CN108424365A - A kind of preparation method of 2,4 dichlorophenoxyacetic acid - Google Patents
A kind of preparation method of 2,4 dichlorophenoxyacetic acid Download PDFInfo
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- CN108424365A CN108424365A CN201710076678.1A CN201710076678A CN108424365A CN 108424365 A CN108424365 A CN 108424365A CN 201710076678 A CN201710076678 A CN 201710076678A CN 108424365 A CN108424365 A CN 108424365A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
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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
- 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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Abstract
The present invention provides a kind of preparation methods of 2,4 dichlorphenoxyacetic acids, include the following steps, polyalcohol and halogenated acetic acids are carried out esterification first, obtain halogenated acetic acids ester；Then the halogenated acetic acids ester and 2 above-mentioned steps obtained, 4 dichloro phenates are reacted, and 2,4 dichlorphenoxyacetic acid esters are obtained；Finally under the action of composite catalyst, reaction is hydrolyzed in 2 that above-mentioned steps are obtained, 4 dichlorphenoxyacetic acid esters, obtains 2,4 dichlorphenoxyacetic acids and polyalcohol；The polyalcohol is the polyalcohol that C atomicities are more than or equal to 2.Adjusting process route of the present invention, carries out inventive improvements on the basis of, and the preparation method, simple for process, mild condition, hydrolysising by-product is few, and product purity is high, and conversion ratio and yield are higher, and intermediate halogenated acetic acids ester is stablized, and is suitble to large-scale industrial production.
Description
Technical field
The invention belongs to benzene oxycarboxylic acid esters synthesis technical fields, more particularly to the preparation of one kind 2,4- dichlorphenoxyacetic acids
Method.
Background technology
2,4- dichlorphenoxyacetic acids also known as 2,4-D, (2,4- dichlorophenoxy) acetic acid or 2,4-D acid etc., molecular formula are
C8H6Cl2O3, fusing point is 140.5 DEG C, and boiling point is 160 DEG C, and it is most of organic molten to be dissolved in alcohol, ether or ketone etc. for white diamond crystallization
Agent is practically insoluble in water.
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, is agriculturally being mainly used for as herbicide or plant growth substance
It uses, in analysis field, the standard etc. of carbon and hydrogen is measured for organic microanalysis.
As herbicide, 2,4- dichlorphenoxyacetic acids in 500ppm or more high concentrations be used for cauline leaf process, can wheat,
The broad leaved weeds such as lamb's-quarters, amaranth and budding period grassy weed are prevented and kill off in the crop fields such as rice, corn, sugarcane, can be entered from root, stem, leaf
In plant, degradation is slow, therefore can accumulate a certain concentration, to interfere plant hormone in vivo to balance, destroys nucleic acid and protein
Metabolism, promotes or inhibits certain organ growths, so that weeds cauline leaf is distorted, stem foot is thicker, swells and splits；With Atrazine, prometryn
Equal herbicide mixtures, or it is mixed with the acidic fertiliziers such as ammonium sulfate, herbicide effect can be increased, but to safety of human and livestock.
As auxin, 2,4- dichlorphenoxyacetic acids are representative synthetic auxins (auxin), are a kind of
Auxin analog.High activity is shown in common auximone sizing technique, but is using auximone standard
In the oat elongation test of sizing technique, effect is quite low.Many synthetic auxins centered on 2,4 dichlorophenoxyacetic acid
There is rapid development applied to agricultural, by large-scale for preventing fruit early fallout agent etc..
Just because of this, 2,4- dichlorphenoxyacetic acids have the larger market demand, but its preparation process always exists
Many defects, the preparation method as disclosed one kind 2,4- dichlorphenoxyacetic acids in CN106278862.This method is with 2,4- dichloros
Phenol is raw material, obtains 2,4- dichloro phenates anhydrous systems by the effect of water entrainer, is obtained by the reaction 2 with methyl chloroacetate afterwards,
4- dichlorphenoxyacetic acid methyl esters, 2,4- dichlorphenoxyacetic acid methyl esters hydrolyze under solid acid catalyst prepares 2,4- Dichlorophenoxy second
Acid；CN106278863 discloses the preparation method of one kind 2,4- dichlorphenoxyacetic acids, and 2,4- dichlorphenoxyacetic acid methyl esters is added
In water, solid acid catalyst, agitating and heating is added, back flow reaction 2~8 hours steams the methanol that reaction generates, after reaction
It is cooled to room temperature, filters, wash, it is dry, obtain 2,4- dichlorphenoxyacetic acids.Process raw material usage amount used in above method
It is larger, and methyl chloroacetate and product 2,4-d methyl esters is unstable, easily hydrolyzed, and conversion ratio and yield are low etc., not only affect
The production of 2,4- dichlorphenoxyacetic acids does not meet the developing direction for the green energy conservation that country advocates yet.
Therefore, a kind of preparation method of more suitable 2,4- dichlorphenoxyacetic acids how is found, above-mentioned technology is overcome to lack
It falls into, is always many line research staff and poly-talented manufacturer widely focus of attention.
Invention content
In view of this, the technical problem to be solved in the present invention is to provide the preparation side of one kind 2,4- dichlorphenoxyacetic acids
Method, preparation process provided by the invention is simple for process, and mild condition, hydrolysising by-product is few, and product purity is high, conversion ratio and yield
It is higher, and intermediate halogenated acetic acids ester is stablized, and large-scale industrial production is suitble to.
The present invention provides the preparation methods of one kind 2,4- dichlorphenoxyacetic acids, include the following steps：
A polyalcohol and halogenated acetic acids) are subjected to esterification, obtain halogenated acetic acids ester；
B) the halogenated acetic acids ester and 2 for obtaining above-mentioned steps, 4- dichloro phenates are reacted, and 2,4- Dichlorophenoxy second is obtained
Acid esters；
C) under the action of composite catalyst, 2, the 4- dichlorphenoxyacetic acid esters that above-mentioned steps obtain are hydrolyzed instead
It answers, obtains 2,4- dichlorphenoxyacetic acids and polyalcohol；
The polyalcohol is the polyalcohol that C atomicities are more than or equal to 2.
Preferably, the polyalcohol is the polyalcohol of C2~C20.
Preferably, the halogenated acetic acids includes one or more in monoxone, bromoacetic acid and iodoacetic acid；
The 2,4- dichloros phenates includes 2,4- sodium dichlorophenol indophenols, 2,4- Dichlorophenols potassium, 2,4- Dichlorophenols calcium, 2,4- Dichlorophenols
It is one or more in magnesium, 2,4- Dichlorophenols zinc and 2,4- Dichlorophenol aluminium.
Preferably, the reaction promoter of the esterification includes the concentrated sulfuric acid；
The temperature of the esterification is 50~200 DEG C；
The time of the esterification is 1~10h.
Preferably, the molar ratio of the polyalcohol and halogenated acetic acids is (1~1.5):1.
Preferably, the step B) in, the temperature of the reaction is 70~200 DEG C；
The time of the reaction is 1~7h.
Preferably, the molar ratio of the halogenated acetic acids ester and 2,4- dichloro phenates is (0.9~1.1)：(0.9~1.1).
Preferably, the temperature of the hydrolysis is 50~200 DEG C；
The time of the hydrolysis is 1~10h.
Preferably, the composite catalyst includes one or more in polyethers, crown ether, quaternary ammonium salt, tertiary amine and quaternary phosphonium salt,
With one or more mixtures in titanate esters, inorganic acid and organic acid.
Preferably, the percentage that the quality of the composite catalyst accounts for 2, the 4- dichlorphenoxyacetic acids ester quality is
0.1%~1%；
The inorganic acid includes sulfuric acid and/or hydrochloric acid；The organic acid includes one in p-methyl benzenesulfonic acid, formic acid and acetic acid
Kind is a variety of.
The present invention provides the preparation methods of one kind 2,4- dichlorphenoxyacetic acids, include the following steps, first by polyalcohol
Esterification is carried out with halogenated acetic acids, obtains halogenated acetic acids ester；Then halogenated acetic acids ester above-mentioned steps obtained and 2,4- bis-
Diclofenac salt is reacted, and 2,4- dichlorphenoxyacetic acid esters are obtained；Finally under the action of composite catalyst, above-mentioned steps are obtained
2,4- dichlorphenoxyacetic acid esters reaction is hydrolyzed, obtain 2,4- dichlorphenoxyacetic acids and polyalcohol；The polyalcohol is C former
Subnumber is more than or equal to 2 polyalcohol.Compared with prior art, the present invention is directed to existing production technology, and there are process raw materials to make
Dosage is big, and intermediate methyl chloroacetate and product 2, and 4-d methyl esters is unstable, easily hydrolyzed, the defects such as conversion ratio and yield are low.
Adjusting process route of the present invention, carries out inventive improvements on the basis of, first use polyols preparation halogenated acetic acids ester, then with system
Standby 2,4- Dichlorophenol reactant salts prepare 2,4- dichlorphenoxyacetic acid esters, then hydrolysis obtains 2 under the action of composite catalyst,
4- dichlorphenoxyacetic acids and polyalcohol.Preparation process provided by the invention, simple for process, mild condition, hydrolysising by-product is few, production
Object purity is high, and conversion ratio and yield are higher, and intermediate halogenated acetic acids ester is stablized, and is suitble to large-scale industrial production.Experiment
The result shows that 2,4- dichlorphenoxyacetic acids prepared by the present invention, purity can reach 99.6%, and yield can reach
99.6%.
Specific implementation mode
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are intended merely to the feature and advantage further illustrated the present invention, rather than to invention claim
Limitation.
All raw materials of the present invention, are not particularly limited its source, buying on the market or according to people in the art
It is prepared by conventional method known to member.
All raw materials of the present invention, are not particularly limited its purity, and present invention preferably employs analyze pure or organic synthesis neck
The conventional purity used in domain.
The present invention provides the preparation methods of one kind 2,4- dichlorphenoxyacetic acids, include the following steps：
A polyalcohol and halogenated acetic acids) are subjected to esterification, obtain halogenated acetic acids ester；
B) the halogenated acetic acids ester and 2 for obtaining above-mentioned steps, 4- dichloro phenates are reacted, and 2,4- Dichlorophenoxy second is obtained
Acid esters；
C) under the action of composite catalyst, 2, the 4- dichlorphenoxyacetic acid esters that above-mentioned steps obtain are hydrolyzed instead
It answers, obtains 2,4- dichlorphenoxyacetic acids and polyalcohol；
The polyalcohol is the polyalcohol that C atomicities are more than or equal to 2.
Polyalcohol and halogenated acetic acids are carried out esterification by the present invention first, obtain halogenated acetic acids ester.
Polyalcohol of the present invention is the polyalcohol that C atomicities are more than or equal to 2, and the present invention is to the polyalcohol without other
Especially limitation is more than or equal to 2 polyalcohol, people in the art with routine C atomicities well known to those skilled in the art
Member can be selected and adjusted according to practical condition, product requirement and quality requirement, and polyalcohol of the present invention is preferred
For the polyalcohol of C2~C20, the more preferably polyalcohol of C3~C10, the most preferably polyalcohol of C4~C8.The present invention is to described
First number of polyalcohol is especially limited without other, with conventional polyol well known to those skilled in the art, art technology
Personnel can select and adjust according to practical condition, product requirement and quality requirement, polyalcohol of the present invention
First number is preferably greater than to be equal to 2, more preferably 2~5, more preferably 2~4, most preferably 2~3.
The halogenated acetic acids is not particularly limited in the present invention, with conventional halogenated acetic acids well known to those skilled in the art
, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
The bright halogenated acetic acids preferably includes one or more in monoxone, bromoacetic acid and iodoacetic acid, more preferably monoxone, bromine second
Acid or iodoacetic acid, most preferably monoxone or bromoacetic acid.
The dosage of the polyalcohol and halogenated acetic acids is not particularly limited in the present invention, with well known to those skilled in the art
The conventional amount used of similar reaction, those skilled in the art can be according to practical condition, product requirement and quality requirement
It is selected and is adjusted, the molar ratio of polyalcohol and halogenated acetic acids of the present invention is preferably (1~1.5):1, more preferably
(1.1~1.4):1, most preferably (1.3~1.3):1.
The temperature of the esterification is not particularly limited in the present invention, with conventional ester well known to those skilled in the art
Change reaction temperature, those skilled in the art can select according to practical condition, product requirement and quality requirement
And adjustment, the temperature of esterification of the present invention is preferably 50~200 DEG C, more preferably 75~175 DEG C, most preferably 100
~150 DEG C.The time of the esterification is not particularly limited in the present invention, with conventional ester well known to those skilled in the art
Change the reaction time, those skilled in the art can select according to practical condition, product requirement and quality requirement
And adjustment, the time of esterification of the present invention is preferably 1~10h, more preferably 3~8h, most preferably 5~6h.
The detailed process of the esterification is not particularly limited in the present invention, with routine well known to those skilled in the art
Esterification reaction process, those skilled in the art can carry out according to practical condition, product requirement and quality requirement
Selection and adjustment, esterification of the present invention is particularly preferred as, under conditions of reaction promoter, by polyalcohol and halogenated acetic acids
Esterification is carried out, halogenated acetic acids ester is obtained.
The reaction promoter is not particularly limited in the present invention, with conventional reaction promoter well known to those skilled in the art
, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
The bright reaction promoter is preferably one or more in toluene, butyl titanate and the concentrated sulfuric acid, more preferably toluene, butyl titanate
With two or more in the concentrated sulfuric acid.The addition of the reaction promoter is not particularly limited in the present invention, with art technology
The addition of popular response auxiliary agent known to personnel, those skilled in the art can want according to practical condition, product
It asks and quality requirement is selected and adjusted.
Above-mentioned steps of the present invention have obtained intermediate halogenated acetic acids ester, and the intermediate stability is good, and byproduct of reaction is few, receive
Rate is high, and then provides good condition for the follow-up yield for preparing 2,4- dichlorphenoxyacetic acids and purity.
The source of 2, the 4- dichloros phenates is not particularly limited in the present invention, in method well known to those skilled in the art
It prepares or commercially available purchase, those skilled in the art can carry out according to practical condition, product requirement and quality requirement
Selection and adjustment, 2,4- dichloros phenates of the present invention are preferably prepared in accordance with the following methods：
After 2,4- Dichlorophenols are reacted with alkali, 2,4- dichloro phenates is obtained.
The alkali is not particularly limited in the present invention, with alkali of the routine well known to those skilled in the art containing metallic element
, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
The metallic element contained in the bright alkali preferably include it is one or more in sodium, potassium, calcium, magnesium, zinc and aluminium, more preferably sodium,
Potassium, calcium, magnesium, zinc or aluminium, most preferably sodium or potassium.Alkali of the present invention preferably include sodium hydroxide, potassium hydroxide, sodium carbonate,
Potassium carbonate, sodium bicarbonate, saleratus, calcium hydroxide, calcium carbonate, calcium bicarbonate, aluminium hydroxide, magnesium hydroxide and zinc hydroxide
In one or more, more preferably sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, saleratus, hydrogen-oxygen
Change calcium, calcium carbonate, calcium bicarbonate, aluminium hydroxide, magnesium hydroxide or zinc hydroxide, most preferably sodium hydroxide, potassium hydroxide, carbon
Sour sodium, potassium carbonate, sodium bicarbonate or saleratus.
2, the 4- dichloros phenates is not particularly limited in the present invention, with well known to those skilled in the art conventional 2,4-
Dichloro phenates, the selection correspondence based on above-mentioned alkali obtain, and those skilled in the art can be according to actual production feelings
Condition, product requirement and quality requirement are selected and are adjusted, and 2,4- dichloros phenates of the present invention preferably includes 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 a variety of, more preferably 2,4- sodium dichlorophenol indophenols, 2,4- Dichlorophenols potassium, 2,4- Dichlorophenols calcium, 2,4- Dichlorophenols magnesium, 2,4- Dichlorophenols
Zinc or 2,4- Dichlorophenol aluminium, most preferably 2,4- sodium dichlorophenol indophenols or 2,4- Dichlorophenol potassium.
The dosage of 2, the 4- Dichlorophenols and alkali is not particularly limited in the present invention, with class well known to those skilled in the art
Like the conventional amount used of reaction, those skilled in the art can according to practical condition, product requirement and quality requirement into
Row selection and adjustment, the molar ratio of 2,4- Dichlorophenols and alkali of the present invention is preferably 1：(1~1.5), more preferably 1：(1.1
~1.4), most preferably 1：(1.2~1.3).
The reaction temperature that the present invention reacts 2, the 4- Dichlorophenols with alkali is not particularly limited, with those skilled in the art
The temperature of well known similar reaction, those skilled in the art can want according to practical condition, product requirement and quality
It asks and is selected and adjusted, the temperature that 2,4- Dichlorophenols of the present invention are reacted with alkali is preferably 50~80 DEG C, more preferably 55
~75 DEG C, most preferably 60~70 DEG C.The reaction time that the present invention reacts 2, the 4- Dichlorophenols with alkali is not particularly limited,
With the reaction time of similar reaction well known to those skilled in the art, those skilled in the art can be according to actual production feelings
Condition, product requirement and quality requirement are selected and are adjusted, and the time that 2,4- Dichlorophenols of the present invention are reacted with alkali is preferably
0.5~1h, more preferably 0.6~0.9h, most preferably 0.7~0.8h.
Then halogenated acetic acids ester and 2 that the present invention obtains above-mentioned steps, 4- dichloro phenates are reacted, and 2,4- bis- is obtained
Chlorophenoxyacetic acid ester.
The condition of 2, the 4- dichloros phenates is not particularly limited in the present invention, with routine well known to those skilled in the art
2,4- dichloro phenates condition, based on above-mentioned alkali selection correspondence obtains, those skilled in the art can root
It is selected and is adjusted according to practical condition, product requirement and quality requirement, 2,4- dichloros phenates of the present invention is preferably
2,4- dichloro phenates solids.
The present invention is to the halogenated acetic acids ester and 2, and the addition of 4- dichloro phenates is not particularly limited, with art technology
The conventional amount used of similar reaction known to personnel, those skilled in the art can be according to practical condition, product requirement
And quality requirement is selected and is adjusted, halogenated acetic acids ester of the present invention and 2, the molar ratio of 4- dichloro phenates is preferably (0.9
~1.1)：(0.9~1.1), more preferably (0.94~1.06)：(0.9~1.1), more preferably (0.98~1.02)：(0.9~
1.1), more preferably (0.9~1.1)：(0.94~1.06), more preferably (0.9~1.1)：(0.98~1.02), most preferably
1:1。
The temperature of the reaction is not particularly limited in the present invention, with the temperature of similar reaction well known to those skilled in the art
Degree, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, this
The temperature for inventing the reaction is preferably 70~200 DEG C, more preferably 90~180 DEG C, more preferably 110~160 DEG C, most preferably
It is 130~140 DEG C.The time of the reaction is not particularly limited in the present invention, with well known to those skilled in the art similar anti-
The reaction time answered, those skilled in the art can select according to practical condition, product requirement and quality requirement
It selects and adjusts, the time of reaction of the present invention is preferably 1~7h, more preferably 2~6h, most preferably 3~5h.
Finally under the action of composite catalyst, 2, the 4- dichlorphenoxyacetic acid esters that above-mentioned steps are obtained carry out the present invention
Hydrolysis obtains 2,4- dichlorphenoxyacetic acids and polyalcohol.
The temperature of the hydrolysis is not particularly limited in the present invention, with similar reaction well known to those skilled in the art
Temperature, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement
Whole, the temperature of hydrolysis of the present invention is preferably 50~200 DEG C, more preferably 70~180 DEG C, more preferably 90~160
DEG C, most preferably 110~140 DEG C.The time of the hydrolysis is not particularly limited in the present invention, with those skilled in the art
In the reaction time of well known similar reaction, those skilled in the art can be according to practical condition, product requirement and matter
Amount requires to be selected and adjusted, and the time of hydrolysis of the present invention is preferably 1~10h, and more preferably 3~8h is optimal
It is selected as 5~6h.
The dosage of the composite catalyst is not particularly limited in the present invention, with well known to those skilled in the art similar anti-
The conventional amount used answered, those skilled in the art can select according to practical condition, product requirement and quality requirement
It selects and adjusts, the percentage that the quality of catalyst of the present invention accounts for 2, the 4- dichlorphenoxyacetic acids ester quality is preferably
0.1%~1%, more preferably 0.3%~0.8%, most preferably 0.5%~0.6%.
The selection of the composite catalyst is not particularly limited in the present invention, and those skilled in the art can be according to practical life
Production situation, product requirement and quality requirement are selected and are adjusted, and composite catalyst of the present invention preferably includes polyethers, hat
It is one or more in ether, quaternary ammonium salt, tertiary amine and quaternary phosphonium salt, and it is one or more in titanate esters, inorganic acid and organic acid
Mixture, more preferably polyethers, crown ether, quaternary ammonium salt, tertiary amine or quaternary phosphonium salt, the mixture with titanate esters, inorganic acid or organic acid.
Wherein, the crown ether is preferably crown ether or cyclic crown ether；The quaternary ammonium salt includes but not limited to tetrabutylammonium bromide；The polyethers
Including but not limited to dialkylethers；The quaternary phosphonium salt includes but not limited to tetrabutyl phosphonium bromide phosphine；The tertiary amine includes
But it is not limited to triethylamine；The inorganic acid preferably includes sulfuric acid and/or hydrochloric acid, more preferably sulfuric acid or hydrochloric acid；The organic acid
It is including but not limited to one or more in p-methyl benzenesulfonic acid, formic acid and acetic acid, more preferably p-methyl benzenesulfonic acid, formic acid or second
Acid.
The present invention is to improve the integrality and operability of technique, ensures the purity and yield of product, the hydrolysis
After the completion, preferably further include post-processing step.
The detailed process and parameter of the post-processing step is not particularly limited in the present invention, ripe with those skilled in the art
The conventional post-processing step known, those skilled in the art can be according to practical condition, product requirement and quality requirements
Selected and adjusted, post-processing step of the present invention preferably include crystallization, filtering and it is dry in it is one or more, it is more excellent
It is selected as crystallization, filtering and drying.The parameter of above-mentioned specific steps is not particularly limited in the present invention, ripe with those skilled in the art
The conventional parameter of crystallization, filtering and the drying known, those skilled in the art can be according to practical condition, product requirements
And quality requirement is selected and is adjusted.
The present invention is to improve the integrality and operability of technique, more specifically, the step C) be specifically as follows it is following
Step：
Under the action of composite catalyst, 2,4- dichlorphenoxyacetic acid esters are hydrolyzed reaction, crystallization, filtering, dry
To 2,4 dichlorophenoxyacetic acid.
Wherein, the temperature of the hydrolysis is preferably 50~200 DEG C, more preferably 70~180 DEG C, more preferably 90~
160 DEG C, most preferably 110~140 DEG C；The time of the hydrolysis is preferably 1~10h, more preferably 3~8h, most preferably
For 5~6h；The hydrolysis is preferably back flow reaction.
The crystallization temperature is preferably 10~20 DEG C；More preferably 10~15 DEG C；The crystallization time is preferably 1~
1.5h；More preferably 1~1.2h.The present invention is for the filtering and dry concrete mode without restriction, art technology
Filtering and drying mode known to personnel.
Or：
It by 2,4- dichlorphenoxyacetic acids ester and aqueous slkali mixed hydrolysis, stirring, then is mixed with acid, finally obtains 2,4- dichloros
Phenoxy acetic acid；More preferably it is specially：2,4- dichlorphenoxyacetic acid esters and aqueous slkali mixed hydrolysis, stirring, then mixed with acid, it ties
Brilliant, filtering, drying, finally obtain 2,4- dichlorphenoxyacetic acids.
Wherein, alkali is preferably one kind in sodium hydroxide, potassium hydroxide；The concentration of the aqueous slkali is preferably 30%~
40%；The mass ratio of the 2,4 dichlorophenoxyacetic acid ester and aqueous slkali is preferably 1：(1~1.5), more preferably 1：(1.1~
1.4), most preferably 1：(1.2~1.3).
The reaction temperature is preferably 90~110 DEG C；More preferably 95~105 DEG C；The reaction time is preferably 2~
4h, more preferably 2.5~3.5h；The present invention for the stirring concrete mode without limiting, those skilled in the art are ripe
The agitating mode known.
The acid is preferably sulfuric acid, hydrochloric acid or nitric acid；The concentration of the acid is preferably 10%~100%；More preferably
30%~60%；More preferably 40%~50%；The additive amount of the acid is preferably 0.1%~5%, more preferably 0.5%~
4%, most preferably 1%~3%.
The crystallization temperature is preferably 10~20 DEG C, more preferably 12~18 DEG C, more preferably 14~16 DEG C；The crystallization
Time is preferably 1~1.5h；More preferably 1~1.2h.The present invention is for the filtering and dry concrete mode without limit
It is fixed, filtering well known to those skilled in the art and drying mode.
The present invention is to improve the integrality and operability of technique, reduces the discharge and pollution of process raw material, the present invention is also
It is preferred that the polyalcohol that above-mentioned steps obtain is back to step A), to realize the circulating repetition profit of process raw material-polyalcohol
With.
Above-mentioned steps of the present invention provide the preparation method of 2,4- dichlorphenoxyacetic acids, adjusting process route of the present invention, from
On the basis of carry out inventive improvements, first use polyols preparation halogenated acetic acids ester, then with 2, the 4- Dichlorophenol reactant salts of preparation,
2,4- dichlorphenoxyacetic acid esters are prepared, the intermediate stability is good, and byproduct of reaction is few, high income, and then prepares 2 to be follow-up,
The yield and purity of 4- dichlorphenoxyacetic acids provide good condition, then hydrolysis obtains 2,4- under the action of composite catalyst
Dichlorphenoxyacetic acid and polyalcohol, the polyalcohol hydrolyzed can also reuse and during preparing halogenated acetic acids ester, realize
Process raw material recycles.Preparation process provided by the invention, simple for process, mild condition, hydrolysising by-product is few, and product is pure
Degree is high, and conversion ratio and yield are higher, and intermediate halogenated acetic acids ester is stablized, and is suitble to large-scale industrial production.Experimental result
Show that 2,4- dichlorphenoxyacetic acids prepared by the present invention, purity can reach 99.6%, yield can reach 99.6%.
In order to further illustrate the present invention, with reference to embodiments to the system of 2,4- dichlorphenoxyacetic acids provided by the invention
Preparation Method is described in detail, but it is to be understood that these embodiments are carried out lower based on the technical solution of the present invention
Implement, give detailed embodiment and specific operating process, be only the feature and advantage further illustrated the present invention,
Rather than limiting to the claimed invention, protection scope of the present invention are also not necessarily limited to following embodiments.
Embodiment 1
32g ethylene glycol, 95g (1mol) monoxone, 50g toluene and 0.1g butyl titanates are mixed, precipitation is dehydrated 6h,
Obtain monoxone second diester.2,4- sodium dichlorophenol indophenols 186g (1mol), insulated and stirred 4h are added, the chlorination that reaction generates is filtered out
Sodium solid, filtrate precipitation go out toluene, obtain 2,4- dichlorphenoxyacetic acid second diester, be added 0.1g dialkylethers,
The 0.1g concentrated sulfuric acids, 50g water, reflux dealcoholysis 5h crystallize 1h at 10 DEG C, filter, filtration cakes torrefaction, it is solid to obtain 2,4- dichlorphenoxyacetic acids
Body 221g.
The product prepared to the embodiment of the present invention 1 is detected and counts, purity 99.5%, yield 99.5%.
Embodiment 2
31g glycerine, 140g (1mol) bromoacetic acid, 50g toluene and the 0.1g concentrated sulfuric acids are mixed, precipitation is dehydrated 6h,
Obtain bromoacetic acid glyceryl ester.2,4- Dichlorophenol potassium 202g (1mol), insulated and stirred 4h is added, filters out the potassium chloride that reaction generates
Solid, filtrate precipitation go out toluene, obtain 2,4- dichlorphenoxyacetic acid glyceryl esters, be added 0.1g18 crown ethers, 0.1g p-methyl benzenesulfonic acid,
50g water, reflux dealcoholysis 5h crystallize 1h at 10 DEG C, filter, filtration cakes torrefaction obtains 2,4- dichlorphenoxyacetic acid solids 221g.
The product prepared to the embodiment of the present invention 2 is detected and counts, purity 99.6%, yield 99.6%.
Embodiment 3
183g sorbierites (1mol), 140g (1mol) bromoacetic acid, 50g toluene and the 0.1g concentrated sulfuric acids are mixed, precipitation
It is dehydrated 8h, obtains bromoacetic acid oneself six esters.2,4- Dichlorophenol potassium 202g (1mol), insulated and stirred 4h is added, filters out reaction and generates
Solid potassium chloride, filtrate precipitation goes out toluene, obtains 2,4- dichlorphenoxyacetic acids oneself six esters, be added 0.1g tetrabutyl phosphonium bromides phosphine,
0.1g acetic acid, 50g water, reflux dealcoholysis 6h crystallize 1h at 10 DEG C, filter, filtration cakes torrefaction obtains 2,4- dichlorphenoxyacetic acid solids
221g。
The product prepared to the embodiment of the present invention 1 is detected and counts, purity 99.3%, yield 99.3%.
A kind of preparation method of 2,4- dichlorphenoxyacetic acids provided by the invention is described in detail above, herein
In apply specific case principle and implementation of the present invention are described, the explanation of above example is only intended to sides
Assistant solves the method and its core concept of the present invention, including best mode, and but also any person skilled in the art all
The present invention can be put into practice, including manufactures and use any device or system, and implements the method for any combination.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvement and modification are also fallen within the protection scope of the claims of the present invention.Patent protection of the present invention
Range be defined by the claims, and may include those skilled in the art it is conceivable that other embodiment.If these
Other embodiment, which has, is not different from the structural element of claim character express, or if they include and claim
Equivalent structural elements of the character express without essence difference, then these other embodiments should also be included in the scope of the claims
It is interior.
Claims (10)
1. one kind 2, the preparation method of 4- dichlorphenoxyacetic acids, which is characterized in that include the following steps：
A polyalcohol and halogenated acetic acids) are subjected to esterification, obtain halogenated acetic acids ester；
B) the halogenated acetic acids ester and 2 for obtaining above-mentioned steps, 4- dichloro phenates are reacted, and 2,4- dichlorphenoxyacetic acids are obtained
Ester；
C) under the action of composite catalyst, reaction is hydrolyzed in 2, the 4- dichlorphenoxyacetic acid esters that above-mentioned steps obtain, is obtained
To 2,4 dichlorophenoxyacetic acid and polyalcohol；
The polyalcohol is the polyalcohol that C atomicities are more than or equal to 2.
2. preparation method according to claim 1, which is characterized in that the polyalcohol is the polyalcohol of C2~C20.
3. preparation method according to claim 1, which is characterized in that the halogenated acetic acids include monoxone, bromoacetic acid and
It is one or more in iodoacetic acid；
The 2,4- dichloros phenates include 2,4- sodium dichlorophenol indophenols, 2,4- Dichlorophenols potassium, 2,4- Dichlorophenols calcium, 2,4- Dichlorophenols magnesium,
It is one or more in 2,4- Dichlorophenols zinc and 2,4- Dichlorophenol aluminium.
4. preparation method according to claim 1, which is characterized in that the reaction promoter of the esterification includes dense sulphur
Acid；
The temperature of the esterification is 50~200 DEG C；
The time of the esterification is 1~10h.
5. preparation method according to claim 1, which is characterized in that the molar ratio of the polyalcohol and halogenated acetic acids is (1
~1.5):1.
6. preparation method according to claim 1, which is characterized in that the step B) in, the temperature of the reaction is 70
~200 DEG C；
The time of the reaction is 1~7h.
7. preparation method according to claim 1, which is characterized in that the halogenated acetic acids ester and 2,4- dichloro phenates rubs
You are than being (0.9~1.1)：(0.9~1.1).
8. preparation method according to claim 1, which is characterized in that the temperature of the hydrolysis is 50~200 DEG C；
The time of the hydrolysis is 1~10h.
9. according to the preparation method described in claim 1~8 any one, which is characterized in that the composite catalyst includes poly-
It is one or more in ether, crown ether, quaternary ammonium salt, tertiary amine and quaternary phosphonium salt, with one kind in titanate esters, inorganic acid and organic acid or more
The mixture of kind.
10. preparation method according to claim 9, which is characterized in that the quality of the composite catalyst accounts for described 2,4-
The percentage of dichlorphenoxyacetic acid ester quality is 0.1%~1%；
The inorganic acid includes sulfuric acid and/or hydrochloric acid；The organic acid include one kind in p-methyl benzenesulfonic acid, formic acid and acetic acid or
It is a variety of.
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| CN112314604A (en) * | 2020-11-03 | 2021-02-05 | 大庆华营化工有限公司 | Preparation method of efficient bactericide for polymer-containing sewage in oil field |
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|---|---|---|---|---|
| CN106242971A (en) * | 2016-08-04 | 2016-12-21 | 山东省化工研究院 | A kind of chloracetate synthesis in water technology and the new method of preparation 2,4 D esters thereof |
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2017
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|---|---|---|---|---|
| CN106242971A (en) * | 2016-08-04 | 2016-12-21 | 山东省化工研究院 | A kind of chloracetate synthesis in water technology and the new method of preparation 2,4 D esters thereof |
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| CN112314604A (en) * | 2020-11-03 | 2021-02-05 | 大庆华营化工有限公司 | Preparation method of efficient bactericide for polymer-containing sewage in oil field |
| CN112314604B (en) * | 2020-11-03 | 2021-11-12 | 大庆华营化工有限公司 | Preparation method of efficient bactericide for polymer-containing sewage in oil field |
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