CN102180804B - Method for preparing 2,4-D choline amine salt - Google Patents
Method for preparing 2,4-D choline amine salt Download PDFInfo
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- CN102180804B CN102180804B CN 201110073837 CN201110073837A CN102180804B CN 102180804 B CN102180804 B CN 102180804B CN 201110073837 CN201110073837 CN 201110073837 CN 201110073837 A CN201110073837 A CN 201110073837A CN 102180804 B CN102180804 B CN 102180804B
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Abstract
The invention discloses a method for preparing 2,4-D choline aqueous solution, which comprises the following step of: reacting choline aqueous solution with a 2,4-D technical in an alkaline environment by using water as a medium to obtain the 2,4-D choline aqueous solution, wherein the reaction temperature is between 50 and 60 DEG C. The 2,4-D choline aqueous solution and a 2,4-D choline technical can be prepared by the method. The obtained 2,4-D choline is environment-friendly, has high stability, low volatility, light peculiar smell and a wider application range, is difficult to crystallize and easy to operate and mix, hardly diffuses and drifts, and is a good substitute of a 2,4-D salt herbicide. The preparation process is simple, wastewater is not generated, distillate and mother liquid can be recycled for preparing the 2,4-D choline aqueous solution, and high environment friendliness is achieved.
Description
Technical field
The present invention relates to a kind of 2, the preparation method of 4-D amine salt, being specifically related to a kind of is the method that raw material prepares 2,4-D amine salt with the former medicine of 2,4-D and choline, belongs to preparation method's technical field of weedicide.
Background technology
2,4-D belongs to Benzene Chloride fluoroacetic acid class weedicide, also can be used as plant-growth regulator.2,4-D sterling is white crystal, and solubleness is very little in water, is soluble in the organic solvents such as ethanol, benzene, but its sodium salt, ammonium salt are then very easily water-soluble.The main formulation of 2,4-D is the missible oil of its ester class and the aqua of its amine salt.Because missible oil has greater environmental impacts, so the proportion reduced year by year of this formulation in pesticide preparation.2, although 4-D amine salt aqua belongs to environmentally friendly formulation, crystallization very easily appears in the aqua of high density, although the lower concentration aqua the crystallization situation can not occur, has but increased packing and transportation cost, also affects to a certain extent thus its use.Studies show that, 2, the 4-D choline is as 2,4-D amine salt a kind of, belong to and inhale the conduction hormone weedkiller in the selectivity, mainly be used in cereal crop, softwood tree, bare place, herbage, lawn, prevent and kill off annual and perennial broadleaf weeds, such as amaranth, lamb's-quarters, Siberian cocklebur, Herba seu Flos Convolvuli arvensis, purslane, Herba Viviae Sativae, Persian veronica, descurainia sophia (l.) webb ex prantl etc.Most of broad leaf crops, particularly cotton, very sensitive to this class weedicide, also can make processing soil treatment agent, preemergence application after soybean is broadcast.2, the 4-D choline has the effectiveness identical with 2,4-D and environment-friendly advantage, but also has more other advantages, such as low volatility, the diffusion drift is less, and peculiar smell is lighter, easy handling and being mixed, application is more extensive opportunity, and its preparation technology is simple, obtain 2,4-D choline product purity is high, stability is strong, good without dust, solvability, also be applicable to prepare 2 of various concentration, 4-D choline aqua crystallization can not occur, and is easy to use, packing and carrying cost are also lower, therefore, 2,4-D choline aqua is real environmentally friendly formulation.But, it is reported that the report of at present relevant 2,4-D choline aqua and former medicament preparation yet there are no all documents.
Summary of the invention
In order to solve problems of the prior art, the invention provides a kind of 2,4-D amine salt---the preparation method of 2,4-D choline, present method provides the preparation of 2,4-D choline aqua and the former medicine of 2,4-D choline simultaneously, preparation technology is simple, discharges without waste water, and environment-friendly type is good, and make 2,4-D choline aqua or former medicine good water solubility, stability are strong, volatility is low, the diffusion drift is less, and peculiar smell is lighter, easy handling and being mixed, application is more extensive opportunity, is the good substitute of 2,4-D class weedicide.
The present invention proposes 2, the 4-D choline amine, be 2, the 4-D salt compound provides a kind of new situation, it water-soluble strong, and stability is strong, make aqua and be difficult for crystallization, can make the high density aqua, also increase the workability of product when having reduced packing and transportation cost, be environmentally friendly formulation.
In order further to save transportation cost, can 2,4-D choline aqua is concentrated, crystallization obtains the former medicine of 2,4-D choline.The former medicine of 2,4-D choline can be used for preparing 2 of various content, and 4-D choline aqua greatly reduces packing and carrying cost, obtain 2, the former medicine purity of 4-D choline is high, stability is strong, good without dust, solvability.
For 2, the problem that exists in the 4-D class weedicide, sixty-four dollar question is to develop a kind ofly can realize environmentally friendly weedicide, as much as possible environmental contamination reduction now, and can large-scale promotion application, Cost reduction increases profit, and the contriver is through a large amount of creative researches, find 2, the 4-D choline can solve the contradiction that exists between the environmental influence and production cost in existing 2, the 4-D class weedicide, reaches simultaneously the purpose of Cost reduction and pollution abatement.In order to obtain 2,4-D choline amine, the present invention has adopted following technical scheme:
A kind of 2, the preparation method of 4-D choline aqua may further comprise the steps: with aqueous choline base solution and the former medicine of 2,4-D react take water as medium, under alkaline environment 2,4-D choline aqua, wherein, temperature of reaction is 50～60 ℃.
Among the above-mentioned preparation method, the mol ratio of described choline and the former medicine of 2,4-D is 1: 0.9 ~ 1.0; The quality percentage composition of choline can be selected 50-80% in the aqueous choline base solution.
Among the above-mentioned preparation method, reaction raw materials carries out under aqueous environment, and the add-on of water is according to required 2, the concentration of 4-D choline aqua and deciding.
Among the above-mentioned preparation method, reaction needs to carry out under alkaline environment, what alkaline environment was provided can be alkali or the alkali lye of commonly using, for example, sodium hydroxide and the aqueous solution thereof, potassium hydroxide and the aqueous solution thereof, calcium hydroxide and the aqueous solution thereof and ammoniacal liquor, the pH value of reaction system preferably is controlled at 8.0 ~ 12.0 in the reaction, and optimum pH value is 8.0 ~ 10.0.
Among the above-mentioned preparation method, reaction needs to carry out under stirring state, and the general reaction times is 35-45min.
For the ease of transportation, above-mentioned aqua can also be prepared into former medicine, and the former drug stabilisation of gained is strong, can arbitrarily be mixed with aqua, its preparation method is: with above-mentioned make 2,4-D choline aqua is evaporated to 80 ~ 90% of original volume, then is cooled to-5～5 ℃ and carries out crystallization, after the crystallization fully concentrated solution suction filtration, filter cake dried 2, the former medicine of 4-D choline.
Further, in order to be easier to crystallization, when concentrated solution is cooled to 18-20 ℃, adds the former medicine of 2,4-D choline in the concentrated solution and promote crystal formationly as nucleus, the add-on of the former medicine of 2,4-D choline accounts for 0.001～0.01% of concentrated solution quality.
In the preparation of above-mentioned former medicine, when 2,4-D choline aqua carried out concentrating under reduced pressure, the temperature when concentrated was 50～100 ℃, the relative pressure when concentrated is-0.1～-0.01Mpa.
In the preparation of above-mentioned former medicine, the filtrate of gained is 2,4-D choline saturated solution behind the suction filtration, can with carry out again concentrating under reduced pressure behind the many batches of filtrate collections, cooling adds nucleus crystallization, this process of suction filtration, also resulting filtrate can be directly used in preparation 2,4-D choline aqua.
In the preparation of above-mentioned former medicine, the speed of concentrated solution cooling is to the certain influence that is formed with of crystallization, but is not clearly, and cooling rate can be selected according to actual needs.
The invention has the beneficial effects as follows: the invention provides the preparation method of 2,4-D choline amine, 2 of gained, 4-D choline environmental friendliness, stability is strong, is difficult for crystallization, and volatility is low, the diffusion drift is less, peculiar smell is lighter, easy handling and being mixed, and application is more extensive opportunity, it is the favorable substitutes of 2,4-D salt weedicide.Preparation technology of the present invention is simple, can prepare 2 of various concentration, and 4-D choline aqua is easy to use, and packing and carrying cost are low; By 2,4-D choline aqua can prepare its former medicine, obtain 2, the former medicine purity of 4-D choline is high, stability is strong, good without dust, solvability, be applicable to prepare 2 of various concentration, 4-D choline aqua, this former medicine preparation technology is simple, non-wastewater discharge, distillate and mother liquor can be back to its aqua of preparation, and the feature of environmental protection is good.
Embodiment
The invention will be further described below in conjunction with specific embodiment, should be understood that, following explanation only is in order to explain the present invention, its content not to be limited.
Embodiment 1
In being housed, the 1L reactor of stirring, cooling and vacuum distillation apparatus adds 100.0g aqueous choline base solution (content of choline is 50%), 95.1g2, the former medicine of 4-D (content 96%) and 135.8g water, stirring makes its reaction, the pH value of control reaction system is 8.0 ~ 10.0, emit heat in the reaction process, temperature of reaction rises to 50 ℃ very soon, continues to stir and 50 ~ 55 ℃ of isothermal reaction 45min, can obtain 2 of 720g/L, 4-D choline aqua.
Embodiment 2-6
Prepare 2,4-D choline aqua according to the operation steps among the embodiment 1, other conditions are constant, used content of choline, 2, and pH value, reaction times and the temperature of 4-D add-on, water add-on, reaction system are as shown in table 1 below.
Embodiment 7
With 2 of embodiment 1 gained, 4-D choline aqua is placed in the 1L reactor that stirring, cooling and vacuum distillation apparatus are housed and concentrates, adopt water bath heating that reactor is heated, and reactor vacuumized make its relative pressure be-0.01MPa, reaction solution comes to life when bath temperature is 50 ℃, in order better to concentrate, continue the rising bath temperature, and hold it in 70 ~ 85 ℃ and concentrate, by the time the distillate quality is when being 49.6g, stop to vacuumize, begin simultaneously cooling.Add 2 of 0.017g when temperature is down to 18.0 ℃, 4-D choline nucleus at this moment will soon crystallize out, continuation is at the whipped state borehole cooling, stir 10min, when temperature is down to-5 ℃, stop cooling, and carry out suction filtration and separate, obtain 2, the 4-D choline product 133.8g that wets, mother liquor 147.5g, after the oven dry 2,4-D choline 130.9g, content are 98.3%.
Embodiment 8
With 2 of embodiment 2 gained, 4-D choline aqua, vacuumize and heat up, vacuum tightness is-0.05MPa in reactor, reacting liquid temperature comes to life when being 50 ℃, continues the rising bath temperature and remain on 50 ~ 70 ℃ to concentrate, by the time the distillate quality is when being 95.5g, stop to vacuumize, begin simultaneously cooling.Add 2 of 0.004g when temperature is down to 18.5 ℃, 4-D choline nucleus at this moment will soon crystallize out, continuation is at the whipped state borehole cooling, stir 15min, when temperature is down to-2 ℃, stop cooling, and carry out suction filtration and separate, obtain 2, the 4-D choline product 149.5g that wets, mother liquor 232.7g, after the oven dry 2,4-D choline 146.8g, content are 98.5%.
Embodiment 9
With 2 of embodiment 3 gained, 4-D choline aqua, vacuumize and heat up, vacuum tightness is-0.03MPa in reactor, come to life during 50 ℃ of reacting liquid temperatures, continue the rising bath temperature and also remain on 60 ~ 80 ℃, by the time the distillate quality is when being 78.5g, stop to vacuumize, begin simultaneously cooling.Add 2 of 0.011g when temperature is down to 19.0 ℃, 4-D choline nucleus at this moment will soon crystallize out, continuation is at the whipped state borehole cooling, stir 20min, when temperature is down to 0 ℃, stop cooling, and carry out suction filtration and separate, obtain 2, the 4-D choline product 175.8g that wets, mother liquor 181.8g, after the oven dry 2,4-D choline 172.5g, content are 98.1%.
Embodiment 10
With 2 of embodiment 4 gained, 4-D choline aqua, vacuumize and heat up, vacuum tightness is-0.07MPa in reactor, come to life during 50 ℃ of reacting liquid temperatures, continue the rising bath temperature and also remain on 85 ~ 100 ℃, by the time the distillate quality is when being 41.5g, stop to vacuumize, begin simultaneously cooling.Add 2 of 0.030g when temperature is down to 19.6 ℃, 4-D choline nucleus at this moment will soon crystallize out, continuation is at the whipped state borehole cooling, stir 25min, when temperature is down to 3 ℃, stop cooling, and carry out suction filtration and separate, obtain 2, the 4-D choline product 183.1g that wets, mother liquor 190.4g, after the oven dry 2,4-D choline 180.6g, content are 98.4%.
Embodiment 11
With 2 of embodiment 5 gained, 4-D choline aqua, vacuumize and heat up, vacuum tightness is-0.10MPa in reactor, come to life during 50 ℃ of reacting liquid temperatures, continue the rising bath temperature and also remain on 75 ~ 90 ℃, by the time the distillate quality is when being 52.9g, stop to vacuumize, begin simultaneously cooling.Add 2 of 0.039g when temperature is down to 20.0 ℃, 4-D choline nucleus at this moment will soon crystallize out, continuation is at the whipped state borehole cooling, stir 30min, when temperature is down to 5 ℃, stop cooling, and carry out suction filtration and separate, obtain 2, the 4-D choline product 192.8g that wets, mother liquor 195.5g, after the oven dry 2,4-D choline 189.1g, content are 98.2%.
Embodiment 12
With 2 of embodiment 6 gained, 4-D choline aqua, vacuumize and heat up, vacuum tightness is-0.05MPa in reactor, come to life during 50 ℃ of reacting liquid temperatures, continue the rising bath temperature and also remain on 75 ~ 85 ℃, by the time the distillate quality is when being 73.3g, stop to vacuumize, begin simultaneously cooling.Add 2 of 0.021g when temperature is down to 19.1 ℃, 4-D choline nucleus at this moment will soon crystallize out, continuation is at the whipped state borehole cooling, stir 28min, when temperature is down to-3 ℃, stop cooling, and carry out suction filtration and separate, obtain 2, the 4-D choline product 165.4g that wets, mother liquor 250.1g, after the oven dry 2,4-D choline 162.2g, content are 98.5%.
Claims (8)
1. one kind 2, the preparation method of 4-D choline aqua is characterized in that may further comprise the steps: with aqueous choline base solution and the former medicine of 2,4-D take water as medium, the pH value react under 8.0 ~ 12.0 the environment 2,4-D choline aqua, wherein, temperature of reaction is 50～60 ℃.
2. preparation method according to claim 1, it is characterized in that: the mol ratio of described choline and the former medicine of 2,4-D is 1: 0.9 ~ 1.0; The quality percentage composition of choline is 50-80% in the aqueous choline base solution.
3. preparation method according to claim 1 is characterized in that: the add-on of water is according to required 2, the concentration of 4-D choline aqua and deciding.
4. preparation method according to claim 1, it is characterized in that: the pH value of reaction system is 8.0 ~ 10.0 in the reaction.
5. each described preparation method according to claim 1-4, it is characterized in that: described reaction is carried out under stirring state, and the reaction times is 35-45min.
6. one kind 2, the preparation method of the former medicine of 4-D choline, it is characterized in that, prepare 2,4-D choline aqua by any method described in the claim 1-5, then will make 2,4-D choline aqua carries out following processing: 2,4-D choline aqua is evaporated to 80 ~ 90% of original volume, then is cooled to-5～5 ℃ and carries out crystallization, after the crystallization fully concentrated solution suction filtration, filter cake dried 2, the former medicine of 4-D choline; The filtrate cycle utilization of gained behind the suction filtration is used for preparation 2,4-D choline aqua, perhaps will concentrate after many batches of filtrates merging, decrease temperature crystalline prepares the former medicine of 2,4-D choline again.
7. preparation method according to claim 6 is characterized in that: when concentrated solution is cooled to 18-20 ℃, adds the former medicine of 2,4-D choline in the concentrated solution and promote crystal formationly, the add-on of the former medicine of 2,4-D choline accounts for 0.001～0.01% of concentrated solution quality.
8. preparation method according to claim 6, it is characterized in that: when 2,4-D choline aqua carried out concentrating under reduced pressure, temperature was 50～100 ℃, relative pressure is-0.1～-0.01Mpa.
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| CN 201110073837 CN102180804B (en) | 2011-03-25 | 2011-03-25 | Method for preparing 2,4-D choline amine salt |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102390352A (en) * | 2011-08-18 | 2012-03-28 | 杨向东 | Automobile anti-theft device of employing machine reading function of second generation ID (identity card) card |
| CN102835395A (en) * | 2012-09-28 | 2012-12-26 | 山东潍坊润丰化工有限公司 | Preparation method of MCPA (2-methyl-4-chloro-phenoxyacetic acid) choline water aqua and raw drug |
| CN102845423A (en) * | 2012-09-28 | 2013-01-02 | 山东潍坊润丰化工有限公司 | Method for preparing dicamba cholinergic agent and dicamba cholinergic active compound |
| CN103086896A (en) * | 2013-01-25 | 2013-05-08 | 山东潍坊润丰化工有限公司 | Method for preparing 2, 4-D choline |
| CN104277071B (en) * | 2013-12-30 | 2017-03-08 | 山东潍坊润丰化工股份有限公司 | A kind of glyphosate choline raw drug, preparation and preparation method thereof |
| CN109761825A (en) * | 2017-11-09 | 2019-05-17 | 山东润博生物科技有限公司 | A kind of preparation method of carboxylic acid cholinomimetic |
| CN109761790A (en) * | 2017-11-09 | 2019-05-17 | 山东润博生物科技有限公司 | A kind of preparation method of carboxylic acid cholinomimetic |
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| CN101525288A (en) * | 2009-04-21 | 2009-09-09 | 山东潍坊润丰化工有限公司 | Preparation method of 2, 4-D dimethylamine salt material drug |
| CN101636089A (en) * | 2007-02-26 | 2010-01-27 | 陶氏益农公司 | Compounds derived from herbicidal carboxylic acids and tetraalkylammonium or (arylalkyl) trialkylammonium hydroxides |
| WO2010123871A1 (en) * | 2009-04-22 | 2010-10-28 | Dow Agrosciences Llc | High-strength, herbicidal compositions of glyphosate and 2,4-d salts |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101636089A (en) * | 2007-02-26 | 2010-01-27 | 陶氏益农公司 | Compounds derived from herbicidal carboxylic acids and tetraalkylammonium or (arylalkyl) trialkylammonium hydroxides |
| CN101525288A (en) * | 2009-04-21 | 2009-09-09 | 山东潍坊润丰化工有限公司 | Preparation method of 2, 4-D dimethylamine salt material drug |
| WO2010123871A1 (en) * | 2009-04-22 | 2010-10-28 | Dow Agrosciences Llc | High-strength, herbicidal compositions of glyphosate and 2,4-d salts |
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