WO2021068271A1 - Compound insecticidal and acaricidal nano aqueous formulation comprising chlorpyrifos and emamectin benzoate, and use thereof - Google Patents

Compound insecticidal and acaricidal nano aqueous formulation comprising chlorpyrifos and emamectin benzoate, and use thereof Download PDF

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WO2021068271A1
WO2021068271A1 PCT/CN2019/111043 CN2019111043W WO2021068271A1 WO 2021068271 A1 WO2021068271 A1 WO 2021068271A1 CN 2019111043 W CN2019111043 W CN 2019111043W WO 2021068271 A1 WO2021068271 A1 WO 2021068271A1
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chlorpyrifos
nano
emamectin benzoate
water
aqueous
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PCT/CN2019/111043
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French (fr)
Chinese (zh)
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郭崇友
陈叶青
张宝俊
洪鹏
马诚义
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南京华洲药业有限公司
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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
    • 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system

Definitions

  • the invention belongs to the field of pesticides, and relates to an insecticidal and acaricidal nano-aqueous agent with chlorpyrifos and emamectin benzoate as main active ingredients and uses thereof.
  • 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. Chlorpyrifos 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.
  • Emamectin Benzoate molecular formula: C 56 H 81 NO 15 .
  • Emamectin benzoate is a new type of high-efficiency semi-synthetic antibiotic insecticide synthesized from the fermented product abamectin B1. It has the characteristics of super high efficiency, low toxicity (nearly non-toxic preparation), low residue, and pollution-free biological pesticides. . It is widely used for the prevention and control of various pests on vegetables, fruit trees, cotton and other crops.
  • 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 conventional dosage forms of chlorpyrifos and emamectin benzoate 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 chlorpyrifos and emamectin benzoate formulations.
  • the object of the present invention is to provide a composite insecticidal and acaricide nano-aqueous solution containing chlorpyrifos and emamectin benzoate (emamectin salt), which contains chlorpyrifos and emamectin benzene Formate compounding has obvious synergistic effect; in addition, the creative discovery uses certain surfactants, adopts surfactant micellar solubilization technology, and uses surfactants without the use of organic solvents to aid solubility.
  • the formed nano-sized micelles carry the insoluble water-soluble chlorpyrifos and the slightly water-soluble emamectin benzoate.
  • the effective ingredients are present in the nano-aqueous agent as nano-sized particles, which is more convenient for its attachment on the target. , Spreading and penetration, more resistant to rain washing, and it does not contain organic solvents, safe and environmentally friendly.
  • a composite insecticidal and acaricidal nano-aqueous agent containing chlorpyrifos and emamectin benzoate contains chlorpyrifos and emamectin benzoate as main active ingredients, and Surfactant and water; wherein, the nano-aqueous agent contains the following ingredients: the weight percentage of chlorpyrifos and emamectin benzoate is 5 to 80%, and the pesticide adjuvant is 5 to 20 %, the balance is water.
  • the weight ratio of the chlorpyrifos and emamectin benzoate is 20:1 to 1:20, preferably 5:1 to 1:5.
  • the weight percentage content of chlorpyrifos and emamectin benzoate in the nano-aqueous agent is preferably 5% to 55%, and more preferably 3% to 12%.
  • the nano-aqueous agent of the present invention can only contain the active ingredients chlorpyrifos and emamectin benzoate, and can also add other components to the active ingredients during use or formulation.
  • the insecticidal composition is effective
  • the ingredients can also be present in the composition in a synergistically effective amount.
  • Said surfactant is selected from fatty alcohol polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, styryl phenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether phosphate, lauramidopropyl hydroxysulfonate
  • betaine tristyryl phenol polyoxyethylene ether phosphate, alkylphenol polyoxyethylene ether phosphate, sodium fatty acid methyl sulfonate, sodium alcohol ether succinate monoester sulfonate, etc.
  • Another object of the present invention is to provide a method for preparing a nano-aqueous formulation containing chlorpyrifos and emamectin benzoate, including:
  • Step (1) at room temperature (10 ⁇ 35°C), mix chlorpyrifos and emamectin benzoate with surfactants and stir to make chlorpyrifos and emamectin benzene
  • the formate is uniformly dispersed in the surfactant
  • Step (2) Add water under stirring and stir evenly to form a surfactant micellar solution containing chlorpyrifos and emamectin benzoate, that is, transparent chlorpyrifos and emamectin benzene Formate nano water agent.
  • the chlorpyrifos and emamectin benzoate 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, it can quickly dissolve with water to form a completely transparent solution, and the dilution stability is qualified;
  • the nano-aqueous agent of the present invention has stable performance, and remains stable after cold storage at 0°C for 7 days and hot storage at 54°C for 14 days, chlorpyrifos will not precipitate, and storage is convenient.
  • step (1) the stirring speed is 60-100 revolutions per second, and the stirring time is 0.5h.
  • the technician can adjust the time so that chlorpyrifos and emamectin benzoate are uniformly dispersed in the surfactant. quasi.
  • 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 cotton bollworm, and the pest mite is cotton spider mites.
  • 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:
  • the compound has obvious synergistic effect, which improves the control effect of harmful mites compared with single agent alone;
  • the present invention is a new dosage form-nano-aqueous agent, which has a nanometer particle size, is more convenient for its attachment, spreading and penetration on the target, is more resistant to rain washing, and it does not contain organic solvents, which is safe and environmentally friendly.
  • Figure 1 shows the 6% chlorpyrifos ⁇ emamectin benzoate nano-aqueous formulation of Example 3.
  • Figure 2 shows the 6% chlorpyrifos ⁇ emamectin benzoate 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.
  • the weight ratio of chlorpyrifos and emamectin benzoate is between 20:1 and 1:20, and the co-toxicity coefficient is greater than 120. It has a synergistic effect on the control of cotton spider mite, especially in Between 5:1 and 1:5, the co-toxicity coefficient is above 180, and the synergistic effect is significant.
  • Preparation method Weigh 20g (based on active ingredients, the same below) chlorpyrifos original drug, 1g (based on active ingredients, the same below) emamectin benzoate, and 6g fatty alcohol polyoxyethylene ether, 8g Sodium alcohol ether succinic acid monoester sulfonate was mixed with 3g lauryl amidopropyl hydroxysultaine, stirred at 78 rpm for 0.5h, kept stirring, added 62g of water, and continued to stir for 0.5h to obtain 21% chlorpyrifos ⁇ Emamectin benzoate nano-aqueous agent.
  • 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 in Example 1, and 11% chlorpyrifos ⁇ emamectin benzoate nano-aqueous formulation is prepared.
  • the nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 120 mPa ⁇ s, and an average particle size of 13.7 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 6% chlorpyrifos ⁇ emamectin benzoate nano-aqueous formulation is prepared.
  • the nano-aqueous agent of this example has a transparent and slightly yellowish appearance, a viscosity of 90 mPa ⁇ s, and an average particle size of 11.0 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 3% chlorpyrifos ⁇ emamectin benzoate nano-aqueous formulation is prepared.
  • the nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 80 mPa ⁇ s, and an average particle size of 10.6 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 in Example 1, and 4% chlorpyrifos ⁇ emamectin benzoate nano-aqueous formulation is prepared.
  • the nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 66 mPa ⁇ s, and an average particle size of 9.8 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 9% chlorpyrifos ⁇ emamectin benzoate nano-aqueous formulation is prepared.
  • the nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 80 mPa ⁇ s, and an average particle size of 10.2 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 that in Example 1, and 12% chlorpyrifos ⁇ emamectin benzoate nano-aqueous formulation is prepared.
  • the nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 80 mPa ⁇ s, and an average particle size of 11.9 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, chlorpyrifos ⁇ methylaminoabamectin benzoate nano-aqueous formulation.
  • the nano-aqueous agent of this example has a transparent and slightly yellowish appearance, a viscosity of 110 mPa ⁇ s, and an average particle size of 12.7 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% chlorpyrifos ⁇ aminoabamectin benzoate nano-aqueous formulation was prepared.
  • the nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 123 mPa ⁇ s, and an average particle size of 12.0 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 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 the aqueous solution is placed at low temperature (below 0°C), chlorpyrifos and emamectin benzoate
  • the original drug will continue to precipitate and cannot be recovered after the temperature rises. It shows that the qualified chlorpyrifos ⁇ aminoabamectin benzoate nano-aqueous agent can not be formulated with the surfactant used in the conventional water agent other than the surfactant or the surfactant composition of the present invention.
  • Test agent Example 1 to Example 9 of chlorpyrifos and emamectin benzoate compound nano-aqueous agent.
  • Control agent 5% emamectin benzoate nano-aqueous; 6% chlorpyrifos nano-aqueous.
  • Preparation method of 5% emamectin benzoate nano-aqueous agent weigh 50g (based on active ingredients) of the original medicine of emamectin benzoate, 10g styrylphenol polyoxyethylene ether, 30g fatty alcohol polyoxyethylene ether , Mix the three, stir at 100 revolutions per second for 0.5 h, add 910 g of water under stirring, and continue stirring for 1 h to obtain 5% emamectin benzoate nano-aqueous solution.
  • 6% chlorpyrifos nano-aqueous preparation method weigh 60g (based on active ingredients) chlorpyrifos original drug, 80g fatty alcohol polyoxyethylene ether, 40g alkylphenol polyoxyethylene ether phosphate, 30g fatty acid methyl ester sulfonate sodium, and The four are mixed and stirred for 0.5 h at a rotation speed of 80 revolutions per second, and 790 water is added under stirring, and the stirring is continued for 1 h to obtain 6% chlorpyrifos nano-aqueous solution.
  • Control object cotton spider mite.
  • 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 30m 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 residual 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
  • Test agent Example 1 to Example 9 of chlorpyrifos and emamectin benzoate compound nano-aqueous agent.
  • Control agent 5% emamectin benzoate nano-aqueous; 6% chlorpyrifos nano-aqueous.
  • Control object cotton bollworm.
  • 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 50 m 2.
  • the experiment was carried out with a knapsack sprayer for spraying the whole cotton. Investigate the number of insect populations before application, and investigate the number of residual 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

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Abstract

Disclosed is a compound insecticidal and acaricidal nano aqueous formulation comprising chlorpyrifos and emamectin benzoate. The nano aqueous formulation is prepared using chlorpyrifos and emamectin benzoate as active ingredients, together with a surfactant and water, wherein the weight percentages are: 5% to 80% of chlorpyrifos and emamectin benzoate, 5% to 20% of a pesticide auxiliary agent, the remainder being water, and the chlorpyrifos and emamectin benzoate having a weight ratio of 20:1 to 1:20. In the present invention, nano-sized micelles formed by the surfactant are used to carry poorly water-soluble chlorpyrifos and sparingly water-soluble emamectin benzoate, such that the two active ingredients exist in the nano aqueous formulation as nano-sized microparticles, which facilitates the adhesion, spreading and penetration of the active ingredients onto, over and into a target, and increases the resistance of the active ingredients to rain wash. With the two active ingredients acting in synergy, the nano aqueous formulation can prevent and treat Lepidoptera and mite pests on agricultural crops with both a fast pesticidal effect and a prolonged efficacy, providing markedly superior prevention and treatment performances to those achieved by separate use of the two ingredients.

Description

含毒死蜱和甲氨基阿维菌素苯甲酸盐的复合杀虫杀螨纳米水剂及其用途Composite insecticidal and acaricidal nano-aqueous agent containing chlorpyrifos and emamectin benzoate and its use 技术领域Technical field
本发明属于农药领域，涉及一种以毒死蜱和甲氨基阿维菌素苯甲酸盐为主要有效成分的杀虫杀螨纳米水剂及其用途。The invention belongs to the field of pesticides, and relates to an insecticidal and acaricidal nano-aqueous agent with chlorpyrifos and emamectin benzoate as main active ingredients and uses thereof.
背景技术Background technique
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。毒死蜱具有胃毒、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. Chlorpyrifos 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.
甲氨基阿维菌素苯甲酸盐(Emamectin Benzoate)，分子式：C 56H 81NO 15。化学名称：4'-表-甲氨基-4'-脱氧阿维菌素B1苯甲酸盐。甲维盐是从发酵产品阿维菌素B1开始合成的一种新型高效半合成抗生素杀虫剂，它具有超高效、低毒(制剂近无毒)、低残留、无公害等生物农药的特点。广泛用于蔬菜、果树、棉花等农作物上的多种害虫的防治。 Emamectin Benzoate, molecular formula: C 56 H 81 NO 15 . Chemical name: 4'-epi-methylamino-4'-deoxyabamectin B1 benzoate. Emamectin benzoate is a new type of high-efficiency semi-synthetic antibiotic insecticide synthesized from the fermented product abamectin B1. It has the characteristics of super high efficiency, low toxicity (nearly non-toxic preparation), low residue, and pollution-free biological pesticides. . It is widely used for the prevention and control of various pests on vegetables, fruit trees, cotton and other crops.
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.
目前，毒死蜱、甲氨基阿维菌素苯甲酸盐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，是毒死蜱、甲氨基阿维菌素苯甲酸盐剂型发展必然之路。At present, the conventional dosage forms of chlorpyrifos and emamectin benzoate 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 chlorpyrifos and emamectin benzoate formulations.
发明内容Summary of the invention
本发明的目的是提供一种含毒死蜱和甲氨基阿维菌素苯甲酸盐(甲维盐)的复合杀虫杀螨纳米水剂，该纳米水剂中毒死蜱和甲氨基阿维菌素苯甲酸盐复配具有明显的协同增效作用；另外，创造性的发现采用某些表面活性剂，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毒死蜱和微溶于水的甲氨基阿维菌素苯甲酸盐，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。The object of the present invention is to provide a composite insecticidal and acaricide nano-aqueous solution containing chlorpyrifos and emamectin benzoate (emamectin salt), which contains chlorpyrifos and emamectin benzene Formate compounding has obvious synergistic effect; in addition, the creative discovery uses certain surfactants, adopts surfactant micellar solubilization technology, and uses surfactants without the use of organic solvents to aid solubility. The formed nano-sized micelles carry the insoluble water-soluble chlorpyrifos and the slightly water-soluble emamectin benzoate. The effective ingredients are present in the nano-aqueous agent as nano-sized particles, which is more convenient for its attachment on the target. , Spreading and penetration, more resistant to rain washing, and it does not contain organic solvents, safe and environmentally friendly.
本发明的目的是通过以下技术方案实现的：The purpose of the present invention is achieved through the following technical solutions:
一种含毒死蜱和甲氨基阿维菌素苯甲酸盐的复合杀虫杀螨纳米水剂，所述的纳米水剂以 毒死蜱和甲氨基阿维菌素苯甲酸盐为主要活性成分，与表面活性剂、水配制成的；其中，所述的纳米水剂含有以下成分：毒死蜱和甲氨基阿维菌素苯甲酸盐的重量百分含量为5～80％，农药助剂5～20％，余量为水。A composite insecticidal and acaricidal nano-aqueous agent containing chlorpyrifos and emamectin benzoate. The nano-aqueous agent contains chlorpyrifos and emamectin benzoate as main active ingredients, and Surfactant and water; wherein, the nano-aqueous agent contains the following ingredients: the weight percentage of chlorpyrifos and emamectin benzoate is 5 to 80%, and the pesticide adjuvant is 5 to 20 %, the balance is water.
所述的毒死蜱和甲氨基阿维菌素苯甲酸盐的重量比为20:1～1:20，优选为5:1～1:5。The weight ratio of the chlorpyrifos and emamectin benzoate is 20:1 to 1:20, preferably 5:1 to 1:5.
所述的纳米水剂中毒死蜱与甲氨基阿维菌素苯甲酸盐的重量百分含量优选为5％～55％，进一步优选为3％～12％。The weight percentage content of chlorpyrifos and emamectin benzoate in the nano-aqueous agent is preferably 5% to 55%, and more preferably 3% to 12%.
本发明所述的纳米水剂可以只含有活性成分毒死蜱和甲氨基阿维菌素苯甲酸盐，也可在使用或配制时向活性成分中加入其他组分，该杀虫组合物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 chlorpyrifos and emamectin benzoate, and can also add other components to the active ingredients during use or formulation. The insecticidal composition is effective The ingredients can also be present in the composition in a synergistically effective amount.
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、月桂酰胺丙基羟磺基甜菜碱、三苯乙烯基苯酚聚氧乙烯醚磷酸酯、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等中的一种或多种组合。Said surfactant is selected from fatty alcohol polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, styryl phenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether phosphate, lauramidopropyl hydroxysulfonate One or more combinations of betaine, tristyryl phenol polyoxyethylene ether phosphate, alkylphenol polyoxyethylene ether phosphate, sodium fatty acid methyl sulfonate, sodium alcohol ether succinate monoester sulfonate, etc. .
本发明的另一个目的是提供一种含毒死蜱和甲氨基阿维菌素苯甲酸盐的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 nano-aqueous formulation containing chlorpyrifos and emamectin benzoate, including:
步骤(1)、在常温(10～35℃)下，将毒死蜱原药、甲氨基阿维菌素苯甲酸盐原药与表面活性剂混合，搅拌，使毒死蜱和甲氨基阿维菌素苯甲酸盐均匀分散在表面活性剂中；Step (1), at room temperature (10～35℃), mix chlorpyrifos and emamectin benzoate with surfactants and stir to make chlorpyrifos and emamectin benzene The formate is uniformly dispersed in the surfactant;
步骤(2)、在搅拌状态下加入水，搅拌均匀，形成含有毒死蜱和甲氨基阿维菌素苯甲酸盐的表面活性剂胶束溶液，即为透明的毒死蜱和甲氨基阿维菌素苯甲酸盐纳米水剂。本发明毒死蜱和甲氨基阿维菌素苯甲酸盐纳米水剂外观透明，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，毒死蜱不会析出，便于贮藏。Step (2). Add water under stirring and stir evenly to form a surfactant micellar solution containing chlorpyrifos and emamectin benzoate, that is, transparent chlorpyrifos and emamectin benzene Formate nano water agent. The chlorpyrifos and emamectin benzoate 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, it can quickly dissolve with water to form a completely transparent solution, and the dilution stability is qualified; The nano-aqueous agent of the present invention has stable performance, and remains stable after cold storage at 0°C for 7 days and hot storage at 54°C for 14 days, chlorpyrifos will not precipitate, and storage is convenient.
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，以使毒死蜱和甲氨基阿维菌素苯甲酸盐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 0.5h. The technician can adjust the time so that chlorpyrifos and emamectin benzoate are uniformly dispersed in the surfactant. quasi.
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。所述的害虫为棉铃虫，所述的害螨为棉红蜘蛛。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 cotton bollworm, and the pest mite is cotton spider mites. 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：Compared with the prior art, the present invention has the following beneficial effects:
(1)、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；(1) The compound has obvious synergistic effect, which improves the control effect of harmful mites compared with single agent alone;
(2)、兼有速效和长效；(2), both quick-acting and long-acting;
(3)、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(3) The combination of two active ingredients reduces the amount of pesticides used, reduces production and use costs and environmental pollution
(4)、延缓害虫害螨对农药的抗性，其效果明显高于其单剂使用。(4) Delay the resistance of pests and mites to pesticides, and its effect is significantly higher than its single-agent use.
(5)、本发明为全新剂型—纳米水剂，具有纳米级粒径大小，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。(5). The present invention is a new dosage form-nano-aqueous agent, which has a nanometer particle size, is more convenient for its attachment, spreading and penetration on the target, is more resistant to rain washing, and it does not contain organic solvents, which is safe and environmentally friendly.
附图说明Description of the drawings
图1为实施例3的6％毒死蜱·甲氨基阿维菌素苯甲酸盐纳米水剂。Figure 1 shows the 6% chlorpyrifos· emamectin benzoate nano-aqueous formulation of Example 3.
图2为对比例2的6％毒死蜱·甲氨基阿维菌素苯甲酸盐纳米水剂。Figure 2 shows the 6% chlorpyrifos· emamectin benzoate nano-aqueous formulation of Comparative Example 2.
具体实施方式Detailed ways
以下结合实施例对本发明作进一步说明，但不以任何方式限制本发明。The present invention will be further described in conjunction with the following examples, but the present invention will not be restricted in any way.
室内毒力测定Indoor toxicity test
1、采用浸渍玻片法进行毒死蜱和甲氨基阿维菌素苯甲酸盐及其复配样品对棉红蜘蛛的毒力测定，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 chlorpyrifos and emamectin benzoate and their compound samples on cotton spider mites were determined by immersion slide method, each treatment was repeated 3 times, each concentration was treated with 30 heads, and the LC 50 value was used. Calculate the co-toxicity coefficient (CTC value) according to Sun Yunpei's method:
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.毒死蜱和甲氨基阿维菌素苯甲酸盐复配对棉红蜘蛛的室内毒力测定Table 1. Indoor virulence determination of chlorpyrifos and emamectin benzoate on cotton spider mite
Figure PCTCN2019111043-appb-000001
Figure PCTCN2019111043-appb-000001
Figure PCTCN2019111043-appb-000002
Figure PCTCN2019111043-appb-000002
由表1可知，毒死蜱和甲氨基阿维菌素苯甲酸盐重量比在20:1～1:20之间，共毒系数都大于120，对棉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180以上，增效作用显著。It can be seen from Table 1 that the weight ratio of chlorpyrifos and emamectin benzoate is between 20:1 and 1:20, and the co-toxicity coefficient is greater than 120. It has a synergistic effect on the control of cotton spider mite, especially in Between 5:1 and 1:5, the co-toxicity coefficient is above 180, and the synergistic effect is significant.
2、采用饲料混毒法，选择棉花棉铃虫为目标害虫，每处理重复三次，用几率值法计算各药剂对棉花棉铃虫的毒力回归方程和致死中浓度LC 50，用LC 50值按照孙云沛法计算共度系数，结果如表2。 2. Using the feed mixing method, select cotton bollworm as the target pest, repeat each treatment three times, use the probability value method to calculate the virulence regression equation of each agent to the cotton bollworm and the lethal concentration LC 50 , and use the LC 50 value according to Sun Yunpei Method to calculate the co-degree coefficient, the results are shown in Table 2.
表2.毒死蜱和甲氨基阿维菌素苯甲酸盐复配对棉铃虫的毒力测定Table 2. Determination of the virulence of chlorpyrifos and emamectin benzoate to the cotton bollworm
Figure PCTCN2019111043-appb-000003
Figure PCTCN2019111043-appb-000003
由表2可知，毒死蜱和甲氨基阿维菌素苯甲酸盐重量比在20:1～1:20之间，共毒系数都大于120，对棉铃虫防治具有增效作用，尤其在5:1～1:5之间，共毒系数在140以上，增效作用显著。It can be seen from Table 2 that the weight ratio of chlorpyrifos and emamectin benzoate is between 20:1 and 1:20, and the co-toxicity coefficient is greater than 120, which has a synergistic effect on the control of cotton bollworm, especially at 5: Between 1 and 1:5, the co-toxicity coefficient is above 140, and the synergistic effect is significant.
实施例1Example 1
配方：20g毒死蜱、1g甲氨基阿维菌素苯甲酸盐、6g脂肪醇聚氧乙烯醚、8g醇醚琥珀酸单酯磺酸钠、3g月桂酰胺丙基羟磺基甜菜碱，加水至100g。Formula: 20g chlorpyrifos, 1g emamectin benzoate, 6g fatty alcohol polyoxyethylene ether, 8g alcohol ether succinic acid monoester sulfonate, 3g lauryl amidopropyl hydroxysultaine, add water to 100g .
制备方法：称取20g(以有效成分计，下同)毒死蜱原药、1g(以有效成分计，下同)甲氨基阿维菌素苯甲酸盐，与6g脂肪醇聚氧乙烯醚、8g醇醚琥珀酸单酯磺酸钠和3g月桂酰胺丙基羟磺基甜菜碱混合，在转速78转/秒下搅拌0.5h，保持搅拌，加入62g水，继续搅拌0.5h，得到21％毒死蜱·甲氨基阿维菌素苯甲酸盐纳米水剂。Preparation method: Weigh 20g (based on active ingredients, the same below) chlorpyrifos original drug, 1g (based on active ingredients, the same below) emamectin benzoate, and 6g fatty alcohol polyoxyethylene ether, 8g Sodium alcohol ether succinic acid monoester sulfonate was mixed with 3g lauryl amidopropyl hydroxysultaine, stirred at 78 rpm for 0.5h, kept stirring, added 62g of water, and continued to stir for 0.5h to obtain 21% chlorpyrifos· Emamectin benzoate nano-aqueous agent.
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2Example 2
配方：10g毒死蜱、1g甲氨基阿维菌素苯甲酸盐、4g苯乙烯基苯酚聚氧乙烯醚、3g脂肪醇聚氧乙烯醚、5g三苯乙烯基苯酚聚氧乙烯醚磷酸酯，加水至100g。Formula: 10g chlorpyrifos, 1g emamectin benzoate, 4g styrylphenol polyoxyethylene ether, 3g fatty alcohol polyoxyethylene ether, 5g tristyrylphenol polyoxyethylene ether phosphate, add water to 100g.
制备方法同实施例1，制得11％毒死蜱·甲氨基阿维菌素苯甲酸盐纳米水剂。The preparation method is the same as in Example 1, and 11% chlorpyrifos· emamectin benzoate nano-aqueous formulation is prepared.
本实施例纳米水剂外观透明微黄，粘度120mPa·s，平均粒径为13.7纳米。The nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 120 mPa·s, and an average particle size of 13.7 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3Example 3
配方：5g毒死蜱、1g甲氨基阿维菌素苯甲酸盐、2g烷基酚甲醛树脂聚氧乙烯醚、4g脂肪醇聚氧乙烯醚磷酸酯，加水至100g。Formula: 5g chlorpyrifos, 1g emamectin benzoate, 2g alkylphenol formaldehyde resin polyoxyethylene ether, 4g fatty alcohol polyoxyethylene ether phosphate, add water to 100g.
制备方法同实施例1，制得6％毒死蜱·甲氨基阿维菌素苯甲酸盐纳米水剂。The preparation method is the same as in Example 1, and 6% chlorpyrifos· emamectin benzoate nano-aqueous formulation is prepared.
本实施例纳米水剂外观透明微黄，粘度90mPa·s，平均粒径为11.0纳米。The nano-aqueous agent of this example has a transparent and slightly yellowish appearance, a viscosity of 90 mPa·s, and an average particle size of 11.0 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4Example 4
配方：2g毒死蜱、1g甲氨基阿维菌素苯甲酸盐、2g苯乙烯基苯酚聚氧乙烯醚、3g烷基酚聚氧乙烯醚磷酸酯，加水至100g。Formula: 2g chlorpyrifos, 1g emamectin benzoate, 2g styrylphenol polyoxyethylene ether, 3g alkylphenol polyoxyethylene ether phosphate, add water to 100g.
制备方法同实施例1，制得3％毒死蜱·甲氨基阿维菌素苯甲酸盐纳米水剂。The preparation method is the same as that in Example 1, and 3% chlorpyrifos· emamectin benzoate nano-aqueous formulation is prepared.
本实施例纳米水剂外观透明微黄，粘度80mPa·s，平均粒径为10.6纳米。The nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 80 mPa·s, and an average particle size of 10.6 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5Example 5
配方：2g毒死蜱、2g甲氨基阿维菌素苯甲酸盐、4g醇醚琥珀酸单酯磺酸钠、3g烷基酚聚氧乙烯醚磷酸酯，加水至100g。Formula: 2g chlorpyrifos, 2g emamectin benzoate, 4g sodium alcohol ether succinate monoester sulfonate, 3g alkylphenol polyoxyethylene ether phosphate, add water to 100g.
制备方法同实施例1，制得4％毒死蜱·甲氨基阿维菌素苯甲酸盐纳米水剂。The preparation method is the same as in Example 1, and 4% chlorpyrifos· emamectin benzoate nano-aqueous formulation is prepared.
本实施例纳米水剂外观透明微黄，粘度66mPa·s，平均粒径为9.8纳米。The nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 66 mPa·s, and an average particle size of 9.8 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6Example 6
配方：3g毒死蜱、6g甲氨基阿维菌素苯甲酸盐、3g烷基酚甲醛树脂聚氧乙烯醚、7g苯乙烯基苯酚聚氧乙烯醚，加水至100g。Formula: 3g chlorpyrifos, 6g emamectin benzoate, 3g alkylphenol formaldehyde resin polyoxyethylene ether, 7g styrylphenol polyoxyethylene ether, add water to 100g.
制备方法同实施例1，制得9％毒死蜱·甲氨基阿维菌素苯甲酸盐纳米水剂。The preparation method is the same as that in Example 1, and 9% chlorpyrifos· emamectin benzoate nano-aqueous formulation is prepared.
本实施例纳米水剂外观透明微黄，粘度80mPa·s，平均粒径为10.2纳米。The nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 80 mPa·s, and an average particle size of 10.2 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7Example 7
配方：2g毒死蜱、10g甲氨基阿维菌素苯甲酸盐、15g苯乙烯基苯酚聚氧乙烯醚、5g脂肪酸甲酯磺酸钠，加水至100g。Formula: 2g chlorpyrifos, 10g emamectin benzoate, 15g styrylphenol polyoxyethylene ether, 5g sodium fatty acid methyl sulfonate, add water to 100g.
制备方法同实施例1，制得12％毒死蜱·甲氨基阿维菌素苯甲酸盐纳米水剂。The preparation method is the same as that in Example 1, and 12% chlorpyrifos· emamectin benzoate nano-aqueous formulation is prepared.
本实施例纳米水剂外观透明微黄，粘度80mPa·s，平均粒径为11.9纳米。The nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 80 mPa·s, and an average particle size of 11.9 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8Example 8
配方：1g毒死蜱、10g甲氨基阿维菌素苯甲酸盐、4g脂肪醇聚氧乙烯醚、3g月桂酰胺丙基羟磺基甜菜碱、8g烷基酚聚氧乙烯醚磷酸酯，加水至100g。Formula: 1g chlorpyrifos, 10g emamectin benzoate, 4g fatty alcohol polyoxyethylene ether, 3g lauramide propyl hydroxysultaine, 8g alkylphenol polyoxyethylene ether phosphate, add water to 100g .
制备方法同实施例1，毒死蜱·甲氨基阿维菌素苯甲酸盐纳米水剂。The preparation method is the same as in Example 1, chlorpyrifos·methylaminoabamectin benzoate nano-aqueous formulation.
本实施例纳米水剂外观透明微黄，粘度110mPa·s，平均粒径为12.7纳米。The nano-aqueous agent of this example has a transparent and slightly yellowish appearance, a viscosity of 110 mPa·s, and an average particle size of 12.7 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9Example 9
配方：0.5g毒死蜱、10g甲氨基阿维菌素苯甲酸盐，苯乙烯基苯酚聚氧乙烯醚10g、醇醚琥珀酸单酯磺酸钠5g，加水至100g。Formula: 0.5g chlorpyrifos, 10g emamectin benzoate, 10g styrylphenol polyoxyethylene ether, 5g sodium alcohol ether succinate monoester sulfonate, add water to 100g.
制备方法同实施例1，制得10.5％毒死蜱·甲氨基阿维菌素苯甲酸盐纳米水剂。The preparation method is the same as that in Example 1, and 10.5% chlorpyrifos·aminoabamectin benzoate nano-aqueous formulation was prepared.
本实施例纳米水剂外观透明微黄，粘度123mPa·s，平均粒径为12.0纳米。The nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 123 mPa·s, and an average particle size of 12.0 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.
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
Figure PCTCN2019111043-appb-000004
Figure PCTCN2019111043-appb-000004
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，毒死蜱和甲氨基阿维菌素苯甲酸盐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, chlorpyrifos and emamectin benzoate 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，毒死蜱和甲氨基阿维菌素苯甲酸盐原药会不断析出，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毒死蜱·甲氨基阿维菌素苯甲酸盐纳米水剂。According to the formula of Comparative Example 3 and Comparative Example 4, an aqueous solution can be prepared at room temperature (10～35℃), but the aqueous solution is placed at low temperature (below 0℃), chlorpyrifos and emamectin benzoate The original drug will continue to precipitate and cannot be recovered after the temperature rises. It shows that the qualified chlorpyrifos·aminoabamectin benzoate nano-aqueous agent can not be formulated with the surfactant used in the conventional water agent other than the surfactant or the surfactant composition of the present invention.
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的毒死蜱·甲氨基阿维菌素苯甲酸盐复配纳米水剂。Test agent: Example 1 to Example 9 of chlorpyrifos and emamectin benzoate compound nano-aqueous agent.
对照药剂：5％甲氨基阿维菌素苯甲酸盐纳米水剂；6％毒死蜱纳米水剂。Control agent: 5% emamectin benzoate nano-aqueous; 6% chlorpyrifos nano-aqueous.
5％甲维盐纳米水剂制备方法：称取50g(以有效成分计)甲氨基阿维菌素苯甲酸盐原药和10g苯乙烯基苯酚聚氧乙烯醚、30g脂肪醇聚氧乙烯醚，将三者混合，在转速100转/秒下 搅拌0.5h，在搅拌状态下加入910g水，继续搅拌1h，得到5％甲维盐纳米水剂。Preparation method of 5% emamectin benzoate nano-aqueous agent: weigh 50g (based on active ingredients) of the original medicine of emamectin benzoate, 10g styrylphenol polyoxyethylene ether, 30g fatty alcohol polyoxyethylene ether , Mix the three, stir at 100 revolutions per second for 0.5 h, add 910 g of water under stirring, and continue stirring for 1 h to obtain 5% emamectin benzoate nano-aqueous solution.
6％毒死蜱纳米水剂制备方法：称取60g(以有效成分计)毒死蜱原药，80g脂肪醇聚氧乙烯醚，40g烷基酚聚氧乙烯醚磷酸酯，30g脂肪酸甲酯磺酸钠，将四者混合，在转速80转/秒条件下搅拌0.5h，在搅拌状态下加入790水，继续搅拌1h，得到6％毒死蜱纳米水剂。6% chlorpyrifos nano-aqueous preparation method: weigh 60g (based on active ingredients) chlorpyrifos original drug, 80g fatty alcohol polyoxyethylene ether, 40g alkylphenol polyoxyethylene ether phosphate, 30g fatty acid methyl ester sulfonate sodium, and The four are mixed and stirred for 0.5 h at a rotation speed of 80 revolutions per second, and 790 water is added under stirring, and the stirring is continued for 1 h to obtain 6% chlorpyrifos nano-aqueous solution.
防除对象：棉红蜘蛛。Control object: cotton spider mite.
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 30m 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 residual 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
处理结果见表4。The treatment results are shown in Table 4.
表4.毒死蜱·甲氨基阿维菌素苯甲酸盐纳米水剂对棉红蜘蛛的田间试验结果Table 4. Field test results of chlorpyrifos· emamectin benzoate nano-aqueous on cotton spider mite
Figure PCTCN2019111043-appb-000005
Figure PCTCN2019111043-appb-000005
田间药效结果表明，毒死蜱·甲氨基阿维菌素苯甲酸盐纳米水剂对棉红蜘蛛具有优良的防治效果，杀虫速度快，持效期长，防治效果均显著好于单剂品种直接作用的效果。Field efficacy results show that chlorpyrifos· emamectin benzoate nano-aqueous formulation has excellent control effect on cotton spider mites, with fast insecticidal speed, long lasting effect, and the control effect is significantly better than single-agent varieties The effect of direct action.
田间药效试验二Field efficacy test two
供试药剂：实施例1-实施例9的毒死蜱·甲氨基阿维菌素苯甲酸盐复配纳米水剂。Test agent: Example 1 to Example 9 of chlorpyrifos and emamectin benzoate compound nano-aqueous agent.
对照药剂：5％甲维盐纳米水剂；6％毒死蜱纳米水剂。Control agent: 5% emamectin benzoate nano-aqueous; 6% chlorpyrifos nano-aqueous.
防除对象：棉铃虫。Control object: cotton bollworm.
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 50 m 2. The experiment was carried out with a knapsack sprayer for spraying the whole cotton. Investigate the number of insect populations before application, and investigate the number of residual 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.毒死蜱·甲氨基阿维菌素苯甲酸盐纳米水剂对棉铃虫的田间试验结果Table 5. Field test results of chlorpyrifos· emamectin benzoate nano-aqueous on cotton bollworm
Figure PCTCN2019111043-appb-000006
Figure PCTCN2019111043-appb-000006
田间药效结果表明，毒死蜱·甲氨基阿维菌素苯甲酸盐纳米水剂对棉铃虫具有优良的防 治效果，杀虫速度快，持效期长，防治效果均显著好于单剂品种直接作用的效果。The field efficacy results showed that the chlorpyrifos· emamectin benzoate nano-aqueous formulation has excellent control effect on cotton bollworm, with fast insecticidal speed, long lasting effect, and the control effect is significantly better than that of single-dose varieties. The effect of the action.

Claims (8)

  1. 一种含毒死蜱和甲氨基阿维菌素苯甲酸盐的复合杀虫杀螨纳米水剂，其特征在于所述的纳米水剂以毒死蜱和甲氨基阿维菌素苯甲酸盐为活性成分，与表面活性剂、水配制成的；其中，毒死蜱和甲氨基阿维菌素苯甲酸盐的重量百分含量为5～80％，农药助剂5～20％，余量为水。A composite insecticidal and acaricidal nano-aqueous agent containing chlorpyrifos and emamectin benzoate, characterized in that the nano-aqueous agent uses chlorpyrifos and emamectin benzoate as active ingredients , Formulated with surfactants and water; wherein the weight percentage of chlorpyrifos and emamectin benzoate is 5 to 80%, pesticide adjuvants are 5 to 20%, and the balance is water.
  2. 根据权利要求1所述的纳米水剂，其特征在于所述的毒死蜱和甲氨基阿维菌素苯甲酸盐的重量比为20:1～1:20。The nano-aqueous formulation of claim 1, wherein the weight ratio of the chlorpyrifos and emamectin benzoate is 20:1 to 1:20.
  3. 根据权利要求1所述的纳米水剂，其特征在于所述的毒死蜱和甲氨基阿维菌素苯甲酸盐的重量比为5:1～1:5。The nano-aqueous formulation of claim 1, wherein the weight ratio of the chlorpyrifos and emamectin benzoate is 5:1 to 1:5.
  4. 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、月桂酰胺丙基羟磺基甜菜碱、三苯乙烯基苯酚聚氧乙烯醚磷酸酯、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一种或多种组合。The nano-aqueous agent according to claim 1, wherein the surfactant is selected from fatty alcohol polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, styrylphenol polyoxyethylene ether, fatty alcohol Polyoxyethylene ether phosphate, lauramidopropyl hydroxysultaine, tristyryl phenol polyoxyethylene ether phosphate, alkylphenol polyoxyethylene ether phosphate, sodium fatty acid methyl sulfonate, alcohol ether succinic acid One or more combinations of sodium monoester sulfonate.
  5. 根据权利要求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，将毒死蜱原药、甲氨基阿维菌素苯甲酸盐原药与表面活性剂混合，搅拌，使毒死蜱和甲氨基阿维菌素苯甲酸盐均匀分散在表面活性剂中；Step (1), at room temperature, mix chlorpyrifos and emamectin benzoate with surfactants and stir to make the chlorpyrifos and emamectin benzoate uniformly dispersed in In surfactants;
    步骤(2)、在搅拌状态下加入水，搅拌均匀，形成含有毒死蜱和甲氨基阿维菌素苯甲酸盐的表面活性剂胶束溶液，即为透明的毒死蜱和甲氨基阿维菌素苯甲酸盐纳米水剂。Step (2). Add water under stirring and stir evenly to form a surfactant micellar solution containing chlorpyrifos and emamectin benzoate, that is, transparent chlorpyrifos and emamectin benzene Formate nano water agent.
  6. 根据权利要求1所述的纳米水剂的制备方法，其特征在于步骤(1)和步骤(2)中，速度为60～100转/秒。The method for preparing nano-aqueous agent according to claim 1, characterized in that in step (1) and step (2), the speed is 60-100 revolutions per second.
  7. 权利要求1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。The use of the nano-aqueous agent according to claim 1 in controlling pests and mites on fruit trees, cotton and vegetables.
  8. 根据权利要求7所述的用途，其特征在于所述的害虫为棉铃虫，所述的害螨为棉红蜘蛛。The use according to claim 7, characterized in that the pest is Helicoverpa armigera, and the pest mites are Red spider mites.
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