CN112956481A - Herbicide based on haloxyfop-methyl, flumetsulam and halosulfuron-methyl - Google Patents
Herbicide based on haloxyfop-methyl, flumetsulam and halosulfuron-methyl Download PDFInfo
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- CN112956481A CN112956481A CN202110157540.0A CN202110157540A CN112956481A CN 112956481 A CN112956481 A CN 112956481A CN 202110157540 A CN202110157540 A CN 202110157540A CN 112956481 A CN112956481 A CN 112956481A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
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Abstract
The invention discloses a herbicide based on haloxyfop, flumetsulam and halosulfuron-methyl, which comprises the following raw materials in parts by weight: 1-15 parts of haloxyfop-methyl, 1-15 parts of flumetsulam, 1-37 parts of halosulfuron-methyl, 1-2 parts of modified antioxidant, 10-12 parts of borax, 6-8 parts of surfactant, 10-12 parts of triethanolamine, 10-12 parts of vegetable oil and 40-42 parts of deionized water. The invention adopts the mixing of the haloxyfop-methyl, the flumetsulam and the halosulfuron-methyl, the effects are complementary, the weeding spectrum is wider, the weeding activity is high, and the weeding effect is more excellent.
Description
Technical Field
The invention belongs to the technical field of herbicides, and relates to a herbicide based on haloxyfop, flumetsulam and halosulfuron-methyl.
Background
Herbicides are agents which cause complete or selective death of weeds, also known as herbicides, and are used to kill or inhibit the growth of plants. The herbicide has the characteristics of low cost, high efficiency, simple and convenient operation, labor saving, obvious weed control effect and the like, and is widely applied in agriculture.
At present, the herbicide is limited by safety, the weed control spectrum is limited, the occurrence of weeds cannot be completely and effectively controlled by singly using a single herbicide, and some herbicides are easy to cause residual toxicity due to large water solubility, too long field lasting period, excessive use amount or uneven application; moreover, proper preservation of the herbicide is also a key factor for maintaining the lasting efficacy of the herbicide, but the herbicide is limited by the influence of complex environment, and the effect of preservation by only relying on shading from light is often not achieved, so that the problem of developing the herbicide which has a wide weeding spectrum and is easy to preserve is urgently needed to be solved in the industry.
Disclosure of Invention
The invention aims to provide a herbicide based on haloxyfop, flumetsulam and halosulfuron-methyl, which is prepared by mixing the high-efficiency haloxyfop, the flumetsulam and the halosulfuron-methyl, has complementary effects, wider weeding spectrum, high weeding activity and more excellent weeding effect, and adds a modified antioxidant in the formula of the herbicide, so that the composite herbicide has the effects of resisting oxidation and aging and ultraviolet light aging, prevents the decomposition and failure of effective components due to light, keeps the efficacy lasting, and has very high application prospect and popularization value.
The purpose of the invention can be realized by the following technical scheme:
a herbicide based on haloxyfop-methyl, flumetsulam and halosulfuron-methyl comprises the following raw materials in parts by weight: 1-15 parts of haloxyfop-methyl, 1-15 parts of flumetsulam, 1-37 parts of halosulfuron-methyl, 1-2 parts of modified antioxidant, 10-12 parts of borax, 6-8 parts of surfactant, 10-12 parts of triethanolamine, 10-12 parts of vegetable oil and 40-42 parts of deionized water;
the herbicide based on haloxyfop, flumetsulam and halosulfuron-methyl is prepared by the following steps:
step A1, mixing haloxyfop-methyl, flumetsulam, halosulfuron-methyl and deionized water, and performing ultrasonic dispersion for 40-60 minutes at the ultrasonic frequency of 80-90kHz to prepare suspension;
step A2, adding a modified antioxidant, borax and a surfactant into the suspension prepared in the step A1, controlling the heating temperature to be 50-55 ℃, and carrying out mixing reaction for 1.5-2 hours under the condition that the stirring speed is 200-220rpm to prepare a mixed liquid medicine;
step A3, mixing and stirring triethanolamine, vegetable oil and the mixed liquid medicine prepared in the step A2 at the speed of 230-240rpm for 0.5 hour, heating to 50-60 ℃, keeping the temperature and reacting for 4-6 hours, and cooling to room temperature to prepare the herbicide.
Further, the surfactant in the step a2 is one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, benzalkonium chloride, fatty glyceride and polysorbate, and is mixed according to any proportion.
Further, the vegetable oil in step A3 is one or more of salad oil, soybean oil, castor oil, corn oil, and olive oil, and is mixed in any proportion.
The specific preparation process of the modified antioxidant described in step A2 is as follows:
step S1, adding p-hydroxybenzaldehyde and ionic liquid [ bmim ] into a three-neck flask]Br3Stirring and reacting at 20 ℃ for 1 hour, adding 100g/L aqueous solution of sodium hydroxide, heating to 90-100 ℃ for reacting for 2 hours, then acidifying to pH 5-5.5 with hydrochloric acid solution, extracting with ethyl acetate, washing the extract with saturated saline, removing ethyl acetate, and recrystallizing the residue with water to obtain white crystals, namely an intermediate 1;
the reaction process is as follows:
step S2, adding the intermediate 1, malonic acid, a catalyst and acetonitrile prepared in the step S1 into a three-neck flask provided with a reflux condenser, introducing nitrogen for protection, stirring and refluxing for 1 hour, filtering and separating out the catalyst, and recrystallizing the filtrate with ethyl acetate to obtain an intermediate 2;
the reaction process is as follows:
step S3, adding 2, 5-di-tert-butylhydroquinone and acetic acid into a three-neck flask provided with a dropping funnel, a condenser tube, a thermometer and a stirring magneton, dropwise adding acetic anhydride, stirring, heating in a water bath to 50 ℃, dropwise adding a mixture of 45g of concentrated nitric acid and acetic acid, keeping the temperature for reaction for 2 hours after dropwise adding, then cooling to room temperature, pouring the cooled reaction solution into 500mL of ice water, continuously stirring, filtering while cold to separate an oily solid, adding the oily solid into 30mL of deionized water, heating to 70 ℃, separating while hot to obtain an oily substance, and cooling to obtain a solid intermediate 3;
the reaction process is as follows:
step S4, adding iron powder and a hydrochloric acid solution into a three-neck flask, refluxing for 0.5 hour at 105 ℃, adding the intermediate 3 prepared in the step S3, continuing to react for 2-3 hours, cooling to 80 ℃, adding 15-20mL of ethyl acetate to heavily separate layers, washing an organic layer with 20mL0.5mol/L sodium hydroxide solution, washing with deionized water to neutrality, filtering to remove iron powder, performing rotary evaporation on the mixture to 1/3 volume in a rotary evaporator, and finally performing freeze drying for 5-10 hours at-45 ℃ to obtain an intermediate 4;
the reaction process is as follows:
step S5, taking the intermediate 2, triethylamine and tetrahydrofuran, magnetically stirring in a three-neck flask, adding the intermediate 4 at 0 ℃, then adding 4-dimethylaminopyridine, adding N, N' -dicyclohexylcarbodiimide after the reaction liquid is clarified, heating to 25 ℃, reacting for 3 hours, concentrating the reaction liquid under reduced pressure, adding 10mL of ethyl acetate into the concentrated liquid, extracting, shaking uniformly, placing in a refrigerator at-1 ℃ for 12 hours, extracting for three times with 10mL of ethyl acetate each time, washing the organic phase with 15mL of 5% sodium bicarbonate solution and 10mL of 1mmol/L hydrochloric acid solution, drying with 0.5-1g of anhydrous sodium sulfate, concentrating under reduced pressure, and obtaining the modified antioxidant.
The reaction process is as follows:
further, p-hydroxybenzaldehyde, ionic liquid [ bmim ] described in step S1]Br3The dosage ratio of the sodium hydroxide aqueous solution, the ethyl acetate and the saturated saline solution is 25mmol: 15mL of: 20-30 mL: 30-35mL, the concentration of the hydrochloric acid solution is 0.1mol/L, and the stirring speed is 250-300 rpm.
Further, the dosage ratio of the intermediate 1, the malonic acid, the catalyst and the acetonitrile in the step S2 is 105 mg: 10 mmol: 90-95 mg: 20-25 mL.
Further, the using amount ratio of the 2, 5-di-tert-butylhydroquinone, the acetic acid and the acetic anhydride in the step S3 is 15 g: 14.6 g: 1g, and mixing concentrated nitric acid and acetic acid in a volume ratio of 1:2, wherein the volume fraction of the concentrated nitric acid is 42%.
Further, the mass ratio of the iron powder, the hydrochloric acid solution and the intermediate 3 in the step S4 is 1:0.5: 3; the dosage ratio of the intermediate 2, triethylamine, tetrahydrofuran, the intermediate 4, 4-dimethylaminopyridine and N, N' -dicyclohexylcarbodiimide in the step S5 is 98-103 mg: 3-5 mL: 5-6 mL: 78-84 mg: 8-10 mg: 12-15 mg.
The catalyst of step S2 is prepared by the steps of:
25g of ZrCl2·8H2Dissolving O in 50mL of distilled water, dropwise adding 25% ammonia water by volume fraction to the pH value of 8 under the stirring of the rotation speed of 200-240rpm, filtering, washing the precipitate by using distilled water until no chloride ion exists, and then placing the precipitate at the temperature of 120 ℃ for drying for 16 hours to obtain ZrO2ZrO of isotropic direction2Adding 60mL of 1mol/L sulfuric acid solution, soaking for 30 minutes, steaming in water bath to remove excessive water, drying at 120 ℃ for 12 hours, and calcining at 650 ℃ for 5 hours to obtain the catalyst.
The invention has the beneficial effects that: the invention adopts the mixture of the high-efficiency haloxyfop, the flumetsulam and the halosulfuron-methyl, the effects are complementary, the weeding spectrum is wider, the weeding activity is high, and the weeding effect is more excellent, wherein the high-efficiency haloxyfop is an aryloxy phenoxy propionic acid herbicide for post-seedling stem and leaf treatment, belongs to the acetyl coenzyme carboxylase inhibitor herbicide, and has the characteristics of high activity, strong selectivity, long application period, good conductivity, stable effect under low temperature condition, and the like Sugarcane, tomato, sweet potato, dried bean, lawn and ornamental crops can be used near houses, and meanwhile, the herbicide has special effect on malignant weeds, namely cyperus rotundus, and can prevent and remove part of broadleaf weeds, so that the application prospect and the popularization value are very high;
in addition, the modified antioxidant is added in the formula of the herbicide, so that the compound herbicide has the effects of resisting oxidation aging and ultraviolet light aging, prevents the effective components from decomposing and losing efficacy by light, keeps the drug effect lasting, wherein the design and synthesis thought of the modified antioxidant is that a catechol structure with phenolic antioxidant activity and a2, 5-di-tert-butyl hydroquinone structure are combined in one molecule through a series of reactions, not only enhances the antioxidant effect, but also keeps the respective excellent properties, the prepared antioxidant can strongly absorb ultraviolet rays with the wavelength of 280-310 nm, avoids the decomposition of effective components, and has unique photo-thermal stability, no coloring property, good dispersibility and good compatibility with an organic matrix, takes p-hydroxybenzaldehyde as a raw material, under the solvent-free condition, 1-butyl-3-methylimidazole ([ bmim) is tribromide with an ionic liquid.]Br3) Selectively brominating, directly hydrolyzing the product with sodium hydroxide solution to synthesize an intermediate 1 without separation, performing Knoevenagel condensation on aldehyde group in the intermediate 1 and carboxyl of malonic acid to generate an intermediate 2 with an olefine acid structure, performing nitration reaction on 2, 5-di-tert-butylhydroquinone to graft a nitro group on a benzene ring of the intermediate to obtain an intermediate 3, and carrying out condensation reaction on the intermediate 33 reacting with iron powder, reducing nitro on benzene ring with iron powder to generate amino to obtain intermediate 4, mixing intermediate 2 with intermediate 4, and reacting with amino-NH of intermediate 42And reacting with-OH of carboxylic acid of the intermediate 2 to generate an amide group, thereby combining a catechol structure with phenol antioxidant activity and a2, 5-di-tert-butyl hydroquinone structure together to realize synergistic antioxidant performance.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A herbicide based on haloxyfop-methyl, flumetsulam and halosulfuron-methyl comprises the following raw materials in parts by weight: 1 part of haloxyfop-methyl, 1 part of flumetsulam, 1 part of halosulfuron-methyl, 1 part of modified antioxidant, 10 parts of borax, 6 parts of surfactant, 10 parts of triethanolamine, 10 parts of vegetable oil and 40 parts of deionized water;
the herbicide based on haloxyfop, flumetsulam and halosulfuron-methyl is prepared by the following steps:
step A1, mixing haloxyfop-methyl, flumetsulam, halosulfuron-methyl and deionized water, and performing ultrasonic dispersion for 40 minutes at 80kHz ultrasonic frequency to prepare suspension;
step A2, adding a modified antioxidant, borax and sodium dodecyl benzene sulfonate into the suspension prepared in the step A1, controlling the heating temperature to be 50 ℃, and mixing and reacting for 1.5 hours at the stirring speed of 200rpm to prepare a mixed liquid medicine;
and step A3, mixing and stirring triethanolamine, salad oil and the mixed liquid medicine prepared in the step A2 at the speed of 230rpm for 0.5 hour, heating to 50 ℃, keeping the temperature for reaction for 4 hours, and cooling to room temperature to prepare the herbicide.
The specific preparation process of the modified antioxidant is as follows:
step S1, adding p-hydroxybenzaldehyde and ionic liquid [ bmim ] into a three-neck flask]Br3Stirring and reacting at 20 ℃ for 1 hour, adding 100g/L aqueous solution of sodium hydroxide, heating to 90 ℃ for reacting for 2 hours, then acidifying with hydrochloric acid solution until the pH value is 5, extracting with ethyl acetate, washing the extract with saturated saline, removing ethyl acetate, and recrystallizing the residue with water to obtain white crystals, namely an intermediate 1;
step S2, adding the intermediate 1, malonic acid, a catalyst and acetonitrile prepared in the step S1 into a three-neck flask provided with a reflux condenser, introducing nitrogen for protection, stirring and refluxing for 1 hour, filtering and separating out the catalyst, and recrystallizing the filtrate with ethyl acetate to obtain an intermediate 2;
step S3, adding 2, 5-di-tert-butylhydroquinone and acetic acid into a three-neck flask provided with a dropping funnel, a condenser tube, a thermometer and a stirring magneton, dropwise adding acetic anhydride, stirring, heating in a water bath to 50 ℃, dropwise adding a mixture of 45g of concentrated nitric acid and acetic acid, keeping the temperature for reaction for 2 hours after dropwise adding, then cooling to room temperature, pouring the cooled reaction solution into 500mL of ice water, continuously stirring, filtering while cold to separate an oily solid, adding the oily solid into 30mL of deionized water, heating to 70 ℃, separating while hot to obtain an oily substance, and cooling to obtain a solid intermediate 3;
step S4, adding iron powder and a hydrochloric acid solution into a three-neck flask, refluxing for 0.5 hour at 105 ℃, adding the intermediate 3 prepared in the step S3, continuing to react for 2 hours, cooling to 80 ℃, adding 20mL of ethyl acetate to re-separate layers, washing an organic layer with 20mL0.5mol/L sodium hydroxide solution, washing with deionized water to neutrality, filtering to remove iron powder, performing rotary evaporation on the mixture to 1/3 volume in a rotary evaporator, and finally performing freeze drying for 5 hours at-45 ℃ to obtain an intermediate 4;
step S5, taking the intermediate 2, triethylamine and tetrahydrofuran, magnetically stirring in a three-neck flask, adding the intermediate 4 at 0 ℃, then adding 4-dimethylaminopyridine, adding N, N' -dicyclohexylcarbodiimide after the reaction liquid is clarified, heating to 25 ℃, reacting for 3 hours, concentrating the reaction liquid under reduced pressure, adding 10mL of ethyl acetate into the concentrated liquid, extracting, shaking uniformly, placing in a refrigerator at-1 ℃ for 12 hours, extracting for three times with 10mL of ethyl acetate each time, washing the organic phase with 15mL of 5% sodium bicarbonate solution and 10mL of 1mmol/L hydrochloric acid solution, drying with 0.5g of anhydrous sodium sulfate, concentrating under reduced pressure, and obtaining the modified antioxidant.
Wherein, the p-hydroxybenzaldehyde and the ionic liquid [ bmim ] in the step S1]Br3The dosage ratio of the sodium hydroxide aqueous solution, the ethyl acetate and the saturated saline solution is 25mmol: 15mL of: 20-30 mL: 30-35mL, the concentration of the hydrochloric acid solution is 0.1mol/L, and the stirring speed is 250 rpm; the dosage ratio of the intermediate 1, the malonic acid, the catalyst and the acetonitrile in the step S2 is 105 mg: 10 mmol: 90 mg: 20 mL; the dosage ratio of the 2, 5-di-tert-butylhydroquinone, the acetic acid and the acetic anhydride in the step S3 is 15 g: 14.6 g: 1g, mixing concentrated nitric acid and acetic acid in a volume ratio of 1:2, wherein the volume fraction of the concentrated nitric acid is 42%; the mass ratio of the iron powder, the hydrochloric acid solution and the intermediate 3 in the step S4 is 1:0.5: 3; the dosage ratio of the intermediate 2, triethylamine, tetrahydrofuran, the intermediate 4, 4-dimethylaminopyridine and N, N' -dicyclohexylcarbodiimide in the step S5 is 98 mg: 3mL of: 5mL of: 78 mg: 8 mg: 15 mg.
The catalyst of step S2 is prepared by the steps of:
25g of ZrCl2·8H2Dissolving O in 50mL of distilled water, dropwise adding ammonia water with volume fraction of 25% under stirring at the rotation speed of 200rpm until the pH value is 8, filtering, washing the precipitate with distilled water until no chloride ion exists, and standing at 120 ℃ for drying for 16 hours to obtain ZrO2ZrO of isotropic direction2Adding 60mL of 1mol/L sulfuric acid solution, soaking for 30 minutes, steaming in water bath to remove excessive water, drying at 120 ℃ for 12 hours, and calcining at 650 ℃ for 5 hours to obtain the catalyst.
Example 2
A herbicide based on haloxyfop-methyl, flumetsulam and halosulfuron-methyl comprises the following raw materials in parts by weight: 8 parts of haloxyfop-methyl, 8 parts of flumetsulam, 18 parts of halosulfuron-methyl, 1 part of modified antioxidant, 11 parts of borax, 7 parts of surfactant, 11 parts of triethanolamine, 11 parts of vegetable oil and 41 parts of deionized water;
the herbicide based on haloxyfop, flumetsulam and halosulfuron-methyl is prepared by the following steps:
step A1, mixing haloxyfop-methyl, flumetsulam, halosulfuron-methyl and deionized water, and ultrasonically dispersing for 50 minutes at 80kHz ultrasonic frequency to prepare suspension;
step A2, adding a modified antioxidant, borax and fatty glyceride into the suspension prepared in the step A1, controlling the heating temperature to be 55 ℃, and mixing and reacting for 1.5 hours under the condition that the stirring speed is 210rpm to prepare a mixed liquid medicine;
and step A3, mixing and stirring triethanolamine, soybean oil and the mixed liquid medicine prepared in the step A2 at the speed of 230rpm for 0.5 hour, heating to 55 ℃, keeping the temperature for reaction for 5 hours, and cooling to room temperature to obtain the herbicide.
The specific preparation process of the modified antioxidant described in step A2 is as follows:
step S1, adding p-hydroxybenzaldehyde and ionic liquid [ bmim ] into a three-neck flask]Br3Stirring and reacting at 20 ℃ for 1 hour, adding 100g/L aqueous solution of sodium hydroxide, heating to 90 ℃ for reacting for 2 hours, then acidifying with hydrochloric acid solution until the pH value is 5, extracting with ethyl acetate, washing the extract with saturated saline, removing ethyl acetate, and recrystallizing the residue with water to obtain white crystals, namely an intermediate 1;
step S2, adding the intermediate 1, malonic acid, a catalyst and acetonitrile prepared in the step S1 into a three-neck flask provided with a reflux condenser, introducing nitrogen for protection, stirring and refluxing for 1 hour, filtering and separating out the catalyst, and recrystallizing the filtrate with ethyl acetate to obtain an intermediate 2;
step S3, adding 2, 5-di-tert-butylhydroquinone and acetic acid into a three-neck flask provided with a dropping funnel, a condenser tube, a thermometer and a stirring magneton, dropwise adding acetic anhydride, stirring, heating in a water bath to 50 ℃, dropwise adding a mixture of 45g of concentrated nitric acid and acetic acid, keeping the temperature for reaction for 2 hours after dropwise adding, then cooling to room temperature, pouring the cooled reaction solution into 500mL of ice water, continuously stirring, filtering while cold to separate an oily solid, adding the oily solid into 30mL of deionized water, heating to 70 ℃, separating while hot to obtain an oily substance, and cooling to obtain a solid intermediate 3;
step S4, adding iron powder and a hydrochloric acid solution into a three-neck flask, refluxing for 0.5 hour at 105 ℃, adding the intermediate 3 prepared in the step S3, continuing to react for 2 hours, cooling to 80 ℃, adding 20mL of ethyl acetate to re-separate layers, washing an organic layer with 20mL0.5mol/L sodium hydroxide solution, washing with deionized water to neutrality, filtering to remove iron powder, performing rotary evaporation on the organic layer to 1/3 volumes in a rotary evaporator, and finally performing freeze drying for 5-10 hours at-45 ℃ to obtain an intermediate 4;
step S5, taking the intermediate 2, triethylamine and tetrahydrofuran, magnetically stirring in a three-neck flask, adding the intermediate 4 at 0 ℃, then adding 4-dimethylaminopyridine, adding N, N' -dicyclohexylcarbodiimide after the reaction liquid is clarified, heating to 25 ℃, reacting for 3 hours, concentrating the reaction liquid under reduced pressure, adding 10mL of ethyl acetate into the concentrated liquid, extracting, shaking uniformly, placing in a refrigerator at-1 ℃ for 12 hours, extracting for three times with 10mL of ethyl acetate each time, washing the organic phase with 15mL of 5% sodium bicarbonate solution and 10mL of 1mmol/L hydrochloric acid solution, drying with 0.5g of anhydrous sodium sulfate, concentrating under reduced pressure, and obtaining the modified antioxidant.
Wherein, the p-hydroxybenzaldehyde and the ionic liquid [ bmim ] in the step S1]Br3The dosage ratio of the sodium hydroxide aqueous solution, the ethyl acetate and the saturated saline solution is 25mmol: 15mL of: 20mL of: 30mL, the concentration of the hydrochloric acid solution is 0.1mol/L, and the stirring speed is 280 rpm; the dosage ratio of the intermediate 1, the malonic acid, the catalyst and the acetonitrile in the step S2 is 105 mg: 10 mmol: 90 mg: 20 mL; the dosage ratio of the 2, 5-di-tert-butylhydroquinone, the acetic acid and the acetic anhydride in the step S3 is 15 g: 14.6 g: 1g, mixing concentrated nitric acid and acetic acid in a volume ratio of 1:2, wherein the volume fraction of the concentrated nitric acid is 42%; the mass ratio of the iron powder, the hydrochloric acid solution and the intermediate 3 in the step S4 is 1:0.5: 3; the dosage ratio of the intermediate 2, triethylamine, tetrahydrofuran, the intermediate 4, 4-dimethylaminopyridine and N, N' -dicyclohexylcarbodiimide in the step S5 is 100 mg: 4mL of: 6mL of: 80 mg: 9 mg: 13 mg.
The catalyst of step S2 is prepared by the steps of:
25g of ZrCl2·8H2O was dissolved in 50mL of distilled water,dropwise adding 25% ammonia water by volume fraction to pH 8 under stirring at the rotation speed of 220rpm, filtering, washing the precipitate with distilled water until no chloride ion is formed, and drying at 120 ℃ for 16 hours to obtain ZrO2ZrO of isotropic direction2Adding 60mL of 1mol/L sulfuric acid solution, soaking for 30 minutes, steaming in water bath to remove excessive water, drying at 120 ℃ for 12 hours, and calcining at 650 ℃ for 5 hours to obtain the catalyst.
Example 3
A herbicide based on haloxyfop-methyl, flumetsulam and halosulfuron-methyl comprises the following raw materials in parts by weight: 15 parts of haloxyfop-methyl, 15 parts of flumetsulam, 37 parts of halosulfuron-methyl, 2 parts of modified antioxidant, 12 parts of borax, 8 parts of surfactant, 12 parts of triethanolamine, 12 parts of vegetable oil and 42 parts of deionized water;
the herbicide based on haloxyfop, flumetsulam and halosulfuron-methyl is prepared by the following steps:
step A1, mixing haloxyfop-methyl, flumetsulam, halosulfuron-methyl and deionized water, and ultrasonically dispersing for 55 minutes at 85kHz ultrasonic frequency to prepare suspension;
step A2, adding a modified antioxidant, borax and polysorbate into the suspension prepared in the step A1, controlling the heating temperature to be 52 ℃, and mixing and reacting for 2 hours under the condition that the stirring speed is 210rpm to prepare a mixed liquid medicine;
and step A3, mixing and stirring triethanolamine, olive oil and the mixed liquid medicine prepared in the step A2 at the speed of 235rpm for 0.5 hour, heating to 55 ℃, keeping the temperature for reaction for 5 hours, and cooling to room temperature to obtain the herbicide.
The specific preparation process of the modified antioxidant described in step A2 is as follows:
step S1, adding p-hydroxybenzaldehyde and ionic liquid [ bmim ] into a three-neck flask]Br3Stirring and reacting at 20 ℃ for 1 hour, adding 100g/L aqueous solution of sodium hydroxide, heating to 100 ℃ for reacting for 2 hours, then acidifying with hydrochloric acid solution until the pH value is 5.2, extracting with ethyl acetate, washing the extract with saturated saline, removing ethyl acetate, and recrystallizing the residue with water to obtain white crystals, namely an intermediate 1;
step S2, adding the intermediate 1, malonic acid, a catalyst and acetonitrile prepared in the step S1 into a three-neck flask provided with a reflux condenser, introducing nitrogen for protection, stirring and refluxing for 1 hour, filtering and separating out the catalyst, and recrystallizing the filtrate with ethyl acetate to obtain an intermediate 2;
step S3, adding 2, 5-di-tert-butylhydroquinone and acetic acid into a three-neck flask provided with a dropping funnel, a condenser tube, a thermometer and a stirring magneton, dropwise adding acetic anhydride, stirring, heating in a water bath to 50 ℃, dropwise adding a mixture of 45g of concentrated nitric acid and acetic acid, keeping the temperature for reaction for 2 hours after dropwise adding, then cooling to room temperature, pouring the cooled reaction solution into 500mL of ice water, continuously stirring, filtering while cold to separate an oily solid, adding the oily solid into 30mL of deionized water, heating to 70 ℃, separating while hot to obtain an oily substance, and cooling to obtain a solid intermediate 3;
step S4, adding iron powder and a hydrochloric acid solution into a three-neck flask, refluxing for 0.5 hour at 105 ℃, adding the intermediate 3 prepared in the step S3, continuing to react for 3 hours, cooling to 80 ℃, adding 17mL of ethyl acetate to stratify, washing an organic layer with 20mL0.5mol/L sodium hydroxide solution, washing with deionized water to neutrality, filtering to remove iron powder, performing rotary evaporation on the organic layer to 1/3 volume in a rotary evaporator, and finally performing freeze drying for 8 hours at-45 ℃ to obtain an intermediate 4;
step S5, taking the intermediate 2, triethylamine and tetrahydrofuran, magnetically stirring in a three-neck flask, adding the intermediate 4 at 0 ℃, then adding 4-dimethylaminopyridine, adding N, N' -dicyclohexylcarbodiimide after the reaction liquid is clarified, heating to 25 ℃, reacting for 3 hours, concentrating the reaction liquid under reduced pressure, adding 10mL of ethyl acetate into the concentrated liquid, extracting, shaking uniformly, placing in a refrigerator at-1 ℃ for 12 hours, extracting for three times with 10mL of ethyl acetate each time, washing the organic phase with 15mL of 5% sodium bicarbonate solution and 10mL of 1mmol/L hydrochloric acid solution, drying with 0.7g of anhydrous sodium sulfate, concentrating under reduced pressure, and obtaining the modified antioxidant.
Wherein, the p-hydroxybenzaldehyde and the ionic liquid [ bmim ] in the step S1]Br3The dosage ratio of the sodium hydroxide aqueous solution, the ethyl acetate and the saturated saline solution is 25mmol: 15mL of: 30mL of: 35mL, the concentration of the hydrochloric acid solution is 0.1mol/L, and the stirring speed is 270 rpm; the dosage ratio of the intermediate 1, the malonic acid, the catalyst and the acetonitrile in the step S2 is 105 mg: 10 mmol: 95 mg: 25 mL; the dosage ratio of the 2, 5-di-tert-butylhydroquinone, the acetic acid and the acetic anhydride in the step S3 is 15 g: 14.6 g: 1g, mixing concentrated nitric acid and acetic acid in a volume ratio of 1:2, wherein the volume fraction of the concentrated nitric acid is 42%; the mass ratio of the iron powder, the hydrochloric acid solution and the intermediate 3 in the step S4 is 1:0.5: 3; the dosage ratio of the intermediate 2, triethylamine, tetrahydrofuran, the intermediate 4, 4-dimethylaminopyridine and N, N' -dicyclohexylcarbodiimide described in the step S5 is 103 mg: 5mL of: 6mL of: 84 mg: 10 mg: 15 mg.
The catalyst of step S2 is prepared by the steps of:
25g of ZrCl2·8H2Dissolving O in 50mL of distilled water, dropwise adding ammonia water with volume fraction of 25% under stirring at the rotation speed of 230rpm until the pH value is 8, filtering, washing the precipitate with distilled water until no chloride ion exists, and standing at 120 ℃ for drying for 16 hours to obtain ZrO2ZrO of isotropic direction2Adding 60mL of 1mol/L sulfuric acid solution, soaking for 30 minutes, steaming in water bath to remove excessive water, drying at 120 ℃ for 12 hours, and calcining at 650 ℃ for 5 hours to obtain the catalyst.
Comparative example 1
A commercially available haloxyfop herbicide.
Comparative example 2
Comparative example 2 a composite herbicide was prepared according to example 1, except that no modified antioxidant was added.
The following performance tests are carried out on the examples 1-3 and the comparative examples 1 and 2, (1) the pesticide effect test is carried out, samples are accurately weighed according to the area of a test cell, a knapsack sprayer is utilized to carry out uniform spraying, a special fan-shaped spray head for herbicide is selected as the spray head, during spraying, the pesticide liquid is required to be uniformly sprayed into the test cell, the phenomena of missed spraying and multiple spraying are avoided, the weed death conditions are observed 20 days and 40 days after the pesticide is sprayed respectively after the test, and the weeding activities of various pesticides are compared; (2) antioxidant experiments, DPPH method was used to compare DPPH free radical clearance, and the test data are shown in table 1 and table 2:
TABLE 1
TABLE 2
As can be seen from table 1, the composite herbicides prepared in examples 1 to 3 have significant control effects on grassy weeds and broadleaf weeds, significant synergy and long duration compared with the comparative examples, and as can be seen from table 2, the composite herbicides prepared in examples 1 to 3 have a DPPH radical scavenging rate of about 91%, which indicates that the composite herbicides prepared in examples 1 to 3 have higher antioxidant activity than the comparative examples and are easy to store.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (9)
1. A herbicide based on haloxyfop-methyl, flumetsulam and halosulfuron-methyl is characterized by comprising the following raw materials in parts by weight: 1-15 parts of haloxyfop-methyl, 1-15 parts of flumetsulam, 1-37 parts of halosulfuron-methyl, 1-2 parts of modified antioxidant, 10-12 parts of borax, 6-8 parts of surfactant, 10-12 parts of triethanolamine, 10-12 parts of vegetable oil and 40-42 parts of deionized water;
the herbicide based on haloxyfop, flumetsulam and halosulfuron-methyl is prepared by the following steps:
step A1, mixing haloxyfop-methyl, flumetsulam, halosulfuron-methyl and deionized water, and performing ultrasonic dispersion for 40-60 minutes at the ultrasonic frequency of 80-90kHz to prepare suspension;
step A2, adding a modified antioxidant, borax and a surfactant into the suspension prepared in the step A1, controlling the heating temperature to be 50-55 ℃, and carrying out mixing reaction for 1.5-2 hours under the condition that the stirring speed is 200-220rpm to prepare a mixed liquid medicine;
step A3, mixing and stirring triethanolamine, vegetable oil and the mixed liquid medicine prepared in the step A2 at the speed of 230-240rpm for 0.5 hour, heating to 50-60 ℃, keeping the temperature and reacting for 4-6 hours, and cooling to room temperature to prepare the herbicide.
2. The haloxyfop, flumetsulam and halosulfuron-methyl based herbicide according to claim 1, characterized in that: the surfactant in the step A2 is one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, benzalkonium chloride, fatty glyceride and polysorbate, and is mixed according to any proportion.
3. The haloxyfop, flumetsulam and halosulfuron-methyl based herbicide according to claim 1, characterized in that: the vegetable oil in the step A3 is one or more of salad oil, soybean oil, castor oil, corn oil and olive oil, and is mixed according to any proportion.
4. The haloxyfop, flumetsulam and halosulfuron-methyl based herbicide according to claim 1, characterized in that: the specific preparation process of the modified antioxidant described in step A2 is as follows:
step S1, adding p-hydroxybenzaldehyde and ionic liquid [ bmim ] into a three-neck flask]Br3Stirring at 20 deg.C for 1 hr, adding 100g/L aqueous solution of sodium hydroxide, heating to 90-100 deg.C, reacting for 2 hr, and dissolving in hydrochloric acidAcidifying the solution to pH 5-5.5, extracting with ethyl acetate, washing the extractive solution with saturated saline, removing ethyl acetate, and recrystallizing the residue with water to obtain white crystal, i.e. intermediate 1;
step S2, adding the intermediate 1, malonic acid, a catalyst and acetonitrile prepared in the step S1 into a three-neck flask provided with a reflux condenser, introducing nitrogen for protection, stirring and refluxing for 1 hour, filtering and separating out the catalyst, and recrystallizing the filtrate with ethyl acetate to obtain an intermediate 2;
step S3, adding 2, 5-di-tert-butylhydroquinone and acetic acid into a three-neck flask provided with a dropping funnel, a condenser tube, a thermometer and a stirring magneton, dropwise adding acetic anhydride, stirring, heating in a water bath to 50 ℃, dropwise adding a mixture of 45g of concentrated nitric acid and acetic acid, keeping the temperature for reaction for 2 hours after dropwise adding, then cooling to room temperature, pouring the cooled reaction solution into 500mL of ice water, continuously stirring, filtering while cold to separate an oily solid, adding the oily solid into 30mL of deionized water, heating to 70 ℃, separating while hot to obtain an oily substance, and cooling to obtain a solid intermediate 3;
step S4, adding iron powder and a hydrochloric acid solution into a three-neck flask, refluxing for 0.5 hour at 105 ℃, adding the intermediate 3 prepared in the step S3, continuing to react for 2-3 hours, cooling to 80 ℃, adding 15-20mL of ethyl acetate to heavily separate layers, washing an organic layer with 20mL0.5mol/L sodium hydroxide solution, washing with deionized water to neutrality, filtering to remove iron powder, performing rotary evaporation on the mixture to 1/3 volume in a rotary evaporator, and finally performing freeze drying for 5-10 hours at-45 ℃ to obtain an intermediate 4;
step S5, taking the intermediate 2, triethylamine and tetrahydrofuran, magnetically stirring in a three-neck flask, adding the intermediate 4 at 0 ℃, then adding 4-dimethylaminopyridine, adding N, N' -dicyclohexylcarbodiimide after the reaction liquid is clarified, heating to 25 ℃, reacting for 3 hours, concentrating the reaction liquid under reduced pressure, adding 10mL of ethyl acetate into the concentrated liquid, extracting, shaking uniformly, placing in a refrigerator at-1 ℃ for 12 hours, extracting for three times with 10mL of ethyl acetate each time, washing the organic phase with 15mL of 5% sodium bicarbonate solution and 10mL of 1mmol/L hydrochloric acid solution, drying with 0.5-1g of anhydrous sodium sulfate, concentrating under reduced pressure, and obtaining the modified antioxidant.
5. The haloxyfop, flumetsulam and halosulfuron-methyl based herbicide according to claim 4, characterized in that: p-hydroxybenzaldehyde and ionic liquid [ bmim ] in step S1]Br3The dosage ratio of the sodium hydroxide aqueous solution, the ethyl acetate and the saturated saline solution is 25mmol: 15mL of: 20-30 mL: 30-35mL, the concentration of the hydrochloric acid solution is 0.1mol/L, and the stirring speed is 250-300 rpm.
6. The haloxyfop, flumetsulam and halosulfuron-methyl based herbicide according to claim 4, characterized in that: the dosage ratio of the intermediate 1, the malonic acid, the catalyst and the acetonitrile in the step S2 is 105 mg: 10 mmol: 90-95 mg: 20-25 mL.
7. The haloxyfop, flumetsulam and halosulfuron-methyl based herbicide according to claim 4, characterized in that: the dosage ratio of the 2, 5-di-tert-butylhydroquinone, the acetic acid and the acetic anhydride in the step S3 is 15 g: 14.6 g: 1g, and mixing concentrated nitric acid and acetic acid in a volume ratio of 1:2, wherein the volume fraction of the concentrated nitric acid is 42%.
8. The haloxyfop, flumetsulam and halosulfuron-methyl based herbicide according to claim 4, characterized in that: the mass ratio of the iron powder, the hydrochloric acid solution and the intermediate 3 in the step S4 is 1:0.5: 3; the dosage ratio of the intermediate 2, triethylamine, tetrahydrofuran, the intermediate 4, 4-dimethylaminopyridine and N, N' -dicyclohexylcarbodiimide in the step S5 is 98-103 mg: 3-5 mL: 5-6 mL: 78-84 mg: 8-10 mg: 12-15 mg.
9. The haloxyfop, flumetsulam and halosulfuron-methyl based herbicide according to claim 4, characterized in that: the catalyst of step S2 is prepared by the steps of:
25g of ZrCl2·8H2Dissolving O in 50mL of distilled water, and dropping the solution with stirring at the rotation speed of 200-240rpmSeparating 25% ammonia water to pH 8, filtering, washing precipitate with distilled water until no chloride ion exists, standing at 120 deg.C, and drying for 16 hr to obtain ZrO2ZrO of isotropic direction2Adding 60mL of 1mol/L sulfuric acid solution, soaking for 30 minutes, steaming in water bath to remove excessive water, drying at 120 ℃ for 12 hours, and calcining at 650 ℃ for 5 hours to obtain the catalyst.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113372851A (en) * | 2021-07-20 | 2021-09-10 | 安徽省奥佳建材有限公司 | Self-adhesive rubber waterproof coiled material and preparation method thereof |
| CN113519516A (en) * | 2021-08-26 | 2021-10-22 | 安徽省圣丹生物化工有限公司 | Propanil emulsifiable concentrate herbicide and preparation method thereof |
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| CN103766334A (en) * | 2013-12-24 | 2014-05-07 | 江苏天容集团股份有限公司 | Application of antioxidant in prevention and treatment of discoloration of amide herbicides |
| CN106332896A (en) * | 2016-08-26 | 2017-01-18 | 江苏富田农化有限公司 | Herbicide composition containing halosulfuron-methyl and haloxyfop-R-methyl and application |
| CN106689154A (en) * | 2016-12-19 | 2017-05-24 | 安徽丰乐农化有限责任公司 | Complex herbicide containing haloxyfop-R-methyl and flumetsulam |
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Patent Citations (3)
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| CN103766334A (en) * | 2013-12-24 | 2014-05-07 | 江苏天容集团股份有限公司 | Application of antioxidant in prevention and treatment of discoloration of amide herbicides |
| CN106332896A (en) * | 2016-08-26 | 2017-01-18 | 江苏富田农化有限公司 | Herbicide composition containing halosulfuron-methyl and haloxyfop-R-methyl and application |
| CN106689154A (en) * | 2016-12-19 | 2017-05-24 | 安徽丰乐农化有限责任公司 | Complex herbicide containing haloxyfop-R-methyl and flumetsulam |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113372851A (en) * | 2021-07-20 | 2021-09-10 | 安徽省奥佳建材有限公司 | Self-adhesive rubber waterproof coiled material and preparation method thereof |
| CN113519516A (en) * | 2021-08-26 | 2021-10-22 | 安徽省圣丹生物化工有限公司 | Propanil emulsifiable concentrate herbicide and preparation method thereof |
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