WO2021093267A1 - Composite insecticidal and acaricidal nano-aqueous agent containing fenpropathrin and chlorpyrifos, and preparation method therefor and use thereof - Google Patents
Composite insecticidal and acaricidal nano-aqueous agent containing fenpropathrin and chlorpyrifos, and preparation method therefor and use thereof Download PDFInfo
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- WO2021093267A1 WO2021093267A1 PCT/CN2020/085541 CN2020085541W WO2021093267A1 WO 2021093267 A1 WO2021093267 A1 WO 2021093267A1 CN 2020085541 W CN2020085541 W CN 2020085541W WO 2021093267 A1 WO2021093267 A1 WO 2021093267A1
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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
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
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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
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
- A01N57/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing heterocyclic radicals
Definitions
- the invention belongs to the field of pesticides, and relates to an insecticidal and acaricidal nano-aqueous agent with fenpropathrin and chlorpyrifos as main active ingredients, and a preparation method and application thereof.
- Fenpropathrin (Fenpropathrin), chemical name: 2-cyano-3-phenoxybenzyl-2,2,3,3-tetramethylcyclopropane ester.
- High-efficiency, broad-spectrum pyrethroids have contact and repellent effects, as well as stomach toxic effects.
- it has good effects on spider mites of various crops, so it has the advantage of eliminating insects and mites. Effective against Lepidopteran larvae, and effective against Diptera or Hemiptera pests. It can be used to control pests on cotton, fruit trees, vegetables, tea and flowers.
- Chlorpyrifos Standard molecular formula: C 9 H 11 Cl 3 NO 3 PS. Chemical name: O,O-diethyl-O-(3,5,6-trichloro-2-pyridyl) phosphorothioate.
- Chlorpyrifos is an acetylcholinesterase inhibitor, a phosphorothioate insecticide. It has the triple effects of stomach poisoning, contact killing and fumigation. It has a good control effect on a variety of chewing and piercing-sucking mouthparts pests on rice, wheat, cotton, fruit trees, vegetables, and tea trees.
- fenpropathrin and chlorpyrifos are difficult to dissolve in water.
- the solubility of fenpropathrin in water at room temperature is only 0.34mg/L, and the solubility of chlorpyrifos in water at 25°C is 2mg/L; at present, fenpropathrin and chlorpyrifos are less soluble in water.
- Conventional dosage forms are mainly emulsifiable concentrates, which contain a large amount of organic solvents, which pose safety hazards in production and cause serious harm to the environment in field use. Reducing the use of organic solvents and developing aqueous formulations are the inevitable way for the development of fenpropathrin and chlorpyrifos formulations.
- Insecticides containing a single ingredient often have shortcomings in the prevention and control of pesticide pests: continuous use is prone to pesticide resistance, narrow insecticidal spectrum, cannot provide comprehensive protection for crops, and high pesticide costs for farmers.
- the combination of two or more active ingredients with synergistic effect can improve the control effect, reduce the dosage of active ingredients, save costs, slow down the occurrence of pests and mite resistance, and expand the control spectrum. Insects can be cured at the same time, reducing the use cost of farmers.
- the purpose of the present invention is to provide a composite insecticidal and acaricidal nano-aqueous agent containing fenpropathrin and chlorpyrifos.
- the compound of fenpropathrin and chlorpyrifos in the nano-aqueous agent has a significant synergistic increase
- the creative discovery of certain surfactants adopts surfactant micellar solubilization technology. Without the use of organic solvents, the nano-scale micelles formed by surfactants are used to carry hardly soluble water.
- the active ingredients of fenpropathrin and chlorpyrifos are present in nano-sized particles as nano-sized particles, which are more convenient for their attachment, spreading and penetration on the target, more resistant to rain washing, and they do not contain organic solvents, which is safe and environmentally friendly.
- a composite insecticidal and acaricidal nano-aqueous formulation containing fenpropathrin and chlorpyrifos (hereinafter referred to as fenpropathrin ⁇ chlorpyrifos composite nano-aqueous formulation), wherein the nano-aqueous formulation has fenpropathrin and chlorpyrifos as main activities
- the ingredients are formulated with surfactants and water, wherein the nano-aqueous agent contains the following ingredients according to weight percentages: fenpropathrin and chlorpyrifos at 3% to 80%, and surfactants at 5 to 20%, The balance is water.
- the weight ratio of fenpropathrin and chlorpyrifos is 20:1 to 1:20, preferably 1:5 to 5:1.
- the weight percentage of fenpropathrin and chlorpyrifos is preferably 3% to 55%, and more preferably 3% to 21%.
- the nano-aqueous agent of the present invention can only contain the active ingredients fenpropathrin and chlorpyrifos, and other components can also be added to the active ingredient during use or preparation.
- the effective ingredients in the nano-aqueous agent can also be synergistically effective. Exist in the composition.
- Said surfactant is selected from fatty alcohol polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, styrylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether phosphate, alkylphenol polyoxyethylene ether One or more combinations of phosphoric acid ester, sodium fatty acid methyl ester sulfonate, and sodium alcohol ether succinic acid monoester sulfonate.
- the surfactant is preferably 5%-16% by weight percentage.
- Another object of the present invention is to provide a method for preparing a composite insecticidal and concealing nano-aqueous agent containing fenpropathrin and chlorpyrifos, which includes:
- Step (1) at room temperature (10-35°C), mix the fenpropathrin technical medicine, the chlorpyrifos technical medicine and the surfactant, and stir to make the fenpropathrin and the chlorpyrifos uniformly dispersed in the surfactant;
- step (2) water is added under stirring and evenly stirred to form a surfactant micellar solution containing fenpropathrin and chlorpyrifos, which is a transparent nano-aqueous solution of fenpropathrin and chlorpyrifos.
- the fenpropathrin and chlorpyrifos nano-aqueous formulations of the present invention have a transparent appearance, and the average particle size of the surfactant micelles is at the nanometer level; after entering water, they can quickly dissolve with water to form a completely transparent solution, and the dilution stability is qualified; the performance of the nano-aqueous formulations of the present invention Stable, it is still stable after cold storage at 0°C for 7 days and 54°C hot storage for 14 days, and the effective ingredients will not precipitate, which is convenient for storage.
- step (1) the stirring speed is 60-100 revolutions per second, and the stirring time is 0.5 h.
- the technician can adjust the time so that the fenpropathrin and chlorpyrifos are uniformly dispersed in the surfactant.
- step (2) the stirring speed is 60-100 revolutions per second, and the stirring is continued for 0.5-1 h after adding water.
- Another object of the present invention is to provide the use of the nano-aqueous agent for controlling pests and harmful mites on fruit trees, cotton and vegetables.
- the pest is rice planthopper, and the pest mite is citrus red spider.
- it can reduce the amount of use, delay the generation of insect pests and mite resistance, and improve the control effect, which is better than single-agent use, saving time and effort, saving costs, reducing environmental pollution, and reducing the burden on farmers.
- the present invention has the following beneficial effects: (1) This application has successfully prepared a nano aqueous formulation of fenpropathrin and chlorpyrifos by adding surfactants, which overcomes the insoluble fenpropathrin and chlorpyrifos insoluble The disadvantages of water, insoluble in water; (2) The compounding of fenpropathrin and chlorpyrifos has obvious synergistic effect, which improves the control effect on harmful mites compared with single agent alone; (3) It has quick effect at the same time. (4) The combination of two active ingredients reduces the amount of pesticides used, reduces production and use costs and environmental pollution; (5) Delays the resistance of pest mites to pesticides, and its effect is significantly higher than that of its single ⁇ Agent use.
- Figure 1 shows the 12% fenpropathrin ⁇ chlorpyrifos compound nano-aqueous formulation of Example 7.
- Figure 2 shows the 12% fenpropathrin ⁇ chlorpyrifos compound nano-aqueous formulation of Comparative Example 2.
- Single-dose toxicity index standard drug LC50/a single-dose LC50 ⁇ 100
- Toxicity Index A single dose toxicity index ⁇ A single dose proportion in the mixture + B single dose toxicity index ⁇ B single dose proportion in the mixture
- ATI Measured Toxicity Index
- CTC measured toxicity index of the mixture (ATI)/theoretical toxicity index of the mixture (TTI) ⁇ 100
- Co-toxicity coefficient classification when CTC is greater than 120, the mixture has synergistic effect, when CTC is less than 80, it is antagonistic, and CTC between 80-120 is additive.
- Preparation method Weigh 20g (based on active ingredients, the same below) technical fenpropathrin, 1g (based on active ingredients, the same below) technical chlorpyrifos, and 10g styrylphenol polyoxyethylene ether, 6g fatty alcohol The polyoxyethylene ether phosphate was mixed, stirred for 0.5 h at a rotation speed of 90 revolutions/sec, and kept stirring, 63 g of water was added, and stirring was continued for 1 h to obtain 21% fenpropathrin ⁇ chlorpyrifos composite nano-aqueous agent.
- the nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 175 mPa ⁇ s, and an average particle size of 15.2 nanometers.
- the nano-aqueous agent of this embodiment can quickly dissolve with water to form a completely transparent solution, and the dilution stability is qualified.
- the preparation method is the same as in Example 1, and 11% fenpropathrin ⁇ chlorpyrifos compound nano-aqueous agent is prepared.
- the nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 165.5 mPa ⁇ s, and an average particle size of 14.8 nanometers.
- the nano-aqueous agent of this embodiment can quickly dissolve with water to form a completely transparent solution, and the dilution stability is qualified.
- the preparation method is the same as that in Example 1, and a 6% fenpropathrin ⁇ chlorpyrifos compound nano-aqueous agent is prepared.
- the nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 200.5 mPa ⁇ s, and an average particle size of 17.6 nanometers.
- the nano-aqueous agent of this embodiment can quickly dissolve with water to form a completely transparent solution, and the dilution stability is qualified.
- the preparation method is the same as that in Example 1, and a 3% fenpropathrin ⁇ chlorpyrifos composite nano-aqueous agent is prepared.
- the nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 180 mPa ⁇ s, and an average particle size of 19 nanometers.
- the nano-aqueous agent of this embodiment can quickly dissolve with water to form a completely transparent solution, and the dilution stability is qualified.
- the preparation method is the same as that in Example 1, and a 4% fenpropathrin ⁇ chlorpyrifos composite nano-aqueous agent is prepared.
- the nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 182.5 mPa ⁇ s, and an average particle size of 16.5 nanometers.
- the nano-aqueous agent of this embodiment can quickly dissolve with water to form a completely transparent solution, and the dilution stability is qualified.
- the above raw materials are prepared according to the nano-aqueous preparation method to form a fenpropathrin ⁇ chlorpyrifos composite nano-aqueous preparation with a main active ingredient content of 9% by weight.
- the nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 160 mPa ⁇ s, and an average particle size of 10.5 nanometers.
- the nano-aqueous agent of this embodiment can quickly dissolve with water to form a completely transparent solution, and the dilution stability is qualified.
- the preparation method is the same as that in Example 1, and a 12% fenpropathrin ⁇ chlorpyrifos composite nano-aqueous agent is prepared.
- the nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 135 mPa ⁇ s, and an average particle size of 11.5 nanometers.
- the nano-aqueous agent of this embodiment can quickly dissolve with water to form a completely transparent solution, and the dilution stability is qualified.
- the preparation method is the same as in Example 1, and 11% fenpropathrin ⁇ chlorpyrifos compound nano-aqueous agent is prepared.
- the nano-aqueous agent of this example has a transparent and slightly yellowish appearance, a viscosity of 145 mPa ⁇ s, and an average particle size of 22.0 nanometers.
- the nano-aqueous agent of this embodiment can quickly dissolve with water to form a completely transparent solution, and the dilution stability is qualified.
- the preparation method is the same as that in Example 1, and 10.5% fenpropathrin ⁇ chlorpyrifos compound nano-aqueous agent is prepared.
- the nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 127.5 mPa ⁇ s, and an average particle size of 21.5 nanometers.
- the nano-aqueous agent of this embodiment can quickly dissolve with water to form a completely transparent solution, and the dilution stability is qualified.
- the water preparation is prepared with the commonly used auxiliary (wetting agent) in the preparation of water preparation, and the specific formula is shown in Table 3.
- the preparation method is the same as in Example 1.
- an aqueous solution can be prepared at room temperature (10-35°C), but when the aqueous solution is placed at a low temperature (below 0°C), the fenpropathrin and chlorpyrifos technical drugs will continue to precipitate. And it cannot be recovered after heating up. It shows that the use of surfactants other than the surfactants or conventional liquids used in the surfactant composition of the present invention cannot be used to prepare qualified fenpropathrin ⁇ chlorpyrifos composite nano-aqueous.
- Test agent Example 1 to Example 9 of the fenpropathrin ⁇ chlorpyrifos compound nano-aqueous agent.
- Control agent 3.5% fenpropathrin nano-aqueous, 2% chlorpyrifos nano-aqueous.
- 3.5% fenpropathrin nano-aqueous preparation method weigh 3.5g (based on active ingredient) fenpropathrin technical, 7g fatty alcohol polyoxyethylene ether, 4g fatty acid methyl ester sulfonate sodium, 5g sorbitol After the three fatty acid ester polyoxyethylene ethers are mixed, they are stirred for 0.5 h at a rotation speed of 85 revolutions per second, and 80.5 g of water is added under stirring, and the stirring is continued for 1 h to obtain 3.5% fenpropathrin nano-aqueous agent.
- 2% chlorpyrifos nano-aqueous preparation method weigh 2g (based on active ingredients) of chlorpyrifos original drug, 8g tristyrylphenol polyoxyethylene ether phosphate and 2g alkylphenol formaldehyde resin polyoxyethylene ether, and mix the three Then, it was stirred for 0.5 h at a rotation speed of 75 revolutions per second, 88 g of water was added under stirring, and the stirring was continued for 0.8 h to obtain 2% chlorpyrifos nano-aqueous solution.
- Control object citrus red spider.
- Test method The normal field dose (active ingredient) was used, the dose treatment was set for three repetitions, and the random block arrangement was repeated. Each repetition was set in an area of 30m 2 , and the experiment was sprayed with a knapsack sprayer. Investigate the number of insect populations before application, and investigate the number of remaining live insects 3 days, 7 days, 14 days, and 30 days after application, and calculate the control effect according to the following method:
- Insect population reduction rate (%) (number of insects before application-number of insects after application) / number of insects before application ⁇ 100
- Corrected control effect (%) (Reduction rate of insect population in the treatment area-Reduction rate of insect population in the control area) / (100-Recession rate of insect population in the control area before and after control) ⁇ 100
- Table 4 Field test results of fenpropathrin ⁇ chlorpyrifos nano-aqueous on citrus red spider
- the field efficacy results showed that the fenpropathrin ⁇ chlorpyrifos composite nano-aqueous agent has an excellent control effect on citrus red spiders, and the control effect is better than the direct effect of a single-dose variety.
- Test agent Example 1 to Example 9 of the fenpropathrin ⁇ chlorpyrifos compound nano-aqueous agent.
- Control agent 3.5% fenpropathrin nano-aqueous, 2% chlorpyrifos nano-aqueous.
- Control object rice planthopper.
- Test method The normal field dosage (active ingredient) was used, the dosage treatment was set for three repetitions, and the random block arrangement was repeated, and the area of each repetition was 50m 2.
- the experiment used a knapsack sprayer to spray the whole cotton. Investigate the number of insect populations before application, and investigate the number of remaining live insects 3 days, 7 days, 14 days, and 30 days after application, and calculate the control effect according to the following method:
- Insect population reduction rate (%) (number of insects before application-number of insects after application) / number of insects before application ⁇ 100
- Corrected control effect (%) (Reduction rate of insect population in the treatment area-Reduction rate of insect population in the control area) / (100-Recession rate of insect population in the control area before and after control) ⁇ 100
- the field efficacy results showed that the fenpropathrin ⁇ chlorpyrifos composite nano-aqueous agent has an excellent control effect on rice planthopper, and the control effect is better than the direct effect of the single-agent variety.
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Abstract
Disclosed is a composite insecticidal and acaricidal nano-aqueous agent containing fenpropathrin and chlorpyrifos. The insecticidal composition is prepared by using fenpropathrin and chlorpyrifos as insecticidal and acaricidal active ingredients, together with a surfactant and water. Specifically, the weight percentage of fenpropathrin and chlorpyrifos is 3% to 80%, the weight percentage of the pesticide adjuvant is 5% to 20%, and the balance is water. The weight ratio of fenpropathrin to chlorpyrifos is 20:1-1:20. In the present invention, the nano-sized micelles formed by the surfactant are used to carry fenpropathrin and chlorpyrifos, which are poorly soluble in water, and the active ingredients are present in the nano-aqueous agent as nano-sized particles, facilitating the adhesion, spreading and penetration thereof on the target, and the pesticide is more resistant to being washed away in the rain. The present invention can control homopteran pests, lepidopteran pests and pest mites that occur on crops, and is especially useful for controlling rice planthoppers and citrus red spider mites, and the effect thereof is significantly higher than that of a single agent therein.
Description
本发明属于农药领域,涉及一种以甲氰菊酯和毒死蜱为主要有效成分的杀虫杀螨纳米水剂及其制备方法和用途。The invention belongs to the field of pesticides, and relates to an insecticidal and acaricidal nano-aqueous agent with fenpropathrin and chlorpyrifos as main active ingredients, and a preparation method and application thereof.
甲氰菊酯(Fenpropathrin),化学名称:2-氰基-3-苯氧基苄基-2,2,3,3-四甲基环丙烷酸酯。高效、广谱拟除虫菊酯,具有触杀和驱避作用,还有胃毒作用。除具有一般合成除虫菊酯特性外,对多种作物叶螨具有良好效果,因此具有虫螨兼除的优点。对鳞翅目幼虫高效,对双翅目或半翅目害虫有效。可用于防治棉花、果树、蔬菜、茶叶、花卉上的害虫。Fenpropathrin (Fenpropathrin), chemical name: 2-cyano-3-phenoxybenzyl-2,2,3,3-tetramethylcyclopropane ester. High-efficiency, broad-spectrum pyrethroids have contact and repellent effects, as well as stomach toxic effects. In addition to the general synthetic pyrethroid properties, it has good effects on spider mites of various crops, so it has the advantage of eliminating insects and mites. Effective against Lepidopteran larvae, and effective against Diptera or Hemiptera pests. It can be used to control pests on cotton, fruit trees, vegetables, tea and flowers.
毒死蜱(Chlorpyrifos Standard),分子式:C
9H
11Cl
3NO
3PS。化学名称:O,O-二乙基-O-(3,5,6-三氯-2-吡啶基)硫代磷酸酯。毒死蜱是乙酰胆碱酯酶抑制剂,属硫代磷酸酯类杀虫剂。具有胃毒、触杀、熏蒸三重作用,对水稻、小麦、棉花、果树、蔬菜、茶树上多种咀嚼式和刺吸式口器害虫均具有较好防效。
Chlorpyrifos Standard, molecular formula: C 9 H 11 Cl 3 NO 3 PS. Chemical name: O,O-diethyl-O-(3,5,6-trichloro-2-pyridyl) phosphorothioate. Chlorpyrifos is an acetylcholinesterase inhibitor, a phosphorothioate insecticide. It has the triple effects of stomach poisoning, contact killing and fumigation. It has a good control effect on a variety of chewing and piercing-sucking mouthparts pests on rice, wheat, cotton, fruit trees, vegetables, and tea trees.
甲氰菊酯和毒死蜱均难溶于水,甲氰菊酯室温下水中溶解度为仅为0.34mg/L,毒死蜱25℃时在水中的溶解度为2mg/L;目前,甲氰菊酯、毒死蜱的常规剂型主要为乳油,其中含有大量有机溶剂,在生产中存在安全隐患,田间使用中会对环境造成严重危害。减少有机溶剂的使用,发展水剂剂型,是甲氰菊酯、毒死蜱剂型发展必然之路。Both fenpropathrin and chlorpyrifos are difficult to dissolve in water. The solubility of fenpropathrin in water at room temperature is only 0.34mg/L, and the solubility of chlorpyrifos in water at 25°C is 2mg/L; at present, fenpropathrin and chlorpyrifos are less soluble in water. Conventional dosage forms are mainly emulsifiable concentrates, which contain a large amount of organic solvents, which pose safety hazards in production and cause serious harm to the environment in field use. Reducing the use of organic solvents and developing aqueous formulations are the inevitable way for the development of fenpropathrin and chlorpyrifos formulations.
含单一成分的杀虫剂品种在农药害虫防治中往往存在缺陷:连续使用容易产生抗药性,杀虫谱窄,不能为作物提供全面的保护,农民用药成本高等。具有增效作用的两种或者两种以上活性成分的组合混配,可以提高防效,减少有效成分地用药量,节约成本,减缓害虫害螨抗性发生、并能扩大防治谱,起到多虫兼治,降低农民的使用成本。Insecticides containing a single ingredient often have shortcomings in the prevention and control of pesticide pests: continuous use is prone to pesticide resistance, narrow insecticidal spectrum, cannot provide comprehensive protection for crops, and high pesticide costs for farmers. The combination of two or more active ingredients with synergistic effect can improve the control effect, reduce the dosage of active ingredients, save costs, slow down the occurrence of pests and mite resistance, and expand the control spectrum. Insects can be cured at the same time, reducing the use cost of farmers.
发明内容Summary of the invention
针对现有问题的不足,本发明的目的是提供一种含甲氰菊酯和毒死蜱的复合 杀虫杀螨纳米水剂,该纳米水剂中甲氰菊酯和毒死蜱复配具有明显的协同增效作用,另外,创造性的发现某些表面活性剂,采用表面活性剂胶束增溶技术,在不使用有机溶剂助溶的情况下,利用表面活性剂形成的纳米级胶束承载难溶于水的甲氰菊酯和毒死蜱,有效成分以纳米级微粒存在于纳米水剂中,更便于其在靶标上附着、展布和渗透,更耐雨水冲刷,且其不含有机溶剂,安全环保。In view of the shortcomings of the existing problems, the purpose of the present invention is to provide a composite insecticidal and acaricidal nano-aqueous agent containing fenpropathrin and chlorpyrifos. The compound of fenpropathrin and chlorpyrifos in the nano-aqueous agent has a significant synergistic increase In addition, the creative discovery of certain surfactants adopts surfactant micellar solubilization technology. Without the use of organic solvents, the nano-scale micelles formed by surfactants are used to carry hardly soluble water. The active ingredients of fenpropathrin and chlorpyrifos are present in nano-sized particles as nano-sized particles, which are more convenient for their attachment, spreading and penetration on the target, more resistant to rain washing, and they do not contain organic solvents, which is safe and environmentally friendly.
本发明解决其技术问题采用的技术方案是:The technical solutions adopted by the present invention to solve its technical problems are:
一种含甲氰菊酯和毒死蜱的复合杀虫杀螨纳米水剂(后续简称甲氰菊酯·毒死蜱复配纳米水剂),所述的纳米水剂以甲氰菊酯和毒死蜱为主要活性成分,与表面活性剂、水配制而成,其中,所述的纳米水剂按照重量百分含量含有以下成分:甲氰菊酯和毒死蜱为3%~80%,表面活性剂5~20%,余量为水。A composite insecticidal and acaricidal nano-aqueous formulation containing fenpropathrin and chlorpyrifos (hereinafter referred to as fenpropathrin·chlorpyrifos composite nano-aqueous formulation), wherein the nano-aqueous formulation has fenpropathrin and chlorpyrifos as main activities The ingredients are formulated with surfactants and water, wherein the nano-aqueous agent contains the following ingredients according to weight percentages: fenpropathrin and chlorpyrifos at 3% to 80%, and surfactants at 5 to 20%, The balance is water.
所述的甲氰菊酯和毒死蜱的重量比为20:1-1:20,优选为1:5-5:1。The weight ratio of fenpropathrin and chlorpyrifos is 20:1 to 1:20, preferably 1:5 to 5:1.
所述的纳米水剂中,甲氰菊酯与毒死蜱的重量百分含量优选为3%~55%,进一步优选为3%~21%。In the nano-aqueous agent, the weight percentage of fenpropathrin and chlorpyrifos is preferably 3% to 55%, and more preferably 3% to 21%.
本发明所述的纳米水剂可以只含有活性成分甲氰菊酯和毒死蜱,也可在使用或配制时向活性成分中加入其他组分,该纳米水剂中的有效成份还可以增效有效量存在于组合物中。The nano-aqueous agent of the present invention can only contain the active ingredients fenpropathrin and chlorpyrifos, and other components can also be added to the active ingredient during use or preparation. The effective ingredients in the nano-aqueous agent can also be synergistically effective. Exist in the composition.
所述的表面活性剂选自脂肪醇聚氧乙烯醚、烷基酚甲醛树脂聚氧乙烯醚、苯乙烯基苯酚聚氧乙烯醚、脂肪醇聚氧乙烯醚磷酸酯、烷基酚聚氧乙烯醚磷酸酯、脂肪酸甲酯磺酸钠、醇醚琥珀酸单酯磺酸钠中的一种或多种组合。Said surfactant is selected from fatty alcohol polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, styrylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether phosphate, alkylphenol polyoxyethylene ether One or more combinations of phosphoric acid ester, sodium fatty acid methyl ester sulfonate, and sodium alcohol ether succinic acid monoester sulfonate.
其中,按照重量百分含量所述表面活性剂优选为5%-16%。Wherein, the surfactant is preferably 5%-16% by weight percentage.
本发明的另一个目的是提供一种含甲氰菊酯和毒死蜱的复合杀虫杀瞒纳米水剂的制备方法,包括:Another object of the present invention is to provide a method for preparing a composite insecticidal and concealing nano-aqueous agent containing fenpropathrin and chlorpyrifos, which includes:
步骤(1),在常温(10~35℃)下,将甲氰菊酯原药、毒死蜱原药与表面活性剂混合,搅拌,使甲氰菊酯和毒死蜱均匀分散在表面活性剂中;Step (1), at room temperature (10-35°C), mix the fenpropathrin technical medicine, the chlorpyrifos technical medicine and the surfactant, and stir to make the fenpropathrin and the chlorpyrifos uniformly dispersed in the surfactant;
步骤(2),在搅拌状态下加入水,搅拌均匀,形成含有甲氰菊酯和毒死蜱的表面活性剂胶束溶液,即为透明的甲氰菊酯和毒死蜱纳米水剂。In step (2), water is added under stirring and evenly stirred to form a surfactant micellar solution containing fenpropathrin and chlorpyrifos, which is a transparent nano-aqueous solution of fenpropathrin and chlorpyrifos.
本发明甲氰菊酯和毒死蜱纳米水剂外观透明,表面活性剂胶束平均粒径为纳米级别;入水后能迅速与水互溶,形成完全透明溶液,稀释稳定性合格;本发明纳米水剂性能稳定,在0℃冷贮7d和54℃热贮14d后仍然稳定,有效成分不会 析出,便于贮藏。The fenpropathrin and chlorpyrifos nano-aqueous formulations of the present invention have a transparent appearance, and the average particle size of the surfactant micelles is at the nanometer level; after entering water, they can quickly dissolve with water to form a completely transparent solution, and the dilution stability is qualified; the performance of the nano-aqueous formulations of the present invention Stable, it is still stable after cold storage at 0°C for 7 days and 54°C hot storage for 14 days, and the effective ingredients will not precipitate, which is convenient for storage.
步骤(1)中,搅拌速度为60~100转/秒,搅拌时间为0.5h,技术人员可以调整时间,以使甲氰菊酯和毒死蜱均匀分散在表面活性剂中为准。In step (1), the stirring speed is 60-100 revolutions per second, and the stirring time is 0.5 h. The technician can adjust the time so that the fenpropathrin and chlorpyrifos are uniformly dispersed in the surfactant.
步骤(2)中,搅拌速度为60~100转/秒,加入水之后继续搅拌0.5~1h。In step (2), the stirring speed is 60-100 revolutions per second, and the stirring is continued for 0.5-1 h after adding water.
本发明的另一目的是提供所述的纳米水剂在防治果树、棉花、蔬菜上的害虫、害螨的用途。所述的害虫为稻飞虱,所述的害螨为柑橘红蜘蛛。在使用过程中,可以减少使用量,延缓害虫害螨抗药性的产生,还能提高防治效果,优于单剂使用,省时省力、节约成本及减少对环境的污染,减轻农民负担。Another object of the present invention is to provide the use of the nano-aqueous agent for controlling pests and harmful mites on fruit trees, cotton and vegetables. The pest is rice planthopper, and the pest mite is citrus red spider. In the process of use, it can reduce the amount of use, delay the generation of insect pests and mite resistance, and improve the control effect, which is better than single-agent use, saving time and effort, saving costs, reducing environmental pollution, and reducing the burden on farmers.
与现有技术相比本发明的有益效果:(1)本申请通过添加表面活性剂成功制备出甲氰菊酯和毒死蜱复配的纳米水剂剂型,克服了甲氰菊酯、毒死蜱难溶于水,不溶于水的缺点;(2)将甲氰菊酯和毒死蜱复配具有明显的协同增效作用,较之单剂单独使用,提高了对害螨的防治效果;(3)兼有速效和长效;(4)两种有效成分复配降低了农药使用量,降低了生产和使用成本及对环境的污染;(5)延缓害螨对农药的抗性,其效果明显高于其单剂使用。Compared with the prior art, the present invention has the following beneficial effects: (1) This application has successfully prepared a nano aqueous formulation of fenpropathrin and chlorpyrifos by adding surfactants, which overcomes the insoluble fenpropathrin and chlorpyrifos insoluble The disadvantages of water, insoluble in water; (2) The compounding of fenpropathrin and chlorpyrifos has obvious synergistic effect, which improves the control effect on harmful mites compared with single agent alone; (3) It has quick effect at the same time. (4) The combination of two active ingredients reduces the amount of pesticides used, reduces production and use costs and environmental pollution; (5) Delays the resistance of pest mites to pesticides, and its effect is significantly higher than that of its single剂用。 Agent use.
图1为实施例7的12%的甲氰菊酯·毒死蜱复配纳米水剂。Figure 1 shows the 12% fenpropathrin·chlorpyrifos compound nano-aqueous formulation of Example 7.
图2为对比例2的12%的甲氰菊酯·毒死蜱复配纳米水剂。Figure 2 shows the 12% fenpropathrin·chlorpyrifos compound nano-aqueous formulation of Comparative Example 2.
以下结合实施例对本发明做进一步详细说明。所用试剂或者仪器设备未注明生产厂商的,均视为可以通过市场购买的常规产品。The present invention will be further described in detail below in conjunction with the embodiments. Reagents or equipment that do not indicate the manufacturer are regarded as conventional products that can be purchased on the market.
实施例1:Example 1:
(一)室内毒力测定(1) Indoor toxicity test
1、采用浸渍玻片法进行甲氰菊酯和毒死蜱及甲氰菊酯·毒死蜱复配纳米水剂对柑橘红蜘蛛的毒力测定,每处理重复3次,每浓度处理30头,用LC
50值依据孙云沛法计算共毒系数(CTC值):
1. The virulence of fenpropathrin, chlorpyrifos and fenpropathrin·chlorpyrifos compound nano-aqueous agent on citrus red spiders was determined by immersion slide method, each treatment was repeated 3 times, each concentration was 30, and LC 50 was used. The value is calculated based on Sun Yunpei’s method of co-toxicity coefficient (CTC value):
单剂毒力指数=标准药剂LC50/某单剂LC50×100Single-dose toxicity index = standard drug LC50/a single-dose LC50×100
理论毒力指数(TTI)=A单剂的毒力指数×A单剂在混剂中所占比例+B单剂的毒力指数×B单剂在混剂中所占比例Theoretical Toxicity Index (TTI) = A single dose toxicity index × A single dose proportion in the mixture + B single dose toxicity index × B single dose proportion in the mixture
实测毒力指数(ATI)=标准单剂的LC50值/混剂的LC50值×100Measured Toxicity Index (ATI) = LC50 value of standard single agent/LC50 value of mixed agent×100
共毒系数(CTC)=混剂实测毒力指数(ATI)/混剂理论毒力指数(TTI)×100Co-toxicity coefficient (CTC) = measured toxicity index of the mixture (ATI)/theoretical toxicity index of the mixture (TTI) × 100
共毒系数分级:CTC大于120时混剂具有协同增效性,CTC小于80时为拮抗,CTC在80-120之间为相加作用。Co-toxicity coefficient classification: when CTC is greater than 120, the mixture has synergistic effect, when CTC is less than 80, it is antagonistic, and CTC between 80-120 is additive.
结果见表1:The results are shown in Table 1:
表1 甲氰菊酯·毒死蜱复配纳米水剂对柑橘红蜘蛛的室内毒力测定Table 1 Indoor toxicity determination of fenpropathrin and chlorpyrifos compound nano-aqueous to citrus red spider
由表1可知,甲氰菊酯和毒死蜱配比范围在20:1-1:20之间,共毒系数都大于120,对柑橘红蜘蛛的防治具有增效作用,尤其在5:1-1:5之间,共毒系数在150以上,增效作用显著。It can be seen from Table 1 that the ratio of fenpropathrin and chlorpyrifos ranges from 20:1 to 1:20, and the co-toxicity coefficient is greater than 120, which has a synergistic effect on the control of citrus red spiders, especially at 5:1 to 1 : Between 5, the co-toxicity coefficient is above 150, and the synergistic effect is significant.
2、采用先浸叶再接虫的试验方法测定甲氰菊酯和毒死蜱及甲氰菊酯·毒死蜱复配纳米水剂对稻飞虱的毒力,每处理重复三次,用LC
50值按照孙云沛法计算共度系数,结果如表2:
2. The virulence of fenpropathrin, chlorpyrifos and fenpropathrin·chlorpyrifos composite nano-aqueous to rice planthoppers was determined by the test method of first soaking leaves and then infestation. Each treatment was repeated three times, and the LC 50 value was used in accordance with Sun Yunpei Method to calculate the co-degree coefficient, the results are shown in Table 2:
表2 甲氰菊酯·毒死蜱复配纳米水剂对稻飞虱的毒力测定Table 2 Toxicity determination of fenpropathrin and chlorpyrifos compound nano-aqueous to rice planthopper
由表2可知,甲氰菊酯和毒死蜱配比范围在20:1-1:20之间,共毒系数都大于120,对稻飞虱防治具有增效作用,尤其在5:1-1:5之间,共毒系数在160以上,增效作用显著。It can be seen from Table 2 that the ratio of fenpropathrin and chlorpyrifos ranges from 20:1 to 1:20, and the co-toxicity coefficient is greater than 120, which has a synergistic effect on the control of rice planthoppers, especially at 5:1 to 1:1: Between 5, the co-toxicity coefficient is above 160, and the synergistic effect is significant.
实施例1:Example 1:
配方:20g甲氰菊酯、1g毒死蜱、10g苯乙烯基苯酚聚氧乙烯醚、6g脂肪醇聚氧乙烯醚磷酸酯,加水至100g。Formula: 20g fenpropathrin, 1g chlorpyrifos, 10g styrylphenol polyoxyethylene ether, 6g fatty alcohol polyoxyethylene ether phosphate, add water to 100g.
制备方法:称取20g(以有效成分计,下同)甲氰菊酯原药、1g(以有效成分计,下同)毒死蜱原药,与10g苯乙烯基苯酚聚氧乙烯醚、6g脂肪醇聚氧乙烯醚磷酸酯混合,在转速90转/秒下搅拌0.5h,保持搅拌,加入63g水,继续搅拌1h,得到21%的甲氰菊酯·毒死蜱复配纳米水剂。Preparation method: Weigh 20g (based on active ingredients, the same below) technical fenpropathrin, 1g (based on active ingredients, the same below) technical chlorpyrifos, and 10g styrylphenol polyoxyethylene ether, 6g fatty alcohol The polyoxyethylene ether phosphate was mixed, stirred for 0.5 h at a rotation speed of 90 revolutions/sec, and kept stirring, 63 g of water was added, and stirring was continued for 1 h to obtain 21% fenpropathrin·chlorpyrifos composite nano-aqueous agent.
本实施例纳米水剂外观透明微黄,粘度175mPa·s,平均粒径为15.2纳米。The nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 175 mPa·s, and an average particle size of 15.2 nanometers.
分别在0℃冷贮7d和54℃热贮14d后制剂均没有发生沉淀现象,仍然稳定。After cold storage at 0°C for 7 days and 54°C heat storage for 14 days, the preparations did not precipitate and remained stable.
本实施例纳米水剂入水后能迅速与水互溶,形成完全透明溶液,稀释稳定性合格。After entering water, the nano-aqueous agent of this embodiment can quickly dissolve with water to form a completely transparent solution, and the dilution stability is qualified.
实施例2:Example 2:
配方:10g甲氰菊酯、1g毒死蜱、3g烷基酚聚氧乙烯醚磷酸酯、3g脂肪醇聚氧乙烯醚、2g醇醚琥珀酸单酯磺酸钠,加水至100g。Formula: 10g fenpropathrin, 1g chlorpyrifos, 3g alkylphenol polyoxyethylene ether phosphate, 3g fatty alcohol polyoxyethylene ether, 2g alcohol ether succinic acid monoester sodium sulfonate, add water to 100g.
制备方法同实施例1,制得11%的甲氰菊酯·毒死蜱复配纳米水剂。The preparation method is the same as in Example 1, and 11% fenpropathrin·chlorpyrifos compound nano-aqueous agent is prepared.
本实施例纳米水剂外观透明微黄,粘度165.5mPa·s,平均粒径为14.8纳米。The nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 165.5 mPa·s, and an average particle size of 14.8 nanometers.
分别在0℃冷贮7d和54℃热贮14d后制剂均没有发生沉淀现象,仍然稳定。After cold storage at 0°C for 7 days and 54°C heat storage for 14 days, the preparations did not precipitate and remained stable.
本实施例纳米水剂入水后能迅速与水互溶,形成完全透明溶液,稀释稳定性合格。After entering water, the nano-aqueous agent of this embodiment can quickly dissolve with water to form a completely transparent solution, and the dilution stability is qualified.
实施例3:Example 3:
配方:5g甲氰菊酯、1g毒死蜱、5g脂肪酸甲酯磺酸钠、3g苯乙烯基苯酚聚氧乙烯醚,加水至100g。Formula: 5g fenpropathrin, 1g chlorpyrifos, 5g sodium fatty acid methyl sulfonate, 3g styrylphenol polyoxyethylene ether, add water to 100g.
制备方法同实施例1,制得6%的甲氰菊酯·毒死蜱复配纳米水剂。The preparation method is the same as that in Example 1, and a 6% fenpropathrin·chlorpyrifos compound nano-aqueous agent is prepared.
本实施例纳米水剂外观透明微黄,粘度200.5mPa·s,平均粒径为17.6纳米。The nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 200.5 mPa·s, and an average particle size of 17.6 nanometers.
分别在0℃冷贮7d和54℃热贮14d后制剂均没有发生沉淀现象,仍然稳定。After cold storage at 0°C for 7 days and 54°C heat storage for 14 days, the preparations did not precipitate and remained stable.
本实施例纳米水剂入水后能迅速与水互溶,形成完全透明溶液,稀释稳定性合格。After entering water, the nano-aqueous agent of this embodiment can quickly dissolve with water to form a completely transparent solution, and the dilution stability is qualified.
实施例4:Example 4:
配方:2g甲氰菊酯、1g毒死蜱、5g醇醚琥珀酸单酯磺酸钠、3g苯乙烯基苯酚聚氧乙烯醚、加水至100g。Formula: 2g fenpropathrin, 1g chlorpyrifos, 5g sodium alcohol ether succinate monoester sulfonate, 3g styrylphenol polyoxyethylene ether, add water to 100g.
制备方法同实施例1,制得3%的甲氰菊酯·毒死蜱复配纳米水剂。The preparation method is the same as that in Example 1, and a 3% fenpropathrin·chlorpyrifos composite nano-aqueous agent is prepared.
本实施例纳米水剂外观透明微黄,粘度180mPa·s,平均粒径为19纳米。The nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 180 mPa·s, and an average particle size of 19 nanometers.
分别在0℃冷贮7d和54℃热贮14d后制剂均没有发生沉淀现象,仍然稳定。After cold storage at 0°C for 7 days and 54°C heat storage for 14 days, the preparations did not precipitate and remained stable.
本实施例纳米水剂入水后能迅速与水互溶,形成完全透明溶液,稀释稳定性合格。After entering water, the nano-aqueous agent of this embodiment can quickly dissolve with water to form a completely transparent solution, and the dilution stability is qualified.
实施例5:Example 5:
配方:2g甲氰菊酯、2g毒死蜱,4g脂肪醇聚氧乙烯醚、8g烷基酚聚氧乙烯 醚磷酸酯、加水至100g。Formula: 2g fenpropathrin, 2g chlorpyrifos, 4g fatty alcohol polyoxyethylene ether, 8g alkylphenol polyoxyethylene ether phosphate, add water to 100g.
制备方法同实施例1,制得4%的甲氰菊酯·毒死蜱复配纳米水剂。The preparation method is the same as that in Example 1, and a 4% fenpropathrin·chlorpyrifos composite nano-aqueous agent is prepared.
本实施例纳米水剂外观透明微黄,粘度182.5mPa·s,平均粒径为16.5纳米。The nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 182.5 mPa·s, and an average particle size of 16.5 nanometers.
分别在0℃冷贮7d和54℃热贮14d后制剂均没有发生沉淀现象,仍然稳定。After cold storage at 0°C for 7 days and 54°C heat storage for 14 days, the preparations did not precipitate and remained stable.
本实施例纳米水剂入水后能迅速与水互溶,形成完全透明溶液,稀释稳定性合格。After entering water, the nano-aqueous agent of this embodiment can quickly dissolve with water to form a completely transparent solution, and the dilution stability is qualified.
实施例6:Example 6:
配方:3g甲氰菊酯、6g毒死蜱,烷基酚甲醛树脂聚氧乙烯醚2g、苯乙烯基苯酚聚氧乙烯醚6g,加水至100g。将以上原料按纳米水剂配制方法,形成主要有效成分的重量百分含量为9%的甲氰菊酯·毒死蜱复配纳米水剂。Formula: 3g fenpropathrin, 6g chlorpyrifos, 2g alkylphenol formaldehyde resin polyoxyethylene ether, 6g styrylphenol polyoxyethylene ether, add water to 100g. The above raw materials are prepared according to the nano-aqueous preparation method to form a fenpropathrin·chlorpyrifos composite nano-aqueous preparation with a main active ingredient content of 9% by weight.
本实施例纳米水剂外观透明微黄,粘度160mPa·s,平均粒径为10.5纳米。The nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 160 mPa·s, and an average particle size of 10.5 nanometers.
分别在0℃冷贮7d和54℃热贮14d后制剂均没有发生沉淀现象,仍然稳定。After cold storage at 0°C for 7 days and 54°C heat storage for 14 days, the preparations did not precipitate and remained stable.
本实施例纳米水剂入水后能迅速与水互溶,形成完全透明溶液,稀释稳定性合格。After entering water, the nano-aqueous agent of this embodiment can quickly dissolve with water to form a completely transparent solution, and the dilution stability is qualified.
实施例7:Example 7:
配方:2g甲氰菊酯、10g毒死蜱,5g烷基酚甲醛树脂聚氧乙烯醚、6g醇醚琥珀酸酯磺酸钠、加水至100g。Formula: 2g fenpropathrin, 10g chlorpyrifos, 5g alkylphenol formaldehyde resin polyoxyethylene ether, 6g alcohol ether succinate sodium sulfonate, add water to 100g.
制备方法同实施例1,制得12%的甲氰菊酯·毒死蜱复配纳米水剂。The preparation method is the same as that in Example 1, and a 12% fenpropathrin·chlorpyrifos composite nano-aqueous agent is prepared.
本实施例纳米水剂外观透明微黄,粘度135mPa·s,平均粒径为11.5纳米。The nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 135 mPa·s, and an average particle size of 11.5 nanometers.
分别在0℃冷贮7d和54℃热贮14d后制剂均没有发生沉淀现象,仍然稳定。After cold storage at 0°C for 7 days and 54°C heat storage for 14 days, the preparations did not precipitate and remained stable.
本实施例纳米水剂入水后能迅速与水互溶,形成完全透明溶液,稀释稳定性合格。After entering water, the nano-aqueous agent of this embodiment can quickly dissolve with water to form a completely transparent solution, and the dilution stability is qualified.
实施例8:Example 8:
配方:1g甲氰菊酯、10g毒死蜱,4g脂肪醇聚氧乙烯醚、2g烷基酚甲醛树脂聚氧乙烯醚,3g烷基酚聚氧乙烯醚磷酸酯,加水至100g。Formula: 1g fenpropathrin, 10g chlorpyrifos, 4g fatty alcohol polyoxyethylene ether, 2g alkylphenol formaldehyde resin polyoxyethylene ether, 3g alkylphenol polyoxyethylene ether phosphate, add water to 100g.
制备方法同实施例1,制得11%的甲氰菊酯·毒死蜱复配纳米水剂。The preparation method is the same as in Example 1, and 11% fenpropathrin·chlorpyrifos compound nano-aqueous agent is prepared.
本实施例纳米水剂外观透明微黄,粘度145mPa·s,平均粒径为22.0纳米。The nano-aqueous agent of this example has a transparent and slightly yellowish appearance, a viscosity of 145 mPa·s, and an average particle size of 22.0 nanometers.
分别在0℃冷贮7d和54℃热贮14d后制剂均没有发生沉淀现象,仍然稳定。After cold storage at 0°C for 7 days and 54°C heat storage for 14 days, the preparations did not precipitate and remained stable.
本实施例纳米水剂入水后能迅速与水互溶,形成完全透明溶液,稀释稳定性 合格。After entering water, the nano-aqueous agent of this embodiment can quickly dissolve with water to form a completely transparent solution, and the dilution stability is qualified.
实施例9:Example 9:
配方:0.5g甲氰菊酯、10g毒死蜱,3g苯乙烯基苯酚聚氧乙烯醚、3g脂肪醇聚氧乙烯醚磷酸酯,加水至100g。Formula: 0.5g fenpropathrin, 10g chlorpyrifos, 3g styrylphenol polyoxyethylene ether, 3g fatty alcohol polyoxyethylene ether phosphate, add water to 100g.
制备方法同实施例1,制得10.5%的甲氰菊酯·毒死蜱复配纳米水剂。The preparation method is the same as that in Example 1, and 10.5% fenpropathrin·chlorpyrifos compound nano-aqueous agent is prepared.
本实施例纳米水剂外观透明微黄,粘度127.5mPa·s,平均粒径为21.5纳米。The nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 127.5 mPa·s, and an average particle size of 21.5 nanometers.
分别在0℃冷贮7d和54℃热贮14d后制剂均没有发生沉淀现象,仍然稳定。After cold storage at 0°C for 7 days and 54°C heat storage for 14 days, the preparations did not precipitate and remained stable.
本实施例纳米水剂入水后能迅速与水互溶,形成完全透明溶液,稀释稳定性合格。After entering water, the nano-aqueous agent of this embodiment can quickly dissolve with water to form a completely transparent solution, and the dilution stability is qualified.
对比例1-对比例4Comparative example 1-Comparative example 4
采用目前配制水剂常用的助剂(润湿剂)配制水剂,具体配方如表3所示。The water preparation is prepared with the commonly used auxiliary (wetting agent) in the preparation of water preparation, and the specific formula is shown in Table 3.
表3.对比例1-对比例4的配方Table 3. Formulations of Comparative Example 1-Comparative Example 4
制备方法同实施例1。The preparation method is the same as in Example 1.
按照对比例1和对比例2的配方,在添加助剂的情况下,甲氰菊酯和毒死蜱仍然无法完全溶解在水中,不能形成合格的水溶液。According to the formulations of Comparative Example 1 and Comparative Example 2, with the addition of additives, fenpropathrin and chlorpyrifos still cannot be completely dissolved in water, and a qualified aqueous solution cannot be formed.
按照对比例3和对比例4的配方,在常温(10~35℃)下能够制备获得水溶液,但将水溶液置于低温(0℃以下)下,甲氰菊酯和毒死蜱原药会不断析出,而且升温后不可恢复。说明利用非本发明中的表面活性剂或表面活性剂组合物之外的常规水剂使用的表面活性剂无法配制出合格的甲氰菊酯·毒死蜱复配纳米水剂。According to the formulations of Comparative Example 3 and Comparative Example 4, an aqueous solution can be prepared at room temperature (10-35°C), but when the aqueous solution is placed at a low temperature (below 0°C), the fenpropathrin and chlorpyrifos technical drugs will continue to precipitate. And it cannot be recovered after heating up. It shows that the use of surfactants other than the surfactants or conventional liquids used in the surfactant composition of the present invention cannot be used to prepare qualified fenpropathrin·chlorpyrifos composite nano-aqueous.
实施例10:生物活性对比Example 10: Comparison of Biological Activity
田间药效试验一Field efficacy test one
供试药剂:实施例1-实施例9的甲氰菊酯·毒死蜱复配纳米水剂。Test agent: Example 1 to Example 9 of the fenpropathrin·chlorpyrifos compound nano-aqueous agent.
对照药剂:3.5%甲氰菊酯纳米水剂、2%毒死蜱纳米水剂。Control agent: 3.5% fenpropathrin nano-aqueous, 2% chlorpyrifos nano-aqueous.
3.5%甲氰菊酯纳米水剂制备方法:称取3.5g(以有效成分计)甲氰菊酯原药、7g脂肪醇聚氧乙烯醚、4g脂肪酸甲酯磺酸钠,5g失水山梨醇脂肪酸酯聚氧乙烯醚三者混合后,在转速85转/秒条件下搅拌0.5h,在搅拌状态下加入80.5g水,继续搅拌1h,得到3.5%甲氰菊酯纳米水剂。3.5% fenpropathrin nano-aqueous preparation method: weigh 3.5g (based on active ingredient) fenpropathrin technical, 7g fatty alcohol polyoxyethylene ether, 4g fatty acid methyl ester sulfonate sodium, 5g sorbitol After the three fatty acid ester polyoxyethylene ethers are mixed, they are stirred for 0.5 h at a rotation speed of 85 revolutions per second, and 80.5 g of water is added under stirring, and the stirring is continued for 1 h to obtain 3.5% fenpropathrin nano-aqueous agent.
2%毒死蜱纳米水剂制备方法:称取2g(以有效成份计)毒死蜱原药,8g三苯乙烯基苯酚聚氧乙烯醚磷酸酯和2g烷基酚甲醛树脂聚氧乙烯醚,将三者混合后在转速75转/秒条件下搅拌0.5h,在搅拌状态下加入88g水,继续搅拌0.8h,得到2%毒死蜱纳米水剂。2% chlorpyrifos nano-aqueous preparation method: weigh 2g (based on active ingredients) of chlorpyrifos original drug, 8g tristyrylphenol polyoxyethylene ether phosphate and 2g alkylphenol formaldehyde resin polyoxyethylene ether, and mix the three Then, it was stirred for 0.5 h at a rotation speed of 75 revolutions per second, 88 g of water was added under stirring, and the stirring was continued for 0.8 h to obtain 2% chlorpyrifos nano-aqueous solution.
防治对象:柑橘红蜘蛛。Control object: citrus red spider.
试验方法:采用正常田间使用剂量(有效成分),剂量处理设置三次重复,重复采用随机区组排列,每个重复设置面积30m
2,试验采用背负式喷雾器进行喷雾。施药前调查虫口基数,药后3天、7天、14天、30天分别调查残留活虫数,按照以下方法计算防效:
Test method: The normal field dose (active ingredient) was used, the dose treatment was set for three repetitions, and the random block arrangement was repeated. Each repetition was set in an area of 30m 2 , and the experiment was sprayed with a knapsack sprayer. Investigate the number of insect populations before application, and investigate the number of remaining live insects 3 days, 7 days, 14 days, and 30 days after application, and calculate the control effect according to the following method:
虫口减退率(%)=(施药前虫数-施药后虫数)/施药前虫数×100Insect population reduction rate (%) = (number of insects before application-number of insects after application) / number of insects before application × 100
校正防治效果(%)=(处理区虫口减退率-对照区虫口减退率)/(100-防治前后对照区虫口减退率)×100Corrected control effect (%) = (Reduction rate of insect population in the treatment area-Reduction rate of insect population in the control area) / (100-Recession rate of insect population in the control area before and after control) × 100
试验结果见表4:The test results are shown in Table 4:
表4:甲氰菊酯·毒死蜱纳米水剂对柑橘红蜘蛛的田间试验结果Table 4: Field test results of fenpropathrin·chlorpyrifos nano-aqueous on citrus red spider
田间药效结果表明,甲氰菊酯·毒死蜱复配纳米水剂对柑橘红蜘蛛具有优良的防治效果,防治效果均好于单剂品种直接作用的效果。The field efficacy results showed that the fenpropathrin·chlorpyrifos composite nano-aqueous agent has an excellent control effect on citrus red spiders, and the control effect is better than the direct effect of a single-dose variety.
田间药效试验二Field efficacy test two
供试药剂:实施例1-实施例9的甲氰菊酯·毒死蜱复配纳米水剂。Test agent: Example 1 to Example 9 of the fenpropathrin·chlorpyrifos compound nano-aqueous agent.
对照药剂:3.5%甲氰菊酯纳米水剂、2%毒死蜱纳米水剂。Control agent: 3.5% fenpropathrin nano-aqueous, 2% chlorpyrifos nano-aqueous.
防治对象:稻飞虱。Control object: rice planthopper.
试验方法:采用正常田间使用剂量(有效成分),剂量处理设置三次重复,重复采用随机区组排列,每个重复设置面积50m
2,试验采用背负式喷雾器进行整株棉花喷雾。施药前调查虫口基数,药后3天、7天、14天、30天分别调查残留活虫数,按照以下方法计算防效:
Test method: The normal field dosage (active ingredient) was used, the dosage treatment was set for three repetitions, and the random block arrangement was repeated, and the area of each repetition was 50m 2. The experiment used a knapsack sprayer to spray the whole cotton. Investigate the number of insect populations before application, and investigate the number of remaining live insects 3 days, 7 days, 14 days, and 30 days after application, and calculate the control effect according to the following method:
虫口减退率(%)=(施药前虫数-施药后虫数)/施药前虫数×100Insect population reduction rate (%) = (number of insects before application-number of insects after application) / number of insects before application × 100
校正防治效果(%)=(处理区虫口减退率-对照区虫口减退率)/(100-防治前后对照区虫口减退率)×100Corrected control effect (%) = (Reduction rate of insect population in the treatment area-Reduction rate of insect population in the control area) / (100-Recession rate of insect population in the control area before and after control) × 100
表5 甲氰菊酯·毒死蜱复配纳米水剂对水稻稻飞虱的田间试验结果Table 5 Field test results of fenpropathrin and chlorpyrifos compound nano-aqueous on rice planthoppers
田间药效结果表明,甲氰菊酯·毒死蜱复配纳米水剂对水稻稻飞虱具有优良的防治效果,防治效果均好于单剂品种直接作用的效果。The field efficacy results showed that the fenpropathrin·chlorpyrifos composite nano-aqueous agent has an excellent control effect on rice planthopper, and the control effect is better than the direct effect of the single-agent variety.
本发明的保护内容不局限于以上实施例。在不背离发明构思的精神和范围下,本领域技术人员能够想到的变化和优点都被包括在本发明中,并且以所附的权利要求为保护范围。The protection content of the present invention is not limited to the above embodiments. Without departing from the spirit and scope of the inventive concept, changes and advantages that those skilled in the art can think of are all included in the present invention, and the appended claims are the protection scope.
Claims (8)
- 一种含甲氰菊酯和毒死蜱的复合杀虫杀螨纳米水剂,其特征在于,所述的纳米水剂以甲氰菊酯和毒死蜱为活性成分,与表面活性剂、水配制而成,其中,按照重量百分含量,甲氰菊酯和毒死蜱为3~80%,表明活性剂5~20%,余量为水。A composite insecticidal and acaricide nano-aqueous agent containing fenpropathrin and chlorpyrifos, characterized in that the nano-aqueous agent uses fenpropathrin and chlorpyrifos as active ingredients, is formulated with a surfactant and water, Among them, according to the weight percentage, the content of fenpropathrin and chlorpyrifos is 3 to 80%, indicating that the active agent is 5 to 20%, and the balance is water.
- 根据权利要求1所述的纳米水剂,其特征在于,所述的甲氰菊酯和毒死蜱的重量比为20:1-1:20。The nano-aqueous formulation of claim 1, wherein the weight ratio of the fenpropathrin and chlorpyrifos is 20:1 to 1:20.
- 根据权利要求2所述的纳米水剂,其特征在于,所述的甲氰菊酯和毒死蜱的重量比为5:1~1:5。The nano-aqueous formulation of claim 2, wherein the weight ratio of the fenpropathrin and chlorpyrifos is 5:1 to 1:5.
- 根据权利要求1所述的纳米水剂,其特征在于,所述的表面活性剂选自脂肪醇聚氧乙烯醚、烷基酚甲醛树脂聚氧乙烯醚、苯乙烯基苯酚聚氧乙烯醚、脂肪醇聚氧乙烯醚磷酸酯、烷基酚聚氧乙烯醚磷酸酯、脂肪酸甲酯磺酸钠、醇醚琥珀酸单酯磺酸钠中的一种或多种组合。The nano-aqueous agent according to claim 1, wherein the surfactant is selected from the group consisting of fatty alcohol polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, styrylphenol polyoxyethylene ether, fatty acid One or more combinations of alcohol polyoxyethylene ether phosphate, alkylphenol polyoxyethylene ether phosphate, sodium fatty acid methyl sulfonate, and sodium alcohol ether succinic acid monoester sulfonate.
- 权利要求1所述的纳米水剂的制备方法,其特征在于,包括:The preparation method of nano-aqueous agent according to claim 1, characterized in that it comprises:步骤(1),在常温下,将甲氰菊酯原药、毒死蜱原药与表面活性剂混合,搅拌,使毒死蜱和甲氰菊酯均匀分散在表面活性剂中;Step (1), at room temperature, mix the fenpropathrin original drug, chlorpyrifos original drug and the surfactant, and stir, so that the chlorpyrifos and fenpropathrin are uniformly dispersed in the surfactant;步骤(2),在搅拌状态下加入水,搅拌均匀,形成含有甲氰菊酯和毒死蜱的表面活性剂胶束溶液,即为透明的甲氰菊酯和毒死蜱纳米水剂。In step (2), water is added under stirring, and the mixture is evenly stirred to form a surfactant micellar solution containing fenpropathrin and chlorpyrifos, which is a transparent nano-aqueous solution of fenpropathrin and chlorpyrifos.
- 根据权利要求5所述的纳米水剂的制备方法,其特征在于,所述步骤(1)和步骤(2)中,搅拌速度为60~100转/秒。The preparation method of nano-aqueous agent according to claim 5, characterized in that, in the step (1) and step (2), the stirring speed is 60-100 revolutions per second.
- 权利要求1所述的纳米水剂在防治果树、蔬菜、棉花上的害虫、害螨的用途。The use of the nano-aqueous agent according to claim 1 to control pests and mites on fruit trees, vegetables, and cotton.
- 根据权利要求7所述的用途,其特征在于,所述的害虫为稻飞虱,所述的害螨为柑橘红蜘蛛。The use according to claim 7, wherein the pest is rice planthopper, and the pest mite is citrus red spider.
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