CN108218696B - Production process of bifenthrin - Google Patents
Production process of bifenthrin Download PDFInfo
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- CN108218696B CN108218696B CN201611191467.4A CN201611191467A CN108218696B CN 108218696 B CN108218696 B CN 108218696B CN 201611191467 A CN201611191467 A CN 201611191467A CN 108218696 B CN108218696 B CN 108218696B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/09—Bromine; Hydrogen bromide
- C01B7/093—Hydrogen bromide
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Abstract
The invention discloses a production process of bifenthrin, which comprises the steps of mixing 2-methyl-3-phenyl benzyl alcohol and a catalyst, putting the mixture into a reaction vessel, heating the mixture to 10-60 ℃ to a molten state, dropwise adding 3- (2-chloro-3, 3, 3-trifluoro-1-propenyl) -2, 2-dimethyl cyclopropane formyl halide under a certain negative pressure condition, and absorbing negative pressure tail gas by using three-stage water to obtain a secondary acid. After the dropwise addition is finished, the reaction is carried out for 1 to 3 hours at the temperature of between 10 and 60 ℃, the reaction is finished when the concentration of the 2-methyl-3-phenyl benzyl alcohol is controlled to be less than 0.1 percent, and the bifenthrin is obtained after the product is washed with water, directly stands, delaminates and removes water. The method of the invention cancels the solvent required by the bifenthrin synthesis, has simple subsequent treatment, does not need recrystallization treatment, recovers halogen acid as a byproduct, does not generate other three wastes, and obviously improves the quality of the obtained bifenthrin. The method has the advantages of simple process, high product quality, byproduct hydrogen halide acid, improved economy and accordance with industrial clean production.
Description
Technical Field
The invention relates to a production method of a compound, in particular to a production process of bifenthrin.
Background
Bifenthrin is a high-efficiency pyrethroid insecticide and acaricide, has the characteristics of high efficiency, low toxicity, low residue and the like, is mainly used for preventing and controlling various lepidoptera larvae, aleyrodid, aphids, phytophagous spider mites and other pests, has the main action mode of contact killing and stomach toxicity, and is widely used in the market at present.
The existing industrial production method is basically characterized in that 2-methyl-3-benzyl alcohol and 3- (2-chloro-3, 3, 3-trifluoro-1-propenyl) -2, 2-dimethyl cyclopropane formyl chloride are subjected to chemical reaction in an acid-binding agent and a corresponding solvent to generate bifenthrin, and the process is synthesized by an aqueous phase method to generate a large amount of high-salt wastewater with the lower content of about 95 percent.
US patent (US4341796) uses trifluorochloromethylchrysanthemic acid (3- (2-chloro-3, 3, 3-trifluoro-1-propenyl) -2, 2-dimethylcyclopropanecarboxylic acid) and 2-methyl-3-chloromethylbiphenyl to perform esterification reaction in acid-binding agent and appropriate solvent, but the process has biphenyl yield as low as 80%, large amount of waste water, and waste gas generation.
In chinese patent CN103145558A, ester synthesis is performed by using trifluoro chrysanthemic acid and methanol, and then ester exchange is performed with biphenyl alcohol to obtain bifenthrin, the method mainly includes that the methanol reaction with water has large circulation and treatment amount of methanol, the reaction time is long, and in the process of ester exchange, the reaction conversion rate is about 93% lower due to excessive biphenyl alcohol, and the residual biphenyl alcohol has a large influence on the quality of bifenthrin.
In addition, pyridine is still used as an acid-binding agent by part of manufacturers to carry out oil phase synthesis, and the method generates a large amount of pyridine wastewater, is difficult to treat, has a large smell and does not meet the requirement of clean production.
Therefore, the invention provides a bifenthrin clean production process, which directly uses trifluoro-chloro-chrysanthemum acyl halide and 2-methyl-biphenyl benzyl alcohol to synthesize under the condition of a certain catalyst without using an organic solvent, generates hydrogen halide tail gas, uses a negative pressure removal system, uses a three-stage falling film tower to absorb water, and produces a byproduct, namely halogen acid. The method has the characteristics of simple process, high content of synthesized products, recyclable byproducts, no solvent, no complicated operations such as desolventizing and solvent treatment, high industrial capacity and the like, and meets the requirement of clean production.
Disclosure of Invention
The invention aims to: the method has the characteristics of simple process, high content of synthesized products, recyclable byproducts, no solvent, no complicated operations such as desolventizing and solvent treatment, high industrial capacity and the like, and meets the requirement of clean production.
The technical scheme adopted by the invention is as follows:
the production process of bifenthrin comprises the following steps:
(1) mixing 2-methyl-3-phenyl benzyl alcohol with a catalyst, putting into a reaction vessel, and heating to 10-60 ℃ to obtain a molten material;
(2) dripping 3- (2-chloro-3, 3, 3-trifluoro-1-propenyl) -2, 2-dimethylcyclopropane formyl halide into the molten material obtained in the step (1) at the temperature of 10-60 ℃ under a certain negative pressure condition, and absorbing negative pressure tail gas by using tertiary water to obtain a by-product acid;
(3) and (3) after the dropwise addition in the step (2), keeping the temperature at 10-60 ℃ for reacting for 1-3 hours, controlling the concentration of the 2-methyl-3-phenyl benzyl alcohol to be less than 0.1%, finishing the reaction, washing the product with water for layering, and removing water to obtain bifenthrin.
In the above technical scheme, in the step (1), the catalyst is any one of triethylamine, o-ethylaniline, triethanolamine, isopropylamine and hexamethyltetramine, or a mixture of two or more of them mixed at any ratio, and preferably is any one of triethylamine or hexamethyltetramine.
In the technical scheme, in the step (1), the dosage of the catalyst is 0.02-0.10% of the weight of the 2-methyl-3-phenyl benzyl alcohol.
In the above technical scheme, in the step (2), the negative pressure is between-0.01 MPa and-0.098 MPa in the reaction process.
In the above technical solution, in the step (2), the molar ratio of the 3- (2-chloro-3, 3, 3-trifluoro-1-propenyl) -2, 2-dimethylcyclopropane carbonyl halide to 2-methyl-3-phenyl benzyl alcohol is 1.0: 1-1.02: 1.
in the technical scheme, in the step (2), the hydrogen halide generated by the reaction is timely removed through negative pressure of the reaction tail gas, and the hydrogen halide is absorbed by water in the three-stage falling film tower.
In the technical scheme of the invention, no solvent is added into the reaction system, and the post-treatment does not need to be purified again.
The 3- (2-chloro-3, 3, 3-trifluoro-1-propenyl) -2, 2-dimethylcyclopropane formyl halide in the step 2) has a structure shown as the following formula (1), wherein X represents Cl or Br:
the structure of the 2-methyl-3-phenyl benzyl alcohol in the step 1) is shown as the following (2):
compared with the prior art, the method has the advantages that bifenthrin is synthesized by a solvent-free method, hydrogen halide generated by reaction is removed by negative pressure, the generated hydrogen halide is absorbed by three stages to form byproduct halogen acid, meanwhile, the reaction is faster by using a high-efficiency catalyst, impurities are less, desolventizing and recrystallization are not needed in the post-treatment process, the bifenthrin is separated by standing and layering, a water washing water jacket is used for absorbing and replenishing water by three stages of water, the reaction conversion rate reaches more than 99%, the byproduct halogen acid meets the industrial standard, the cost is greatly reduced, the generation of three wastes is removed, the single-kettle capacity is greatly increased after the solvent is removed, and the economy and the environmental protection are greatly improved.
In a word, compared with the prior art, the invention improves the product quality yield, greatly reduces the three wastes, improves the economy by-product hydrogen halogen acid, has simple production process and greatly simplified post-treatment process, and meets the requirement of industrial clean production.
Detailed Description
The technical solutions and effects of the present invention are explained in detail below in the form of examples, but the present invention is not limited to the following examples.
Example 1:
the production process of bifenthrin comprises the following steps: adding 400KG of 2-methyl-3-phenyl benzyl alcohol and 0.1KG of triethylamine into a 2000L reaction kettle with a stirrer, heating to 40 ℃, absorbing tail gas by adopting three-stage series falling film tower water, controlling the temperature of the reaction kettle to be 40-45 ℃ under the negative pressure of-0.02 MPa, beginning to dropwise add 528KG of trichloro-chrysanthemic chloride into the synthesis kettle, ending dropwise adding for 3 hours, preserving heat for 2 hours, controlling 0.05% of 2-methyl-3-phenyl benzyl alcohol in the heat preservation and ensuring that the conversion rate is 99.5%. Discharging to a post-treatment kettle, adding 500L of ionized water, washing at 40-45 ℃, standing for layering after washing, separating crude oil from the lower layer, and removing water to obtain the bifenthrin 837.3KG with the content of 99.1% and the yield of 98.1%. The water layer is applied to the falling film tower for water absorption, and the byproduct, namely the recovered hydrochloric acid is 226.5KG, and the content is 30.19%.
Example 2:
the production process of bifenthrin comprises the following steps: adding 400KG of 2-methyl-3-phenyl benzyl alcohol and 0.1KG of hexamethyltetramine into a 2000L reaction kettle with a stirrer, heating to 40 ℃, absorbing tail gas by adopting three-stage series falling film tower water, controlling the temperature of the reaction kettle to be 40-45 ℃ under the negative pressure of-0.02 MPa, beginning to dropwise add 529KG of trichloro-chrysanthemumyl chloride into the synthesis kettle, ending dropwise adding for 3 hours, preserving heat for 2 hours, controlling the content of 0.06 percent of 2-methyl-3-phenyl benzyl alcohol in the heat preservation and controlling the conversion rate to be 99.6 percent. Discharging to a post-treatment kettle, adding 500L of ionized water, washing at 40-45 ℃, standing for layering after washing, separating crude oil from the lower layer, and removing water to obtain the bifenthrin 838.1KG with the content of 99.3% and the yield of 98.5%. The water layer is applied to the falling film tower for water absorption, and the byproduct, namely recovered hydrochloric acid 222.6KG has the content of 30.39%.
Example 3:
the production process of bifenthrin comprises the following steps: adding 400KG of 2-methyl-3-phenyl benzyl alcohol and 0.1KG of triethylamine into a 2000L reaction kettle with a stirrer, heating to 40 ℃, absorbing tail gas by adopting three-stage series falling film tower water, controlling the temperature of the reaction kettle to be 30-35 ℃ under the negative pressure of-0.05 MPa, beginning to dropwise add 528KG of trichloro-chrysanthemic chloride into the synthesis kettle, ending dropwise adding for 3 hours, preserving heat for 2 hours, controlling 0.03% of 2-methyl-3-phenyl benzyl alcohol in the heat preservation and controlling the conversion rate to be 99.4%. Discharging to a post-treatment kettle, adding 500L of ionized water, washing at 40-45 ℃, standing for layering after washing, separating crude oil from the lower layer, and removing water to obtain the bifenthrin 837.9KG with the content of 99.0% and the yield of 98.3%. The water layer is applied to the falling film tower for water absorption, and the byproduct, namely recovered hydrochloric acid 218.5KG, has the content of 31.08 percent.
Example 4:
the production process of bifenthrin comprises the following steps: adding 400KG of 2-methyl-3-phenyl benzyl alcohol and 0.1KG of triethylamine into a 2000L reaction kettle with a stirrer, heating to 40 ℃, absorbing tail gas by adopting a three-stage series falling film tower, controlling the temperature of the reaction kettle to be 30-35 ℃ under the negative pressure of-0.05 MPa, beginning to dropwise add 619.2KG of trichloro-chrysanthemum acyl bromide into the synthesis kettle, finishing dropwise adding for 3 hours, preserving heat for 2 hours, controlling the concentration of 0.03 percent of 2-methyl-3-phenyl benzyl alcohol and the conversion rate to be 99.5 percent. Discharging to a post-treatment kettle, adding 500L of ionized water, washing at 40-45 ℃, standing for layering after washing, separating crude oil from the lower layer, and removing water to obtain the bifenthrin 837.5KG with the content of 99.1% and the yield of 98.1%. The water layer is applied to the falling film tower for water absorption, and the byproduct, namely recovered hydrobromic acid 314.7KG has the content of 49.12 percent.
Example 5:
the production process of bifenthrin comprises the following steps: adding 400KG of 2-methyl-3-phenyl benzyl alcohol and 0.2KG of triethanolamine into a 2000L reaction kettle with a stirrer, heating to 40 ℃, absorbing tail gas by adopting three-stage series falling film tower water, controlling the temperature of the reaction kettle to be 30-35 ℃ under the negative pressure of-0.05 MPa, beginning to dropwise add 528.2KG of trichlorochlorochrysanthemic chloride into the synthesis kettle, ending dropwise adding for 3 hours, preserving heat for 2 hours, controlling the concentration of 0.06 percent of 2-methyl-3-phenyl benzyl alcohol and the conversion rate to be 99.6 percent. Discharging to a post-treatment kettle, adding 500L of ionized water, washing at 40-45 ℃, standing for layering after washing, separating crude oil from the lower layer, and removing water to obtain the bifenthrin 836.9KG with the content of 99.2% and the yield of 98.2%. The water layer is applied to the falling film tower for water absorption, and the byproduct, namely the recovered hydrochloric acid 212.1KG has the content of 31.39 percent.
Example 6:
the production process of bifenthrin comprises the following steps: adding 400KG of 2-methyl-3-phenyl benzyl alcohol and 0.5KG of triethylamine into a 2000L reaction kettle with a stirrer, heating to 40 ℃, absorbing tail gas by adopting three-stage series falling film tower water, controlling the temperature of the reaction kettle to be 40-45 ℃ under the negative pressure of-0.02 MPa, beginning to dropwise add 528.5KG of trichlorochlorochrysanthemic chloride into the synthesis kettle, ending dropwise adding for 3 hours, preserving heat for 2 hours, controlling 0.05% of 2-methyl-3-phenyl benzyl alcohol in the heat preservation and ensuring that the conversion rate is 99.4%. Discharging to a post-treatment kettle, adding 500L of ionized water, washing at 40-45 ℃, standing for layering after washing, separating crude oil from the lower layer, and removing water to obtain the bifenthrin 837.9KG with the content of 99.3% and the yield of 98.4%. The water layer is applied to the falling film tower for water absorption, and the byproduct, namely the recovered hydrochloric acid 221.1KG has the content of 30.45 percent.
Example 7:
the production process of bifenthrin comprises the following steps: adding 400KG of 2-methyl-3-phenyl benzyl alcohol and 0.05KG of triethylamine into a 2000L reaction kettle with a stirrer, heating to 40 ℃, absorbing tail gas by adopting a three-stage series falling film tower, controlling the temperature of the reaction kettle to be 40-45 ℃ under the condition that the system has negative pressure of-0.03 MPa, beginning to dropwise add 528.5KG of chlorotrifluoro chrysanthemumic chloride into the synthesis kettle, ending dropwise adding for 2 hours, preserving heat for 2 hours, controlling 0.04% of 2-methyl-3-phenyl benzyl alcohol in the heat preservation and having the conversion rate of 99.3%. Discharging to a post-treatment kettle, adding 500L of ionized water, washing at 40-45 ℃, standing for layering after washing, separating crude oil from the lower layer, and removing water to obtain the bifenthrin 837.9KG with the content of 99.2% and the yield of 98.5%. The water layer is applied to the falling film tower for water absorption, and the byproduct, namely recovered hydrochloric acid 227.3KG, has the content of 30.36 percent.
The above examples are only for illustrating the technical concept and features of the present invention, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (5)
1. A production process of bifenthrin is characterized in that 3- (2-chloro-3, 3, 3-trifluoro-1-propenyl) -2, 2-dimethyl cyclopropane formyl halide and 2-methyl-3-phenyl benzyl alcohol are synthesized by a solvent-free method under certain negative pressure and in the presence of a catalyst, and the production process comprises the following steps:
(1) mixing 2-methyl-3-phenyl benzyl alcohol with a catalyst, putting into a reaction vessel, and heating to 10-60 ℃ to obtain a molten material; the catalyst is a mixture formed by mixing any one, two or more than two of triethylamine, triethanolamine and hexamethyltetramine in any proportion;
(2) dripping 3- (2-chloro-3, 3, 3-trifluoro-1-propenyl) -2, 2-dimethylcyclopropane formyl halide into the molten material obtained in the step (1) at the temperature of 10-60 ℃ under a certain negative pressure condition, and absorbing negative pressure tail gas by using tertiary water to obtain a by-product acid;
(3) and (3) after the dropwise addition in the step (2), keeping the temperature at 10-60 ℃ for reacting for 1-3 hours, controlling the concentration of the 2-methyl-3-phenyl benzyl alcohol to be less than 0.1%, finishing the reaction, washing the product with water for layering, and removing water to obtain bifenthrin.
2. The process according to claim 1, characterized in that: in the step (1), the dosage of the catalyst is 0.02-0.10% of the weight of the 2-methyl-3-phenyl benzyl alcohol.
3. The process according to claim 1, characterized in that: in the step (2), the negative pressure in the reaction process is between-0.01 MPa and-0.098 MPa.
4. The process according to claim 1, characterized in that: in the step (2), the molar ratio of the 3- (2-chloro-3, 3, 3-trifluoro-1-propenyl) -2, 2-dimethylcyclopropane formyl halide to the 2-methyl-3-phenyl benzyl alcohol is 1.0: 1-1.02: 1.
5. the process according to claim 1, characterized in that: in the step (2), the hydrogen halide generated by the reaction is removed in time by the reaction tail gas through negative pressure, and is absorbed by water in a three-stage falling film tower.
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| CN102167667B (en) * | 2010-08-31 | 2014-04-30 | 黄鉴前 | Method for synthesizing pentaerythritol tetrabenzoate |
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| CN104628569A (en) * | 2013-11-15 | 2015-05-20 | 江苏扬农化工股份有限公司 | Method for producing bifenthrin with clean synthesizing process |
| CN105817248B (en) * | 2015-01-27 | 2019-03-22 | 中国石油化工股份有限公司 | One kind nano-carbon material containing hetero atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method |
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