CN113698430B - Preparation method of herbicide anilofos - Google Patents
Preparation method of herbicide anilofos Download PDFInfo
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- CN113698430B CN113698430B CN202111266718.1A CN202111266718A CN113698430B CN 113698430 B CN113698430 B CN 113698430B CN 202111266718 A CN202111266718 A CN 202111266718A CN 113698430 B CN113698430 B CN 113698430B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/1651—Esters of thiophosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/143—X-type faujasite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
Abstract
The invention discloses a preparation method of herbicide anilofos, which comprises the steps of preparing hollow microspheres, preparing a catalyst, preparing N-chloroacetyl-N-isopropyl-p-chloroaniline and preparing anilofos; the preparation method comprises the following steps of placing X-type porous zeolite powder in a calcining furnace, calcining to obtain calcined X-type porous zeolite powder, mixing the calcined X-type porous zeolite powder with absolute ethyl alcohol, dimethyl diallyl ammonium chloride, acetic acid and nickel nitrate, and then performing ultrasonic dispersion to obtain a dispersed raw material after the ultrasonic dispersion is finished; freezing the dispersed raw materials, slowly heating, and stirring at 90-100 deg.C; the method for preparing the anilofos can improve the yield and the purity of the anilofos raw pesticide, reduce the granularity of the prepared anilofos raw pesticide and improve the uniformity and the fluidity of the granularity distribution.
Description
Technical Field
The invention relates to a preparation method of herbicide anilofos, belonging to the technical field of herbicides.
Background
The anilofos is a white or milky powder with 96% content, density of 1.4(20 deg.C), melting point of 47-50 deg.C, decomposition at 150 deg.C, light insensitivity, stability at pH 5-9 and temperature of 22 deg.C, half-life period in soil of 30-45 days (23 deg.C), brown liquid appearance, phosphate smell, and storage stability at normal temperature of 2 years.
The anilofos is mainly used for paddy rice, belongs to an organic phosphorus selective systemic conduction herbicide, and is absorbed by young buds and underground stems of plants to inhibit cell fission and extension, so that new leaves of weeds are not easy to draw out, the growth stops, and the weeds are died finally, and the effect on the normal-germinating weeds is the best; the effect on grown weeds is poor, the weeds stop growing after receiving the herbicide, the leaves are dark green and are decolorized sometimes, the leaves are shortened and thick, the leaves are easy to break, the core leaves are not easy to pull out, and finally the whole plant withers, so that the barnyard grass and cyperaceae weeds in the 3-leaf period can be effectively prevented and killed, and the herbicide is safe for rice.
The main control objects of anilofos include annual grassy weeds and sedges such as barnyard grass, moleplant seed, cyperus rotundus, monochoria vaginalis, fimbristylis, petaloides, and the like.
The existing preparation method of anilofos technical comprises the following steps: p-chloronitrobenzene, chloroacetephthalein chloride and the like are used as main raw materials, and are subjected to reduction alkylation, phthalylation and condensation for 3 steps to synthesize the raw anilofos; p-chloroaniline and chloro-isopropyl propane are used as initial raw materials, an intermediate 4-chloro-N-isopropyl aniline is prepared through alkylation, an intermediate 2-chloro-N- (4-chlorphenyl) -N- (isopropyl) acetamide is prepared through acylation, and finally a anilofos technical is prepared through condensation reaction; condensation reaction of 2-chloro-N- (4-chlorophenyl) -N-isopropyl acetamide with an aqueous solution of a methyl sulfide salt in the presence of a phase transfer catalyst, and the like.
However, the anilofos raw material prepared by the method has the advantages of large particle size, uneven particle size distribution and poor liquidity, and when the anilofos raw material is prepared into a preparation, grinding treatment or other pretreatment is needed, but other impurities are easily introduced in the grinding or other pretreatment processes, so that the use effect of the anilofos is influenced; if the granularity is controlled in the preparation process of the anilofos raw pesticide, the production difficulty is increased, and the yield and the purity of the anilofos are influenced. Therefore, the development of a method for preparing the anilofos technical material can reduce the granularity of the prepared anilofos technical material and improve the uniformity and the fluidity of the granularity distribution while improving the yield and the purity of the anilofos technical material, and is a technical problem which is urgently needed to be solved at present.
Patent CN102260287B discloses a preparation method of herbicide anilofos, which specifically comprises the following steps: preparing anilofos by using water as a solvent, adding a proper amount of phase transfer catalyst in the reaction, completing condensation and crystallization in one step, cooling the reaction liquid after the reaction is finished, directly separating the anilofos into crystals in the water, and filtering, washing and drying to obtain an anilofos product; the patent has the following defects: the prepared anilofos technical material has larger granularity and uneven granularity distribution.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the preparation method of the herbicide anilofos, which can reduce the granularity of the prepared anilofos raw material and improve the uniformity degree and the fluidity of the granularity distribution while improving the yield and the purity of the anilofos raw material.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a process for preparing the herbicide anilofos includes preparing hollow microballs, preparing catalyst, preparing N-chloroacetyl-N-isopropyl-p-chloroaniline, and preparing anilofos.
Preparing hollow microspheres, namely placing X-type porous zeolite powder in a calcining furnace, controlling the temperature of the calcining furnace to be 350-400 ℃, calcining for 2-3h to obtain calcined X-type porous zeolite powder, mixing the calcined X-type porous zeolite powder with absolute ethyl alcohol, a dimethyl diallyl ammonium chloride aqueous solution, acetic acid and nickel nitrate, and then performing ultrasonic dispersion, controlling the frequency of the ultrasonic dispersion to be 20-30kHz, and the time of the ultrasonic dispersion to be 20-30min, and obtaining a dispersed raw material after the ultrasonic dispersion is finished; cooling the dispersed raw materials to-20 to-10 ℃, freezing the raw materials at-20 to-10 ℃ for 30 to 40min, slowly heating the raw materials to 90 to 100 ℃, controlling the heating speed to be 2 to 3 ℃/min, and heating the raw materials to 90 to 100 ℃ to obtain the frozen raw materials; then controlling the temperature to 90-100 ℃, stirring the frozen raw materials at the stirring speed of 200-220rpm for 1.5-2h, and stopping stirring to obtain the hollow microspheres.
The mass ratio of the calcined X-type porous zeolite powder to absolute ethyl alcohol, dimethyl diallyl ammonium chloride aqueous solution, acetic acid and nickel nitrate in the step of preparing the hollow microspheres is 10-12:35-40:1-2:3-5: 1-2.
The particle size of the X-type porous zeolite powder is 0.3-0.5 mu m.
The mass percent of the dimethyl diallyl ammonium chloride in the dimethyl diallyl ammonium chloride aqueous solution is 65%.
The preparation of the catalyst comprises the steps of mixing hollow microspheres, PEG400, Tween 80, potassium nitrate and water, adding the mixture into a microwave reactor for reaction, controlling the temperature of the microwave reactor to be 50-55 ℃, the microwave power to be 600-700W, and the reaction time to be 1-1.5h, and obtaining the hollow microspheres after primary treatment after the reaction is finished; and then mixing the primarily treated hollow microspheres, 45-55% of sulfuric acid aqueous solution and potassium persulfate, then acidifying, controlling the acidification temperature to be 40-45 ℃ and the acidification time to be 30-40min, carrying out vacuum spray drying after the acidification is finished, controlling the vacuum degree of the vacuum spray drying to be 0.05-0.06MPa, controlling the inlet temperature to be 90-100 ℃ and the outlet temperature to be 50-60 ℃, and finishing the vacuum spray drying to obtain the catalyst.
In the step of preparing the catalyst, the mass ratio of the hollow microspheres, PEG400, Tween 80, potassium nitrate and water is 35-40:15-17:2-3:1-3: 90-100.
The hollow microspheres subjected to primary treatment in the catalyst preparation step comprise 45-55% of sulfuric acid aqueous solution and 20-25:35-40:1-3 of potassium persulfate by mass.
The preparation method comprises the steps of preparing N-chloroacetyl-N-isopropyl-p-chloroaniline, placing the N-isopropyl-p-chloroaniline in a reactor, heating the reactor to 50-55 ℃, starting stirring of the reactor, controlling the stirring speed to 350rpm, slowly adding chloroacetyl chloride into the reactor, controlling the adding speed to be 20-30ml/min, increasing the stirring speed to 500rpm when the chloroacetyl chloride is added, simultaneously carrying out 60 Co-gamma ray radiation, controlling the radiation dose rate to be 1-2kGy/h and the radiation time to be 1.5-2h, stopping stirring when the radiation is finished, increasing the temperature of the reactor to 60-65 ℃, standing for 20-30min, adding 10% sodium hydroxide aqueous solution and N-hexane, controlling the stirring speed of the reactor to 250rpm when the radiation is finished, stirring for 30-40min, stopping stirring to obtain a primary reactant, performing reduced pressure heating treatment on the primary reactant, controlling the pressure in the reduced pressure heating process to be 0.06-0.08MPa, raising the temperature to 115 ℃ and 120 ℃, controlling the time of the reduced pressure heating treatment to be 1.5-2h, and obtaining the N-chloroacetyl-N-isopropyl-p-chloroaniline after the reduced pressure heating is finished.
In the step of preparing the N-chloroacetyl-N-isopropyl-p-chloroaniline, the chloroacetyl chloride, a 10% sodium hydroxide aqueous solution and N-hexane are mixed in a mass ratio of 170-180:130-140:5-10: 20-30.
The method for preparing the anilofos comprises the steps of mixing N-chloroacetyl-N-isopropyl-p-chloroaniline with a catalyst, controlling the temperature to 35-40 ℃, then carrying out ultrasonic oscillation, setting the temperature to 2-5 ℃ after the ultrasonic oscillation is finished, then adding 50-55% of O, O-dimethyl ammonium dithiophosphate aqueous solution, slowly heating while stirring, controlling the stirring speed to be 100 plus materials and 120rpm, the heating speed to be 0.2-0.5 ℃/min, stopping heating when the temperature is raised to 45-50 ℃, keeping the temperature at 45-50 ℃ for 3-4h to obtain a reactant, stopping stirring, carrying out suction filtration on the reactant, washing a filter cake for 2-3 times by using deionized water, and drying at 50-55 ℃ to obtain the anilofos technical grade.
The frequency of the ultrasonic oscillation is 60-70Hz, and the time of the ultrasonic oscillation is 20-30 min.
The mass ratio of the N-chloroacetyl-N-isopropyl-p-chloroaniline, the catalyst and the 50-55% O, O-dimethyl ammonium dithiophosphate aqueous solution in the step of preparing the anilofos is 240-250: 5-10: 350-360.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the preparation method of the herbicide anilofos, disclosed by the invention, the purity and the yield of the N-chloroacetyl-N-isopropyl-p-chloroaniline can be improved by performing 60 Co-gamma ray radiation in the process of preparing the N-chloroacetyl-N-isopropyl-p-chloroaniline, the purity of the prepared N-chloroacetyl-N-isopropyl-p-chloroaniline is 98.9% -99.4%, and the yield is 98.6% -99.3%;
(2) according to the preparation method of the herbicide anilofos, the catalyst prepared by the hollow microspheres is used, and the temperature is gradually increased in the anilofos preparation process, so that the purity and yield of the anilofos can be improved, and the purity of the anilofos prepared is 98.8% -99.4%, and the yield is 98.8% -99.5%;
(3) according to the preparation method of the herbicide anilofos, the catalyst prepared by the hollow microspheres is used, and the temperature is gradually increased in the anilofos preparation process, so that the particle size of the anilofos can be reduced, the uniformity of the particle size distribution of the anilofos is improved, the subsequent grinding process of the anilofos is avoided, the anilofos can be directly used for producing preparations, and the particle size D90 of the anilofos prepared by the preparation method is 3-12 mu m;
(4) the preparation method of the herbicide anilofos provided by the invention generates little waste water, and the preparation process is safe and environment-friendly.
Detailed Description
In order to more clearly understand the technical features, objects, and effects of the present invention, specific embodiments of the present invention will now be described.
Example 1
A preparation method of herbicide anilofos comprises the following steps:
1. preparing hollow microspheres: placing X-type porous zeolite powder in a calcining furnace, controlling the temperature of the calcining furnace to 350 ℃, calcining for 2h to obtain calcined X-type porous zeolite powder, mixing 10g of calcined X-type porous zeolite powder with 35g of absolute ethyl alcohol, 1g of dimethyl diallyl ammonium chloride aqueous solution, 3g of acetic acid and 1g of nickel nitrate, and then carrying out ultrasonic dispersion, controlling the frequency of the ultrasonic dispersion to be 20kHz and the time of the ultrasonic dispersion to be 20min, and obtaining dispersed raw materials after the ultrasonic dispersion is finished; cooling the dispersed raw materials to-20 ℃, freezing the raw materials at-20 ℃ for 30min, slowly heating the raw materials to 90 ℃, controlling the heating speed to be 2 ℃/min, and heating the raw materials to 90 ℃ to obtain the frozen raw materials; and then controlling the temperature to 90 ℃, stirring the frozen raw materials at the stirring speed of 200rpm for 1.5h, and stopping stirring to obtain the hollow microspheres.
The particle size of the X-type porous zeolite powder is 0.3 mu m.
The mass percent of the dimethyl diallyl ammonium chloride in the dimethyl diallyl ammonium chloride aqueous solution is 65%.
2. Preparing a catalyst: mixing 35g of hollow microspheres, 15g of PEG400, 2g of Tween 80, 1g of potassium nitrate and 90g of water, adding the mixture into a microwave reactor for reaction, controlling the temperature of the microwave reactor to be 50 ℃, the microwave power to be 600W and the reaction time to be 1h, and obtaining the hollow microspheres after primary treatment after the reaction is finished; and then mixing 20g of primarily treated hollow microspheres, 35g of 45 mass percent sulfuric acid aqueous solution and 1g of potassium persulfate, then acidifying, controlling the acidification temperature to be 40 ℃ and the acidification time to be 30min, carrying out vacuum spray drying after the acidification is finished, controlling the vacuum degree of the vacuum spray drying to be 0.05MPa, controlling the inlet temperature to be 90 ℃ and the outlet temperature to be 50 ℃, and finishing the vacuum spray drying to obtain the catalyst.
3. Preparation of N-chloroacetyl-N-isopropyl-p-chloroaniline: placing 170g N-isopropyl parachloroaniline in a reactor, heating the reactor to 50 ℃, starting stirring of the reactor, controlling the stirring speed to 300rpm, slowly adding 130g of chloroacetyl chloride into the reactor, controlling the adding speed to 20ml/min, increasing the stirring speed to 450rpm after the chloroacetyl chloride is added, simultaneously carrying out 60 Co-gamma ray radiation, controlling the radiation dose rate to 1kGy/h and the radiation time to 1.5h, stopping stirring when the radiation is finished, raising the temperature of the reactor to 60 ℃, standing for 20min, adding 5g of 10% sodium hydroxide aqueous solution and 20g of n-hexane, controlling the stirring speed of the reactor to 200rpm, stopping stirring after stirring for 30min to obtain a primary reactant, carrying out reduced pressure heating treatment on the primary reactant, controlling the pressure in the reduced pressure heating process to 0.06MPa, the temperature is increased to 115 ℃, the time of the reduced pressure heating treatment is 1.5h, and after the reduced pressure heating treatment is finished, 245.3g N-chloracetyl-N-isopropyl-p-chloroaniline with the purity of 98.9 percent and the yield of 98.6 percent is obtained.
4. Preparing anilofos: after 240g of N-chloroacetyl-N-isopropyl-p-chloroaniline prepared in the step 3 is mixed with 5g of catalyst, the temperature is controlled to 35 ℃, then ultrasonic oscillation is carried out, the frequency of the ultrasonic oscillation is controlled to be 60Hz, the time of the ultrasonic oscillation is 20min, the temperature is set to 2 ℃ after the ultrasonic oscillation is finished, 350g of O, O-dimethyl ammonium dithiophosphate aqueous solution with the concentration of 50% is added, then the temperature is slowly raised while stirring, the stirring speed is controlled to be 100rpm, the heating speed is controlled to be 0.2 ℃/min, the temperature is stopped when the temperature is raised to 45 ℃, the temperature is stopped, the temperature is kept at 45 ℃ for 3h to obtain a reactant, the stirring is stopped, the reactant is subjected to suction filtration, a filter cake is washed for 2 times by deionized water and dried at 50 ℃ to obtain 355.4g of raw anilofos, the purity is 99.2%, and the yield is 99.3%.
Example 2
A preparation method of herbicide anilofos comprises the following steps:
1. preparing hollow microspheres: placing X-type porous zeolite powder in a calcining furnace, controlling the temperature of the calcining furnace to 370 ℃, calcining for 2.5h to obtain calcined X-type porous zeolite powder, mixing 11g of calcined X-type porous zeolite powder with 37g of absolute ethyl alcohol, 1.5g of dimethyl diallyl ammonium chloride aqueous solution, 4g of acetic acid and 1.5g of nickel nitrate, and then carrying out ultrasonic dispersion, controlling the frequency of ultrasonic dispersion to be 25kHz and the time of ultrasonic dispersion to be 25min, and obtaining a dispersed raw material after the ultrasonic dispersion is finished; cooling the dispersed raw materials to-15 ℃, freezing at-15 ℃ for 35min, slowly heating to 95 ℃, controlling the heating speed to be 2.5 ℃/min, and heating to 95 ℃ to obtain the frozen raw materials; and then controlling the temperature to 95 ℃, stirring the frozen raw materials at the stirring speed of 210rpm for 1.7h, and stopping stirring to obtain the hollow microspheres.
The particle size of the X-type porous zeolite powder is 0.4 mu m.
The mass percent of the dimethyl diallyl ammonium chloride in the dimethyl diallyl ammonium chloride aqueous solution is 65%.
2. Preparing a catalyst: mixing 37g of hollow microspheres, 16g of PEG400, 2.5g of Tween 80, 2g of potassium nitrate and 95g of water, adding the mixture into a microwave reactor for reaction, controlling the temperature of the microwave reactor to be 52 ℃, the microwave power to be 650W and the reaction time to be 1.2h, and obtaining the hollow microspheres after primary treatment after the reaction is finished; and then mixing 22g of primarily treated hollow microspheres, 37g of sulfuric acid aqueous solution with the mass fraction of 50% and 2g of potassium persulfate, then acidifying, controlling the acidification temperature to be 42 ℃ and the acidification time to be 35min, carrying out vacuum spray drying after the acidification is finished, controlling the vacuum degree of the vacuum spray drying to be 0.055MPa, controlling the inlet temperature to be 95 ℃ and the outlet temperature to be 55 ℃, and finishing the vacuum spray drying to obtain the catalyst.
3. Preparation of N-chloroacetyl-N-isopropyl-p-chloroaniline: placing 175g of N-isopropyl-p-chloroaniline in a reactor, heating the reactor to 52 ℃, starting stirring of the reactor, controlling the stirring speed to 320rpm, slowly adding 135g of chloroacetyl chloride into the reactor, controlling the adding speed to 25ml/min, after the chloroacetyl chloride is added, increasing the stirring speed to 470rpm, simultaneously carrying out 60 Co-gamma ray radiation, controlling the radiation dose rate to 1.5kGy/h and the radiation time to 1.7h, stopping stirring when the radiation is finished, raising the temperature of the reactor to 62 ℃, standing for 25min, adding 7g of 10% sodium hydroxide aqueous solution and 25g of n-hexane, controlling the stirring speed of the reactor to 220rpm, stirring for 35min, stopping stirring to obtain a primary reactant, carrying out reduced pressure heating treatment on the primary reactant, controlling the pressure in the reduced pressure heating process to 0.07MPa, the temperature is increased to 117 ℃, the time of the reduced pressure heating treatment is 1.7h, and after the reduced pressure heating treatment is finished, 253.2g N-chloracetyl-N-isopropyl-parachloroaniline with the purity of 99.4 percent and the yield of 99.3 percent is obtained.
4. Preparing anilofos: 245g of N-chloroacetyl-N-isopropyl-p-chloroaniline prepared in the step 3 is mixed with 7g of catalyst, the temperature is controlled to 37 ℃, then ultrasonic oscillation is carried out, the frequency of the ultrasonic oscillation is controlled to be 65Hz, the time of the ultrasonic oscillation is 25min, the temperature is set to 4 ℃ after the ultrasonic oscillation is finished, 355g of O, O-dimethyl ammonium dithiophosphate aqueous solution with the concentration of 52% is added, the temperature is slowly raised while stirring, the stirring speed is controlled to be 110rpm, the heating speed is controlled to be 0.3 ℃/min, the temperature is stopped when the temperature is raised to 47 ℃, the temperature is stopped, the temperature is kept at 47 ℃ for 3.5h to obtain a reactant, the stirring is stopped, the reactant is subjected to suction filtration, a filter cake is washed for 2 times by deionized water and dried at 52 ℃ to obtain 364g of raw anilofos, the purity is 98.8%, and the yield is 98.8%.
Example 3
A preparation method of herbicide anilofos comprises the following steps:
1. preparing hollow microspheres: placing X-type porous zeolite powder in a calcining furnace, controlling the temperature of the calcining furnace to 400 ℃, calcining for 3h to obtain calcined X-type porous zeolite powder, mixing 12g of calcined X-type porous zeolite powder with 40g of absolute ethyl alcohol, 2g of dimethyl diallyl ammonium chloride aqueous solution, 5g of acetic acid and 2g of nickel nitrate, and then carrying out ultrasonic dispersion, controlling the frequency of the ultrasonic dispersion to be 30kHz and the time of the ultrasonic dispersion to be 30min, and obtaining a dispersed raw material after the ultrasonic dispersion is finished; cooling the dispersed raw materials to-10 ℃, freezing at-10 ℃ for 40min, slowly heating to 100 ℃, controlling the heating speed to be 3 ℃/min, and heating to 100 ℃ to obtain the frozen raw materials; and then controlling the temperature to be 100 ℃, stirring the frozen raw materials at the stirring speed of 220rpm for 2 hours, and stopping stirring to obtain the hollow microspheres.
The particle size of the X-type porous zeolite powder is 0.5 mu m.
The mass percent of the dimethyl diallyl ammonium chloride in the dimethyl diallyl ammonium chloride aqueous solution is 65%. 2. Preparing a catalyst: mixing 40g of hollow microspheres, 17g of PEG400, 3g of Tween 80, 3g of potassium nitrate and 100g of water, adding the mixture into a microwave reactor for reaction, controlling the temperature of the microwave reactor to be 55 ℃, the microwave power to be 700W, and the reaction time to be 1.5h, and obtaining the hollow microspheres after primary treatment after the reaction is finished; and then mixing 25g of primarily treated hollow microspheres, 40g of 45-55 mass percent sulfuric acid aqueous solution and 3g of potassium persulfate for acidification, controlling the acidification temperature to be 45 ℃ and the acidification time to be 40min, and performing vacuum spray drying after the acidification is finished, wherein the vacuum degree of the vacuum spray drying is controlled to be 0.06MPa, the inlet temperature is 100 ℃, the outlet temperature is 60 ℃, and the vacuum spray drying is finished to obtain the catalyst.
3. Preparation of N-chloroacetyl-N-isopropyl-p-chloroaniline: putting 180g N-isopropyl parachloroaniline into a reactor, heating the reactor to 55 ℃, starting stirring of the reactor, controlling the stirring speed to 350rpm, then slowly adding 140g of chloroacetyl chloride into the reactor, controlling the adding speed to 30ml/min, after the chloroacetyl chloride is added, increasing the stirring speed to 500rpm, simultaneously carrying out 60 Co-gamma ray radiation, controlling the radiation dose rate to 2kGy/h and the radiation time to 2h, stopping stirring when the radiation is finished, raising the temperature of the reactor to 65 ℃, standing for 30min, adding 10g of 10% sodium hydroxide aqueous solution and 30g of n-hexane, controlling the stirring speed of the reactor to 250rpm, stopping stirring after stirring for 40min to obtain a primary reactant, carrying out temperature raising treatment on the primary reactant, controlling the pressure in the pressure reducing and temperature raising process to 0.08MPa, the temperature is increased to 120 ℃, the time of the reduced pressure heating treatment is 2 hours, and 260.3g N-chloracetyl-N-isopropyl-p-chloroaniline is obtained after the reduced pressure heating treatment, the purity is 99 percent, and the yield is 98.9 percent.
4. Preparing anilofos: mixing 250g of N-chloroacetyl-N-isopropyl-p-chloroaniline prepared in the step 3 with 10g of catalyst, controlling the temperature to 40 ℃, then carrying out ultrasonic oscillation, controlling the frequency of the ultrasonic oscillation to be 70Hz, controlling the time of the ultrasonic oscillation to be 30min, setting the temperature to 5 ℃ after the ultrasonic oscillation is finished, then adding 369g of O, O-dimethyl ammonium dithiophosphate aqueous solution with the concentration of 55%, slowly heating while stirring, controlling the stirring speed to be 120rpm, the heating speed to be 0.5 ℃/min, stopping heating when the temperature is raised to 50 ℃, keeping the temperature at 50 ℃ for 4h to obtain a reactant, stopping stirring, carrying out suction filtration on the reactant, washing a filter cake for 3 times by using deionized water, and drying at 55 ℃ to obtain 370.1g of raw anilofos, wherein the purity is 99.4% and the yield is 99.5%.
Comparative example 1
Steps 1-3 are the same as example 1, except that:
step 4 is changed into: after 240g of N-chloroacetyl-N-isopropyl-p-chloroaniline prepared in the step 3 is mixed with 5g of catalyst, the temperature is controlled to 35 ℃, then ultrasonic oscillation is carried out, the frequency of the ultrasonic oscillation is controlled to be 60Hz, the time of the ultrasonic oscillation is 20min, the temperature is set to 45 ℃, 350g of O, O-dimethyl dithiophosphate ammonium salt aqueous solution with the concentration of 50% is added, stirring is started simultaneously, the stirring speed is controlled to be 100rpm, the temperature is kept at 45 ℃ for 6.5h to obtain a reactant, the stirring is stopped, the reactant is subjected to suction filtration, a filter cake is washed for 2 times by deionized water and dried at 50 ℃, 344.1g of anilofos technical product is obtained, the purity is 95.2%, and the yield is 91.8%.
Comparative example 2
Steps 1-2 and step 4 are the same as in example 1 except that: the step 3 does not carry out 60 Co-gamma ray radiation;
241.2g N-chloracetyl-N-isopropyl-p-chloroaniline is obtained in the step 3, the purity is 88.7 percent, and the yield is 87 percent;
325.7g of anilofos raw material is obtained in step 4, the purity is 90.4%, and the yield is 92.5%.
Comparative example 3
Steps 3-4 are the same as example 1, except that: step 1 is omitted, and the hollow microspheres in step 2 are changed into X-shaped porous zeolite powder with the particle size of 0.3 mu m;
245.4g N-chloracetyl-N-isopropyl-p-chloroaniline is obtained in the step 3, the purity is 98.8 percent, and the yield is 98.6 percent;
327.1g of anilofos raw material is obtained in step 4, the purity is 86.8%, and the yield is 80.1%.
The anilofos bulk drugs prepared in examples 1-3 and comparative examples 1-3 were subjected to particle size D90 test, and the results were as follows:
all percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A preparation method of herbicide anilofos is characterized by comprising the steps of preparing hollow microspheres, preparing a catalyst, preparing N-chloroacetyl-N-isopropyl-p-chloroaniline and preparing anilofos;
preparing hollow microspheres, namely placing X-type porous zeolite powder in a calcining furnace, controlling the temperature of the calcining furnace to be 350-400 ℃, calcining for 2-3h to obtain calcined X-type porous zeolite powder, mixing the calcined X-type porous zeolite powder with absolute ethyl alcohol, a dimethyl diallyl ammonium chloride aqueous solution, acetic acid and nickel nitrate, and then performing ultrasonic dispersion, wherein the frequency of the ultrasonic dispersion is controlled to be 20-30kHz, the time of the ultrasonic dispersion is 20-30min, and after the ultrasonic dispersion is finished, a dispersed raw material is obtained; cooling the dispersed raw materials to-20 to-10 ℃, freezing the raw materials at-20 to-10 ℃ for 30 to 40min, slowly heating the raw materials to 90 to 100 ℃, controlling the heating speed to be 2 to 3 ℃/min, and heating the raw materials to 90 to 100 ℃ to obtain the frozen raw materials; then controlling the temperature to 90-100 ℃, stirring the frozen raw materials at the stirring speed of 200-220rpm for 1.5-2h, and stopping stirring to obtain hollow microspheres;
the preparation of the catalyst comprises the steps of mixing hollow microspheres, PEG400, Tween 80, potassium nitrate and water, adding the mixture into a microwave reactor for reaction, controlling the temperature of the microwave reactor to be 50-55 ℃, the microwave power to be 600-700W, and the reaction time to be 1-1.5h, and obtaining the hollow microspheres after primary treatment after the reaction is finished; then mixing the primarily treated hollow microspheres, 45-55% of sulfuric acid aqueous solution and potassium persulfate, then acidifying, controlling the acidification temperature to be 40-45 ℃ and the acidification time to be 30-40min, carrying out vacuum spray drying after the acidification is finished, controlling the vacuum degree of the vacuum spray drying to be 0.05-0.06MPa, the inlet temperature to be 90-100 ℃ and the outlet temperature to be 50-60 ℃, and finishing the vacuum spray drying to obtain a catalyst;
the preparation method comprises the steps of preparing N-chloroacetyl-N-isopropyl-p-chloroaniline, placing the N-isopropyl-p-chloroaniline in a reactor, heating the reactor to 50-55 ℃, starting stirring of the reactor, controlling the stirring speed to 350rpm, slowly adding chloroacetyl chloride into the reactor, controlling the adding speed to be 20-30ml/min, increasing the stirring speed to 500rpm when the chloroacetyl chloride is added, simultaneously carrying out 60 Co-gamma ray radiation, controlling the radiation dose rate to be 1-2kGy/h and the radiation time to be 1.5-2h, stopping stirring when the radiation is finished, increasing the temperature of the reactor to 60-65 ℃, standing for 20-30min, adding 10% sodium hydroxide aqueous solution and N-hexane, controlling the stirring speed of the reactor to 250rpm when the radiation is finished, stirring for 30-40min, stopping stirring to obtain a primary reactant, performing reduced pressure heating treatment on the primary reactant, controlling the pressure in the reduced pressure heating process to be 0.06-0.08MPa, raising the temperature to 115 ℃ and 120 ℃, controlling the time of the reduced pressure heating treatment to be 1.5-2h, and obtaining the N-chloroacetyl-N-isopropyl-p-chloroaniline after the reduced pressure heating is finished;
the method for preparing the anilofos comprises the steps of mixing N-chloroacetyl-N-isopropyl-p-chloroaniline with a catalyst, controlling the temperature to 35-40 ℃, then carrying out ultrasonic oscillation, setting the temperature to 2-5 ℃ after the ultrasonic oscillation is finished, then adding 50-55% of O, O-dimethyl ammonium dithiophosphate aqueous solution, slowly heating while stirring, controlling the stirring speed to be 100 plus materials and 120rpm, the heating speed to be 0.2-0.5 ℃/min, stopping heating when the temperature is raised to 45-50 ℃, keeping the temperature at 45-50 ℃ for 3-4h to obtain a reactant, stopping stirring, carrying out suction filtration on the reactant, washing a filter cake for 2-3 times by using deionized water, and drying at 50-55 ℃ to obtain the anilofos technical grade.
2. The preparation method of the herbicide anilofos as claimed in claim 1, characterized in that the mass ratio of the calcined X-type porous zeolite powder to the absolute ethyl alcohol, the aqueous solution of dimethyldiallylammonium chloride, the acetic acid and the nickel nitrate in the step of preparing the hollow microspheres is 10-12:35-40:1-2:3-5: 1-2.
3. The preparation method of the herbicide anilofos as claimed in claim 1, characterized in that the mass ratio of the hollow microspheres, PEG400, Tween 80, potassium nitrate and water in the preparation step of the catalyst is 35-40:15-17:2-3:1-3: 90-100.
4. The method for preparing the herbicide anilofos as claimed in claim 1, wherein the mass ratio of the hollow microspheres after primary treatment, 45-55% by mass of sulfuric acid aqueous solution and potassium persulfate in the catalyst preparation step is 20-25:35-40: 1-3.
5. The method for preparing the herbicide anilofos as claimed in claim 1, wherein the mass ratio of N-isopropyl-p-chloroaniline, chloroacetyl chloride, 10% aqueous sodium hydroxide solution and N-hexane in the step of preparing N-chloroacetyl-N-isopropyl-p-chloroaniline is 170-180:130-140:5-10: 20-30.
6. The process for the preparation of the herbicide anilofos according to claim 1, characterized in that the frequency of the ultrasonic oscillation is 60-70Hz and the time of the ultrasonic oscillation is 20-30 min.
7. The process for preparing the herbicide anilofos as claimed in claim 1, wherein the mass ratio of N-chloroacetyl-N-isopropyl-p-chloroaniline, catalyst, 50-55% aqueous solution of ammonium O, O-dimethyldithiophosphate in the anilofos preparation step is 240-250: 5-10: 350-360.
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| JPS5318735A (en) * | 1976-08-03 | 1978-02-21 | Nippon Tokushu Noyaku Seizo Kk | Herbicide |
| US4418021A (en) * | 1977-07-13 | 1983-11-29 | Gulf Oil Corporation | N-Isopropylcarbanilylmethyl dithiophosphates |
| BR7804448A (en) * | 1977-07-13 | 1979-02-28 | Gulf Oil Corp | PROCESS TO COMBAT UNDESIRABLE VEGETATIONS AND INSECT PESTES IN AGRICULTURAL CULTURE FIELDS; PESTICIDE COMPOUND; AND PROCESS TO COMBAT UNDESIRABLE VEGETATIONS IN SOYBEAN PLANTATIONS |
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| ES8104796A1 (en) * | 1979-07-25 | 1981-05-16 | Hoechst Ag | Fungicidal thioglycolic acid anilides, process for their preparation and pesticides containing them. |
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| CN102260287B (en) * | 2010-05-31 | 2014-07-09 | 中国中化股份有限公司 | Preparation method of herbicide anilofos |
| CN103073634B (en) * | 2011-10-25 | 2014-07-02 | 天津科技大学 | Specific antibody against herbicide anilofos |
| CN104528763A (en) * | 2014-12-17 | 2015-04-22 | 上海大学 | Preparation method of X-type zeolite molecular sieve |
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