CN101397263A - Preparation method of diacetyl ethylenediamine - Google Patents
Preparation method of diacetyl ethylenediamine Download PDFInfo
- Publication number
- CN101397263A CN101397263A CN 200810121998 CN200810121998A CN101397263A CN 101397263 A CN101397263 A CN 101397263A CN 200810121998 CN200810121998 CN 200810121998 CN 200810121998 A CN200810121998 A CN 200810121998A CN 101397263 A CN101397263 A CN 101397263A
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- CN
- China
- Prior art keywords
- preparation
- add
- diacetyl ethylenediamine
- ethylenediamine
- quadrol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- WNYIBZHOMJZDKN-UHFFFAOYSA-N n-(2-acetamidoethyl)acetamide Chemical compound CC(=O)NCCNC(C)=O WNYIBZHOMJZDKN-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000706 filtrate Substances 0.000 claims abstract description 14
- 239000000047 product Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 5
- 229940043232 butyl acetate Drugs 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 claims description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 4
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical group C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 239000011964 heteropoly acid Substances 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 2
- 239000012452 mother liquor Substances 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000004064 recycling Methods 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 abstract description 4
- 230000002829 reductive effect Effects 0.000 abstract description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 239000012024 dehydrating agents Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000002386 leaching Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 238000010992 reflux Methods 0.000 abstract 1
- 238000002834 transmittance Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000013019 agitation Methods 0.000 description 3
- 239000010413 mother solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- FRPJTGXMTIIFIT-UHFFFAOYSA-N tetraacetylethylenediamine Chemical compound CC(=O)C(N)(C(C)=O)C(N)(C(C)=O)C(C)=O FRPJTGXMTIIFIT-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of diacetyl ethylenediamine, which comprises the following steps: a. adding a catalyst and a dehydrating agent into acetic acid, and uniformly mixing; b. controlling the temperature to be 25-80 ℃, and dropwise adding ethylenediamine into the acetic acid solution obtained in the step a, wherein the molar ratio of ethylenediamine to acetic acid is 1: 2-2.5; c. stirring the mixed solution, heating to reflux, keeping the temperature for 1 hour, and dehydrating; d. cooling the dehydrated reaction material to 25 ℃, leaching after solid is separated out, and recycling filtrate; and drying the obtained solid to obtain the diacetyl ethylenediamine product. The invention has simple process route, low production cost and good product quality. The mother liquor is decolorized by a reducing agent, so that the transmittance is obviously improved, the application times can be prolonged, and the production cost is reduced.
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, and it can make SPC-D, Sodium peroxoborate react at normal temperatures, is a kind of activator that can adapt to cold bleaching, and diacetyl ethylenediamine (DAED) important intermediate of this activator just.
At present, the main dewatering agent that uses toluene as diacetyl ethylenediamine in the production technique of diacetyl ethylenediamine, 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 influenced the product appearance quality, need 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 acetate recycling use, but yield is not high.
The production method of German patent DE 2941023 disclosed diacetyl ethylenediamines is a raw material with quadrol and acetate, directly will react the water that generates and remove under nitrogen protection, and temperature of reaction reaches 160-180 ℃.
The preparation method of the disclosed diacetyl ethylenediamine of patent WO8805041 adds entrainer in reaction, form azeotropic with water and anhydrate the direct recycled of mother liquor that reaction obtains to remove.
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 acetate, add catalyzer, dewatering agent, mixing;
B. controlled temperature is added drop-wise to quadrol in the acetic acid solution of step a gained between 25～80 ℃, and the mol ratio of quadrol and acetate 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 a quadrol weight.Add catalyzer, can make reactant obtain activation, shortened the reaction times, help improving 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 a 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, add in zinc powder, iron powder, aluminium powder, magnesium powder, the tin protochloride one or more and decolour, its add-on is 1～3% of a 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, and can prolong and apply mechanically 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 acetate, 0.5g phosphoric acid, 100g butylacetate, mixing.
Controlled temperature is 25～80 ℃, slowly drips the 45g quadrol to above-mentioned acetic acid solution with constant pressure funnel, stirs then and is warming up to backflow, is incubated and dewaters after 1 hour, until no water generates.
Under agitation condition, the reaction mass after the dehydration is cooled to 25 ℃, to treat to carry out suction filtration after solid is separated out, 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%, reacts 30 minutes down in 100 ℃, filters gained filtrate and can be used as new mother liquor continuation recycled again.
Embodiment 2:
In the 500ml four-hole bottle, add 108g acetate, 0.9g tosic acid, 100g butylacetate, mixing.
Controlled temperature is 25～80 ℃, slowly drips the 45g quadrol to above-mentioned acetic acid solution with constant pressure funnel, stirs then and is warming up to backflow, is incubated and dewaters after 1 hour, until no water generates.
Under agitation condition, the reaction mass after the dehydration is cooled to 25 ℃, to treat to carry out suction filtration after solid is separated out, 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%, reacts 60 minutes down in 80 ℃, filters gained filtrate and can be used as new mother liquor continuation recycled again.
Embodiment 3:
Add in the 500ml four-hole bottle 100g acetate, 0.9g tosic acid, 150g mixed solvent (toluene: butylacetate=50:50, wt%), mixing.
Controlled temperature is 25～80 ℃, slowly drips the 45g quadrol to above-mentioned acetic acid solution with constant pressure funnel, stirs then and is warming up to backflow, is incubated and dewaters after 1 hour, until no water generates.
Under agitation condition, the reaction mass after the dehydration is cooled to 25 ℃, to treat to carry out suction filtration after solid is separated out, 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%, reacts 40 minutes down in 100 ℃, filters gained filtrate and can be used as new mother liquor continuation recycled again.
Those of ordinary skill in the art will be appreciated that; above embodiment is used for illustrating 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 (4)
1, a kind of preparation method of diacetyl ethylenediamine is characterized in that may further comprise the steps:
A. in acetate, add catalyzer, dewatering agent, mixing;
B. controlled temperature is added drop-wise to quadrol in the acetic acid solution of step a gained between 25～80 ℃, and the mol ratio of quadrol and acetate 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.
2, the preparation method of diacetyl ethylenediamine according to claim 1, it is characterized in that: described catalyzer is one or more in the vitriol oil, phosphoric acid, tosic acid, the heteropolyacid, its add-on is 1～3% of a quadrol weight.
3, the preparation method of diacetyl ethylenediamine according to claim 1, it is characterized in that: described dewatering agent is hexanaphthene, toluene, dimethylbenzene, butylacetate, in pentyl acetate, diethyl carbonate, methyl iso-butyl ketone (MIBK), the methyl-n-butyl ketone one or more, its add-on are 80～500% of quadrol weight.
4, the preparation method of diacetyl ethylenediamine according to claim 1, it is characterized in that: in the steps d, reaction mass suction filtration gained filtrate recycle repeatedly after, add in zinc powder, iron powder, aluminium powder, magnesium powder, the tin protochloride one or more and decolour, its add-on is 1～3% of a 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810121998 CN101397263B (en) | 2008-11-06 | 2008-11-06 | Method for preparing diacetyl ethylenediamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101397263A true CN101397263A (en) | 2009-04-01 |
| CN101397263B CN101397263B (en) | 2013-03-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200810121998 Active CN101397263B (en) | 2008-11-06 | 2008-11-06 | Method for preparing diacetyl ethylenediamine |
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| Country | Link |
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| CN (1) | CN101397263B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102285897A (en) * | 2011-06-28 | 2011-12-21 | 浙江金科日化原料有限公司 | Application of combined use of polyphosphoric acid and metal zinc to decolorization of tetraacetyl ethylene diamine mother liquor |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1255376C (en) * | 2002-06-27 | 2006-05-10 | 浙江金科化工股份有限公司 | Preparation method of tetraacetylethylenediamine |
-
2008
- 2008-11-06 CN CN 200810121998 patent/CN101397263B/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102285897A (en) * | 2011-06-28 | 2011-12-21 | 浙江金科日化原料有限公司 | Application of combined use of polyphosphoric acid and metal zinc to decolorization of tetraacetyl ethylene diamine mother liquor |
| 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 |
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| Publication number | Publication date |
|---|---|
| CN101397263B (en) | 2013-03-13 |
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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. |
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