WO2004002942A1 - Method of preparing tetraacetylethylenediamine - Google Patents

Method of preparing tetraacetylethylenediamine Download PDF

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WO2004002942A1
WO2004002942A1 PCT/CN2003/000416 CN0300416W WO2004002942A1 WO 2004002942 A1 WO2004002942 A1 WO 2004002942A1 CN 0300416 W CN0300416 W CN 0300416W WO 2004002942 A1 WO2004002942 A1 WO 2004002942A1
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reaction
tetraacetylethylenediamine
acetic acid
preparing
ethylenediamine
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PCT/CN2003/000416
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French (fr)
Chinese (zh)
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Zhigang Zhu
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Zhejiang Jinke Chemistry Co., Ltd
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Priority to AU2003234900A priority Critical patent/AU2003234900A1/en
Publication of WO2004002942A1 publication Critical patent/WO2004002942A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
    • C01B15/055—Peroxyhydrates; Peroxyacids or salts thereof
    • C01B15/10—Peroxyhydrates; Peroxyacids or salts thereof containing carbon
    • C01B15/103—Peroxyhydrates; Peroxyacids or salts thereof containing carbon containing only alkali metals as metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
    • C07C233/35—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
    • C07C233/36—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton

Definitions

  • the present invention relates to a process for preparing tetraacetylethylenediamine, and belongs to the technical field of preparation of bleach activators in detergents.
  • Tetraacetylethylenediamine which can bleach sodium percarbonate and sodium perborate at room temperature under the condition of 0.5 ⁇ 5%, is an activator that can adapt to low temperature bleaching.
  • TAED Tetraacetylethylenediamine
  • the synthesis of TAED mostly uses ethylenediamine, acetic acid and acetic anhydride as raw materials, and adopts a two-step same-tank preparation process.
  • British patent GB1335204 discloses that in the first step, ethylenediamine and acetic acid are used to synthesize glyoxylethylenediamine (DAED), and then the second step is acetylation with acetic anhydride.
  • European patent EP8369 discloses that the continuous operation is used to synthesize ethylene diamine and acetic acid stalk directly on the steamed pill, but it requires the use of expensive acetic anhydride as the raw material for all acetylation, which is extremely costly.
  • British patents GB20-96133A and GB2106903A disclose that a two-column reactor is used. The first column completes the reaction of acetic acid and ethylenediamine, the second column performs the acetic anhydride acetylation reaction, and the by-products are returned to the first column and replaced with acetic acid.
  • a dehydrating agent is usually added to form an azeotrope with water.
  • catalysts such as phosphoric acid, sulfuric acid, boric acid, zinc acetate and the like are added.
  • the added dehydrating agent usually causes side reactions with acetic acid and acetic anhydride.
  • the reaction speed of acetic anhydride and diacetylethylenediamine is slow, it is necessary to increase the reaction temperature to accelerate the reaction speed. Therefore, the general reaction temperature is above 135 ° C to obtain a higher yield.
  • the increase of reaction temperature will increase the number of side reactions, and the color of the obtained product will be deepened, which will affect the appearance quality of TAED products.
  • the invention provides a two-step method for synthesizing acetylethylenediamine, which can inhibit side reactions, reduce raw material and energy consumption, and has good product quality.
  • the technical scheme of the present invention is: synthesizing diacetylethylenediamine from ethylenediamine and acetic acid, and then synthesizing tetraacetylethylenediamine from diacetylethylenediamine and acetic anhydride, which is characterized by adding an azeotrope with acetic acid in the synthesis reaction Solvent; Triethanolamine tungstate, tetrabutylammonium chloride, one and several mixtures of activated clay and p-toluenesulfonic acid are used as catalysts in the synthesis reaction; molar ratio of ethylenediamine to acetic acid 1 : 2.3-3.0, reaction dehydration temperature 90 ⁇ 120 ° C; reaction molar ratio of diacetylethylenediamine to liver acetate is 1: 4-9, synthesis reaction temperature 110 132 ° C.
  • the azeotropic solvent is a mixed solution of one or more of diisobutyl ether, toluene, ethylbenzene, xylene, chlorobenzene, 1, 3-difluorenylcycloethane, and octane. It is 80 ⁇ 800% of ethylenediamine, and 30 ⁇ 400% of diacetylethylenediamine in the second step reaction.
  • the amount of the catalyst added in the first step is 1 ⁇ 3% of ethylenediamine; the second step is 1 ⁇ 10% of diacetylethylenediamine.
  • ethylenediamine is added to a mixed solution of acetic acid and an azeotropic solvent at a temperature lower than 80 ° C, and the solution is heated to reflux and dehydrated after dropping.
  • the synthetic reaction filtrate can be recycled after adding additional reactants.
  • a solvent capable of azeotroping with acetic acid is required.
  • solvents include diisobutyl ether, 1,3-dimethylcyclohexane, toluene, ethylbenzene, xylene, o-xylene, and octane. , Chlorobenzene, benzene. These solvents usually do not react side-by-side with acetic acid and acetic anhydride.
  • Another technical effect of the present invention is to add a catalyst in the first step reaction.
  • the catalyst used in the two step reaction has a better activation effect with the reactants, thereby reducing the temperature of the synthesis reaction, which is beneficial to improving the color of the reaction product.
  • the third technical effect of the present invention is that the filtrate of the two-step reaction can be reused, or the reaction solution of the first step can be used for the second step reaction, which not only reduces the consumption of raw materials, but also recycles the mother liquor, which will improve the purity of the crystalline product. .
  • the performance of the TAED prepared by the present invention compared with the tetraacetylethylenediamine prepared by the ordinary two-step method is as follows:
  • Example 1 In the first step, the reaction solution in Example 1 was reused. 288 g of acetic anhydride was added, 1.2 g of p-toluenesulfonic acid, and 120 g of ethylenediamine were added dropwise. The same operation as in Example 1 was performed to obtain 285.3 g of diacetylethylenediamine.
  • Example 3 86.4 g of diacetylethylenediamine, 1.3 g of activated clay, 100 g of chlorobenzene, and 150 g of acetic anhydride were added to the filtrate in the second step of the reaction in Example 1. The temperature was raised to 125 ° C, and the reaction was performed for 8 hours. The solution was cooled and filtered to obtain TAED 102.6 g .
  • Example three 86.4 g of diacetylethylenediamine, 1.3 g of activated clay, 100 g of chlorobenzene, and 150 g of acetic anhydride were added to the filtrate in the second step of the reaction in Example 1. The temperature was raised to 125 ° C, and the reaction was performed for 8 hours. The solution was cooled and filtered to obtain TAED 102.6 g .
  • Example three 86.4 g of diacetylethylenediamine, 1.3 g of activated clay, 100 g of chlorobenzene, and 150 g of acetic anhydr

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A method of preparing tetraacetylethylenediamine, belongs to the Field of preparing technology of bleaching activator in detergent. First reaction of ethylene diamine with acetic acid to synthesize diacetyl ethylenediamine, then reacted with acetic anhydride to synthesize tetraacetylethyl enediamine. The invention is characterized by adding solvent which can be azeotropic with acetic acid but no side reaction with acetic acid and acetic anhydride during synthesis, meanwhile adding catalyst in both two step reactions. In first step reaction adding ethylene diamine to acetic acid solution below 80 ºC, then warming-up, refluxing and dewatering; the temperature of the second step reaction does not exceed 132 ºC. Both filtrates of two step reactions can be recycled, so it is beneficial to improve the purity of product and decrease the consumption of raw material and energy. Tetraacetylethylenediamine prepared according to the invention is white in appearance, purity > 99 %, and adoption of the invention has significant benefit.

Description

一种四乙酰乙二胺制备方法 技术领域  Technical field for preparing tetraacetylethylenediamine
本发明涉及四乙酰乙二胺制备工艺， 属于洗涤剂中漂白活化剂的制备技 术领域 背景技术  The present invention relates to a process for preparing tetraacetylethylenediamine, and belongs to the technical field of preparation of bleach activators in detergents.
四乙酰乙二胺（TAED ), 它在含量 0.5~5%情况下， 能使过碳酸钠、 过硼 酸钠在常温下发生漂白作用， 因此是一种能适应低温漂白的活化剂。 目前， TAED的合成制备多以乙二胺、乙酸和乙酸酐为原料，采用二步同釜制备工艺。 英国专利 GB1335204 公开， 第一步先用乙二胺和乙酸合成乙二酰乙二胺 ( DAED ), 然后再用乙酸酐进行第二步乙酰化。 欧州专利 EP8369公开， 采 用连续操作， 由乙二胺和乙酸秆直接在蒸榴柱上合成， 但它需使用昂贵的乙 酸酐作为全部乙酰化原料，成本极高。英国专利 GB20-96133A, GB2106903A, 公开采用双柱的反应器， 第一柱完成乙酸和乙二胺反应， 第二柱进行乙酸酐 乙酰化反应， 副产物返回第一柱回用替代乙酸。  Tetraacetylethylenediamine (TAED), which can bleach sodium percarbonate and sodium perborate at room temperature under the condition of 0.5 ~ 5%, is an activator that can adapt to low temperature bleaching. At present, the synthesis of TAED mostly uses ethylenediamine, acetic acid and acetic anhydride as raw materials, and adopts a two-step same-tank preparation process. British patent GB1335204 discloses that in the first step, ethylenediamine and acetic acid are used to synthesize glyoxylethylenediamine (DAED), and then the second step is acetylation with acetic anhydride. European patent EP8369 discloses that the continuous operation is used to synthesize ethylene diamine and acetic acid stalk directly on the steamed pill, but it requires the use of expensive acetic anhydride as the raw material for all acetylation, which is extremely costly. British patents GB20-96133A and GB2106903A disclose that a two-column reactor is used. The first column completes the reaction of acetic acid and ethylenediamine, the second column performs the acetic anhydride acetylation reaction, and the by-products are returned to the first column and replaced with acetic acid.
在二步法合成反应中， 为提高反应效率， 通常采用加入脱水剂 ， 形成与 水共沸。 在第二步反应中加入如磷酸、 硫酸、 硼酸、 乙酸锌等催化剂 。 但是 加入的脱水剂通常会与乙酸、 乙酸酐产生副反应。 同时， 由于乙酸酐与二乙 酰乙二胺的反应速度较慢， 需要通过提高反应温度来加快反应速度， 因此一 般反应温度在 135°C以上， 以获取较高的收率。但是反应温度的提高会使副反 应增多， 获得的产品色泽加深而影响 TAED的产品外观质量。 发明内容  In the two-step synthesis reaction, in order to improve the reaction efficiency, a dehydrating agent is usually added to form an azeotrope with water. In the second step reaction, catalysts such as phosphoric acid, sulfuric acid, boric acid, zinc acetate and the like are added. However, the added dehydrating agent usually causes side reactions with acetic acid and acetic anhydride. At the same time, since the reaction speed of acetic anhydride and diacetylethylenediamine is slow, it is necessary to increase the reaction temperature to accelerate the reaction speed. Therefore, the general reaction temperature is above 135 ° C to obtain a higher yield. However, the increase of reaction temperature will increase the number of side reactions, and the color of the obtained product will be deepened, which will affect the appearance quality of TAED products. Summary of the Invention
本发明提供一种能抑制副反应，降低原料和能源消耗，产品质量好的二步 合成乙酰乙二胺的制备方法。  The invention provides a two-step method for synthesizing acetylethylenediamine, which can inhibit side reactions, reduce raw material and energy consumption, and has good product quality.
本发明的技术方案为： 由乙二胺和乙酸合成二乙酰乙二胺，再由二乙酰乙 二胺和乙酸酐合成四乙酰乙二胺， 其特征是在合成反应中加入与乙酸共沸的 溶剂； 合成反应中加入钨硅酸三乙醇胺盐， 氯化四特丁基铵， 活性白土和对 曱苯磺酸的一种和数种的混合物为催化剂； 乙二胺与乙酸反应的摩尔比 1: 2.3-3.0, 反应脱水温度 90~120°C ; 二乙酰乙二胺与乙酸肝反应摩尔比为 1: 4-9, 合成反应温度 110 132 °C。 所述的共沸溶剂为二异丁基醚、 曱苯、 乙苯、 二甲苯、 氯苯、 1 , 3 -二曱 基环乙烷、 辛烷的一种或数种的混合溶液， 加入量为乙二胺的 80〜800%, 第二 步反应时为二乙酰乙二胺的 30〜400%。 The technical scheme of the present invention is: synthesizing diacetylethylenediamine from ethylenediamine and acetic acid, and then synthesizing tetraacetylethylenediamine from diacetylethylenediamine and acetic anhydride, which is characterized by adding an azeotrope with acetic acid in the synthesis reaction Solvent; Triethanolamine tungstate, tetrabutylammonium chloride, one and several mixtures of activated clay and p-toluenesulfonic acid are used as catalysts in the synthesis reaction; molar ratio of ethylenediamine to acetic acid 1 : 2.3-3.0, reaction dehydration temperature 90 ~ 120 ° C; reaction molar ratio of diacetylethylenediamine to liver acetate is 1: 4-9, synthesis reaction temperature 110 132 ° C. The azeotropic solvent is a mixed solution of one or more of diisobutyl ether, toluene, ethylbenzene, xylene, chlorobenzene, 1, 3-difluorenylcycloethane, and octane. It is 80 ~ 800% of ethylenediamine, and 30 ~ 400% of diacetylethylenediamine in the second step reaction.
所述的催化剂加入量第一步反应为乙二胺的 1〜3%； 第二步反应为二乙酰 乙二胺的 1~10%。  The amount of the catalyst added in the first step is 1 ~ 3% of ethylenediamine; the second step is 1 ~ 10% of diacetylethylenediamine.
所述的笫一步反应在低于 80°C温度下乙二胺加入乙酸与共沸溶剂的混合 液中， 滴加后升温回流脱水。  In the one-step reaction, ethylenediamine is added to a mixed solution of acetic acid and an azeotropic solvent at a temperature lower than 80 ° C, and the solution is heated to reflux and dehydrated after dropping.
所述的合成反应滤液补加反应物后可循环使用。  The synthetic reaction filtrate can be recycled after adding additional reactants.
本发明在合成反应需加入能与乙酸共沸的溶剂， 这些溶剂包括二异丁醚、 1 , 3-二甲基环已烷、 曱苯、 乙苯、 二曱苯、 邻二甲苯、 辛烷、 氯苯、 苯。 这 些溶剂通常不会与乙酸和乙酸酐产生副反应。  In the present invention, in the synthesis reaction, a solvent capable of azeotroping with acetic acid is required. These solvents include diisobutyl ether, 1,3-dimethylcyclohexane, toluene, ethylbenzene, xylene, o-xylene, and octane. , Chlorobenzene, benzene. These solvents usually do not react side-by-side with acetic acid and acetic anhydride.
本发明的另一个技术效果是在第一步反应中加入催化剂 ,两步反应所用的 催化剂具有与反应物更好的活化作用 , 从而使合成反应温度降低， 有利于改 善反应产物的色泽。  Another technical effect of the present invention is to add a catalyst in the first step reaction. The catalyst used in the two step reaction has a better activation effect with the reactants, thereby reducing the temperature of the synthesis reaction, which is beneficial to improving the color of the reaction product.
本发明的第三个技术效果是两步反应的滤液可以回用，或者第一步反应液 可用于第二步反应， 这样不仅可降低原料消耗， 而且母液的循环套用， 会提 高结晶产物的纯度。  The third technical effect of the present invention is that the filtrate of the two-step reaction can be reused, or the reaction solution of the first step can be used for the second step reaction, which not only reduces the consumption of raw materials, but also recycles the mother liquor, which will improve the purity of the crystalline product. .
经对比试验测定， 本发明制备的 TAED与普通两步法制备的四乙酰乙二 胺的性能对比如下：  The performance of the TAED prepared by the present invention compared with the tetraacetylethylenediamine prepared by the ordinary two-step method is as follows:
Figure imgf000003_0001
具体实施方式
Figure imgf000003_0001
detailed description
实施例一  Example one
在 1000ML装有温度计、 塔分离柱， 滴液漏斗、 搅拌器的四口反应瓶中， 加入氯苯 400克， 冰乙酸 288克， 对曱苯磺酸 1.2克， 在< 80°€温度下搅拌滴 加 120克乙二胺， 经 40分钟滴加完毕， 然后升温至 100Γ， 回流 1小时， 脱 水 1小时， 降温至 20°C , 洗涤、 烘干， 得二乙酰乙二胺 270克。  In a four-neck reaction flask equipped with a thermometer, a column separation column, a dropping funnel, and a stirrer, add 1000 g of chlorobenzene, 288 g of glacial acetic acid, and 1.2 g of p-toluenesulfonic acid, and stir at a temperature of <80 ° €. 120 g of ethylenediamine was added dropwise. After the addition was completed in 40 minutes, the temperature was increased to 100 Γ, refluxed for 1 hour, dehydrated for 1 hour, cooled to 20 ° C, washed and dried to obtain 270 g of diacetylethylenediamine.
取二乙酰乙二胺 86.4克，加入钨硅酸三乙醇胺 1.3克， 氯苯 100克， 乙酸 酐 550克， 搅拌升温至 125°C , 保温 3小时， 反应 6小时后， 升温至 132°C， 然后冷却， 过滤， 得含量 99.4%TAED65.66克。 实施例二 Take 86.4 g of diacetylethylenediamine, add 1.3 g of triethanolamine tungstate, 100 g of chlorobenzene, and 550 g of acetic anhydride, heat up to 125 ° C with stirring, hold for 3 hours, and heat up to 132 ° C after 6 hours of reaction. It was then cooled and filtered to obtain 99.4% TAED 65.66 g. Example two
例一中第一步反应液回用， 加入乙酸酐 288克， 对甲苯磺酸 1.2克， 滴加 乙二胺 120克， 操作同实施例一， 得二乙酰乙二胺 285.3克。  In the first step, the reaction solution in Example 1 was reused. 288 g of acetic anhydride was added, 1.2 g of p-toluenesulfonic acid, and 120 g of ethylenediamine were added dropwise. The same operation as in Example 1 was performed to obtain 285.3 g of diacetylethylenediamine.
例一中第二步反应的滤液加入二乙酰乙二胺 86.4克，活性白土 1.3克，氯 苯 100克，乙酸酐 150克，升温至 125°C ,反应 8小时，冷却过滤，得 TAED 102.6 克。 实施例三  86.4 g of diacetylethylenediamine, 1.3 g of activated clay, 100 g of chlorobenzene, and 150 g of acetic anhydride were added to the filtrate in the second step of the reaction in Example 1. The temperature was raised to 125 ° C, and the reaction was performed for 8 hours. The solution was cooled and filtered to obtain TAED 102.6 g . Example three
在 1000ML四口反应瓶中， 加入乙酸 100.8克， 氯苯 300克， 对曱^ 酸 0.36克， 在<80 温度下， 滴加乙二胺 36克， 升温回流 1小时， 然后加入乙 酸酐 559克， 氯化四特丁基铵 1.3克， 升温至 125 °C , 保温反应 3小时， 蒸餾 8小时， 冷却过滤， 获得 TAED70.3克。 实施例四  In a 1000ML four-neck reaction flask, add 100.8 g of acetic acid, 300 g of chlorobenzene, and 0.36 g of p-acetic acid. Add 36 g of ethylenediamine dropwise at a temperature of <80, heat up to reflux for 1 hour, and then add 559 g of acetic anhydride. 1.3 g of tetra-t-butylammonium chloride, heated to 125 ° C, held for 3 hours, distilled for 8 hours, cooled and filtered to obtain 70.3 g of TAED. Example 4
在 1000ML四口反应瓶中，加入乙酸 100.8克，氯苯 300克，活性白土 0.36 克， 温度控制在 80°C以下， 滴力 p 36克乙二胺， 加毕升温， 回流 1小时， 加入 例三的滤液， 加入钨硅酸三乙醇铵 1.3克， 升温至 125 C , 保温回流 3小时， 蒸馏 8小时， 冷却过滤， 获得 TAED103.4克。  In a 1000ML four-neck reaction flask, add 100.8 g of acetic acid, 300 g of chlorobenzene, 0.36 g of activated clay, and control the temperature below 80 ° C. The dropping power is 36 g of ethylenediamine. After the temperature is increased, the mixture is refluxed for 1 hour. Three filtrates were added with 1.3 g of triethanolammonium tungstate, heated to 125 C, kept at reflux for 3 hours, distilled for 8 hours, cooled and filtered to obtain 103.4 g of TAED.

Claims

权利要求书 Claim
1. 一种四乙酰乙二胺的制备方法， 由乙二胺和乙酸合成二乙酰乙二胺， 再由二乙酰乙二胺和乙酸酐合成四乙酰乙二胺， 其特征是在合成反应中加入 与乙酸共沸的溶剂； 合成反应中加入钨硅酸三乙醇胺盐， 氯化四特丁基按， 活性白土和对甲苯横酸的一种和数种的混合物为催化剂； 乙二胺与乙酸反应 摩尔比 1 : 2.3 -3.0, 反应温度 90〜： 140°C ; 二乙酰乙二胺与乙酸酐反应摩尔比 1 : 4-9, 合成反应温度 110〜132°C。  1. A method for preparing tetraacetylethylenediamine, synthesizing diacetylethylenediamine from ethylenediamine and acetic acid, and then synthesizing tetraacetylethylenediamine from diacetylethylenediamine and acetic anhydride, which is characterized in the synthesis reaction Add azeotropic solvent with acetic acid; add triethanolamine tungstate, tetrabutyl chlorochloride, one and several mixtures of activated clay and p-toluene acid as catalysts in the synthesis reaction; ethylenediamine and acetic acid The reaction molar ratio is 1: 2.3 -3.0, the reaction temperature is 90 ~: 140 ° C; the reaction molar ratio of diacetylethylenediamine and acetic anhydride is 1: 4-9, and the synthesis reaction temperature is 110 ~ 132 ° C.
2.根据权利要求 1所述的四乙酰乙二胺的制备方法， 其特征是所述的共 沸溶剂为二异丁基醚、 曱苯、 乙苯、 二甲苯、 氯苯、 1 , 3-二曱基环乙烷、 辛 綻的一种或数种的混合溶液， 加入量为乙二胺的 80~800%。  The method for preparing tetraacetylethylenediamine according to claim 1, characterized in that the azeotropic solvent is diisobutyl ether, toluene, ethylbenzene, xylene, chlorobenzene, 1, 3- One or several mixed solutions of difluorenylcycloethane and octane, and the added amount is 80-800% of ethylenediamine.
3.根据权利要求 1所述的四乙酰乙二胺的制备方法， 其特征是所述的催 化剂加入量第一步反应为乙二胺的 1〜3%； 第二步反应为二乙酰乙二胺的 1~10%。  The method for preparing tetraacetylethylenediamine according to claim 1, characterized in that the amount of the catalyst added in the first step is 1 to 3% of ethylenediamine; the second step is diacetylethylene 1 to 10% of the amine.
4.根据权利要求 1所述的四乙酰乙二胺的制备方法， 其特征是所述的第 一步反应在低于 8CTC温度下乙二胺加入乙酸与共沸溶剂的混合液中， 滴加后 升温回流脱水。  The method for preparing tetraacetylethylenediamine according to claim 1, characterized in that, in the first reaction step, ethylenediamine is added to a mixed solution of acetic acid and an azeotropic solvent at a temperature lower than 8CTC, and the solution is added dropwise. Heat to reflux and dehydrate.
5.根据权利要求 1所述的四乙酰乙二胺的制备方法， 其特征是合成反应 滤液补加反应物后循环使用。  The method for preparing tetraacetylethylenediamine according to claim 1, characterized in that the filtrate of the synthesis reaction is supplemented with a reactant and recycled.
PCT/CN2003/000416 2002-06-27 2003-05-30 Method of preparing tetraacetylethylenediamine WO2004002942A1 (en)

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