CN101372448B - Production method of chloromethyl ethyl ether - Google Patents
Production method of chloromethyl ethyl ether Download PDFInfo
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- CN101372448B CN101372448B CN2008101558382A CN200810155838A CN101372448B CN 101372448 B CN101372448 B CN 101372448B CN 2008101558382 A CN2008101558382 A CN 2008101558382A CN 200810155838 A CN200810155838 A CN 200810155838A CN 101372448 B CN101372448 B CN 101372448B
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- ethyl ether
- chloromethyl ethyl
- methyl isocyanate
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Abstract
The invention relates to a method for producing chloromethyl ethyl ether. The chloromethyl ethyl ether with high yield and high purity is made by adding a by-product chlorine hydride generated by production of methyl isocyanate to a mixture of ethanol and paraformaldehyde while stirring for reaction at the temperature of 0-50 DEG C, wherein, the mass ratio of the paraformaldehyde to the ethanol is 1-2:1. In the process of producing the chloromethyl ethyl ether by the method, as the by-product chlorine hydride generated by production of the methyl isocyanate is used, the waste gas from the methyl isocyanate is utilized, which improves environment and lowers cost; in the method for producing the chloromethyl ethyl ether, a little amount of impurities such as the methyl isocyanate, and the like, contained in the chlorine hydride facilitate the reaction and improve the reaction yield.
Description
Technical field
Invention relates to a kind of production method of chloromethyl ether.
Background technology
Chloromethyl ethyl ether is the important source material of producing acetochlor and bromothalonil, also is the raw material commonly used of chloromethylation in the organic synthesis.Acetochlor is one of premier in the world large-tonnage weedicide, characteristics such as tool safety, efficient, broad weed-killing spectrum can be prevented and kill off a series of weeds such as lady's-grass, barnyard grass grass, Herba Setariae Viridis, amur foxtail, Herba Eragrostidis pilosae, Herba Eleusines Indicae, hard grass, ox chickweed, amaranth lamb's-quarters, Stellaria alsine Grim., purslane.Be widely used in corn, on the crops such as paddy rice; Bromothalonil is remarkable broad spectrum pesticide, 70 various pests in the orders such as lepidopteran, Homoptera, Coleoptera all there is fabulous preventive effect, especially to special efficacys such as the small cabbage moth in the vegetables resistant insect, beet armyworm, prodenia litura, Americal rice leaf miner, the wild snout moth's larva of beans, thrips, red spiders, it belongs to bionic pesticide, toxicity is low, and desinsection speed is fast.
Magazine Synthesis (11), 942-944,1982 and patent JP02282344 a kind of method for preparing chloromethyl ethyl ether is disclosed, this method is in the presence of hydrochloric acid, ethanol and formaldehyde reaction make chloromethyl ether.This method needs commodity hydrochloric acid, and production cost is increased.
1998 37 volumes of agricultural chemicals magazine the 9th phase 19 pages of preparation methods that disclose a kind of chloromethyl ether, this method is used phosphorus trichloride and industrial alcohol, and chloromethyl ether is produced in the formalin reaction.This method productive rate can be improved, but produces a large amount of phosphorus-containing wastewaters after the phosphorus trichloride hydrolysis, and aftertreatment is more loaded down with trivial details, and production cost is higher simultaneously.
Summary of the invention
The purpose of this invention is to provide a kind of production method that improves output and the purity chloromethyl ethyl ether that cost is lower again simultaneously.
Through a large amount of research, it is unexpected that the hydrogenchloride of the by-product of production methyl isocyanate of finding can replace commodity hydrochloric acid of the prior art, and find that the byproduct hydrogen chloride of producing methyl isocyanate helps the generation of target product chloromethyl ethyl ether, thereby finished the present invention.
Methyl isocyanate is by the Methylaminoformyl chloride thermal degradation, and condensation obtains the methyl isocyanate of liquid phase and the hydrogenchloride of gas phase, produces chloromethyl ethyl ether with this hydrogenchloride and can obtain higher productive rate.
Technical scheme of the present invention is as follows:
A kind of chloromethyl ethyl ether production method, it is in the mixture of ethanol and Paraformaldehyde 96, under agitation feeding the byproduct hydrogen chloride of producing methyl isocyanate reacts, temperature of reaction is 0-50 ℃, Paraformaldehyde 96: the ratio of ethanol amount of substance is 1:1-2:1, obtains high yield, highly purified chloromethyl ethyl ether.
The production method of above-mentioned chloromethyl ethyl ether, described ethanol can be anhydrous or technical grade ethanol.
The production method of above-mentioned chloromethyl ethyl ether contains the methyl isocyanate of 0.01-0.1% in the byproduct hydrogen chloride of described production methyl isocyanate.
The production method of above-mentioned chloromethyl ethyl ether, described Paraformaldehyde 96 also can substitute with formalin.
The production method of above-mentioned chloromethyl ethyl ether, described temperature of reaction is 0-30 ℃.
The present invention has beneficial effect: the method for (1) production chloromethyl ethyl ether of the present invention, in reaction process owing to used the byproduct hydrogen chloride of methyl isocyanate, make methyl isocyanate waste gas be able to utilization of waste material, improved environment, also reduced cost simultaneously.(2) method of production chloromethyl ethyl ether of the present invention, a small amount of methyl isocyanate that contains in the hydrogenchloride have improved the yield of reaction to having reacted promoted effect.(3) method of production chloromethyl ethyl ether of the present invention, in reaction process, hydrogenchloride is reactant and play the effect of catalyzer still not, help the depolymerization of Paraformaldehyde 96, participate in reaction simultaneously, the water and the reaction product layering that generate have reduced the production concentration in the organic phase, and reaction is constantly carried out to the direction that generates product, make to react completely.
Embodiment
Reaction equation is as follows:
Embodiment 1
In 1000 milliliters reaction flask, drop into the 320g Paraformaldehyde 96, the 460g dehydrated alcohol, start stirring, controlled temperature feeds the by-product hydrogen chloride of producing methyl isocyanate between 0-20 ℃, standing demix when ethanol content is lower than 0.5%, the heavy 928g of bottom chloromethyl ethyl ether, content 99.1%, yield are 97.3%, with alcohol meter, can directly carry out the synthetic of compound such as acetochlor; Formaldehyde in the upper water solution is recyclable to be applied mechanically.
Reference examples 1.
In 1000 milliliters reaction flask, drop into 320g Paraformaldehyde 96 and 460g dehydrated alcohol, start stirring, controlled temperature is between 0-20 ℃, be added dropwise to commodity hydrochloric acid (37%), standing demix when ethanol content is lower than 0.5%, the heavy 930g of bottom chloromethyl ethyl ether, content 89.2%, yield is 87.8%, with alcohol meter, can directly carry out the synthetic of compound such as acetochlor; Formaldehyde in the upper water solution is recyclable to be applied mechanically.
Embodiment 2.
In 1000 milliliters reaction flask, drop into the Paraformaldehyde 96 of 320g, 95% ethanol (technical grade) of 485g, start stirring, controlled temperature feeds the by-product hydrogen chloride of producing methyl isocyanate between 0-20 ℃, standing demix when ethanol content is lower than 0.5%, the heavy 885g of bottom chloromethyl ethyl ether, content 99.1%, yield are 92.8%, with alcohol meter, can directly carry out the synthetic of compound such as acetochlor; Formaldehyde in the upper water solution is recyclable to be applied mechanically.
Embodiment 3.
37% of input 865g formalin and 95% ethanol of 485g in 1000 milliliters reaction flask, start stirring, controlled temperature feeds standing demix when ethanol content is lower than 0.5% with the by-product hydrogen chloride of producing methyl isocyanate between 0-20 ℃, the heavy 875g of bottom chloromethyl ether, content 98.3%, yield is 91.0%, with alcohol meter, can directly carry out the synthetic of compound such as acetochlor, the formaldehyde in the upper water solution is recyclable to be applied mechanically.
Claims (4)
1. chloromethyl ethyl ether production method, it is characterized in that: it is in the mixture of ethanol and Paraformaldehyde 96, under agitation feeding the byproduct hydrogen chloride of producing methyl isocyanate reacts, temperature of reaction is 0-50 ℃, Paraformaldehyde 96: the ratio of ethanol amount of substance is 1: 1-2: 1, obtain high yield, highly purified chloromethyl ethyl ether.
2. the production method of chloromethyl ethyl ether according to claim 1, it is characterized in that: described ethanol is dehydrated alcohol or industrial alcohol.
3. the production method of chloromethyl ethyl ether according to claim 1 is characterized in that: the methyl isocyanate that contains 0.01-0.1% in the byproduct hydrogen chloride of described production methyl isocyanate.
4. the production method of chloromethyl ethyl ether according to claim 1, it is characterized in that: described temperature of reaction is 0-30 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008101558382A CN101372448B (en) | 2008-10-10 | 2008-10-10 | Production method of chloromethyl ethyl ether |
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| CN2008101558382A CN101372448B (en) | 2008-10-10 | 2008-10-10 | Production method of chloromethyl ethyl ether |
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| CN101372448A CN101372448A (en) | 2009-02-25 |
| CN101372448B true CN101372448B (en) | 2011-10-19 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102417440B (en) * | 2011-11-01 | 2014-05-21 | 山东胜邦绿野化学有限公司 | Novel technology for synthesizing acetochlor intermediate chloroethyl methyl ether |
| CN103848768B (en) * | 2012-12-05 | 2015-10-28 | 湖南国发精细化工科技有限公司 | The application method of a kind of Methylaminoformyl chloride decomposed tail gas hydrogenchloride in cartap synthesis |
| CN105859528B (en) * | 2016-05-30 | 2018-04-24 | 芜湖融汇化工有限公司 | The device and its operating method that the byproduct hydrogen chloride of TCE productions is used to produce chloromethyl methyl ether |
| CN112619395A (en) * | 2020-12-22 | 2021-04-09 | 李通 | Tail gas absorption process for producing chloromethyl ethyl ether by high-purity hydrogen chloride method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1752065A (en) * | 2004-09-24 | 2006-03-29 | 陈世强 | Green chemical technology for producing chloracetyl chloride |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1752065A (en) * | 2004-09-24 | 2006-03-29 | 陈世强 | Green chemical technology for producing chloracetyl chloride |
Non-Patent Citations (1)
| Title |
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| Boris G..Preparation of…….《synthesis》.1982,(第11期),第942页. * |
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Application publication date: 20090225 Assignee: JIANGSU CHANGLONG CHEMICALS CO., LTD. Assignor: Changlong Chemical Co., Ltd., Jiangsu Prov. Contract record no.: 2014320000481 Denomination of invention: Production method of chloromethyl ethyl ether Granted publication date: 20111019 License type: Exclusive License Record date: 20140610 |
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Effective date of registration: 20161125 Address after: 225442 Taixing Economic Development Zone, Jiangsu province unity River Road, No. 8, No. Patentee after: JIANGSU CHANGLONG CHEMICALS CO., LTD. Address before: Xinbei Longhu Tong Road 213031 Jiangsu city of Changzhou province No. 12 Patentee before: Changlong Chemical Co., Ltd., Jiangsu Prov. |