was repeated, 9.00 g of [BMIM]HSO _{4 was added} as a catalyst, and the remaining composition addition ratio was maintained to be the same as the operation reaction conditions to obtain 73.50 g of the product tetraethylenesulfonylethylenediamine in a yield of 77.4%.

Example 16: Preparation of tetraethylenemethyldiamine-2hr-catalyst 10% by weight

The procedure of Example 12 was repeated, and 6.00 g of [EMIM]HSO _{4 was added} as a catalyst, and the remaining composition addition ratio was maintained to be the same as the operation reaction conditions to obtain 73.40 g of the product tetraethylenesulfonethylenediamine in a yield of 77.3%.

The reaction times of Examples 12 to 16 were compressed to 2 hours. In Example 12, the catalyst was not added, and the yield of the reaction fell below 60%, and the yield obtained by 6 hours was drastically decreased by 20.6%. In Examples 13-15, the yield was increased to 74.6 to 77.4% by the addition of the imidazole hydrogensulfate type ionic liquid [BMIM]HSO ₄ , and the increase was as high as 15.2% to 18.0%. Example 16 changed the functional group substituted on the imidazole, using [EMIM]HSO ₄ , and the results showed that the catalytic effect of the ionic liquid was comparable to that of [BMIM]HSO ₄ , and both exhibited an excellent performance of 18%. The above results show that the ionic liquid of the invention can successfully increase the reaction rate, shorten the reaction time, increase the equipment productivity, and solve the problem that the reaction time of tetraethylene ethanediamine is too long.

Claims (6)

A method for producing tetraethenyldiamine diamine, which is subjected to a oximation reaction of diethyl hydrazine diamine and a carboxylic acid anhydride under catalysis of an ionic liquid catalyst to form tetraethenyldiamine, wherein the ion A liquid catalyst is an ionic compound consisting of one or more cations and one or more anions, wherein the cation is selected from the group consisting of an imidazole compound, a pyridine-derived cation, and combinations thereof. The group, and the anion are selected from the group consisting of HSO ₄ , CH ₃ SO ₃ , CH ₃ SO ₄ , H ₂ PO ₄ , CF ₃ COO, CH ₃ COO, NO _{3 ,} and combinations thereof. The production method of claim 1, wherein the diethenyldiamine-based alkylene chain has a diacetylalkylenediamine having 2 to 6 carbon atoms. The method of producing a second aspect of the invention, wherein the diethyl hydrazine diamine is diethyl ethanediamine. The production method of claim 1, wherein the carboxylic anhydride is acetic anhydride. The method of claim 1, wherein the ionic liquid catalyst is added in an amount of at least 1% by weight of the diethylidene diamine. For example, in the method of claim 1, wherein the reaction is carried out at a temperature of 120 to 160 °C.