CN108424368A - A kind of preparation method and its production system of 2,4 dichlorophenoxyacetic acid emulsifiable concentrate - Google Patents
A kind of preparation method and its production system of 2,4 dichlorophenoxyacetic acid emulsifiable concentrate Download PDFInfo
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- CN108424368A CN108424368A CN201710076667.3A CN201710076667A CN108424368A CN 108424368 A CN108424368 A CN 108424368A CN 201710076667 A CN201710076667 A CN 201710076667A CN 108424368 A CN108424368 A CN 108424368A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
- A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
- A01N39/04—Aryloxy-acetic acids; Derivatives thereof
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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
Abstract
The present invention provides a kind of preparation method and its production system of 2,4 dichlorphenoxyacetic acid emulsifiable concentrates, this method includes：A) the esterification that alcohol and halogenated acetic acids are dehydrated by 3~5 grades of overflows, obtains halogenated acetic acids ester；B) the halogenated acetic acids ester and 2, it is layered by 3~5 grades of continuous condensation reactions after the mixing of 4 dichloro phenates, obtain 2,4 dichlorphenoxyacetic acid esters；C described 2,4 dichlorphenoxyacetic acid esters are mixed with solvent and emulsifier), obtain 2,4 dichlorphenoxyacetic acid missible oil.Production system of the present invention includes mainly：Multistage esterification device, multistage condensation device, decker and missible oil device for formulating.2,4 dichlorphenoxyacetic acid emulsifiable concentrates are prepared using specific continuous process in the present invention, improve reaction production capacity, easy to operate, and high with product yield, and product is stablized, and exhaust gas and dust effectively controls and missible oil product substitutes the advantages such as pulvis good drug efficacy.
Description
Technical field
The present invention relates to technical field of organic synthesis, more particularly, to the preparation of one kind 2,4- dichlorphenoxyacetic acid emulsifiable concentrates
Method and its production system.
Background technology
2,4- dichlorphenoxyacetic acid class compounds are a kind of very important compounds, are that usage history is longest in the world
Organic synthesis herbicide kind, is still being widely used now.Wherein, 2,4- dichlorphenoxyacetic acids ester referred to as 2,4-D esters or 2,4-d
Ester；It is in missible oil to be prepared, and the main dosage form as herbicide is used in global range.
The preparation method of 2,4 dichlorophenoxyacetic acid esters missible oil disclosed in the prior art is mainly：2,4 dichloro benzene oxygen second
Acid synthesis 2,4- Dichlorophenoxy acid esters, adds auxiliary agent, solvent is configured to missible oil.Wherein, 2,4- dichlorphenoxyacetic acid esters are synthesized
All it is intermittent reaction with missible oil is prepared, the problems such as it is low that there are production capacities, and product yield is low, and exhaust gas and dust is difficult to control.Also, gained
The missible oil product arrived substitutes existing 2,4- dichloros pulvis, there is also easily causing product to bond, is not easy to disperse to suspend in water, or
Phenomena such as blocking nozzle, precipitation is caused in sprayer, causes to spray irregular, so that crop is locally generated the main of poisoning and asking
Topic.
Invention content
In view of this, the technical problem to be solved in the present invention is to provide the system of one kind 2,4- dichlorphenoxyacetic acid emulsifiable concentrates
2,4- dichlorphenoxyacetic acid emulsifiable concentrates are prepared in Preparation Method and its production system, preparation method provided by the invention, and product is steady
It is fixed, high income, and production capacity height is reacted, and it is easy to operate, it can effectively control the good drug efficacy of exhaust gas and dust and missible oil product.
The present invention provides the preparation methods of one kind 2,4- dichlorphenoxyacetic acid emulsifiable concentrates, include the following steps：
A) the esterification that alcohol and halogenated acetic acids are dehydrated by 3~5 grades of overflows, obtains halogenated acetic acids ester；
B) the halogenated acetic acids ester and 2, it is layered by 3~5 grades of continuous condensation reactions after the mixing of 4- dichloro phenates, it obtains
To 2,4 dichlorophenoxyacetic acid ester；
C 2, the 4- dichlorphenoxyacetic acids ester is mixed with solvent and emulsifier), obtains 2,4- dichlorphenoxyacetic acid breasts
Oil.
Preferably, 2, the 4- dichloros phenates is prepared by the following method：2,4- Dichlorophenols are reacted with alkali, obtain 2,4- dichloros
Phenates.
Preferably, the step B) in reaction existing for phase transfer catalyst under the conditions of carry out.
Preferably, the halogenated acetic acids ester is selected from one or more of chloracetate, bromacetate and Alkyl Iodoacetates.
Preferably, 2, the 4- dichloros phenates is selected from 2,4- sodium dichlorophenol indophenols, 2,4- Dichlorophenols potassium, 2,4- Dichlorophenols calcium, 2,
One or more of 4- Dichlorophenols magnesium, 2,4- Dichlorophenols zinc and 2,4- Dichlorophenol aluminium.
Preferably, 2, the 4- dichloros phenates is selected from 2,4- sodium dichlorophenol indophenols or 2,4- Dichlorophenol potassium.
The present invention also provides the production systems of one kind 2,4- dichlorphenoxyacetic acid emulsifiable concentrates comprising：
Level-one esterification device, the level-one esterification device have halogenated acetic acids import, alcohol import and esterification products outlet；
With sequentially connected 2~4 grades of esterification devices of the level-one esterification device；
The level-one condensation device being connected to last 1 grade of esterification device, level-one condensation device have halogenated acetic acids ester into
Mouth, 2,4- dichloro phenates imports and condensation product outlet；
With sequentially connected 2~4 grades of condensations device of level-one condensation device；
The decker that import is connected to last 1 grade condensation device, the decker have 2,4- dichlorphenoxyacetic acids
Ester exports；
The missible oil device for formulating of import and decker 2,4 dichlorophenoxyacetic acid ester outlet.
Preferably, further include：
Outlet is condensed device 2, the neutralization device of 4- dichloro phenates imports connection with the level-one, and the neutralization device has
The import of 2,4- Dichlorophenols and alkali import.
Preferably, the level-one condensation device also has phase transfer catalyst import.
Preferably, further include：
The filter device that import is connected to missible oil device for formulating, the filter device have 2,4- dichlorphenoxyacetic acids ester breast
Oily product outlet.
Compared with prior art, the present invention provides the preparation methods of one kind 2,4- dichlorphenoxyacetic acid emulsifiable concentrates, including
Following steps：A) the esterification that alcohol and halogenated acetic acids are dehydrated by 3~5 grades of overflows, obtains halogenated acetic acids ester；B) described halogenated
Acetic acid esters and 2, it is layered by 3~5 grades of continuous condensation reactions after the mixing of 4- dichloro phenates, obtain 2,4- dichlorphenoxyacetic acids
Ester；C 2, the 4- dichlorphenoxyacetic acids ester is mixed with solvent and emulsifier), obtains 2,4- dichlorphenoxyacetic acid missible oil.This hair
It is bright to use specific continuous process and production system, 2,4- dichlorphenoxyacetic acid emulsifiable concentrates are prepared, improve reaction production
Can, easy to operate and high with product yield, product is stablized, and exhaust gas and dust effectively controls and missible oil product substitutes pulvis
The advantages such as good drug efficacy.
Description of the drawings
Fig. 1 is the schematic diagram of the production system of 2,4 dichlorophenoxyacetic acid emulsifiable concentrate provided by the embodiments of the present application.
Specific implementation mode
The present invention provides the preparation method of one kind 2,4- dichlorphenoxyacetic acid emulsifiable concentrates, includes the following steps：
A) the esterification that alcohol and halogenated acetic acids are dehydrated by 3~5 grades of overflows, obtains halogenated acetic acids ester；
B) the halogenated acetic acids ester and 2, it is layered by 3~5 grades of continuous condensation reactions after the mixing of 4- dichloro phenates, it obtains
To 2,4 dichlorophenoxyacetic acid ester；
C 2, the 4- dichlorphenoxyacetic acids ester is mixed with solvent and emulsifier), obtains 2,4- dichlorphenoxyacetic acid breasts
Oil.
Preparation method provided by the invention can overcome reaction production capacity caused by intermittent reaction existing in the prior art low, behaviour
The problems such as work is complicated, and product yield is low, and product is unstable, and exhaust gas and dust is not easy to control, pulvis drug effect is poor.
Halogenated acetic acids ester is prepared in the embodiment of the present invention first, prepares by the following method：Alcohol and halogenated acetic acids by 3~
The esterification of 5 grades of overflows dehydration, obtains halogenated acetic acids ester.Wherein, the alcohol can be methanol and other monohydric alcohols.Every grade of ester
Precipitation can be dehydrated at 80~180 DEG C by changing reaction, then enter next stage esterification by overflow.Wherein, every grade of residence time
It can be controlled in 0.1h~2.0h.In some embodiments of the invention, the esterification has 4 grades.
In the present invention, the preparation method of the halogenated acetic acids ester is preferably specially：By the monohydric alcohol of C2 or more and halogenated
Acetic acid continuous esterification obtains halogenated acetic acids ester.The monohydric alcohol and halogenated acetic acids of more preferably specific C2 or more is in catalyst
Under the action of be mixed, halogenated acetic acids ester is obtained by the reaction in continuous dehydration.The present invention for the stirring concrete mode not into
Row limits, agitating mode well known to those skilled in the art.
The monohydric alcohol of C2 the or more more than monohydric alcohol of C2 or more of the present invention namely two carbon atoms；Preferably C2
The monohydric alcohol of~C20；The more preferably monohydric alcohol of C2~C10；The most preferably monohydric alcohol of C3~C9.The halogenated acetic acids is preferred
Selected from one or more of monoxone, bromoacetic acid and iodoacetic acid；The alcohol and the catalyst of halogenated acetic acids reaction are preferably selected from
The concentrated sulfuric acid, toluene and butyl titanate.Wherein, the molar ratio of the monohydric alcohol of the C2 or more and halogenated acetic acids be preferably (1~
1.5):1；More preferably (1~1.2):1；Most preferably (1~1.1):1；The additive amount of the catalyst be preferably 1wt ‰~
1wt%.
In embodiments of the present invention, the halogenated acetic acids ester in chloracetate, bromacetate and Alkyl Iodoacetates one
Kind is several, preferably chloracetate or bromacetate.
The halogenated acetic acids ester intermediate stability that the present invention is preferably prepared is good, and byproduct of reaction is few, high income；In turn
Yield and purity subsequently to prepare provide good condition.
In addition, 2,4- dichloro phenates can be prepared in the embodiment of the present invention, such as 2,4- Dichlorophenols are reacted with alkali, obtain 2,4-
Dichloro phenates.It is preferred that being specially：2,4- Dichlorophenols are reacted with aqueous slkali in 70~95 DEG C, obtain 2,4- dichloro phenates.The alkali
The alkaline substance solutions such as sodium hydroxide, potassium hydroxide or solid may be used；The molar ratio of the 2,4- Dichlorophenols and alkali is 1:1
~1:1.5.
In an embodiment of the present invention, 2, the 4- dichloros phenates is selected from 2,4- sodium dichlorophenol indophenols, 2,4- Dichlorophenols potassium, 2,4-
Dichlorophenol calcium, 2,4- Dichlorophenols magnesium, 2,4- Dichlorophenols zinc and 2, one or more of 4- Dichlorophenol aluminium, preferably 2,4- dichloros
Phenol sodium or 2,4- Dichlorophenol potassium.
The present invention use oil phase halogenated acetic acids ester and 2,4- dichloro phenates, preferably phase transfer catalyst act under, instead
2,4- dichlorphenoxyacetic acid esters should be prepared, advantageously reduce and hydrolyze by-product in entire reaction process, accelerate reaction speed, carry
High conversion and yield reduce the wastewater flow rate of generation.
In the present invention, the phase transfer catalyst preferably is selected from one in polyethers, crown ether, quaternary ammonium salt, tertiary amine and quaternary phosphonium salt
Kind is several, more preferably quaternary ammonium salt, crown ether, tertiary amine or quaternary phosphonium salt.The crown ether such as cyclic crown ether；In the preferred reality of the present invention
It applies in example, the phase transfer catalyst is tetrabutylammonium bromide, 18 crown ethers, triethylamine or tetrabutyl phosphonium bromide phosphine.Wherein, the phase
The dosage of transfer catalyst is the 0.1%~5% of 2,4 dichlorophenoxyacetic acid ester quality.
The embodiment of the present invention is by the halogenated acetic acids ester and 2, after the mixing of 4- dichloro phenate solutions, passes through 3~5 grades of continuous contractings
Reaction is closed, 2,4- dichlorphenoxyacetic acid esters are obtained after layering.
In an embodiment of the present invention, 2,4- dichloros phenate solution is mixed with the halogenated acetic acids ester that esterification obtains, is carried out
Then level-one condensation reaction enters next stage condensation reaction by overflow, is finally layered, obtain 2,4- dichlorphenoxyacetic acid esters.
Wherein, the molar ratio of the halogenated acetic acids ester and 2,4- dichloro phenates can be (0.9~1.1)：(0.9~1.1).Every grade of condensation is anti-
The temperature answered is preferably 70~200 DEG C, more preferably 80~100 DEG C；Every grade of residence time can be controlled in 0.1h~2.0h.At this
In some embodiments of invention, the condensation reaction has 4 grades.It is described to be layered as technological means well known to those skilled in the art,
The present invention is not particularly limited, if separation time can be 0.1h~2.0h.
It is after being continuously available 2,4- dichlorphenoxyacetic acid esters, 2, the 4- dichlorphenoxyacetic acids ester and solvent and emulsifier is mixed
It closes, obtains 2,4- dichlorphenoxyacetic acid missible oil.
In the present invention, the solvent can be dimethylbenzene, polar solvent, solvent naphtha, one or more in vegetable oil etc..
The emulsifier preferably includes the first emulsifier (emulsifier 1) and the second emulsifier (emulsifier 2), and first emulsifier is optional
From any one or two kinds in calcium dodecyl benzene sulfonate and neopelex；Second emulsifier can be selected from benzene
Ethyl phenol polyoxyethylene poly-oxygen propylene aether, phenethyl phenol polyethenoxy ether, phenethyl phenol polyethenoxy ether, nonyl phenol bring up polyoxy alkene
Ether, Ben-zylphenol Polyoxyethyl Ether, any one or more in fatty alcohol polyoxyethylene ether and castor oil polyoxyethylene ether.It is described
The ratio of 2,4- dichlorphenoxyacetic acid esters and the mixing of solvent and emulsifier, different content mass ratioes is different, can only be 2,4- bis-
Chlorophenoxyacetic acid ester mass fraction 1%-90%, emulsifier mass fraction 5%-12%, solvent quality score 5%-85%.
Wherein, described to be mixed into technical means commonly used by such a person skilled in the art.Layering institute can be used in the embodiment of the present invention
The substance obtained, is added solvent, emulsifier for mixing, and heating and heat preservation obtains 2,4- dichlorphenoxyacetic acid emulsifiable concentrate finished products by press filtration.
Ranging from 25 DEG C~60 DEG C, preferably 30~50 DEG C of the holding temperature.
2,4- dichlorphenoxyacetic acid emulsifiable concentrates are prepared using specific continuous process in the present invention, improve reaction production
Can, easy to operate and high with product yield, product is stablized, and exhaust gas and dust effectively controls and missible oil product substitutes pulvis
The advantages such as good drug efficacy are conducive to apply.
Correspondingly, the present invention also provides the production systems of one kind 2,4- dichlorphenoxyacetic acid emulsifiable concentrates, including：
Level-one esterification device, the level-one esterification device have halogenated acetic acids import, alcohol import and esterification products outlet；
With sequentially connected 2~4 grades of esterification devices of the level-one esterification device；
The level-one condensation device being connected to last 1 grade of esterification device, level-one condensation device have halogenated acetic acids ester into
Mouth, 2,4- dichloro phenates imports and condensation product outlet；
With sequentially connected 2~4 grades of condensations device of level-one condensation device；
The decker that import is connected to last 1 grade condensation device, the decker have 2,4- dichlorphenoxyacetic acids
Ester exports；
The missible oil device for formulating of import and decker 2,4 dichlorophenoxyacetic acid ester outlet.
Using the production system of 2,4- dichlorphenoxyacetic acids emulsifiable concentrate provided by the invention, energy serialization is prepared 2,4-
Dichlorphenoxyacetic acid emulsifiable concentrate, product are stablized, high income, and react production capacity height, easy to operate, can effectively control exhaust gas and dust,
And the good drug efficacy of missible oil product.
Referring to Fig. 1, Fig. 1 is the signal of the production system of 2,4- dichlorphenoxyacetic acids emulsifiable concentrate provided by the embodiments of the present application
Figure.
Production system provided by the present application includes level-one esterification device, with halogenated acetic acids import, alcohol import and esterification
Product exit；In level-one esterification device, the alcohol and halogenated acetic acids that are added from each import carry out esterification, obtain halogenated acetic acids
Ester.Level-one esterification device described in the embodiment of the present invention is esterifying kettle commonly used in the art；The level-one esterification device, which also has, urges
Agent feeding port makes alcohol and halogenated acetic acids react and carries out under the action of catalyst.
Production system provided by the present application include with sequentially connected 2~4 grades of esterification devices of the level-one esterification device, with
Continuously, it is sufficiently carried out above-mentioned esterification.In some embodiments of the invention, including the esterification of sequentially connected two level fills
It sets, three-level esterification device and level Four esterification device.Esterifying kettle commonly used in the art can be used in esterification devices at different levels；In the present invention
Specific embodiment in, every grade of residence time can be controlled in 0.1h~2.0h.
Production system provided by the present application includes the level-one condensation device being connected to last 1 grade of esterification device, with halogen
It is exported for acetic acid esters import, 2,4- dichloro phenates imports and condensation product.It is condensed in device in level-one, via the 2,4- of each import
Dichloro phenates carries out condensation reaction with continuous halogenated acetic acids ester obtained, obtains 2,4- dichlorphenoxyacetic acid esters, also referred to as
2,4-d esters or 2,4-D esters.
Production system provided by the present application preferably further includes：Outlet is condensed device 2,4- dichloro phenates imports with the level-one
The neutralization device of connection has the import of 2,4- Dichlorophenols and alkali import.In and in device, from 2, the 4- bis- of each import addition
Chlorophenol is reacted with alkali, obtains 2,4- dichloro phenates.The present invention is not particularly limited the neutralization device, using it is well known that
Neutralization kettle.
Level-one condensation device is condensation kettle commonly used in the art described in the embodiment of the present invention；The level-one condensation device is preferred
Also have phase transfer catalyst import, make condensation reaction existing for phase transfer catalyst under the conditions of carry out.
Production system provided by the present application includes and sequentially connected 2~4 grades of level-one condensation device is condensed device；With
Continuously, it is sufficiently carried out above-mentioned condensation reaction.In some embodiments of the invention, including the condensation of sequentially connected two level fills
It sets, three-level condensation device and level Four are condensed device.Condensation kettle commonly used in the art can be used in condensation devices at different levels；In the present invention
Specific embodiment in, every grade of residence time can be controlled in 0.1h~2.0h.
Production system provided by the present application includes：The decker that import is connected to last 1 grade condensation device, the layering
Device is exported with 2,4 dichlorophenoxyacetic acid ester；It preferably includes：Import is connect by three-way pipeline with last 1 grade condensation device
Decker, condensation gained reaction solution by three-way pipeline flow into decker, the decker 2,4- Dichlorophenoxy second
Acid esters outlet is used for output 2,4-d esters.Layering kettle well known in the art, layering tank can be used in the decker, separates upper layer,
It can be obtained the 2,4-d esters of water white transparency.I.e. the application can prepare the cream preparation of the ester Han 2,4-d, reaction production with serialization
It can be high.
Production system provided by the present application includes：The breast of import and decker 2,4 dichlorophenoxyacetic acid ester outlet
Oily device for formulating.Layering gained 2,4- dichlorphenoxyacetic acid esters are introduced such as prepares kettle in missible oil device for formulating, and solvent and breast is added
Agent is stirred, and obtains 2,4- dichlorphenoxyacetic acid missible oil.The application preferably further includes：Import connects with missible oil device for formulating
Logical filter device, the filter device have 2,4- dichlorphenoxyacetic acid emulsifiable concentrate product outlets.The filter device is preferred
For filter-pressing device commonly used in the art；The embodiment of the present application addition solvent and emulsifier for mixing, heating and heat preservation, by press filtration, i.e.,
Obtain 2,4 dichlorophenoxyacetic acid emulsifiable concentrate finished product.
Raw material, reaction condition involved by the above production system etc. can be as previously described；The present invention to each import, go out
Mouth, and the mode of connection, connection are also not particularly limited.
Production system of the present invention includes mainly：Multistage esterification device, multistage condensation device, decker and missible oil prepare dress
It sets.Technological process using the above-mentioned production system of the embodiment of the present application includes：A) alcohol and halogenated acetic acids are filled by 3~5 grades of esterifications
It sets, carries out continuous esterification, obtain halogenated acetic acids ester；B) the halogenated acetic acids ester and 2 passes through 3 after the mixing of 4- dichloro phenates
~5 grades of condensation devices, carry out continuous condensating reaction, and layered device layering obtains 2,4- dichlorphenoxyacetic acid esters；It C) will be described
2,4- dichlorphenoxyacetic acid esters are mixed with solvent and emulsifier in missible oil device for formulating, and heating and heat preservation after press filtration, obtains 2,4-
Dichlorphenoxyacetic acid missible oil finished product.2,4 dichlorophenoxyacetic acid ester breast is prepared using specific continuous process in the present invention
Oil improves reaction production capacity, easy to operate, and high with product yield, and product is stablized, and exhaust gas and dust effectively controls, and
Missible oil product substitutes the advantages such as pulvis good drug efficacy, is conducive to apply.
In order to further illustrate the present invention, with reference to embodiments to 2,4- dichlorphenoxyacetic acids ester provided by the invention breast
The preparation method and its production system of oil are described in detail.
Embodiment 1
2000kg butanol, 950kg (10kmol) monoxones and the 1kg concentrated sulfuric acids input level-one esterifying kettle are mixed, 80
DEG C precipitation is dehydrated 1h, then sequentially enters two, three-level esterifying kettle by overflow, feed rate 3000kg/h, and every grade when stopping
Between control in 1h, obtain butyl chloroacetate.
By 2,4 dichloro phenol 1640kg (10kmo1), the sodium hydrate aqueous solution 1250kg of mass fraction 32%
(10kmol) is mixed, and is warming up to 70 DEG C, obtains 2,4- sodium dichlorophenol indophenol solution.
2, the 4- sodium dichlorophenol indophenols solution is put into and is esterified obtained butyl chloroacetate and is mixed into level-one condensation kettle, 80
After DEG C stirring 0.5h, then sequentially enter two by overflow, three, level Four condensation kettle, feed rate 3000kg/h, every grade of stop
Time control enters layering kettle in 0.5h, then condensation gained reaction solution, separates 2, the 4- dichloros that upper layer obtains water white transparency
Phenoxy acetic acid butyl ester 2772kg, content 98.5%, yield 98.6%.
Gained ester, which enters, to be prepared in kettle, and solvent xylene 208kg is added, and 1 dodecane of 130kg emulsifiers is added in stirring
Base benzene sulfonic acid calcium；2 castor oil polyoxyethylene ether of 164kg emulsifiers is added, by heating and heat preservation, press filtration obtains 3270kg 2,4-
Dichlorobenzene oxygen butyl acetate 1000g/L missible oil, up-to-standard, yield 99.87%.
Embodiment 2
2000kg ethyl alcohol, 1400kg (10kmol) bromoacetic acids and the 1kg concentrated sulfuric acids are mixed, 100 DEG C of precipitation dehydrations
0.8h, then sequentially enters two, three-level esterifying kettle, feed rate 2500kg/h by overflow, and every grade of residence time control exists
0.8h obtains bromoacetate.
By 2,4 dichloro phenol 1640kg (10kmo1), the potassium hydroxide aqueous solution 1122kg of mass fraction 50%
(10kmol) is mixed, and is warming up to 70 DEG C, obtains 2,4- Dichlorophenol potassium solutions.
The obtained bromoacetate of 2,4- Dichlorophenols potassium solution input esterification is mixed into level-one condensation kettle, 90 DEG C
After stirring 0.5h, then sequentially enter two by overflow, three, level Four condensation kettle, feed rate 2000kg/h, every grade when stopping
Between control in 0.5h, then condensation reaction solution enters layering kettle, separates 2, the 4- Dichlorophenoxy second that upper layer obtains water white transparency
Acetoacetic ester 2772kg, content 98.3%, yield 98.4%.
Gained ester, which enters, to be prepared in kettle, and solvent methyl oleate 208kg is added, and 130kg emulsifiers 10 two are added in stirring
Alkyl benzene calcium sulfonate；2 phenethyl phenol polyethenoxy ether of 164kg emulsifiers is added, phenethyl phenol polyethenoxy ether is protected by heating
Temperature, press filtration obtain 3265kg 2,4- dichlorphenoxyacetic acid ethyl ester 1000g/L missible oil, up-to-standard, yield 99.7%.
Embodiment 3
2000kg methanol, 950kg (10kmol) monoxones and the 1kg concentrated sulfuric acids input level-one esterifying kettle are mixed, 80
DEG C precipitation is dehydrated 0.3h, then sequentially enter two by overflow, three, level Four esterifying kettle, feed rate 3000kg/h, every grade is stopped
It stays time control in 0.3h, obtains methyl chloroacetate.
By 2,4 dichloro phenol 1640kg (10kmo1), the sodium hydrate aqueous solution 1250kg of mass fraction 32%
(10kmol) is mixed, and is warming up to 70 DEG C, obtains 2,4- sodium dichlorophenol indophenol solution.
2, the 4- sodium dichlorophenol indophenols solution is put into and is esterified obtained methyl chloroacetate and is mixed into level-one condensation kettle, 80
After DEG C stirring 0.5h, then sequentially enter two by overflow, three, level Four condensation kettle, feed rate 2000kg/h, every grade of stop
Time control enters layering kettle in 0.5h, then condensation gained reaction solution, separates 2, the 4- dichloros that upper layer obtains water white transparency
Methyl phenoxyacetate 2772kg, content 98.5%, yield 98.6%.
Gained ester, which enters, to be prepared in kettle, and solvent naphtha 208kg is added, and 1 detergent alkylate of 130kg emulsifiers is added in stirring
Sulfoacid calcium；2 phenethyl phenol polyoxyethylene poly-oxygen propylene aether of 164kg emulsifiers is added, by heating and heat preservation, press filtration obtains 3270kg
2,4- dichlorphenoxyacetic acid methyl esters 1000g/L missible oil, up-to-standard, yield 99.87%.
As seen from the above embodiment, the present invention uses specific continuous process and production system, and 2,4- bis- is prepared
Chlorophenoxyacetic acid emulsifiable concentrate；Qualified product, yield is 98% or more.Show that the present invention improves reaction production capacity, operation letter
Single and high with product yield, product is stablized, and exhaust gas and dust effectively controls and missible oil product substitutes pulvis good drug efficacy etc.
Advantage.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. one kind 2, the preparation method of 4- dichlorphenoxyacetic acid emulsifiable concentrates, include the following steps：
A) the esterification that alcohol and halogenated acetic acids are dehydrated by 3~5 grades of overflows, obtains halogenated acetic acids ester；
B) the halogenated acetic acids ester and 2, it is layered by 3~5 grades of continuous condensation reactions after the mixing of 4- dichloro phenates, 2 are obtained,
4- dichlorphenoxyacetic acid esters；
C 2, the 4- dichlorphenoxyacetic acids ester is mixed with solvent and emulsifier), obtains 2,4- dichlorphenoxyacetic acid missible oil.
2. preparation method according to claim 1, which is characterized in that 2, the 4- dichloros phenates is prepared by the following method：
2,4- Dichlorophenols are reacted with alkali, obtain 2,4- dichloro phenates.
3. preparation method according to claim 1, which is characterized in that the step B) in reaction deposited in phase transfer catalyst
It carries out under the conditions.
4. preparation method according to claim 1, which is characterized in that the halogenated acetic acids ester is selected from chloracetate, bromine second
One or more of acid esters and Alkyl Iodoacetates.
5. preparation method according to claim 1, which is characterized in that 2, the 4- dichloros phenates is selected from 2,4- Dichlorophenols
One kind in sodium, 2,4- Dichlorophenols potassium, 2,4- Dichlorophenols calcium, 2,4- Dichlorophenols magnesium, 2,4- Dichlorophenols zinc and 2,4- Dichlorophenol aluminium
Or it is several.
6. preparation method according to claim 5, which is characterized in that 2, the 4- dichloros phenates is selected from 2,4- sodium dichlorophenol indophenols
Or 2,4- Dichlorophenol potassium.
7. one kind 2, the production system of 4- dichlorphenoxyacetic acid emulsifiable concentrates, which is characterized in that including：
Level-one esterification device, the level-one esterification device have halogenated acetic acids import, alcohol import and esterification products outlet；
With sequentially connected 2~4 grades of esterification devices of the level-one esterification device；
The level-one condensation device being connected to last 1 grade of esterification device, the level-one condensation device have the import of halogenated acetic acids ester, 2,
4- dichloro phenates imports and condensation product outlet；
With sequentially connected 2~4 grades of condensations device of level-one condensation device；
There is 2,4- dichlorphenoxyacetic acid esters to go out for the decker that import is connected to last 1 grade condensation device, the decker
Mouthful；
The missible oil device for formulating of import and decker 2,4 dichlorophenoxyacetic acid ester outlet.
8. production system according to claim 7, which is characterized in that further include：
Outlet is condensed device 2, the neutralization device of 4- dichloro phenates imports connection with the level-one, and the neutralization device has 2,4-
Dichlorophenol import and alkali import.
9. production system according to claim 7, which is characterized in that the level-one condensation device also has phase transfer catalysis (PTC)
Agent import.
10. production system according to claim 7, which is characterized in that further include：
The filter device that import is connected to missible oil device for formulating, the filter device have 2,4- dichlorphenoxyacetic acids emulsifiable concentrate at
Product export.
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