CN109928876A - The production technology of diformazan cyclopropyl carboxylic ester - Google Patents
The production technology of diformazan cyclopropyl carboxylic ester Download PDFInfo
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- CN109928876A CN109928876A CN201711370986.1A CN201711370986A CN109928876A CN 109928876 A CN109928876 A CN 109928876A CN 201711370986 A CN201711370986 A CN 201711370986A CN 109928876 A CN109928876 A CN 109928876A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a kind of production technologies of diformazan cyclopropyl carboxylic ester: dimethylformamide, the tert-butyl alcohol and sodium tert-butoxide being put into cyclization reaction kettle and stirred, and open the cooling of jacket refrigerating salt water, 3 are added dropwise at -20~0 DEG C, 3- dimethyl -4,6,6- tri- chloro- 7,7,7- trifluoro heptanoate obtains Synthesis liquid after -20~-5 DEG C or less reactions 0.5~4h, middle control addition product < 1% after being added dropwise；Acid is added into Synthesis liquid and neutralizes excessive sodium tert-butoxide, the Synthesis liquid after adjusting acid is filtered by PM film, and sodium chloride is recycled in sodium chloride and liquid separation；Liquid recycles the tert-butyl alcohol, dimethylformamide and product followed by lightness-removing column, rectifying column.Present invention process, at low cost, energy saving, the recycling protected environment, be directly realized by sodium chloride using PM film, realizes non-wastewater discharge.Effectively reduce the production cost of enterprise.
Description
Technical field
The present invention relates to suitable, the cleanings of trans- 3- (the chloro- 3,3,3- trifluoro propyl of 2,2- bis-) -2,2- diformazan cyclopropyl carboxylic ester
Metaplasia production. art, and in particular to a kind of to realize sodium chloride and liquid (solvent and production using PM film (nanometer micropore secondary filter film)
Product) separation, utilize lightness-removing column and rectifying column to realize the isolated cleanly production technique of solvent and product；Belong to pyrethroid
Ester pesticide product cleanly production technology field.
Background technique
Suitable, trans- 3- (the chloro- 3,3,3- trifluoro propyl of 2,2- bis-) the existing production method of -2,2- diformazan cyclopropyl carboxylic ester is
1. dimethylformamide, t-butanol solvent and sodium tert-butoxide are put into succession in cyclization reaction kettle, stirring is opened, and open folder
Chilled brine cooling is covered, when material temperature drops to -10 DEG C or less, starts that addition product (3,3- dimethyl -4,6,6- tri- are added dropwise inward
Chloro- 7,7,7- trifluoro heptanoates), it is added dropwise and finishes, be maintained at 0 DEG C or less reaction 1h, then middle control addition product < 1% stops
Reaction.The Synthesis liquid is prepared to enter into next step postprocessing working procedures；2. Synthesis liquid (solidliquid mixture) is squeezed into precipitation kettle, and (one-pot is grasped
Make), precipitation recycling design, solvent overhead recycled are carried out, tower reactor solidliquid mixture adds water to realize product and sodium chloride waste water
Separation；3. sodium chloride waste water recycles dimethylformamide by upper tower rectifying, tower reactor sodium chloride waste water is evaporated into MVR
(Mechanical Vapor Re-compression- function of mechanical steam recompression) system precipitation recycles sodium chloride, deviates from water into life
It is discharged after the processing of change system is qualified.
The method process flow is complicated, and processing energy consumption is high, and number of devices is more and seriously corroded, wastewater flow rate are big.In the present invention
The separation of sodium chloride and liquid (solvent and product) is realized using PM film；Solvent and product are realized using lightness-removing column and rectifying column
Separation, simplifies operating process, greatly saves production cost.
Summary of the invention
The technical problem to be solved by the present invention is to be directed to the deficiencies in the prior art, and provide one kind suitable, trans- 3-
The production technology of (2,2- bis- chloro- 3,3,3- trifluoro propyls) -2,2- diformazan cyclopropyl carboxylic ester, realization is suitable, and (2,2- bis- is chloro- by trans- 3-
3,3,3- trifluoro propyls) -2,2- diformazan cyclopropyl carboxylic ester and sodium chloride separation method, which overcomes the prior art
The problem of, save production cost.
To achieve the goals above, the present invention adopts the following technical scheme:
Suitable, trans- 3- (the chloro- 3,3,3- trifluoro propyl of the 2,2- bis-) -2,2- diformazan cyclopropyl carboxylic of one kind structure as shown in formula (1)
The production technology of acid esters, comprising the following steps:
R is methyl or ethyl；
(1) dimethylformamide, solvent and sodium tert-butoxide are put into succession in cyclization reaction kettle, opens stirring, and beat
The cooling of jacket refrigerating salt water is opened, when material temperature drops to -20~0 DEG C, starts that addition product is added dropwise inward, is added dropwise and finishes, be maintained at -20
Stop reaction after~-5 DEG C of reactions 0.5~4h, middle control addition product < 1%, obtains Synthesis liquid；
The solvent is the tert-butyl alcohol；
The addition product is the chloro- 7,7,7- trifluoro heptanoate of 3,3- dimethyl -4,6,6- three；
(2) a certain amount of acid is added in the Synthesis liquid obtained to step (1), Synthesis liquid is carried out to adjust acid, neutralizes Synthesis liquid
In excessive sodium tert-butoxide；The Synthesis liquid after acid will be adjusted to be filtered by PM film, sodium chloride and liquid are separated, recycle by-product
Sodium chloride；
(3) liquid for obtaining step (3) is followed by lightness-removing column, rectifying column, recycle the tert-butyl alcohol, dimethylformamide and
Product is suitable, trans- 3- (the chloro- 3,3,3- trifluoro propyl of 2,2- bis-) -2,2- diformazan cyclopropyl carboxylic ester.
In above-mentioned technical proposal, in step (1), the addition product, dimethylformamide, the tert-butyl alcohol weight ratio be 1:
0.5-1.5:2-8；The molar ratio of the addition product, sodium tert-butoxide is 1:1.05-1.55.
In above-mentioned technical proposal, in step (2), when carrying out adjusting acid to Synthesis liquid, temperature is in -25 DEG C to -10 DEG C (Synthesis liquids
Adjust sour temperature≤- 10 DEG C).
In above-mentioned technical proposal, in step (2), when carrying out adjusting acid to Synthesis liquid, sour type is inorganic acid, preferably sulphur
Acid, hydrochloric acid, phosphoric acid, acetic acid etc..
In above-mentioned technical proposal, in step (2), adjust acid after Synthesis liquid, PH is between 1-6.
In above-mentioned technical proposal, in step (2), when the Synthesis liquid after tune acid is filtered by PM film, filtration temperature
At 10-100 DEG C, filter pressure controls 0-10MPa for control.
In above-mentioned technical proposal, in step (3), liquid flows through lightness-removing column when carrying out taking off light, and taking off light temperature is 75-105 DEG C；
Isolate the tert-butyl alcohol, tert-butyl alcohol recovery in lightness-removing column top；Lightness-removing column kettle isolates liquid, and liquid, which enters, carries out essence in rectifying column
It evaporates.
In above-mentioned technical proposal, in step (3), liquid flow through rectifying column carry out rectifying when, rectification temperature be 75-105 DEG C,
Rectifying vacuum degree -80KPa~-15KPa；Rectifying tower top isolates dimethylformamide, recovery；Rectifying tower reactor is isolated
Suitable, trans- 3- (2,2- bis- chloro- 3,3,3- trifluoro propyls) -2,2- diformazan cyclopropyl carboxylic ester makes for the synthesis of next procedure time acid
With.
Compared with prior art, the invention has the benefit that
1, it reduces product and post-processes desolventizing equipment quantity, reduce post-processing energy consumption, effectively reduce the production cost of enterprise；
2, the separation that product and sodium chloride are realized using PM film, realizes non-wastewater discharge；Entire process engineering is without waste water
It generates, effectively solves the wastewater treatment and environmental issue of agricultural chemicals enterprise；
3, the separation that solvent and product are realized using lightness-removing column and rectifying column, is effectively reduced equipment corrosion condition, shortens
The period is post-processed, operating process is simplified, saves production cost.
Specific embodiment
The specific embodiment of technical solution of the present invention is described in detail below, but the present invention is not limited in being described below
Hold:
Embodiment 1:
It is suitable, the synthesis of trans- 3- (the chloro- 3,3,3- trifluoro propyl of 2,2- bis-) -2,2- diformazan cyclopropyl carboxylic ester:
(1) dimethylformamide 100Kg, t-butanol solvent 220Kg and sodium tert-butoxide 21Kg are put into 1000L ring in succession
It closes in reaction kettle, unlatching stirring, and opens the cooling of jacket refrigerating salt water, when material temperature drops to -15 DEG C, beginning is added dropwise inward to be added
At object 100Kg (3,3- dimethyl -4,6,6- tri- chloro- 7,7,7- trifluoro heptanoates), it is added dropwise and finishes, be maintained at -12 DEG C of reaction 1h, in
Addition product 0.8% is controlled, reaction is then stopped；The Synthesis liquid is prepared to enter into next step postprocessing working procedures；
(2) completely reacted Synthesis liquid is at -12 DEG C, is added in 2.5Kg20% hydrochloric acid and excessive sodium tert-butoxide in Synthesis liquid,
Tune system PH=2.5；10 DEG C are warming up to, PM film (commercial product, such as my high-tech produces nanofiltration membrane long) filtering, filtration pressure are passed through
Power 2.5MPa separates sodium chloride and liquid, recycles byproduct sodium chloride 32.5Kg；
(3) obtained liquid is passed through in lightness-removing column and is taken off gently, liquid takes off 90 DEG C of light temperature, and tower top isolates the tert-butyl alcohol
215Kg recovery；The liquid that lightness-removing column kettle obtains is separated into rectifying column, 100 DEG C of rectification temperature, vacuum degree -15KPa, tower top
Dimethylformamide 99K g recovery out；Tower reactor extraction product is suitable, trans- 3- (the chloro- 3,3,3- trifluoro propyl of 2,2- bis-) -2,
2- diformazan cyclopropyl carboxylic ester 88.5K g, content 98.4%.
Embodiment 2:
(1) dimethylformamide 80Kg, t-butanol solvent 400Kg and sodium tert-butoxide 21Kg are put into 1000L ring in succession
It closes in reaction kettle, unlatching stirring, and opens the cooling of jacket refrigerating salt water, when material temperature drops to -2 DEG C, beginning is added dropwise inward to be added
At object 100Kg (3,3- dimethyl -4,6,6- tri- chloro- 7,7,7- trifluoro heptanoates), it is added dropwise and finishes, be maintained at -15 DEG C of reaction 4h, in
Addition product 0.3% is controlled, reaction is then stopped；The Synthesis liquid is prepared to enter into next step postprocessing working procedures；
(2) completely reacted Synthesis liquid is at -15 DEG C, is added in 17% hydrochloric acid of 3Kg and excessive sodium tert-butoxide in Synthesis liquid,
Tune system PH=2.7；20 DEG C are warming up to, is filtered by PM film (commercial product), filter pressure 3MPa, by sodium chloride and liquid point
From recycling byproduct sodium chloride 32.3Kg；
(3) obtained liquid is passed through in lightness-removing column and is taken off gently, liquid takes off 100 DEG C of light temperature, and tower top isolates the tert-butyl alcohol
370Kg recovery；The liquid that lightness-removing column kettle obtains is separated into rectifying column, 100 DEG C of rectification temperature, vacuum degree -20KPa, tower top
Dimethylformamide 78K g recovery out；Tower reactor extraction product is suitable, trans- 3- (the chloro- 3,3,3- trifluoro propyl of 2,2- bis-) -2,
The synthesis 88.7K g of 2- diformazan cyclopropyl carboxylic ester, content 98.7%.
Embodiment 3:
(1) dimethylformamide 150Kg, t-butanol solvent 300Kg and sodium tert-butoxide 23Kg are put into 1000L ring in succession
It closes in reaction kettle, unlatching stirring, and opens the cooling of jacket refrigerating salt water, when material temperature drops to -12 DEG C, beginning is added dropwise inward to be added
At object 100Kg (3,3- dimethyl -4,6,6- tri- chloro- 7,7,7- trifluoro heptanoates), it is added dropwise and finishes, be maintained at -20 DEG C of reaction 3h, in
Addition product 0.4% is controlled, reaction is then stopped；The Synthesis liquid is prepared to enter into next step postprocessing working procedures；
(2) completely reacted Synthesis liquid is added in 25% hydrochloric acid of 2.1Kg and the excessive tert-butyl alcohol in Synthesis liquid at -10 DEG C
Sodium adjusts system PH=3；30 DEG C are warming up to, is filtered by PM film (commercial product), filter pressure 4MPa, by sodium chloride and liquid
Byproduct sodium chloride 33.7Kg is recycled in separation；
(3) obtained liquid is passed through in lightness-removing column and is taken off gently, liquid takes off 80 DEG C of light temperature, and tower top isolates the tert-butyl alcohol
280Kg recovery；The liquid that lightness-removing column kettle obtains is separated into rectifying column, 100 DEG C of rectification temperature, vacuum degree -20KPa, tower top
Dimethylformamide 147K g recovery out；Tower reactor extraction product is suitable, trans- 3- (the chloro- 3,3,3- trifluoro propyl of 2,2- bis-) -2,
The synthesis 87.3K g of 2- diformazan cyclopropyl carboxylic ester, content 98.8%.
Examples detailed above is technical conception and technical characteristics to illustrate the invention, can not be limited with this of the invention
Protection scope.The equivalent transformation or modification that all essence according to the present invention is done, should all cover in protection scope of the present invention
Within.
Claims (8)
1. a kind of suitable, trans- 3- (the chloro- 3,3,3- trifluoro propyl of 2,2- bis-) -2,2- diformazan cyclopropyl carboxylic acid of the structure as shown in formula (1)
The synthetic method of ester, which comprises the following steps:
R is methyl or ethyl；
(1) the chloro- 7,7,7- trifluoro heptanoate of 3,3- dimethyl -4,6,6- three is added dropwise to dimethylformamide at -20~0 DEG C
In the t-butanol solution of sodium tert-butoxide, is reacted after being added dropwise at -20~-5 DEG C or less, obtain Synthesis liquid；
(2) a certain amount of acid is added in the Synthesis liquid obtained to step (1), Synthesis liquid is carried out to adjust acid, neutralizes mistake in Synthesis liquid
The sodium tert-butoxide of amount；The Synthesis liquid after acid will be adjusted to be filtered by PM film, sodium chloride and liquid are separated, recycle by-product chlorination
Sodium；
(3) for the liquid for obtaining step (3) followed by lightness-removing column, rectifying column, isolated product is suitable, trans- 3- (2,2- bis-
Chloro- 3,3,3- trifluoro propyl) -2,2- diformazan cyclopropyl carboxylic ester and recycle the tert-butyl alcohol and dimethylformamide.
2. production technology according to claim 1, which is characterized in that in step (1), the addition product, dimethyl methyl
Amide, the tert-butyl alcohol weight ratio be 1:0.5-1.5:2-8；The molar ratio of the addition product, sodium tert-butoxide is 1:1.05-
1.55。
3. production technology according to claim 1, which is characterized in that in step (2), when carrying out adjusting acid to Synthesis liquid, temperature
Degree control is at -25 DEG C to -10 DEG C.
4. production technology according to claim 1, which is characterized in that in step (2), when carrying out adjusting acid to Synthesis liquid, acid
Type be inorganic acid, specially sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid.
5. production technology according to claim 1, which is characterized in that in step (2), adjust acid after Synthesis liquid, PH is in 1-6
Between.
6. production technology according to claim 1, which is characterized in that in step (2), the Synthesis liquid after acid will be adjusted to pass through PM
When film is filtered, at 10-100 DEG C, filter pressure controls 0-10MPa for filtration temperature control.
7. production technology according to claim 1, which is characterized in that in step (3), liquid flows through lightness-removing column and take off gently
When, taking off light temperature is 75-105 DEG C；Isolate the tert-butyl alcohol, tert-butyl alcohol recovery in lightness-removing column top；Lightness-removing column kettle isolates liquid,
Liquid, which enters, carries out rectifying in rectifying column.
8. production technology according to claim 1, which is characterized in that in step (3), liquid flows through rectifying column and carries out rectifying
When, rectification temperature is 75-105 DEG C, rectifying vacuum degree -80KPa~-15KPa；Rectifying tower top isolates dimethylformamide, returns
Receipts are applied；Rectifying tower reactor isolates suitable, trans- 3- (2,2- bis- chloro- 3,3,3- trifluoro propyls) -2,2- diformazan cyclopropyl carboxylic ester, uses
It synthesizes and uses in next procedure time acid.
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| CN201711370986.1A CN109928876A (en) | 2017-12-19 | 2017-12-19 | The production technology of diformazan cyclopropyl carboxylic ester |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4243677A (en) * | 1978-01-20 | 1981-01-06 | Fmc Corporation | Insecticidal perhaloalkylvinylcyclopropanecarboxylates |
| US4333950A (en) * | 1979-05-24 | 1982-06-08 | Fmc Corporation | (+)-4-Substituted-2-indanol insecticidal ester derivatives |
| CN102092869A (en) * | 2010-12-28 | 2011-06-15 | 济源市金利冶炼有限责任公司 | Processing method of waste acid in acid producing system |
| CN106008210A (en) * | 2016-05-25 | 2016-10-12 | 无锡青苹果工程勘察设计院 | Method for synthesizing lambda cyhalthrin acid by using loop reactor |
| CN106518645A (en) * | 2016-09-29 | 2017-03-22 | 江苏中能化学科技股份有限公司 | Synthetic technology of high-cis-lambda-chrysanthemumic acid |
-
2017
- 2017-12-19 CN CN201711370986.1A patent/CN109928876A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4243677A (en) * | 1978-01-20 | 1981-01-06 | Fmc Corporation | Insecticidal perhaloalkylvinylcyclopropanecarboxylates |
| US4333950A (en) * | 1979-05-24 | 1982-06-08 | Fmc Corporation | (+)-4-Substituted-2-indanol insecticidal ester derivatives |
| CN102092869A (en) * | 2010-12-28 | 2011-06-15 | 济源市金利冶炼有限责任公司 | Processing method of waste acid in acid producing system |
| CN106008210A (en) * | 2016-05-25 | 2016-10-12 | 无锡青苹果工程勘察设计院 | Method for synthesizing lambda cyhalthrin acid by using loop reactor |
| CN106518645A (en) * | 2016-09-29 | 2017-03-22 | 江苏中能化学科技股份有限公司 | Synthetic technology of high-cis-lambda-chrysanthemumic acid |
Non-Patent Citations (1)
| Title |
|---|
| 无: "PM膜过滤器-集五大优势于一身的突破性产品", 《精细化工》 * |
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Application publication date: 20190625 |