CN101397263B - Method for preparing diacetyl ethylenediamine - Google Patents
Method for preparing diacetyl ethylenediamine Download PDFInfo
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- CN101397263B CN101397263B CN 200810121998 CN200810121998A CN101397263B CN 101397263 B CN101397263 B CN 101397263B CN 200810121998 CN200810121998 CN 200810121998 CN 200810121998 A CN200810121998 A CN 200810121998A CN 101397263 B CN101397263 B CN 101397263B
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- acetic acid
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- quadrol
- filtrate
- ethylene diamine
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Abstract
The invention discloses a method for preparing diacetyl ethylene diamine. The method includes the following steps: a. a catalyst and a dehydrating agent are added into an acetic acid and mixed evenly with the acetic acid; b. the temperature is controlled to be between 25 and 80 DEG C and the ethylene diamine is dropped in the acetic acid solvent obtained in the step a, wherein the molar ratio between the ethylene diamine and the acetic acid is 1:2 to 2.5; c. the mixed liquid is stirred and heated for reflux and the temperature is preserved for one hour and then dehydrated; and d. a dehydratedreagent is cooled to 25 DEG C and is extracted and filtered after solids are precipitated; a filtrate is recycled; an obtained solid is dried to obtain the diacetyl ethylene diamine. The process of the method is simple; the manufacturing cost is low and the product quality is good; and the permeation rate of the mother liquid decolorized by reducing agents is enhanced dramatically, thus being capable of increasing the application times and reducing the manufacturing cost.
Description
Technical field
The invention belongs to the preparing technical field of aminated compounds in the organic chemistry, particularly a kind of preparation method of diacetyl ethylenediamine.
Background technology
Tetraacetyl ethylene diamine (TAED) is a kind of bleach-activating agent, it can make SPC-D, Sodium peroxoborate react at normal temperatures, a kind of activator that can adapt to cold bleaching, and diacetyl ethylenediamine (DAED) important intermediate of this activator just.
At present, the main toluene that uses is as the dewatering agent of diacetyl ethylenediamine in the production technique of diacetyl ethylenediamine, and dewatering time is grown (generally needing more than 10 hours).Particularly along with mother liquor reuse number of times increases, the transmitance of mother liquor reduces gradually, and the color of the diacetyl ethylenediamine product that obtains also deepens thereupon, has affected the product appearance quality, need to carry out aftertreatment to product and just can reach requirement, and production cost is higher.
German patent DE 2828765 discloses a kind of production method of diacetyl ethylenediamine, is to be raw material with quadrol and acetic acid aqueous solution, at high temperature boils off the water that reaction generates, and with excessive acetic acid recycling use, but yield is not high.
The production method of German patent DE 2941023 disclosed diacetyl ethylenediamines take quadrol and acetic acid as raw material, directly will be reacted the water that generates and remove under nitrogen protection, temperature of reaction reaches 160-180 ℃.
The preparation method of the disclosed diacetyl ethylenediamine of patent WO8805041 adds entrainer in reaction, form azeotropic with except anhydrating with water, reacts the mother liquor direct circulation that obtains and applies mechanically.
Aforesaid method complex process, production cost height, and the diacetyl ethylenediamine product appearance is of poor quality.
Summary of the invention
The object of the present invention is to provide that a kind of operational path is simple, production cost is low, the preparation method of the diacetyl ethylenediamine of good product quality.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of diacetyl ethylenediamine, it may further comprise the steps:
A. in acetic acid, add catalyzer, dewatering agent, mixing;
B. control temperature between 25～80 ℃, quadrol is added drop-wise in the acetic acid solution of step a gained, the mol ratio of quadrol and acetic acid is 1:2～2.5;
C. above-mentioned mixed solution is stirred and be warming up to backflow, be incubated dehydration after 1 hour;
D. the reaction mass after will dewatering is cooled to 25 ℃, carries out suction filtration, filtrate recycle after solid is separated out; With the oven dry of gained solid, get the diacetyl ethylenediamine product.
Further, described catalyzer is one or more in the vitriol oil, phosphoric acid, tosic acid, the heteropolyacid, and its add-on is 1～3% of quadrol weight.Add catalyzer, can make reactant obtain activation, shortened the reaction times, be conducive to improve the yield of speed of reaction and product.
Described dewatering agent is hexanaphthene, toluene, dimethylbenzene, butylacetate, one or more in pentyl acetate, diethyl carbonate, methyl iso-butyl ketone (MIBK), the methyl-n-butyl ketone, and its add-on is 80～500% of quadrol weight, dehydrating effect is good, and is consuming time few.
Further, in the steps d reaction mass suction filtration gained filtrate recycle repeatedly after, one or more that add in zinc powder, iron powder, aluminium powder, magnesium powder, the tin protochloride are decoloured, its add-on is 1～3% of filtrate weight.Significantly improve through the filtrate transmitance after the decolouring of above-mentioned reductive agent, can be used as mother liquor and continue recycled, but and the extending sleeve number of times, the diacetyl ethylenediamine product colour of gained is shallow, exterior quality good, can reduce production costs.
Embodiment
Embodiment 1:
In the 500ml four-hole bottle, add 108g acetic acid, 0.5g phosphoric acid, 100g butylacetate, mixing.
The control temperature is 25～80 ℃, slowly drips the 45g quadrol to above-mentioned acetic acid solution with constant pressure funnel, then stirs and is warming up to backflow, is incubated and dewaters after 1 hour, until without water generates.
Under agitation condition, the reaction mass after the dehydration is cooled to 25 ℃, after separating out, solid carries out suction filtration, and filtrate is as the mother liquor reuse; With the oven dry of gained solid, get diacetyl ethylenediamine product 106.5g.
After the Recycling Mother Solution reuse 10 times, color is obviously deepened, and adds the zinc powder that is equivalent to mother liquor weight 1.5%, in 100 ℃ of lower reactions 30 minutes, filters gained filtrate and can be used as again new mother liquor continuation recycled.
Embodiment 2:
In the 500ml four-hole bottle, add 108g acetic acid, 0.9g tosic acid, 100g butylacetate, mixing.
The control temperature is 25～80 ℃, slowly drips the 45g quadrol to above-mentioned acetic acid solution with constant pressure funnel, then stirs and is warming up to backflow, is incubated and dewaters after 1 hour, until without water generates.
Under agitation condition, the reaction mass after the dehydration is cooled to 25 ℃, after separating out, solid carries out suction filtration, and filtrate is as the mother liquor reuse; With the oven dry of gained solid, get diacetyl ethylenediamine product 107.2g, purity 99.1%.
After the Recycling Mother Solution reuse 10 times, color is obviously deepened, and adds the aluminium powder that is equivalent to mother liquor weight 1%, in 80 ℃ of lower reactions 60 minutes, filters gained filtrate and can be used as again new mother liquor continuation recycled.
Embodiment 3:
Add in the 500ml four-hole bottle 100g acetic acid, 0.9g tosic acid, 150g mixed solvent (toluene: butylacetate=50:50, wt%), mixing.
The control temperature is 25～80 ℃, slowly drips the 45g quadrol to above-mentioned acetic acid solution with constant pressure funnel, then stirs and is warming up to backflow, is incubated and dewaters after 1 hour, until without water generates.
Under agitation condition, the reaction mass after the dehydration is cooled to 25 ℃, after separating out, solid carries out suction filtration, and filtrate is as the mother liquor reuse; With the oven dry of gained solid, get diacetyl ethylenediamine product 105.5g.
After the Recycling Mother Solution reuse 10 times, color is obviously deepened, and adds the zinc powder that is equivalent to mother liquor weight 2.0%, in 100 ℃ of lower reactions 40 minutes, filters gained filtrate and can be used as again new mother liquor continuation recycled.
Those of ordinary skill in the art will be appreciated that; above embodiment illustrates the present invention; and be not as limitation of the invention; as long as in essential scope of the present invention, all will fall within the protection domain of claims of the present invention variation, the modification of above embodiment.
Claims (1)
1. the preparation method of a diacetyl ethylenediamine is characterized in that may further comprise the steps:
A. in acetic acid, add catalyzer, dewatering agent, mixing; Described catalyzer is phosphoric acid, and its add-on is 1～3% of quadrol weight; Described dewatering agent is butylacetate, and its add-on is 80～500% of quadrol weight;
B. control temperature between 25～80 ℃, quadrol is added drop-wise in the acetic acid solution of step a gained, the mol ratio of quadrol and acetic acid is 1: 2～2.5;
C. above-mentioned mixed solution is stirred and be warming up to backflow, be incubated dehydration after 1 hour;
D. the reaction mass after will dewatering is cooled to 25 ℃, carries out suction filtration, filtrate recycle after solid is separated out; With the oven dry of gained solid, get the diacetyl ethylenediamine product; Reaction mass suction filtration gained filtrate recycle repeatedly after, one or more that add in zinc powder, iron powder, aluminium powder, magnesium powder, the tin protochloride are decoloured, its add-on is 1～3% of filtrate weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810121998 CN101397263B (en) | 2008-11-06 | 2008-11-06 | Method for preparing diacetyl ethylenediamine |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810121998 CN101397263B (en) | 2008-11-06 | 2008-11-06 | Method for preparing diacetyl ethylenediamine |
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| CN101397263A CN101397263A (en) | 2009-04-01 |
| CN101397263B true CN101397263B (en) | 2013-03-13 |
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| CN 200810121998 Active CN101397263B (en) | 2008-11-06 | 2008-11-06 | Method for preparing diacetyl ethylenediamine |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102285897B (en) * | 2011-06-28 | 2013-09-18 | 浙江金科日化原料有限公司 | Application of combined use of polyphosphoric acid and metal zinc in decolorization of tetraacetyl ethylene diamine mother liquor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1463963A (en) * | 2002-06-27 | 2003-12-31 | 浙江金科化工有限公司 | Preparation method of tetraacetylethylenediamine |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1463963A (en) * | 2002-06-27 | 2003-12-31 | 浙江金科化工有限公司 | Preparation method of tetraacetylethylenediamine |
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Address after: 312369 Hangzhou Shangyu economic and Technological Development Zone, Shaoxing, Zhejiang Patentee after: Zhejiang Jinke Daily Chemical New Materials Co.,Ltd. Address before: 312369 Shangyu Industrial Park, Hangzhou Bay, Zhejiang Province Patentee before: ZHEJIANG JINKE HOUSEHOLD CHEMICAL MATERIALS Co.,Ltd. |