CN113979965A - Continuous production method of 4, 5-dichloro-2-octyl-4-isothiazoline-3-ketone - Google Patents
Continuous production method of 4, 5-dichloro-2-octyl-4-isothiazoline-3-ketone Download PDFInfo
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- A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
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Abstract
The invention relates to a continuous production method of 4, 5-dichloro-2-octyl-4-isothiazoline-3-ketone. The method can obtain high-purity 4, 5-dichloro-2-octyl-4-isothiazoline-3-ketone, has high production yield, adopts continuous production, is safe and controllable in production process, reduces energy consumption and improves production efficiency. In order to achieve the purpose, the method adopts the technical scheme that the method comprises the following steps: preparing N, N '-dioctyl-3, 3' -dithiodipropionamide and ethyl acetate to form a mixed solution; pumping into a first section of sleeve type tubular reactor with a jacket and a second section of sleeve type tubular reactor with a jacket, introducing ethylene glycol chilled water into the jacket of the first section of tubular reactor, introducing hot water into the jacket of the second section of tubular reactor, controlling the reaction temperature to be 55-60 ℃, and mixing and staying materials in the pipe for 5-10 minutes; and after the continuous reaction is finished, directly feeding the reaction liquid into a film evaporator, adding methanol for recrystallization, and performing cooling centrifugation, leaching and drying treatment to obtain the powdery DCOIT product.
Description
The technical field is as follows:
the invention relates to the technical field of continuous production of bactericides, in particular to a continuous production method of 4, 5-dichloro-2-octyl-4-isothiazoline-3-ketone.
Background art:
4, 5-dichloro-2-octyl-4-isothiazoline-3-ketone (DCOIT for short) is a novel isothiazolinone bactericide, is mainly used in the fields of marine antifouling paint, coating, metal cutting fluid, wood and the like as a mildew-proof algaecide, and has a very wide application range.
Chinese patent CN104072440B discloses a method for preparing DCOIT, which comprises the steps of mixing N, N '-dioctyl-3, 3' -dithiodipropionamide as a raw material with a chlorinated solvent, adding a composite catalyst consisting of metal chloride, thiophene compounds and crown ether compounds, slowly adding a chlorinating agent under the condition of low temperature to perform closed-loop chlorination, and separating and purifying to obtain DCOIT, wherein the purity of the DCOIT is over 98% through detection, and the product yield can reach 65-75%. The adopted preparation method is an intermittent preparation method, the post-treatment steps are multiple, the operation is very complex, a large amount of salt-containing wastewater is generated in the process, and the product quality and the reaction yield are not ideal enough.
Chinese patent CN 110483438A discloses a pipeline type continuous production method of 3-isothiazolinone compounds, N '-dioctyl-3, 3' -dithiodipropionamide, sodium iodide, chlorobenzene and chlorine are subjected to mixed reaction through a pipeline reactor system, and after the reaction is finished, a DCOIT product is obtained through post-treatment; mixing and preheating reaction raw materials according to a proportion, uniformly mixing a solid-liquid mixture through a static mixer to form slurry, and then sending the slurry into a pipeline reactor for reaction, introducing chlorine gas into the pipeline reactor at multiple points, and controlling the temperature through a temperature control system, wherein the reaction temperature is 55-60 ℃, and the retention time is 20 minutes; the DCOIT content is described to be more than 98 percent, and the synthesis yield is 82 percent. The continuous production method has the following defects: materials need to enter the tubular reactor only through a preheating system and a mixing system, and the operation is complex; sodium iodide does not play any catalytic role in the reaction system; the mixed slurry is simply introduced into the pipeline reactor at multiple points, and side reactions cannot be inhibited at all.
The invention content is as follows:
in view of the above, the invention provides a continuous production method of 4, 5-dichloro-2-octyl-4-isothiazoline-3-ketone, which can obtain high-purity 4, 5-dichloro-2-octyl-4-isothiazoline-3-ketone, has high production yield, adopts continuous production, has safe and controllable production process, reduces energy consumption and improves production efficiency.
In order to achieve the purpose, the invention adopts the technical scheme that: 1. a continuous production method of 4, 5-dichloro-2-octyl-4-isothiazoline-3-ketone is characterized by comprising the following steps: the method comprises the following steps:
1) n, N '-dioctyl-3, 3' -dithiodipropionamide and ethyl acetate in a weight ratio of 1: 1.5-2.0 to form a mixed solution;
2) pumping the mixed solution into a first section of sleeve type tubular reactor with a jacket by a pump, contacting N, N '-dioctyl-3, 3' -dithiodipropionyl in the mixed solution with chlorine at the inlet of the tubular reactor in proportion, introducing glycol chilled water into the jacket of the first section of tubular reactor, controlling the reaction temperature at 0-5 ℃, and mixing and retaining the materials in the tube for 10-15 minutes;
3) the reaction material enters a second section of sleeve type tubular reactor with a jacket, N '-dioctyl-3, 3' -dithio-dipropionyl in the reaction liquid contacts with chlorine gas at the inlet of the tubular reactor according to the proportion, hot water is introduced into the jacket of the second section of tubular reactor, the reaction temperature is controlled to be 55-60 ℃, and the material is mixed and stays in the tube for 5-10 minutes;
4) and after the continuous reaction is finished, the reaction liquid directly enters a film evaporator, hydrogen chloride and ethyl acetate are taken as light components to be evaporated, heavy components continuously enter a receiving kettle, then methanol is added for recrystallization, and the powdery DCOIT product is obtained through the working procedures of cooling centrifugation, leaching and drying.
Further, the mol ratio of the chlorine used in the step 2) to the N, N '-dioctyl-3, 3' -dithiodipropionamide in the step 1) is 4.3-4.5: 1.
further, the mol ratio of the chlorine used in the step 3) to the N, N '-dioctyl-3, 3' -dithiodipropionamide in the step 1) is 2.7-3.3: 1.
compared with the prior art, the invention has the following advantages and effects:
1) according to the invention, through the research on the main and side reaction mechanisms, the inventor creatively discovers that the 5-chloro OIT intermediate is generated by controlling the reaction ratio and the reaction temperature of N, N '-dioctyl-3, 3' -dithiodipropionamide and chlorine, and then the DCOIT is generated by continuous chlorination, so that the generation of polychlorinated byproducts is effectively inhibited, and thus, the high-purity and high-yield DCOIT product is obtained, the purity reaches more than 99%, and the whole production yield is more than 85%.
2) The invention also effectively realizes the continuous production of DCOIT, has simple operation and easy control of the production process, not only reduces the energy consumption, but also improves the production efficiency and simultaneously realizes the safety and the controllability of the production process.
3) According to the invention, when chlorine gas is introduced for the first time, the molar ratio of the chlorine gas to the N, N '-dioctyl-3, 3' -dithiodipropionamide in the step 1) is limited, so that the N, N '-dioctyl-3, 3' -dithiodipropionamide (POA) is converted into an intermediate product 5-chloro OIT as far as possible after chlorination.
4) According to the invention, when chlorine is introduced for the second time, the molar ratio of the chlorine to the N, N '-dioctyl-3, 3' -dithiodipropionamide in the step 1) is limited, and excessive chlorination to polychlorinated byproducts is avoided while the chlorination reaction is completed.
The specific implementation mode is as follows:
in order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example (b):
a continuous production method of 4, 5-dichloro-2-octyl-4-isothiazolin-3-ketone comprises the following steps:
1. n, N '-dioctyl-3, 3' -dithiodipropionamide and ethyl acetate in a weight ratio of 1: 1.5-2.0 to form a mixed solution of the two components.
2. Pumping the mixed solution into a first-stage sleeve pipe type reactor with a jacket by using a pump, wherein the mol ratio of N, N '-dioctyl-3, 3' -dithio-dipropionyl to chlorine in the mixed solution is 4.3-4.5: 1 is contacted at the inlet of the tubular reactor, glycol chilled water is introduced into the jacket of the first section of the tubular reactor, the reaction temperature is controlled to be 0-5 ℃, and the materials are mixed and stay in the tube for 10-15 minutes.
3. The reaction materials enter a second section of sleeve type tubular reactor with a jacket, and N, N '-dioctyl-3, 3' -dithio-dipropyl and chlorine in the reaction liquid have the mol ratio of 2.7-3.3: 1 is contacted at the inlet of the tubular reactor, hot water is introduced into the jacket of the second section of the tubular reactor, the reaction temperature is controlled to be 55-60 ℃, and the materials are mixed and stay in the tube for 5-10 minutes.
4. After the continuous reaction is finished, the reaction liquid directly enters a film evaporator, hydrogen chloride and ethyl acetate are taken as light components to be evaporated, heavy components continuously enter a receiving kettle, methanol is added for recrystallization after a certain amount of the heavy components is reached, and the powdery DCOIT product is obtained through the working procedures of cooling centrifugation, leaching and drying.
The DCOT continuous production uses a special tubular reactor, the tubular reactor is divided into two sections, each section is provided with a jacket with different media, the first section is a low-temperature chlorination section, ethylene glycol chilled water with the temperature controlled at about-10 ℃ is introduced into the reactor jacket, the second section is a high-temperature chlorination section, and hot water with the temperature of 50 ℃ is introduced into the reactor jacket; the porous baffle is arranged in the tubular reactor, so that the mass transfer and heat transfer processes can be effectively enhanced.
Chlorine gas is introduced in two parts, wherein the first part is introduced at multiple points at the inlet of the first section of tubular reactor, and the second part is introduced at multiple points at the inlet of the second section of tubular reactor.
N, N '-dioctyl-3, 3' -dithiodipropionamide, ethyl acetate as 100: 200 weight ratio drops into in the pulping jar in advance, and in the certain velocity of flow of pump control sent into first section tubular reactor after the homogeneous mixing, let in chlorine at tubular reactor entrance, the speed of letting in of control chlorine, chlorine: n, N '-dioctyl-3, 3' -dithiodipropionamide (molar ratio) 4.3 to 4.5: 1, controlling the temperature of chlorination at 0-5 ℃ in the first stage, and mixing and staying the materials in the tube for 10-15 minutes.
The first-stage chlorination reaction liquid enters a second-stage tubular reactor, chlorine gas is introduced at the inlet of the tubular reactor, the introduction speed of the chlorine gas is controlled, and the chlorine gas: n, N '-dioctyl-3, 3' -dithiodipropionamide (molar ratio) 2.7 to 3.2: 1, introducing hot water with the temperature of 50 ℃ into a jacket of a second-stage tubular reactor, controlling the temperature of 55-60 ℃ by utilizing reaction heat release in the second-stage chlorination, and mixing and staying the materials in the tube for 5-10 minutes.
And the chlorination reaction liquid in the second stage directly enters a film evaporator to be decompressed and evaporated to remove ethyl acetate and hydrogen chloride, the heavy components are slightly cooled to 50-55 ℃, then methanol is added for recrystallization, and the DCOIT powdery solid with the content of 99% is obtained through the working procedures of cooling centrifugation, washing, drying and the like, and the continuous production yield is 87%.
The ethyl acetate evaporated by the method is directly recycled to the next batch of continuous production, and the methanol mother liquor obtained by centrifugation is combined with the leacheate and then is simply distilled to recycle methanol for recycling to the next batch of recrystallization operation.
The hydrogen chloride separated in the process of the invention is removed to the hydrogen chloride absorption system.
The reaction process of reacting N, N '-dioctyl-3, 3' -dithiodipropionamide with chlorine to generate DCOIT is as follows:
the N, N '-dioctyl-3, 3' -dithiodipropionamide reacts with chlorine to generate a mixture of 2-octyl-4-isothiazoline-3-ketone (OIT for short), 4-chlorine OIT and 5-chlorine OIT, and then the mixture is continuously chlorinated to obtain the target product DCOIT.
The main side reaction in the chlorination process is a series of side reactions to generate polychlorinated byproducts, and the reaction process is as follows:
the key to improving the quality and synthesis yield of DCOIT is how to suppress the production of polychlorinated by-products.
Through a large number of experiments, the generation of polychlorinated byproducts is closely related to the generation of 4-chloro OIT in a reaction system, and the reaction process is as follows:
experiments show that the selectivity of the 4-chloro OIT during the continuous chlorination to generate DCOIT is very poor, a large amount of polychlorinated byproducts are generated during the reaction, and the 4-OIT can be directly chlorinated to generate the polychlorinated byproducts without generating DCOIT.
According to the invention, if N, N '-dioctyl-3, 3' -dithiodipropionamide reacts with chlorine to generate 5-chloro OIT firstly, and then the chlorination is continued to generate DCOIT, the reaction selectivity is far higher than that of the former generation of OIT and 4-chloro OIT, only DCOIT is generated after the chlorination of 5-chloro OIT, the polychlorinated by-product is mainly generated by the continuous chlorination of DCOIT, and the reaction process is as follows:
research on the chlorination process shows that the chlorination synthesis of DCOIT needs to be controlled in a segmented mode, and the generation amount of 5-chloro-OIT needs to be increased as much as possible in the early chlorination stage, which is the key point for improving the reaction selectivity and yield.
A great deal of experimental research is carried out aiming at improving the generation amount of the 5-chloro OIT, and the molar ratio of the N, N '-dioctyl-3, 3' -dithiodipropionamide to the chlorine gas at the early stage of chlorination is strictly controlled to be more than 4.0, and the optimal range is between 4.3 and 4.5, and the generation amount of the 5-chloro OIT in the reaction system is the highest. The inventors have also studied the reaction temperature for forming 5-chloro OIT, and found that the reaction temperature is not more than 10 ℃ and the optimum range is 0 to 5 ℃ when chlorine is introduced.
It has been mentioned above that the DCOIT product continues to undergo consecutive side reactions during the chlorination process to produce polychlorinated by-products, and the DCOIT product should be removed from the reaction system in time, in addition to the reaction temperature not being too high and the chlorine gas ratio not being excessive, in order to suppress the consecutive side reactions.
The continuous synthesis can well solve the problems, and the method uses a tubular reactor for continuous operation, continuously feeds raw materials and continuously discharges products, so that the occurrence of serial side reactions taking DCOIT as the raw material can be effectively avoided.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention.
Claims (3)
1. A continuous production method of 4, 5-dichloro-2-octyl-4-isothiazoline-3-ketone is characterized by comprising the following steps: the method comprises the following steps:
1) n, N '-dioctyl-3, 3' -dithiodipropionamide and ethyl acetate in a weight ratio of 1: 1.5-2.0 to form a mixed solution;
2) pumping the mixed solution into a first-stage sleeve-type tubular reactor with a jacket by using a pump, wherein N, N '-dioctyl-3, 3' -dithiodipropionyl in the mixed solution is contacted with chlorine gas at the inlet of the tubular reactor in proportion, glycol chilled water is introduced into the jacket of the first-stage tubular reactor, the reaction temperature is controlled to be 0-5 ℃, and the materials are mixed and stay in the tube for 10-15 minutes;
3) the reaction material enters a second section of sleeve type tubular reactor with a jacket, N '-dioctyl-3, 3' -dithio-dipropionyl in the reaction liquid contacts with chlorine gas at the inlet of the tubular reactor according to the proportion, hot water is introduced into the jacket of the second section of tubular reactor, the reaction temperature is controlled to be 55-60 ℃, and the material is mixed and stays in the tube for 5-10 minutes;
4) and after the continuous reaction is finished, the reaction liquid directly enters a film evaporator, hydrogen chloride and ethyl acetate are taken as light components to be evaporated, heavy components continuously enter a receiving kettle, then methanol is added for recrystallization, and the powdery DCOIT product is obtained through the working procedures of cooling centrifugation, leaching and drying.
2. The continuous production method of 4, 5-dichloro-2-octyl-4-isothiazolin-3-one according to claim 1, wherein the continuous production method comprises the following steps: the mol ratio of the chlorine used in the step 2) to the N, N '-dioctyl-3, 3' -dithiodipropionamide in the step 1) is 4.3-4.5: 1.
3. the continuous production method of 4, 5-dichloro-2-octyl-4-isothiazolin-3-one according to claim 1 or 2, characterized in that: the mol ratio of the chlorine used in the step 3) to the N, N '-dioctyl-3, 3' -dithiodipropionamide in the step 1) is 2.7-3.3: 1.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040039974A (en) * | 2002-11-05 | 2004-05-12 | 주식회사 한서켐 | The manufacturing process for a salt of 2-methyl-4-isothiazoline-3-one |
| CN102786491A (en) * | 2011-05-19 | 2012-11-21 | 大连百傲化学有限公司 | Preparation method of 2-methyl-4-isothiazolin-3-one |
| CN103319433A (en) * | 2013-07-08 | 2013-09-25 | 王建国 | Production technology of CMI (cell-mediated immunity) industrial antibacterial agent |
| CN103880773A (en) * | 2012-12-23 | 2014-06-25 | 北京合创同盛科技有限公司 | Isothiazolinone derivative production method |
| CN104072440A (en) * | 2014-07-17 | 2014-10-01 | 上海化学试剂研究所有限公司 | Preparation method of 4,5-dichloro-N-n-octyl isothiazolinone |
| CN104961705A (en) * | 2015-07-02 | 2015-10-07 | 大连百傲化学股份有限公司 | Process for synthesizing 4,5-dichloro-2-methylisothiazolinone by one-pot method |
| CN110483438A (en) * | 2019-09-09 | 2019-11-22 | 大连百傲化学股份有限公司 | A kind of duct type continuous production method of 3- iso thiazoline ketone compound |
| CN110698423A (en) * | 2019-10-29 | 2020-01-17 | 吉金学 | Preparation method of 5-chloro-alkyl isothiazolinone |
| CN111100088A (en) * | 2019-12-25 | 2020-05-05 | 山东普洛得邦医药有限公司 | Method for continuously synthesizing ethyl dithiaoximate |
| CN112110870A (en) * | 2020-09-28 | 2020-12-22 | 大连百傲化学股份有限公司 | Preparation method of 2-methyl-4-isothiazoline-3-ketone aqueous solution |
| CN112110871A (en) * | 2020-11-03 | 2020-12-22 | 大连百傲化学股份有限公司 | Preparation method of 3-isothiazolinone compound |
| CN112159365A (en) * | 2020-10-13 | 2021-01-01 | 大连百傲化学股份有限公司 | Method for co-producing OIT and DCOIT |
-
2021
- 2021-10-27 CN CN202111256083.7A patent/CN113979965B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040039974A (en) * | 2002-11-05 | 2004-05-12 | 주식회사 한서켐 | The manufacturing process for a salt of 2-methyl-4-isothiazoline-3-one |
| CN102786491A (en) * | 2011-05-19 | 2012-11-21 | 大连百傲化学有限公司 | Preparation method of 2-methyl-4-isothiazolin-3-one |
| CN103880773A (en) * | 2012-12-23 | 2014-06-25 | 北京合创同盛科技有限公司 | Isothiazolinone derivative production method |
| CN103319433A (en) * | 2013-07-08 | 2013-09-25 | 王建国 | Production technology of CMI (cell-mediated immunity) industrial antibacterial agent |
| CN104072440A (en) * | 2014-07-17 | 2014-10-01 | 上海化学试剂研究所有限公司 | Preparation method of 4,5-dichloro-N-n-octyl isothiazolinone |
| CN104961705A (en) * | 2015-07-02 | 2015-10-07 | 大连百傲化学股份有限公司 | Process for synthesizing 4,5-dichloro-2-methylisothiazolinone by one-pot method |
| CN110483438A (en) * | 2019-09-09 | 2019-11-22 | 大连百傲化学股份有限公司 | A kind of duct type continuous production method of 3- iso thiazoline ketone compound |
| CN110698423A (en) * | 2019-10-29 | 2020-01-17 | 吉金学 | Preparation method of 5-chloro-alkyl isothiazolinone |
| CN111100088A (en) * | 2019-12-25 | 2020-05-05 | 山东普洛得邦医药有限公司 | Method for continuously synthesizing ethyl dithiaoximate |
| CN112110870A (en) * | 2020-09-28 | 2020-12-22 | 大连百傲化学股份有限公司 | Preparation method of 2-methyl-4-isothiazoline-3-ketone aqueous solution |
| CN112159365A (en) * | 2020-10-13 | 2021-01-01 | 大连百傲化学股份有限公司 | Method for co-producing OIT and DCOIT |
| CN112110871A (en) * | 2020-11-03 | 2020-12-22 | 大连百傲化学股份有限公司 | Preparation method of 3-isothiazolinone compound |
Non-Patent Citations (2)
| Title |
|---|
| 吴红菱: "2－甲基－异噻唑啉酮和5－氯－2－甲基－异噻唑啉酮的合成研究", 郧阳医学院学报, no. 01, pages 37 - 41 * |
| 姜晓辉;于良民;董磊;安正国;: "4, 5-二氯-2-甲氧基丙基-4-异噻唑啉-3-酮的合成及其防污性能的研究", 涂料工业, no. 10, pages 5 - 7 * |
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