CN111972404A - Solvent for bensulfuron methyl, pretilachlor and fenclorim original drugs and missible oil preparation thereof - Google Patents
Solvent for bensulfuron methyl, pretilachlor and fenclorim original drugs and missible oil preparation thereof Download PDFInfo
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- CN111972404A CN111972404A CN202010913967.4A CN202010913967A CN111972404A CN 111972404 A CN111972404 A CN 111972404A CN 202010913967 A CN202010913967 A CN 202010913967A CN 111972404 A CN111972404 A CN 111972404A
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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
- A01N25/02—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 liquids as carriers, diluents or solvents
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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
- A01N25/02—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 liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
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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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
- A01N37/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides
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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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
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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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- Agronomy & Crop Science (AREA)
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Abstract
The invention relates to a pesticide solvent and an emulsifiable concentrate preparation, in particular to a solvent for bensulfuron-methyl, pretilachlor and fenclorim original drugs and an emulsifiable concentrate preparation thereof. The solvent comprises, by weight, 10-18 parts of a polar solvent, 1-2 parts of modified illegal cooking oil and 1-3 parts of an emulsifier. The raw materials of the emulsifiable concentrate preparation of the bensulfuron methyl, the pretilachlor and the fenclorim are solvent, bensulfuron methyl, pretilachlor and fenclorim. The solvent for the original medicines of the bensulfuron-methyl, the pretilachlor and the fenclorim has the advantages of low volatility, strong wetting permeability and high expansibility, and the obtained emulsifiable concentrate preparation of the original medicines of the bensulfuron-methyl, the pretilachlor and the fenclorim has good stability, is convenient to use and has good control effect on weeds.
Description
Technical Field
The invention relates to a pesticide solvent and an emulsifiable concentrate preparation, in particular to a solvent for bensulfuron-methyl, pretilachlor and fenclorim original drugs and an emulsifiable concentrate preparation thereof.
Background
China is a big agricultural country, weeds are an important factor influencing the crop yield in crop planting, and then a large number of herbicides are emerged on the market, and the herbicides usually exist in the dosage forms of missible oil, wettable powder and suspending agent. The suspending agent has high drug effect, environmental friendliness and high safety, but is easy to delaminate and agglomerate; the wettable powder is convenient to transport and use and cheap to process, but has the defects of dust pollution and toxicity; the missible oil preparation has the advantages of simple processing, stable quality, convenient use and mature processing technology, so the missible oil preparation has multiple varieties, large yield and wide application range, and is a main preparation formulation in China at present.
The most solvents used in the preparation of the emulsifiable concentrate preparation are benzene and xylene, which are strong carcinogenic substances, are inflammable and explosive and pollute the ecological environment, and some vegetable oil is also used in the market at present to replace benzene and xylene, but the vegetable oil is derived from green plants, so that the use of a large amount of vegetable oil is not beneficial to the full utilization of resources, and the emulsifiable concentrate preparation prepared by using the vegetable oil as the solvent has poor pesticide activity. The bensulfuron methyl technical, the pretilachlor technical and the fenclorim technical are commonly used herbicides, the bensulfuron methyl technical, the pretilachlor technical and the fenclorim technical are usually put together for use in the using process, and common solvents of the bensulfuron methyl technical are difficult to dissolve, so that the bensulfuron methyl technical is prepared into a suspending agent in the using process at present, but the suspending agent is easy to delaminate, agglomerate and has poor stability, so that a solvent is urgently needed to be prepared for dissolving the three technical to form an emulsifiable concentrate preparation with stable property, low volatility and strong wetting permeability.
Disclosure of Invention
In order to solve the technical problems, the invention provides a solvent for bensulfuron-methyl, pretilachlor and fenclorim technical materials, which comprises the following components of a polar solvent, modified illegal cooking oil and an emulsifier.
According to a preferable technical scheme, the solvent comprises, by weight, 10-18 parts of a polar solvent, 1-2 parts of modified illegal cooking oil and 1-3 parts of an emulsifier.
In a preferred embodiment of the present invention, the polar solvent is at least one selected from DMF, DMAC, acetone, ethanol, chloroform, diethyl ether, acetonitrile, methanol, tetrahydrofuran, dichloromethane, dioxane, propanol, n-butanol, and ethyl acetate.
As a preferable technical scheme, the modified illegal cooking oil is prepared by the following preparation method:
(1) preheating the illegal cooking oil to 100-120 ℃, and performing vacuum dehydration;
(2) adding methanol and Amberlyst 15 ion exchange resin into the illegal cooking oil dehydrated in the step (1), and heating and refluxing for 1-1.5h at the temperature of 110-120 ℃, wherein the adding amount of the methanol is 10-15% of the total mass of the illegal cooking oil, and the adding amount of the ion exchange resin is 0.8-2.3% of the total mass of the illegal cooking oil;
(3) carrying out sedimentation separation, discharging the lower-layer material in the step (2), and heating and stirring the upper-layer material at 100-120 ℃ for 1-3 h;
(4) washing the material treated in the step (3) with water for 5-7 times, adding potassium carbonate, reacting and stirring at the temperature of 90-110 ℃ for 12-18 min; the weight ratio of the potassium carbonate to the material treated in the step (3) is 1: 2.8 to 4.5;
(5) and (4) carrying out reduced pressure distillation on the material treated in the step (4) at 195-220 ℃ under 70-85 mmHg to obtain the modified illegal cooking oil.
In a preferred embodiment of the present invention, the emulsifier is an anionic surfactant and/or a nonionic surfactant.
As a preferred technical scheme of the invention, the anionic surfactant is perfluoroalkyl polyether phosphate; the nonionic surfactant is selected from at least one of Tween T-80, Tween T-60, Tween T-20, perfluoroalkyl polyether, isomeric tridecanol polyoxyethylene ether ES-1303, isomeric tridecanol polyoxyethylene ether ES-1305, isomeric tridecanol polyoxyethylene ether ES-1306, isomeric tridecanol polyoxyethylene ether ES-1307, isomeric tridecanol polyoxyethylene ether ES-1308, nonylphenol polyoxyethylene ether TX-4, nonylphenol polyoxyethylene ether TX-9, nonylphenol polyoxyethylene ether TX-7 and nonylphenol polyoxyethylene ether TX-9.
As a preferable technical scheme of the invention, the emulsifier is a mixture of perfluoroalkyl polyether and perfluoroalkyl polyether phosphate.
The second aspect of the invention provides an emulsifiable concentrate preparation of bensulfuron methyl, pretilachlor and fenclorim technical materials, which comprises the following components: solvent, bensulfuron methyl technical, pretilachlor technical and fenclorim technical; the solvent is the solvent of the present invention.
As a preferable technical scheme, the emulsifiable concentrate preparation of the bensulfuron methyl, the pretilachlor and the fenclorim is prepared by the following preparation processes:
(1) mixing and stirring a polar solvent and the modified illegal cooking oil uniformly, conveying the mixture into a reaction kettle by using a pneumatic diaphragm pump, adding a bensulfuron methyl original drug into the reaction kettle, and mixing and dissolving for 10-30min at the condition of 60-80 rpm/min;
(2) continuously conveying the pretilachlor technical and the fenclorim technical to the reaction materials in the step (1) by using a pneumatic diaphragm pump, and mixing and dissolving for 20-50min at the speed of 60-80 rpm/min;
(3) and (3) mixing and stirring the emulsifier and the modified illegal cooking oil uniformly, then throwing the mixture into the reaction material treated in the step (2) by using a pneumatic diaphragm pump, and mixing and dissolving the mixture for 40-120min under the condition of 60-80 rpm/min to prepare the emulsifiable concentrate preparation of bensulfuron methyl, pretilachlor and fenclorim original drugs.
As a preferable technical scheme of the invention, the weight ratio of the polar solvent, the modified gutter oil and the bensulfuron methyl raw pesticide in the step (1) is (50-68): (10-24): (1-4); the ratio of the addition amount of the pretilachlor technical and the fenclorim technical in the step (2) to the weight of the bensulfuron methyl technical in the step (1) is (15-40): (5-15): (1-5); the weight ratio of the emulsifier and the modified illegal cooking oil in the step (3) to the polar solvent in the step (1) is (5-15): (5-8): (50-68).
The invention has the following beneficial effects:
1. the solvent for the bensulfuron methyl, pretilachlor and fenclorim technical has the advantages of low volatility, strong wetting permeability and high expansibility;
2. the illegal cooking oil is reasonably used, the waste raw materials are utilized, the pollution is reduced, and the product cost is low;
3. amberlyst 15 ion exchange resin is adopted in the process of preparing the modified illegal cooking oil, and the Amberlyst 15 ion exchange resin is a strong acid type catalyst which can be repeatedly used;
4. the reasonable preparation steps of the emulsifiable concentrate preparation of the bensulfuron methyl, the pretilachlor and the fenclorim raw pesticide enable the stability of the finally prepared emulsifiable concentrate preparation of the bensulfuron methyl, the pretilachlor and the fenclorim raw pesticide to be better;
5. the stability of the emulsifiable concentrate preparation of the original pesticide bensulfuron-methyl, pretilachlor and fenclorim is better by adding a proper amount of emulsifier, the synergistic action of the emulsifier and the modified illegal cooking oil;
6. compared with the pesticide suspending agent, the emulsifiable concentrate preparation of the bensulfuron methyl, the pretilachlor and the fenclorim technical material has stable quality and convenient use.
Detailed Description
The invention provides a solvent for bensulfuron-methyl, pretilachlor and fenclorim technical, which comprises a polar solvent, modified illegal cooking oil and an emulsifier.
Preferably, the solvent comprises, by weight, 10-18 parts of a polar solvent, 1-2 parts of modified illegal cooking oil and 1-3 parts of an emulsifier.
The polar solvent is at least one selected from DMF, DMAC, acetone, ethanol, chloroform, diethyl ether, acetonitrile, methanol, tetrahydrofuran, dichloromethane, dioxane, propanol, n-butanol and ethyl acetate.
Preferably, the polar solvent is a mixture of DMAC, acetone, ethanol, n-butanol.
More preferably, the polar solvent is 9-12 wt% of DMAC, 8-11 wt% of acetone, 36-48 wt% of ethanol, 29-47 wt% of n-butanol.
The polar solvent is excellent in solubility, and can disperse a pesticide dissolved therein into a stable homogeneous liquid to improve the flowability of the resulting product. And the DMAC, the acetone, the ethanol and the n-butyl alcohol are mixed together, so that the DMAC, the acetone, the ethanol and the n-butyl alcohol can be well dissolved with organic solvents such as ether, ketone and ester, can be well dissolved with raw medicines, and can also be well dissolved with water. Acetone, the water solubility of ethanol is better than DMAC, n-butanol, but acetone, ethanol, the flash point of n-butanol is lower, and chemical property is more active, compares, and DMAC can be better mutually soluble with organic solvent to it has the thermal stability height, is difficult for hydrolysising, advantage such as corrosion-resistant, so when using the built polar solvent of DMAC, acetone, ethanol, n-butanol, make polar solvent's solubility, thermal stability better.
The modified illegal cooking oil is prepared by the following preparation method:
(1) preheating the illegal cooking oil to 100-120 ℃, and performing vacuum dehydration;
(2) adding methanol and Amberlyst 15 ion exchange resin into the illegal cooking oil dehydrated in the step (1), and heating and refluxing for 1-1.5h at the temperature of 110-120 ℃, wherein the adding amount of the methanol is 10-15% of the total mass of the illegal cooking oil, and the adding amount of the ion exchange resin is 0.8-2.3% of the total mass of the illegal cooking oil;
(3) carrying out sedimentation separation, discharging the lower-layer material in the step (2), and heating and stirring the upper-layer material at 100-120 ℃ for 1-3 h;
(4) washing the material treated in the step (3) with water for 5-7 times, adding potassium carbonate, reacting and stirring at the temperature of 90-110 ℃ for 12-18 min; the weight ratio of the potassium carbonate to the material treated in the step (3) is 1: 2.8 to 4.5;
(5) and (4) carrying out reduced pressure distillation on the material treated in the step (4) at 195-220 ℃ under 70-85 mmHg to obtain the modified illegal cooking oil.
The waste cooking oil is waste edible oil of catering industry obtained from industrial and commercial departments.
The Amberlyst 15 ion exchange resin was purchased from Keye chemical industry.
The emulsifier is anionic surfactant and/or nonionic surfactant.
The anionic surfactant is perfluoroalkyl polyether phosphate.
The nonionic surfactant is selected from at least one of Tween T-80, Tween T-60, Tween T-20, perfluoroalkyl polyether, isomeric tridecanol polyoxyethylene ether ES-1303, isomeric tridecanol polyoxyethylene ether ES-1305, isomeric tridecanol polyoxyethylene ether ES-1306, isomeric tridecanol polyoxyethylene ether ES-1307, isomeric tridecanol polyoxyethylene ether ES-1308, nonylphenol polyoxyethylene ether TX-4, nonylphenol polyoxyethylene ether TX-9, nonylphenol polyoxyethylene ether TX-7 and nonylphenol polyoxyethylene ether TX-9.
Preferably, the emulsifier is a mixture of perfluoroalkyl polyether and perfluoroalkyl polyether phosphate.
More preferably, the emulsifier is a mixture of 30-50 wt% perfluoroalkyl polyether and 50-70 wt% perfluoroalkyl polyether phosphate.
The anionic surfactant and the nonionic surfactant are purchased from Heisen chemical Co., Ltd.
The anionic surfactant can ionize hydrophilic anions in water, so that the anionic surfactant has good hydrophilicity, and the nonionic surfactant has lipophilic groups and hydrophilic groups, so that the nonionic surfactant can be dissolved in an organic solvent and water, and has extremely high thermal stability and chemical stability. The nonionic surfactant and the anionic surfactant have good compatibility, and the emulsifying property of the compounded emulsifier is better.
The solvent for the bensulfuron methyl, the pretilachlor and the fenclorim raw pesticide can be prepared into the emulsifiable concentrate preparation by mixing the components of the solvent together to dissolve the raw pesticide and can also be prepared into the emulsifiable concentrate preparation by adding the components of the pesticide solvent into the raw pesticide in multiple steps to dissolve the raw pesticide.
The second aspect of the invention provides an emulsifiable concentrate preparation of bensulfuron methyl, pretilachlor and fenclorim technical materials, which comprises the following components: solvent, bensulfuron methyl technical, pretilachlor technical and fenclorim technical; the solvent is the solvent of the present invention.
The emulsifiable concentrate preparation of the bensulfuron methyl, the pretilachlor and the fenclorim is prepared by the following preparation process:
(1) mixing and stirring a polar solvent and the modified illegal cooking oil uniformly, conveying the mixture into a reaction kettle by using a pneumatic diaphragm pump, adding a bensulfuron methyl original drug into the reaction kettle, and mixing and dissolving for 10-30min at the condition of 60-80 rpm/min;
(2) continuously conveying the pretilachlor technical and the fenclorim technical to the reaction materials in the step (1) by using a pneumatic diaphragm pump, and mixing and dissolving for 20-50min at the speed of 60-80 rpm/min;
(3) and (3) mixing and stirring the emulsifier and the modified illegal cooking oil uniformly, then throwing the mixture into the reaction material treated in the step (2) by using a pneumatic diaphragm pump, and mixing and dissolving the mixture for 40-120min under the condition of 60-80 rpm/min to prepare the emulsifiable concentrate preparation of bensulfuron methyl, pretilachlor and fenclorim original drugs.
Preferably, the weight ratio of the polar solvent, the modified gutter oil and the bensulfuron methyl raw pesticide in the step (1) is (50-68): (10-24): (1-4); the ratio of the addition amount of the pretilachlor technical and the fenclorim technical in the step (2) to the weight of the bensulfuron methyl technical in the step (1) is (15-40): (5-15): (1-5); the weight ratio of the emulsifier and the modified illegal cooking oil in the step (3) to the polar solvent in the step (1) is (5-15): (5-8): (50-68).
More preferably, the weight ratio of the emulsifier and the modified illegal cooking oil in the step (3) to the polar solvent in the step (1) is (8-12): (5-8): (50-68).
The bensulfuron methyl, pretilachlor and fenclorim original pesticide emulsifiable concentrate preparation is prepared by firstly adding bensulfuron methyl original pesticide into a mixture of a polar solvent and modified illegal cooking oil, and mixing and dissolving for a period of time; then adding the pretilachlor technical and the fenclorim technical, mixing and dissolving for a period of time, wherein the technical is added step by step, so that the material has better dispersion performance in the preparation process, and the finally formed missible oil preparation is more stable; and finally, mixing the emulsifier and the modified illegal cooking oil, adding the emulsifier and the modified illegal cooking oil into the materials, wherein the main chemical component of the modified illegal cooking oil is fatty acid methyl ester which can be well compatible with the emulsifier, so that the viscosity of the emulsifier is reduced, and the emulsifier can better play the role of the emulsifier.
The polar solvent is a compound of DMAC, acetone, ethanol and n-butyl alcohol, can be dissolved in water and can also be dissolved in the original drug, so that the polar solvent can well dilute the original drug, the original drug is dispersed to form stable homogeneous liquid, and the fluidity of the missible oil preparation is improved; the modified illegal cooking oil has strong spreadability and detention property, can increase the coverage of pesticides on crops, is not easy to be washed away by rainwater and run off, has strong stability, and has high flash point and low volatility of the prepared solvent, namely the prepared missible oil preparation containing the pesticide solvent has good stability, so the production, storage and transportation of the missible oil preparation are safe, and the emulsification effect and the system stability of the emulsifier are improved due to the synergistic effect between the modified illegal cooking oil and the emulsifier; the addition of the emulsifier can form an interfacial film on the surface of a raw pesticide, so that the stability of a system is maintained, and the oil phase surface energy formed by the raw pesticide and an organic solvent is reduced, so that the raw pesticide in the emulsifiable concentrate preparation can be uniformly dispersed in water in the later use process to form stable emulsion, the emulsifier is preferably a mixture of 30-50 wt% of perfluoroalkyl polyether and 50-70 wt% of perfluoroalkyl polyether phosphate, the interfacial film formed by the synergistic action of the two emulsifiers has higher strength, so that the stability of the system is better, and the applicant finds that the stability of the emulsifiable concentrate preparation containing the solvent is influenced by the excessive or insufficient dosage of the emulsifier, and the possible reason is that: the surface tension of the raw pesticide is reduced along with the increase of the emulsifying agent, when the emulsifying agent is increased to a certain degree, the surface tension of the raw pesticide reaches an equilibrium state, at the moment, the emulsifying agent is most effectively adsorbed on the surface of the raw pesticide, the formed membrane is most stable, if the emulsifying agent is continuously increased, the increased emulsifying agent can not be adsorbed on the surface of the raw pesticide, but the equilibrium state of the system is damaged, so that the stability of the system is reduced.
Several specific examples of the present invention are given below, but the present invention is not limited by the examples.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Examples
Example 1
A solvent for bensulfuron-methyl, pretilachlor and fenclorim raw medicines comprises, by weight, 10 parts of a polar solvent, 1 part of modified illegal cooking oil and 1 part of an emulsifier.
The polar solvent is 9 wt% of DMAC, 8 wt% of acetone, 48 wt% of ethanol and 35 wt% of n-butanol.
The modified illegal cooking oil is prepared by the following preparation method:
(1) preheating the swill-cooked dirty oil to 100 ℃, and performing vacuum dehydration;
(2) adding methanol and Amberlyst 15 ion exchange resin into the drainage oil dehydrated in the step (1), and heating and refluxing for 1.5h at 110 ℃, wherein the addition amount of the methanol is 10% of the total mass of the drainage oil, and the addition amount of the ion exchange resin is 0.8% of the total mass of the drainage oil;
(3) carrying out sedimentation separation, discharging the lower-layer material in the step (2), and heating and stirring the upper-layer material at 100 ℃ for 3 h;
(4) washing the material treated in the step (3) with water for 5 times, adding potassium carbonate, reacting and stirring at the temperature of 90 ℃ for 18 min; the weight ratio of the potassium carbonate to the material treated in the step (3) is 1: 2.8 of;
(5) and (4) carrying out reduced pressure distillation on the material treated in the step (4) at 195 ℃ and 85mmHg to obtain the modified illegal cooking oil.
The emulsifier is a mixture of 30 wt% perfluoroalkyl polyether and 70 wt% perfluoroalkyl polyether phosphate.
The emulsifiable concentrate preparation of the bensulfuron methyl, the pretilachlor and the fenclorim is prepared by the following preparation process:
(1) mixing and stirring the polar solvent and the modified swill-cooked dirty oil uniformly, conveying the mixture into a reaction kettle by using a pneumatic diaphragm pump, adding the bensulfuron methyl raw pesticide into the reaction kettle, and mixing and dissolving for 30min at the condition of 60 rpm/min;
(2) continuously conveying the pretilachlor technical and the fenclorim technical to the reaction materials in the step (1) by using a pneumatic diaphragm pump, and mixing and dissolving for 50min at the speed of 60 rpm/min;
(3) and (3) mixing and stirring the emulsifier and the modified illegal cooking oil uniformly, then throwing the mixture into the reaction material treated in the step (2) by using a pneumatic diaphragm pump, and mixing and dissolving the mixture for 120min under the condition of 60rpm/min to prepare the emulsifiable concentrate preparation of the bensulfuron methyl, the pretilachlor and the fenclorim original drugs.
The weight ratio of the polar solvent, the modified gutter oil and the bensulfuron methyl raw pesticide in the step (1) is 50: 10: 1; the weight ratio of the addition amount of the pretilachlor technical and the fenclorim technical in the step (2) to the bensulfuron methyl technical in the step (1) is 15: 5: 1; the weight ratio of the emulsifier and the modified illegal cooking oil in the step (3) to the polar solvent in the step (1) is 5: 5: 50.
example 2
A solvent for bensulfuron-methyl, pretilachlor and fenclorim raw medicines comprises, by weight, 18 parts of a polar solvent, 2 parts of modified illegal cooking oil and 3 parts of an emulsifier.
The polar solvent is 12 wt% of DMAC, 11 wt% of acetone, 39 wt% of ethanol and 38 wt% of n-butanol.
The modified illegal cooking oil is prepared by the following preparation method:
(1) preheating the swill-cooked dirty oil to 120 ℃, and performing vacuum dehydration;
(2) adding methanol and Amberlyst 15 ion exchange resin into the drainage oil dehydrated in the step (1), and heating and refluxing for 1h at 120 ℃, wherein the addition amount of the methanol is 15% of the total mass of the drainage oil, and the addition amount of the ion exchange resin is 2.3% of the total mass of the drainage oil;
(3) carrying out sedimentation separation, discharging the lower-layer material in the step (2), and heating and stirring the upper-layer material at 120 ℃ for 1 h;
(4) washing the material treated in the step (3) with water for 7 times, adding potassium carbonate, reacting and stirring at the temperature of 110 ℃ for 12 min; the weight ratio of the potassium carbonate to the material treated in the step (3) is 1: 4.5;
(5) and (4) carrying out reduced pressure distillation on the material treated in the step (4) at 220 ℃ under 70mmHg to obtain the modified illegal cooking oil.
The emulsifier is a mixture of 50 wt% perfluoroalkyl polyether and 50 wt% perfluoroalkyl polyether phosphate.
The emulsifiable concentrate preparation of the bensulfuron methyl, the pretilachlor and the fenclorim is prepared by the following preparation process:
(1) mixing and stirring the polar solvent and the modified swill-cooked dirty oil uniformly, conveying the mixture into a reaction kettle by using a pneumatic diaphragm pump, adding the bensulfuron methyl raw pesticide into the reaction kettle, and mixing and dissolving for 10min at the condition of 80 rpm/min;
(2) continuously conveying the pretilachlor technical and the fenclorim technical to the reaction materials in the step (1) by using a pneumatic diaphragm pump, and mixing and dissolving for 20min at the condition of 80 rpm/min;
(3) and (3) mixing and stirring the emulsifier and the modified illegal cooking oil uniformly, then throwing the mixture into the reaction material treated in the step (2) by using a pneumatic diaphragm pump, and mixing and dissolving the mixture for 40min under the condition of 80rpm/min to prepare the emulsifiable concentrate preparation of the bensulfuron methyl, the pretilachlor and the fenclorim original drugs.
The weight ratio of the polar solvent, the modified gutter oil and the bensulfuron methyl raw pesticide in the step (1) is 68: 24: 4; the weight ratio of the addition amount of the pretilachlor technical and the fenclorim technical in the step (2) to the bensulfuron methyl technical in the step (1) is 20: 7: 2; the weight ratio of the emulsifier and the modified illegal cooking oil in the step (3) to the polar solvent in the step (1) is 15: 8: 68.
example 3
A solvent for bensulfuron-methyl, pretilachlor and fenclorim raw medicines comprises, by weight, 15 parts of a polar solvent, 1.5 parts of modified illegal cooking oil and 1.5 parts of an emulsifier.
The polar solvent is 11 wt% of DMAC, 10 wt% of acetone, 42 wt% of ethanol and 37 wt% of n-butanol.
The modified illegal cooking oil is prepared by the following preparation method:
(1) preheating the swill-cooked dirty oil to 110 ℃, and performing vacuum dehydration;
(2) adding methanol and Amberlyst 15 ion exchange resin into the drainage oil dehydrated in the step (1), and heating and refluxing for 1.3h at 115 ℃, wherein the addition amount of the methanol is 12% of the total mass of the drainage oil, and the addition amount of the ion exchange resin is 1.5% of the total mass of the drainage oil;
(3) carrying out sedimentation separation, discharging the lower-layer material in the step (2), and heating and stirring the upper-layer material at 110 ℃ for 1.5 h;
(4) washing the material treated in the step (3) with water for 6 times, adding potassium carbonate, reacting and stirring at the temperature of 100 ℃ for 15 min; the weight ratio of the potassium carbonate to the material treated in the step (3) is 1: 3.5;
(5) and (4) carrying out reduced pressure distillation on the material treated in the step (4) at 210 ℃ and 75mmHg to obtain the modified illegal cooking oil.
The emulsifier is a mixture of 40 wt% perfluoroalkyl polyether and 60 wt% perfluoroalkyl polyether phosphate.
The emulsifiable concentrate preparation of the bensulfuron methyl, the pretilachlor and the fenclorim is prepared by the following preparation process:
(1) mixing and stirring the polar solvent and the modified swill-cooked dirty oil uniformly, conveying the mixture into a reaction kettle by using a pneumatic diaphragm pump, adding the bensulfuron methyl raw pesticide into the reaction kettle, and mixing and dissolving for 20min at the condition of 70 rpm/min;
(2) continuously conveying the pretilachlor technical and the fenclorim technical to the reaction materials in the step (1) by using a pneumatic diaphragm pump, and mixing and dissolving for 40min at the condition of 70 rpm/min;
(3) and (3) mixing and stirring the emulsifier and the modified illegal cooking oil uniformly, then throwing the mixture into the reaction material treated in the step (2) by using a pneumatic diaphragm pump, and mixing and dissolving the mixture for 80min under the condition of 70rpm/min to prepare the emulsifiable concentrate preparation containing the bensulfuron methyl, the pretilachlor and the fenclorim original drugs.
The weight ratio of the polar solvent, the modified gutter oil and the bensulfuron methyl raw pesticide in the step (1) is 60: 17: 2; the weight ratio of the addition amount of the pretilachlor technical and the fenclorim technical in the step (2) to the bensulfuron methyl technical in the step (1) is 28: 8: 2; the weight ratio of the emulsifier and the modified illegal cooking oil in the step (3) to the polar solvent in the step (1) is 10: 6: 60.
comparative example 1
A solvent for bensulfuron-methyl, pretilachlor and fenclorim raw medicines comprises, by weight, 15 parts of a polar solvent, 1.5 parts of modified illegal cooking oil and 1.5 parts of an emulsifier.
The polar solvent is 35 wt% de acetone and 65 wt% ethanol.
The preparation method of the modified illegal cooking oil is the same as that of the example 3.
The emulsifier was the same as in example 3.
The preparation process of the emulsifiable concentrate preparation of the bensulfuron methyl, the pretilachlor and the fenclorim is the same as that of the embodiment 3.
Comparative example 2
A solvent for bensulfuron-methyl, pretilachlor and fenclorim raw medicines comprises, by weight, 15 parts of a polar solvent, 1.5 parts of modified illegal cooking oil and 1.5 parts of an emulsifier.
The polar solvent is 35 wt% of DMAC and 65 wt% of n-butanol.
The preparation method of the modified illegal cooking oil is the same as that of the example 3
The emulsifier was the same as in example 3.
The preparation process of the emulsifiable concentrate preparation of the bensulfuron methyl, the pretilachlor and the fenclorim is the same as that of the embodiment 3.
Comparative example 3
A solvent for bensulfuron-methyl, pretilachlor and fenclorim original drugs, which is the solvent in example 3.
The emulsifiable concentrate preparation of the bensulfuron methyl, the pretilachlor and the fenclorim is prepared by the following preparation process:
(1) mixing and stirring the polar solvent and the modified swill-cooked dirty oil uniformly, conveying the mixture into a reaction kettle by using a pneumatic diaphragm pump, adding the bensulfuron methyl raw pesticide into the reaction kettle, and mixing and dissolving for 20min at the condition of 70 rpm/min;
(2) continuously conveying the pretilachlor technical and the fenclorim technical to the reaction materials in the step (1) by using a pneumatic diaphragm pump, and mixing and dissolving for 40min at the condition of 70 rpm/min;
(3) and (3) mixing and stirring the emulsifier and the modified illegal cooking oil uniformly, then throwing the mixture into the reaction material treated in the step (2) by using a pneumatic diaphragm pump, and mixing and dissolving the mixture for 80min under the condition of 70rpm/min to prepare the emulsifiable concentrate preparation of the bensulfuron methyl, the pretilachlor and the fenclorim original drugs.
The weight ratio of the polar solvent, the modified gutter oil and the bensulfuron methyl raw pesticide in the step (1) is 60: 17: 2; the weight ratio of the addition amount of the pretilachlor technical and the fenclorim technical in the step (2) to the bensulfuron methyl technical in the step (1) is 28: 8: 2; the weight ratio of the emulsifier and the modified illegal cooking oil in the step (3) to the polar solvent in the step (1) is 5: 6: 60.
comparative example 4
A solvent for bensulfuron-methyl, pretilachlor and fenclorim original drugs, which is the solvent in example 3.
The emulsifiable concentrate preparation of the bensulfuron methyl, the pretilachlor and the fenclorim is prepared by the following preparation process:
(1) mixing and stirring the polar solvent and the modified swill-cooked dirty oil uniformly, conveying the mixture into a reaction kettle by using a pneumatic diaphragm pump, adding the bensulfuron methyl raw pesticide into the reaction kettle, and mixing and dissolving for 20min at the condition of 70 rpm/min;
(2) continuously conveying the pretilachlor technical and the fenclorim technical to the reaction materials in the step (1) by using a pneumatic diaphragm pump, and mixing and dissolving for 40min at the condition of 70 rpm/min;
(3) and (3) mixing and stirring the emulsifier and the modified illegal cooking oil uniformly, then throwing the mixture into the reaction material treated in the step (2) by using a pneumatic diaphragm pump, and mixing and dissolving the mixture for 80min under the condition of 70rpm/min to prepare the emulsifiable concentrate preparation of the bensulfuron methyl, the pretilachlor and the fenclorim original drugs.
The weight ratio of the polar solvent, the modified gutter oil and the bensulfuron methyl raw pesticide in the step (1) is 60: 17: 2; the weight ratio of the addition amount of the pretilachlor technical and the fenclorim technical in the step (2) to the bensulfuron methyl technical in the step (1) is 28: 8: 2; the weight ratio of the emulsifier and the modified illegal cooking oil in the step (3) to the polar solvent in the step (1) is 8: 6: 60.
comparative example 5
A solvent for bensulfuron-methyl, pretilachlor and fenclorim original drugs, which is the solvent in example 3.
The emulsifiable concentrate preparation of the bensulfuron methyl, the pretilachlor and the fenclorim is prepared by the following preparation process:
(1) mixing and stirring the polar solvent and the modified swill-cooked dirty oil uniformly, conveying the mixture into a reaction kettle by using a pneumatic diaphragm pump, adding the bensulfuron methyl raw pesticide into the reaction kettle, and mixing and dissolving for 20min at the condition of 70 rpm/min;
(2) continuously conveying the pretilachlor technical and the fenclorim technical to the reaction materials in the step (1) by using a pneumatic diaphragm pump, and mixing and dissolving for 40min at the condition of 70 rpm/min;
(3) and (3) mixing and stirring the emulsifier and the modified illegal cooking oil uniformly, then throwing the mixture into the reaction material treated in the step (2) by using a pneumatic diaphragm pump, and mixing and dissolving the mixture for 80min under the condition of 70rpm/min to prepare the emulsifiable concentrate preparation of the bensulfuron methyl, the pretilachlor and the fenclorim original drugs.
The weight ratio of the polar solvent, the modified gutter oil and the bensulfuron methyl raw pesticide in the step (1) is 60: 17: 2; the weight ratio of the addition amount of the pretilachlor technical and the fenclorim technical in the step (2) to the bensulfuron methyl technical in the step (1) is 28: 8: 2; the weight ratio of the emulsifier and the modified illegal cooking oil in the step (3) to the polar solvent in the step (1) is 15: 6: 60.
comparative example 6
A solvent for bensulfuron-methyl, pretilachlor and fenclorim raw pesticide comprises 15 parts by weight of polar solvent and 1.5 parts by weight of emulsifier.
The polar solvent is 11 wt% of DMAC, 10 wt% of acetone, 42 wt% of ethanol and 37 wt% of n-butanol.
The emulsifier is a mixture of 40 wt% perfluoroalkyl polyether and 60 wt% perfluoroalkyl polyether phosphate.
The emulsifiable concentrate preparation of the bensulfuron methyl, the pretilachlor and the fenclorim is prepared by the following preparation process:
(1) conveying a polar solvent into a reaction kettle by using a pneumatic diaphragm pump, adding a bensulfuron methyl original drug into the reaction kettle, and mixing and dissolving for 20min at the condition of 70 rpm/min;
(2) continuously conveying the pretilachlor technical and the fenclorim technical to the reaction materials in the step (1) by using a pneumatic diaphragm pump, and mixing and dissolving for 40min at the condition of 70 rpm/min;
(3) and (3) putting an emulsifier into the reaction material treated in the step (2) by using a pneumatic diaphragm pump, and mixing and dissolving for 80min under the condition of 70rpm/min to prepare the emulsifiable concentrate preparation of the bensulfuron methyl, the pretilachlor and the fenclorim original drugs.
The weight ratio of the polar solvent to the bensulfuron methyl technical in the step (1) is 60: 2; the weight ratio of the addition amount of the pretilachlor technical and the fenclorim technical in the step (2) to the bensulfuron methyl technical in the step (1) is 28: 8: 2; the weight ratio of the emulsifier in the step (3) to the polar solvent in the step (1) is 10: 60.
after the emulsifiable concentrate preparation of the bensulfuron methyl, the pretilachlor and the fenclorim original drug prepared in the examples 1 to 3 and the comparative examples 1 to 6 is subjected to cold storage (0 +/-2 ℃) for 7 days and (54 +/-2 ℃) for 14 days, the average decomposition rate of the bensulfuron methyl original drug, the pretilachlor original drug and the fenclorim original drug is detected. The results are shown in table 1:
TABLE 1
| Examples and comparative examples | Storing for 7 days at 0 +/-2 DEG C | Through heat storage (54 +/-2 ℃) for 14 days |
| Example 1 | 0.08％ | 0.35％ |
| Example 2 | 0.04％ | 0.18％ |
| Example 3 | 0.02％ | 0.15％ |
| Comparative example 1 | 0.06％ | 0.22％ |
| Comparative example 2 | 0.04％ | 0.79％ |
| Comparative example 3 | 0.26％ | 0.47％ |
| Comparative example 4 | 0.07％ | 0.32％ |
| Comparative example 5 | 0.18％ | 0.42％ |
| Comparative example 6 | 0.19％ | 0.61％ |
The stability test of the emulsifiable concentrate preparation of bensulfuron-methyl, pretilachlor and fenclorim is carried out on examples 1-3 and comparative examples 1-6, and example 3 is the best example of the embodiment of the invention.
Claims (10)
1. A solvent for bensulfuron-methyl, pretilachlor and fenclorim raw pesticide is characterized by comprising a polar solvent, modified illegal cooking oil and an emulsifier.
2. The solvent for bensulfuron, pretilachlor and fenclorim raw pesticide as claimed in claim 1, wherein the solvent comprises 10-18 parts by weight of polar solvent, 1-2 parts by weight of modified gutter oil and 1-3 parts by weight of emulsifier.
3. The solvent for bensulfuron, pretilachlor and fenclorim technical product according to claim 1 or 2, characterized in that the polar solvent is selected from at least one of DMF, DMAC, acetone, ethanol, chloroform, diethyl ether, acetonitrile, methanol, tetrahydrofuran, dichloromethane, dioxane, propanol, n-butanol and ethyl acetate.
4. The solvent for bensulfuron, pretilachlor and fenclorim raw pesticide as claimed in claim 1 or 2, wherein the modified gutter oil is prepared by the following preparation method:
(1) preheating the illegal cooking oil to 100-120 ℃, and performing vacuum dehydration;
(2) adding methanol and Amberlyst 15 ion exchange resin into the illegal cooking oil dehydrated in the step (1), and heating and refluxing for 1-1.5h at the temperature of 110-120 ℃, wherein the adding amount of the methanol is 10-15% of the total mass of the illegal cooking oil, and the adding amount of the ion exchange resin is 0.8-2.3% of the total mass of the illegal cooking oil;
(3) carrying out sedimentation separation, discharging the lower-layer material in the step (2), and heating and stirring the upper-layer material at 100-120 ℃ for 1-3 h;
(4) washing the material treated in the step (3) with water for 5-7 times, adding potassium carbonate, reacting and stirring at the temperature of 90-110 ℃ for 12-18 min; the weight ratio of the potassium carbonate to the material treated in the step (3) is 1: 2.8 to 4.5;
(5) and (4) carrying out reduced pressure distillation on the material treated in the step (4) at 195-220 ℃ under 70-85 mmHg to obtain the modified illegal cooking oil.
5. The solvent for bensulfuron, pretilachlor and fenclorim technical product according to claim 1 or 2, characterized in that the emulsifier is an anionic surfactant and/or a nonionic surfactant.
6. The solvent for bensulfuron, pretilachlor and fenclorim technical product as claimed in claim 5, characterized in that the anionic surfactant is perfluoroalkyl polyether phosphate; the nonionic surfactant is selected from at least one of Tween T-80, Tween T-60, Tween T-20, perfluoroalkyl polyether, isomeric tridecanol polyoxyethylene ether ES-1303, isomeric tridecanol polyoxyethylene ether ES-1305, isomeric tridecanol polyoxyethylene ether ES-1306, isomeric tridecanol polyoxyethylene ether ES-1307, isomeric tridecanol polyoxyethylene ether ES-1308, nonylphenol polyoxyethylene ether TX-4, nonylphenol polyoxyethylene ether TX-9, nonylphenol polyoxyethylene ether TX-7 and nonylphenol polyoxyethylene ether TX-9.
7. The solvent for bensulfuron, pretilachlor and fenclorim technical according to claim 6, characterized in that the emulsifier is a mixture of perfluoroalkyl polyether and perfluoroalkyl polyether phosphate.
8. An emulsifiable concentrate preparation of bensulfuron methyl, pretilachlor and fenclorim raw pesticide is characterized by comprising the following components: solvent, bensulfuron methyl technical, pretilachlor technical and fenclorim technical; the solvent is the solvent for bensulfuron-methyl, pretilachlor and fenclorim technical product as claimed in any one of claims 1 to 7.
9. The emulsifiable concentrate preparation of bensulfuron-methyl, pretilachlor and fenclorim as claimed in claim 8, which is prepared from the following raw materials:
(1) mixing and stirring a polar solvent and the modified illegal cooking oil uniformly, conveying the mixture into a reaction kettle by using a pneumatic diaphragm pump, adding a bensulfuron methyl original drug into the reaction kettle, and mixing and dissolving for 10-30min at the condition of 60-80 rpm/min;
(2) continuously conveying the pretilachlor technical and the fenclorim technical to the reaction materials in the step (1) by using a pneumatic diaphragm pump, and mixing and dissolving for 20-50min at the speed of 60-80 rpm/min;
(3) and (3) mixing and stirring the emulsifier and the modified illegal cooking oil uniformly, then throwing the mixture into the reaction material treated in the step (2) by using a pneumatic diaphragm pump, and mixing and dissolving the mixture for 40-120min under the condition of 60-80 rpm/min to prepare the emulsifiable concentrate preparation of bensulfuron methyl, pretilachlor and fenclorim original drugs.
10. An emulsifiable concentrate formulation as claimed in claim 9, wherein the weight ratio of the polar solvent, the modified gutter oil and the bensulfuron methyl raw pesticide in step (1) is (50-68): (10-24): (1-4); the ratio of the addition amount of the pretilachlor technical and the fenclorim technical in the step (2) to the weight of the bensulfuron methyl technical in the step (1) is (15-40): (5-15): (1-5); the weight ratio of the emulsifier and the modified illegal cooking oil in the step (3) to the polar solvent in the step (1) is (5-15): (5-8): (50-68).
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