CN103086960A - Novel process for producing chlopyrifos from pyridone by using aqueous phase method - Google Patents
Novel process for producing chlopyrifos from pyridone by using aqueous phase method Download PDFInfo
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- CN103086960A CN103086960A CN2011103301666A CN201110330166A CN103086960A CN 103086960 A CN103086960 A CN 103086960A CN 2011103301666 A CN2011103301666 A CN 2011103301666A CN 201110330166 A CN201110330166 A CN 201110330166A CN 103086960 A CN103086960 A CN 103086960A
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Abstract
The invention relates to a novel process for producing chlopyrifos from pyridone by using an aqueous phase method, and belongs to the field of chemical synthesis. The novel process is finished by the following steps of mixing trichloro-acetic chloride, acrylonitrile and a solvent according to a certain molar ratio to form the pyridine under the effect of a catalyst; putting desalinized water, pyridone, sodium chloride, caustic soda flake (adjusting pH value of the system within 8 to 10), boric acid, an emulsifier and a phase-transfer catalyst into a condensation kettle successively; stirring uniformly; adding a certain amount of 0,0-diethyl thiophosphoryl chloride slowly; reacting at a temperature of 45-50 DEG C to form a chlopyrifos solution; layering; dehydrating; press filtering; cooling; crystallizing; centrifuging for separation and drying to obtain a raw powder of the chlopyrifos with a purity higher than 99%. The novel process reduces production cost, has little process wastewater and can synthesize the raw powder of the chlopyrifos with relatively high purity.
Description
Technical field
The present invention relates to a kind of novel process for preparing Chlorpyrifos 94, belong to chemical industry and synthesize the field.
Background technology
The chemical name of Chlorpyrifos 94 is 0,0-diethyl-0-(3,5,6 ,-trichloro-2-pyridyl) thiophosphatephosphorothioate.It is a kind of high-efficiency broad spectrum, the organophosphorus desinsection miticide of middle low toxicity, safety, to replace riskiest pesticide one of product preferably, can effectively prevent and treat snout moth's larva, tortrix moth, leaf miner, bollworm, mythimna separata, scale insect, aphid, thrips, leafhopper and various acarid on vegetables, corn, tealeaves, fruit tree and flowers etc., also can prevent and treat the external parasite of subterranean pest-insect and domestic animal, having a extensive future, is a kind of at first kind that replaces riskiest pesticide.
Generally the production method of Chlorpyrifos 94 is divided into organic solvent method, Double solvent method and water method according to reaction conditions.Organic solvent method is solvent mainly with methylene dichloride and benzene greatly, and test-results shows, not only do not improve yield, and solvent load is large, and loss is serious, has increased production cost.Although Double solvent method can suppress the hydrolysis of 0,0-o,o-diethylthiophosphoryl chloride preferably, this method also needs to consume organic solvent, and is very large to environment thus, and organic solvent toxicity is high, can damage HUMAN HEALTH and increase production cost.The water method can overcome a large amount of organic solvents of consumption in organic solvent method and Double solvent method well, increases production cost, and the very large shortcoming of environmental pollution.Usually the water method of Chlorpyrifos 94 is that the pyridine sodium alkoxide is added to the water, and after adding phase-transfer catalyst, then drips 0,0-o,o-diethylthiophosphoryl chloride, and decrease temperature crystalline directly gets the Chlorpyrifos 94 powder.
The present invention replaces the pyridine sodium alkoxide to carry out the preparation of Chlorpyrifos 94 with pyridone, pyridone is a kind of intermediate product of producing the pyridine sodium alkoxide, the present invention compared with prior art, have the advantages that to save solvent, reduce three industrial wastes and enhance productivity, the technique environmental protection, the alkaline hydrolysis of saving over, the centrifugal or links such as press filtration, drying greatly reduce production cost, are suitable for large-scale industrial production.
Summary of the invention
The objective of the invention is to overcome the shortcoming of existing synthetic method, provide a kind of conservation, easy operation also can obtain the production method of the higher Chlorpyrifos 94 of yield.
The present invention is that a kind of pyridone preparation and water method production Chlorpyrifos 94 novel process is characterized in that
(1) new distilled trichoroacetic chloride, vinyl cyanide, solvent are reacted in 90-120 ℃ under the cuprous chloride catalyst effect so that the certain mol proportion mixing is rear, and remove the hydrogen chloride gas of institute's output by under refluxad operation, generate 2,2,4-, three chloro-4-cyano group butyryl chloride dilute solutions.
(2) 2,2,4-, three chloro-4-cyano group butyryl chloride mixed solutions are carried out underpressure distillation, reclaim unreacted raw material (being mainly vinyl cyanide, trichoroacetic chloride and partial solvent), filter out catalyzer, filtrate is 2,2,4-, three chloro-4-cyano group butyryl chloride strong solutions.
(3) adding appropriate solvent in 2,2,4-, three chloro-4-cyano group butyryl chloride strong solutions, is that 30-150KPa, temperature are to react under the effect of 30-100 ℃ and catalyzer to generate pyridone solution in gauge pressure.Pyridone solution is carried out obtaining dry pyridone after crystallisation by cooling, separation.
(4) phase-transfer catalyst of the emulsifying agent of the boric acid of the sheet alkali (the regulation system pH value is at 8-10) of the sodium-chlor of the pyridone of the water of 3-4 weight part, 0.8-1.2 weight part, 0.2-0.25 weight part, 0.04-0.06 weight part, 0.03-0.04 weight part, 0.001-0.003 weight part and 0.0005-0.0008 weight part is dropped in condensation kettle successively stir, then slowly drip 0 of 0.7-0.9 weight part, the 0-o,o-diethylthiophosphoryl chloride.Because of heat release in reaction process, system temperature can from rising, must be controlled temperature of reaction at 45～50 ℃.Drip the follow-up continuation of insurance temperature of diethylaluminum monochloride reaction 1h, then stop condensation kettle and stir, controlling temperature is 50 ± 2 ℃, is incubated layering after standing 2h, lower floor's (oil phase) imports prepares in the drainage still to filter, and upper strata (water) imports in extraction kettle and extract.
(5) add again a certain amount of de-salted water at the drainage still, and add flocculating aids, begin to filter under 60 ± 3 ℃ after the stirring certain hour.Filtrate imports in quantizer, controls temperature at 60 ± 3 ℃, be incubated layering after standing 2h, and lower floor's (oil phase) imports dehydrating kettle, applies mechanically when next condensation in upper strata (water) importing condensation kettle.
(6) crude oil that imports dehydrating kettle carries out processed.Require vacuum tightness 〉=0.08MPa in whole dehydration, temperature is 60 ± 3 ℃, until in crude oil, moisture content is qualified.Oil phase after dehydration obtains purity greater than the former powder of 99% Chlorpyrifos 94 through press filtration, cooling, crystallization, centrifugation, drying.
Embodiment
Embodiment 1:
Add new distilled trichoroacetic chloride 200g, vinyl cyanide 87g, solvent 566g, cuprous chloride 0.66g in the 1000ml flask, react in 90-120 ℃, and remove the hydrogen chloride gas of institute's output by under refluxad operation, generate 2,2,4-, three chloro-4-cyano group butyryl chloride dilute solutions.
2,2,4-, three chloro-4-cyano group butyryl chloride mixed solutions are carried out underpressure distillation, reclaim unreacted raw material (being mainly vinyl cyanide, trichoroacetic chloride and partial solvent), filter out catalyzer, filtrate is 2,2,4-, three chloro-4-cyano group butyryl chloride strong solutions.
Adding appropriate solvent in 2,2,4-, three chloro-4-cyano group butyryl chloride strong solutions, is that 30-150KPa, temperature are to react under the effect of 30-100 ℃ and catalyzer to generate pyridone solution in gauge pressure.Pyridone solution is carried out obtaining dry pyridone after crystallisation by cooling, separation.
Add water 300g in the flask of 500mL, pyridone 78.4g, add by a certain percentage 1 of catalyzer 0.05g, boric acid 2.8g, refined salt 18g, alkali 1.5g and emulsifying agent, then begin to drip diethylaluminum monochloride 65.5g, 40～50 ℃ of reactions 3 hours, control reaction end and get Chlorpyrifos 94, get Chlorpyrifos 94 after washing, layering, dehydration, yield is more than 97%, and content is more than 99%.
Embodiment 2:
Add new distilled trichoroacetic chloride 990kg, vinyl cyanide 435kg, solvent 2830g, cuprous chloride 3.3kg in the 5000L reactor, react in 90-120 ℃, and remove the hydrogen chloride gas of institute's output by under refluxad operation, generate 2,2,4-, three chloro-4-cyano group butyryl chloride dilute solutions.
2,2,4-, three chloro-4-cyano group butyryl chloride mixed solutions are carried out underpressure distillation, reclaim unreacted raw material (being mainly vinyl cyanide, trichoroacetic chloride and partial solvent), filter out catalyzer, filtrate is 2,2,4-, three chloro-4-cyano group butyryl chloride strong solutions.
Adding appropriate solvent in 2,2,4-, three chloro-4-cyano group butyryl chloride strong solutions, is that 30-150KPa, temperature are to react under the effect of 30-100 ℃ and catalyzer to generate pyridone solution in gauge pressure.Pyridone solution is carried out obtaining dry pyridone after crystallisation by cooling, separation.
Add water 3000kg in the reactor of 3000L, pyridone 784kg, add by a certain percentage catalyzer 0.5kg, refined salt 180kg, boric acid 28kg, alkali 15kg and emulsifying agent 1.5kg, then slowly 655kg drips diethylaluminum monochloride, drips the follow-up continuation of insurance temperature of diethylaluminum monochloride reaction 1h, then stops condensation kettle and stirs, controlling temperature is 50 ± 2 ℃, be incubated layering after standing 2h, lower floor's (oil phase) imports prepares in the drainage still to filter, and upper strata (water) imports in extraction kettle and extract.
Add again a certain amount of de-salted water at the drainage still, and add flocculating aids, begin to filter under 60 ± 3 ℃ after the stirring certain hour.Filtrate imports in quantizer, controls temperature at 60 ± 3 ℃, be incubated layering after standing 2h, and lower floor's (oil phase) imports dehydrating kettle, applies mechanically when next condensation in upper strata (water) importing condensation kettle.
The crude oil that imports dehydrating kettle carries out processed.Require vacuum tightness 〉=0.08MPa in whole dehydration, temperature is 60 ± 3 ℃, until in crude oil, moisture content is qualified.Oil phase after dehydration obtains purity greater than the former powder of 99% Chlorpyrifos 94 through press filtration, cooling, crystallization, centrifugation, drying, and yield is more than 97%.
Claims (6)
1. a pyridone prepares and water method production Chlorpyrifos 94 novel process, and its feature comprises following process:
(1) new distilled trichoroacetic chloride, vinyl cyanide, certain solvent are reacted in 90-120 ℃ under the cuprous chloride catalyst effect so that the certain mol proportion mixing is rear, and remove the hydrogen chloride gas of institute's output by under refluxad operation, generate 2,2,4-, three chloro-4-cyano group butyryl chloride dilute solutions.
(2) 2,2,4-, three chloro-4-cyano group butyryl chloride mixed solutions are carried out underpressure distillation, reclaim unreacted raw material (being mainly vinyl cyanide, trichoroacetic chloride and partial solvent), filter out catalyzer, filtrate is 2,2,4-, three chloro-4-cyano group butyryl chloride strong solutions.
(3) adding appropriate solvent in 2,2,4-, three chloro-4-cyano group butyryl chloride strong solutions, is that 30-150KPa, temperature are to react under the effect of 30-100 ℃ and catalyzer to generate pyridone solution in gauge pressure.Pyridone solution is carried out obtaining dry pyridone after crystallisation by cooling, separation.
(4) phase-transfer catalyst of the emulsifying agent of the boric acid of the sheet alkali (the regulation system pH value is at 8-10) of the sodium-chlor of the pyridone of the de-salted water of 3-4 weight part, 0.8-1.2 weight part, 0.2-0.25 weight part, 0.04-0.06 weight part, 0.03-0.04 weight part, 0.001-0.003 weight part and 0.0005-0.0008 weight part is dropped in condensation kettle successively stir, then slowly drip 0 of 0.7-0.9 weight part, the 0-o,o-diethylthiophosphoryl chloride.Because of heat release in reaction process, system temperature can from rising, must be controlled temperature of reaction at 45～50 ℃.Drip the follow-up continuation of insurance temperature of diethylaluminum monochloride reaction 1h, then stop condensation kettle and stir, controlling temperature is 50 ± 2 ℃, is incubated layering after standing 2h, lower floor's (oil phase) imports prepares in the drainage still to filter, and upper strata (water) imports in extraction kettle and extract.
(5) add again a certain amount of de-salted water at the drainage still, and add flocculating aids, begin to filter under 60 ± 3 ℃ after the stirring certain hour.Filtrate imports in quantizer, controls temperature at 60 ± 3 ℃, be incubated layering after standing 2h, and lower floor's (oil phase) imports dehydrating kettle, applies mechanically when next condensation in upper strata (water) importing condensation kettle.
(6) crude oil that imports dehydrating kettle carries out processed.Require vacuum tightness 〉=0.08MPa in whole dehydration, temperature is 60 ± 3 ℃, until in crude oil, moisture content is qualified.Oil phase after dehydration obtains purity greater than the former powder of 99% Chlorpyrifos 94 through press filtration, cooling, crystallization, centrifugation, drying.
(7) add again a certain amount of dimethylbenzene to extraction kettle, standing 2h layering after stirring 2～30min under 40～50 ℃.Lower floor's water is drained, and upper oil phase is stayed in extraction kettle in order to continuing to apply mechanically.Apply mechanically and add a certain amount of flocculating aids in the oil phase after three times, carry out vacuum filtration in the rear importing suction filtration tank that stirs.Import in oily quantizer standing 2h after suction filtration with higher slice.With a small amount of aqueous phase layer discharging of lower floor, obtain containing the xylene solution of finite concentration Chlorpyrifos 94 after upper oil phase layer importing precipitation still carrying out precipitation treatment, allocate rear for the production of chlorpyrifos ec with the former powder of Chlorpyrifos 94.
2. a kind of pyridone preparation according to claim 1 and water method are produced the Chlorpyrifos 94 novel process, it is characterized in that certain solvent in (1) can be orthodichlorobenzene, chlorobenzene, oil of mirbane, toluene etc., vinyl cyanide, trichoroacetic chloride, certain solvent molar feed ratio are 1: 1.5～2.0: 4.3.
3. a kind of pyridone preparation according to claim 1 and water method are produced the Chlorpyrifos 94 novel process, it is characterized in that the pyridone in (3), (4) refers to 3,3,5,6-tetrachloro-3,4-dihydropyridine-2-ketone.(3) solvent in can be one or more in orthodichlorobenzene, chlorobenzene, oil of mirbane, toluene etc., can be also the solution that in (3), pyridone solution is carried out crystallisation by cooling, obtains after separating.(3) catalyzer in can be the halogenide of dry hydrogen chloride gas, zinc, one or more in Vanadium Pentoxide in FLAKES, and its quality is 0.012% of solution total amount.
4. a kind of pyridone preparation according to claim 1 and water method are produced the Chlorpyrifos 94 novel process, it is characterized in that the emulsifying agent in (4) can be sulfonate surfactant, Sulfates tensio-active agent, quaternary ammonium salt surface active agent, betaines tensio-active agent, humic-acid kind polymeric surface active agent or some specific surfactants such as 0213-L etc.
5. a kind of pyridone preparation according to claim 1 and water method are produced the Chlorpyrifos 94 novel process, it is characterized in that the phase-transfer catalyst in (4) can be high fatty amine class or quaternary ammonium salt surface active agent, as alkyl trimethyl ammonium halide, benzyl dimethyl ethyl ammonium halide, DMAP etc.
6. a kind of pyridone preparation according to claim 1 and water method are produced the Chlorpyrifos 94 novel process, it is characterized in that flocculating aids in (5), (7) can be one or both and the two or more component in diatomite, perlite, Mierocrystalline cellulose, asbestos, Graphite Powder 99, sawdust, magnesium oxide, gypsum, gac.
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| CN2011103301666A CN103086960A (en) | 2011-10-27 | 2011-10-27 | Novel process for producing chlopyrifos from pyridone by using aqueous phase method |
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| CN2011103301666A CN103086960A (en) | 2011-10-27 | 2011-10-27 | Novel process for producing chlopyrifos from pyridone by using aqueous phase method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104402926A (en) * | 2014-11-03 | 2015-03-11 | 天津河清化学工业有限公司 | Continuously-synthesized chlorpyrifos step-by-step crystallization process |
| CN104710350A (en) * | 2015-03-17 | 2015-06-17 | 湖北犇星农化有限责任公司 | Synthesis method of sodium trichloro pyridinol |
Citations (3)
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| CN1047281A (en) * | 1989-05-12 | 1990-11-28 | 陶氏化学公司 | Preparation 3,5, the improving one's methods of 6-trichloropyridine-2-alcohol |
| CN101709065A (en) * | 2009-11-13 | 2010-05-19 | 安徽广信农化股份有限公司 | Process for preparing chlorpyrifos |
| CN101735273A (en) * | 2008-11-13 | 2010-06-16 | 吴士成 | Method for producing 3,5,6-trichloro-2-pyridyl fenitrothion propyl ester |
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2011
- 2011-10-27 CN CN2011103301666A patent/CN103086960A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047281A (en) * | 1989-05-12 | 1990-11-28 | 陶氏化学公司 | Preparation 3,5, the improving one's methods of 6-trichloropyridine-2-alcohol |
| CN101735273A (en) * | 2008-11-13 | 2010-06-16 | 吴士成 | Method for producing 3,5,6-trichloro-2-pyridyl fenitrothion propyl ester |
| CN101709065A (en) * | 2009-11-13 | 2010-05-19 | 安徽广信农化股份有限公司 | Process for preparing chlorpyrifos |
Non-Patent Citations (1)
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| 邓燕清: "三氯乙酰氯合成述评", 《湖北化工》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104402926A (en) * | 2014-11-03 | 2015-03-11 | 天津河清化学工业有限公司 | Continuously-synthesized chlorpyrifos step-by-step crystallization process |
| CN104402926B (en) * | 2014-11-03 | 2016-11-02 | 天津河清化学工业有限公司 | It is continuously synthesizing to the Steppecd crystallization of chlopyrifos |
| CN104710350A (en) * | 2015-03-17 | 2015-06-17 | 湖北犇星农化有限责任公司 | Synthesis method of sodium trichloro pyridinol |
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Application publication date: 20130508 |