WO2021093268A1 - 一种高效氯氟氰菊酯纳米水剂及其制备方法和应用 - Google Patents

一种高效氯氟氰菊酯纳米水剂及其制备方法和应用 Download PDF

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WO2021093268A1
WO2021093268A1 PCT/CN2020/085561 CN2020085561W WO2021093268A1 WO 2021093268 A1 WO2021093268 A1 WO 2021093268A1 CN 2020085561 W CN2020085561 W CN 2020085561W WO 2021093268 A1 WO2021093268 A1 WO 2021093268A1
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cyhalothrin
lambda
nano
surfactant
aqueous agent
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PCT/CN2020/085561
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English (en)
French (fr)
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陈叶青
张宝俊
杨琴
白杰
洪鹏
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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
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • 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
    • 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
    • A01N25/30—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 characterised by the surfactants

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  • the invention belongs to the technical field of pesticide production and processing, and specifically relates to a lambda-cyhalothrin nano-aqueous agent, and a preparation method and application thereof.
  • Cyhalothrin can be widely used in wheat, rape, vegetables, cotton, fruit trees, tea, tobacco and other crops such as aphids, armyworms, diamondback moth, Pieris rapae, tobacco caterpillars, golden bollworm, red Control of pests such as bollworm, peach small, small pear borer, citrus leaf miner, tea caterpillar, tea looper, tea green leafhopper and other pests.
  • Lambda-cyhalothrin is insoluble in water.
  • the pesticide formulations developed with lambda-cyhalothrin as the original drug are mainly emulsifiable concentrates and water emulsions.
  • both emulsifiable concentrates and water emulsions contain a large amount of organic solvents.
  • organic solvents will not only cause serious harm to the environment, but also seriously affect the quality of agricultural products, accelerate food safety crisis, and endanger human health.
  • the present invention provides a lambda-cyhalothrin nano-aqueous agent and its preparation method and application; the inventive discovery of the present invention adopts certain surfactants and adopts surfactant micellar solubilization technology, Without the use of organic solvents to aid solubility, nano-scale micelles formed by surfactants are used to carry the water-insoluble pesticide component lambda cyhalothrin, thereby forming a new type of nano-aqueous agent.
  • a lambda-cyhalothrin nano-aqueous agent which uses lambda-cyhalothrin, surfactant and water as raw materials, does not contain any organic solvents, and is prepared by a surfactant micellar solubilization method
  • the mass percentage of lambda-cyhalothrin in the nano-aqueous agent is 0.5-10%, the mass percentage of surfactant is 5-20%, and the balance is water
  • the mass percentage of lambda-cyhalothrin is 1-5%
  • the mass percentage of the surfactant is 5-20%
  • the balance is water.
  • Said surfactant is selected from fatty alcohol polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, styryl phenol polyoxyethylene ether, tristyryl phenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene Any one or more of vinyl ether phosphate, alkylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether sodium sulfate, and sodium fatty acid methyl sulfonate.
  • the surfactants are 1-4 kinds.
  • the above-mentioned lambda-cyhalothrin can be used as a nano-aqueous solution alone, or it can be compounded with other insecticide and acaricides, and a suitable surfactant is selected to be used as a nano-aqueous solution.
  • Another object of the present invention is to provide a method for preparing lambda-cyhalothrin nano-aqueous agent. Firstly, lambda-cyhalothrin is mixed with a surfactant, and then water is added and stirred to form a surfactant micellar solution. It is a nano-aqueous agent containing lambda-cyhalothrin.
  • the preparation method of the lambda-cyhalothrin nano-aqueous agent includes the following steps:
  • Step (1) at room temperature (10-35°C), the lambda-cyhalothrin and the surfactant are mixed and stirred to uniformly disperse the lambda-cyhalothrin in the surfactant;
  • step (2) water is added and stirred evenly to form a surfactant micelle solution, which is the lambda-cyhalothrin nano-aqueous agent.
  • the stirring speed is adjusted according to the actual situation, so that the beta-cypermethrin is uniformly dispersed in the surfactant.
  • the stirring speed is 60-100 revolutions per second, and the stirring time is generally 0.5h.
  • the technician can adjust the time so that the lambda-cyhalothrin is uniformly dispersed in the surfactant. quasi.
  • the stirring speed is adjusted according to the actual situation, and the stirring is uniform to form a surfactant micelle solution.
  • the stirring speed is 60-100 revolutions per second, and the stirring time is 0.5-1 h.
  • lambda-cyhalothrin nano-aqueous agent is used for aphids, armyworms, diamondback moths, cabbage caterpillars, tobacco caterpillars, golden bollworms, red bollworms on crops such as wheat, rape, vegetables, cotton, fruit trees, tea, tobacco, etc.
  • pests such as small peach, small pear borer, citrus leaf miner, tea caterpillar, tea looper, tea small green leafhopper and other pests.
  • the effective ingredients in the nano-aqueous preparations of the present invention are insoluble in water and cannot form a true true solution. Instead, they are coated with nano-scale surfactant micelles and uniformly dispersed in water to form a true solution. .
  • the nano-aqueous agent containing lambda-cyhalothrin is transparent and colorless in 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 lambda-cyhalothrin nano-aqueous agent of the present invention does not contain any organic solvents, is safe and environmentally friendly, and belongs to an environment-friendly dosage form. It is not only suitable for agricultural medicines, but also suitable for sanitary medicine needs, and can be widely used in agriculture, households and public Health field.
  • the active ingredients of the present invention are carried by nano-sized micelles, it can form a true solution, and the formulation is more stable. It is still stable after cold storage at 0°C for 7 days and 54°C hot storage for 14 days. Lambda-cyhalothrin will not precipitate, which is convenient Storage, shelf life is longer.
  • the present invention is a nano-preparation product with extremely small drug fineness, no particle precipitation, better drug effect, and more suitable for drone application technology.
  • the nano-aqueous agent of the present invention has excellent quick-acting and sustained-acting properties, and will not cause adverse reactions such as drug damage.
  • the high-efficiency cyhalothrin nano-aqueous agent of the present invention has low production cost, simple preparation process, and very good economic efficiency.
  • Figure 1 shows the state of the 4.5% lambda-cyhalothrin nano-aqueous preparation prepared in Example 8 after being placed at a low temperature (0°C) for 1-2 days and then heated to room temperature.
  • Figure 2 shows the state of the 4.5% lambda-cyhalothrin solution prepared at room temperature in Comparative Example 4 after being placed at low temperature (0°C) for 1-2 days and then heated to room temperature.
  • the Zetasizer Nano S a highly sensitive Malvern nano-particle size analyzer, was used to measure the particle size of the surfactant micelles in the pesticide nano-aqueous agent (25°C).
  • Preparation method Weigh 10g lambda-cyhalothrin technical (based on active ingredients, the same below) and 60g fatty alcohol polyoxyethylene ether, mix the two, stir at 100 rpm for 0.5h, and then Add 930g of water under the state and continue stirring for 1h to obtain 1% lambda-cyhalothrin nano-aqueous agent.
  • the nano-aqueous agent of this embodiment is transparent and colorless in appearance, has a viscosity of 82 mPa ⁇ s, and an average particle size of 224 nanometers. 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.
  • the preparation method is the same as in Example 1, and 1.5% lambda-cyhalothrin nano-aqueous agent is prepared.
  • the nano-aqueous agent of this embodiment is transparent and colorless in appearance, has a viscosity of 100 mPa ⁇ s, and an average particle size of 21.1 nanometers. 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.
  • the preparation method is the same as in Example 1, and the lambda-cyhalothrin nano-aqueous agent is prepared.
  • the nano-aqueous agent of this embodiment is transparent and colorless in appearance, has a viscosity of 95 mPa ⁇ s, and an average particle size of 18.4 nanometers. 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.
  • the preparation method is the same as in Example 1, and 2.5% lambda-cyhalothrin nano-aqueous agent is prepared.
  • the nano-aqueous agent of this embodiment is transparent and colorless in appearance, has a viscosity of 102 mPa.s, and an average particle size of 15.8 nanometers. 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.
  • the preparation method is the same as in Example 1, and 3% lambda-cyhalothrin nano-aqueous agent is prepared.
  • the nano-aqueous agent of this embodiment has a transparent appearance and a colorless appearance, a viscosity of 78 mPa ⁇ s, and an average particle size of 22.3 nanometers. 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.
  • the preparation method is the same as in Example 1, and the 3.5% lambda-cyhalothrin nano-aqueous agent is prepared.
  • the nano-aqueous agent of this embodiment is transparent and colorless in appearance, has a viscosity of 89 mPa ⁇ s, and an average particle size of 19.5 nanometers. 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.
  • the preparation method is the same as in Example 1, and 4% lambda-cyhalothrin nano-aqueous agent is prepared.
  • the nano-aqueous agent of this embodiment has a transparent appearance and a colorless appearance, a viscosity of 86 mPa ⁇ s, and an average particle size of 24.5 nanometers. 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.
  • the preparation method is the same as in Example 1, and the 4.5% lambda-cyhalothrin nano-aqueous agent is prepared.
  • the nano-aqueous agent of this embodiment is transparent and colorless in appearance, has a viscosity of 92 mPa.s, and an average particle size of 18.7 nanometers. 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.
  • the preparation method is the same as in Example 1, and 5% lambda-cyhalothrin nano-aqueous agent is prepared.
  • the nano-aqueous agent of this embodiment is transparent and colorless in appearance, has a viscosity of 102 mPa ⁇ s, and an average particle size of 20.4 nanometers. 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.
  • 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 low temperature (below 0°C), lambda-cyhalothrin will precipitate, and after heating up Unrecoverable. It shows that the use of surfactants other than the surfactants or conventional water agents used in the surfactant composition of the present invention cannot be used to prepare qualified lambda-cyhalothrin nano water agents.
  • Figure 1 shows the 4.5% lambda-cypermethrin nano-aqueous prepared in Example 8 The water solution was placed at low temperature (0°C) for 1-2 days and then heated to room temperature;
  • Figure 2 shows the 4.5% lambda-cyhalothrin solution prepared at room temperature in Comparative Example 4 at low temperature (0°C) 1- After 2 days, the temperature is increased to normal temperature.
  • the lambda-cypermethrin nano-aqueous agent of the present application is still stable after being placed for 1-2 days, the solution is clear and transparent, while the solution of the comparative example becomes turbid and viscous, and lambda-cyhalothrin is precipitated.
  • Test agent Lambda-cyhalothrin nano-aqueous agent of Example 1 to Example 9.
  • Control agent 2.5% lambda-cyhalothrin EC (commercially available).
  • Control object cotton bollworm.
  • Test method The normal field usage (active ingredient) of lambda-cyhalothrin was used, and the test plots were arranged in random blocks. The area of each plot was 667m 2 , and the drone was used for spraying, and the drug load was 10L. Set a flying height of 1.5m, a spraying width of 4.1m, a flying speed of 5m/s, and a spraying rate of 0.9L/mu with water, respectively, 1 day, 3 days, 7 days, 15 days, 30 days, 45 days, 60 days after treatment The number of larvae of cotton bollworm was surveyed every day, and the method and statistical analysis of the data were carried out in accordance with the relevant standards of GB/T17980.5-2000.
  • Test agents 9 kinds of lambda-cyhalothrin nano-aqueous agents in Examples 1-9.
  • Control agent 2.5% lambda-cyhalothrin EC (commercially available).
  • Control object wheat aphids.
  • Test method The normal field dose of lambda-cyhalothrin (active ingredient) was used, and the dose treatment was set for three repetitions, and the random block arrangement was repeated. Each repetition was set with an area of 20m 2 , and the knapsack sprayer was used for routine spraying and treated separately After 1 day, 3 days, 7 days, 15 days, 30 days, 45 days, and 60 days, the number of aphids larvae was investigated. The method and statistical analysis of the data were carried out in accordance with the relevant standards of GB/T17980.79-2004.
  • the lambda-cyhalothrin nano-aqueous agent has excellent quick-acting and lasting effect in the prevention and control of wheat aphids, and the effective period is more than one month. During the experiment, no adverse reactions such as drug damage were found, which has practical application value.
  • Test agents 9 kinds of lambda-cyhalothrin nano-aqueous agents in Examples 1-9.
  • Control agent 2.5% lambda-cyhalothrin EC (commercially available).
  • Control object Chinese cabbage borer.
  • Test method The normal field dose of lambda-cyhalothrin (active ingredient) was used, and the dose treatment was set for three repetitions, and the random block arrangement was repeated. Each repetition was set with an area of 20m 2 , and the knapsack sprayer was used for routine spraying and treated separately After 1 day, 3 days, 7 days, 15 days, 30 days, 45 days, and 60 days, the number of the larvae of the cabbage borer was investigated. The method and statistical analysis of the data were carried out in accordance with the relevant standards of GB/T17980.14-2000.
  • the lambda-cyhalothrin nano-aqueous agent has excellent quick-acting and lasting effect in the control of Chinese cabbage borer, and the effective period is more than one month. During the experiment, no adverse reactions such as drug damage were found, which has practical application value.

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Abstract

本发明属于农药技术领域，公开了一种高效氯氟氰菊酯纳米水剂，该纳米水剂以高效氯氟氰菊酯、表面活性剂和水为原料，不添加任何有机溶剂，采用表面活性剂胶束增溶方法制成的；其中，高效氯氟氰菊酯质量百分含量0.5-10％，表面活性剂5-20％，余量为水。本发明采用表面活性剂胶束增溶方法制成纳米水剂，与常规农药剂型相比，具有优异的稳定性，分别在0℃冷贮7d和54℃热贮14d后仍然稳定，高效氯氟氰菊酯纳米水剂不会析出，便于贮藏，货架期更长；本发明纳米水剂具有较低的生产成本和更优异的速效性和持效性，不会出现药害等不良反应，更适合无人机用药。

Description

一种高效氯氟氰菊酯纳米水剂及其制备方法和应用 技术领域
本发明属于农药生产加工技术领域，具体涉及一种高效氯氟氰菊酯纳米水剂及其制备方法和应用。
背景技术
高效氯氟氰菊酯(Cyhalothrin)，可广泛用于小麦、油菜、蔬菜、棉花、果树、茶叶、烟草等作物上的蚜虫、粘虫、小菜蛾、菜青虫、烟青虫、锦铃虫、红铃虫、桃小、梨小食心虫、柑桔潜叶蛾、茶毛虫、茶尺蠖、茶小绿叶蝉等害虫的防治。
高效氯氟氰菊酯不溶于水，目前以高效氯氟氰菊酯为原药开发的农药剂型主要为乳油和水乳剂等。但无论是乳油还是水乳剂均含有大量有机溶剂，在使用过程中，有机溶剂不但会对环境造成严重危害，还会严重影响农产品的品质，加速食品安全危机，并危害人类健康。
随着使用者环保意识不断提高以及卫生用药的快速增长需求，高效氯氟氰菊酯的现有剂型已经无法满足使用需求。为了确保在安全环保的前提下，加速高效氯氟氰菊酯产品推广使用，开发一种能够对人畜和环境友好的，便于无人机等航空植保技术和设备施药的新型制剂尤为必要。
发明内容
针对现有问题的不足，本发明提供一种高效氯氟氰菊酯纳米水剂及其制备方法和应用；本发明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不溶于水的农药成分高效氯氟氰菊酯，进而形成新型的纳米水剂。
本发明的目的可以通过以下技术方案实现：
一种高效氯氟氰菊酯纳米水剂，所述的纳米水剂以高效氯氟氰菊酯、表面活性剂和水为原料，不含任何有机溶剂，采用表面活性剂胶束增溶方法制成的，其中，纳米水剂中高效氯氟氰菊酯的质量百分含量为0.5-10％，表面活性剂的质量百分含量为5-20％，余量为水
优选的，所述高效氯氟氰菊酯的质量百分含量为1-5％，表面活性剂的质量百分含量为5～20％，余量为水。
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、三苯乙烯基苯酚聚氧乙烯醚磷酸酯、脂肪醇聚氧乙烯醚磷酸酯、烷基酚聚氧乙烯醚磷酸酯、脂肪醇聚氧乙烯醚硫酸钠、脂肪酸甲酯磺酸钠中的任意1种或多种。
优选的，所述表面活性剂为1-4种。
通过将非离子表面活性剂、阴离子表面活性剂等复配使用或单独使用，与有效成分高效氯氟氰菊酯再进行复配，得到一种稳定性好、药效更优的高效氯氟氰菊酯纳米水剂。
优选的，上述高效氯氟氰菊酯可以单独制成纳米水剂使用，也可以与其他除虫除螨药剂复配，选择合适的表面活性剂，制成纳米水剂使用。
本发明的另一个目的是提供一种高效氯氟氰菊酯纳米水剂的制备方法，先将高效氯氟氰菊酯与表面活性剂混合，再加入水，搅拌形成表面活性剂胶束溶液，即为含高效氯氟氰菊酯的纳米水剂。
具体的，所述高效氯氟氰菊酯纳米水剂的制备方法包括以下步骤：
步骤(1)，在常温(10～35℃)下，将高效氯氟氰菊酯与表面活性剂混合，搅拌，使高效氯氟氰菊酯均匀分散在表面活性剂中；
步骤(2)，加入水，搅拌均匀，形成表面活性剂胶束溶液，即为高效氯氟氰菊酯纳米水剂。
优选的，所述步骤(1)中，搅拌速度根据实际情况调整，以使高效氯氰菊酯均匀分散在表面活性剂中为准。
优选的，所述步骤(1)中，搅拌速度为60～100转/秒，搅拌时间一般为0.5h，技术人员可以调整时间，以使高效氯氟氰菊酯均匀分散在表面活性剂中为准。
优选的，所述步骤(2)中，搅拌速度根据实际情况调整，以搅拌均匀，形成表面活性剂胶束溶液为准。
优选的，所述步骤(2)中，搅拌速度为60～100转/秒，搅拌时间为0.5～1h。
上述高效氯氟氰菊酯纳米水剂用于小麦、油菜、蔬菜、棉花、果树、茶叶、烟草等作物上的蚜虫、粘虫、小菜蛾、菜青虫、烟青虫、锦铃虫、红铃虫、桃小、 梨小食心虫、柑桔潜叶蛾、茶毛虫、茶尺蠖、茶小绿叶蝉等害虫的防治。
有别于常规农药水剂，本发明纳米水剂中的有效成分不溶于水，不能形成真正的真溶液，而是被纳米级的表面活性剂胶束包覆并均匀分散在水中，形成真溶液。
本发明含高效氯氟氰菊酯的纳米水剂外观透明无色，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。
与现有技术相比，本发明的有益效果为：
1、本发明高效氯氟氰菊酯纳米水剂不含任何有机溶剂，安全环保，属于环境友好型剂型，不但适用于农业用药，同时适用于卫生用药需求，可广泛应用于农业、家庭和公共卫生领域。
2、本发明因为有效成份被纳米级胶束承载，可形成真溶液，制剂更稳定，在0℃冷贮7d和54℃热贮14d后仍然稳定，高效氯氟氰菊酯不会析出，便于贮藏，货架期更长。
3、本发明为纳米制剂产品，药物细度极小，无颗粒沉淀，药效更优，更适用于无人机施药技术。
4、本发明纳米水剂具有优异的速效性和持效性，不会出现药害等不良反应。
5、本发明高效氯氟氰菊酯纳米水剂生产成本低，制备工艺简单，具有非常好的经济性。
附图说明
图1为实施例8制得的4.5％高效氯氟氰菊酯纳米水剂在低温(0℃)放置1-2d后再升温至常温后的状态。
图2为对比例4常温制得的4.5％高效氯氟氰菊酯水剂在低温(0℃)放置1-2d后再升温至常温后的状态。
具体实施方式
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。
纳米水剂的粒径检测方法：
利用马尔文高灵敏纳米粒度分析仪Zetasizer Nano S进行农药纳米水剂中表面活性剂胶束的粒径测量(25℃)。
实施例1
Figure PCTCN2020085561-appb-000001
制备方法：称取10g高效氯氟氰菊酯原药(以有效成分计，下同)和60g脂肪醇聚氧乙烯醚，将两者混合，在转速100转/秒下搅拌0.5h，在搅拌状态下加入930g水，继续搅拌1h，得到1％高效氯氟氰菊酯纳米水剂。
本实施例纳米水剂外观透明无色，粘度82mPa.s，平均粒径为224纳米。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。
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。
实施例2
Figure PCTCN2020085561-appb-000002
制备方法同实施例1，制得1.5％高效氯氟氰菊酯纳米水剂。
本实施例纳米水剂外观透明无色，粘度100mPa.s，平均粒径为21.1纳米。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。
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。
实施例3
Figure PCTCN2020085561-appb-000003
制备方法同实施例1，制得高效氯氟氰菊酯纳米水剂。
本实施例纳米水剂外观透明无色，粘度95mPa.s，平均粒径为18.4纳米。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。
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。
实施例4
Figure PCTCN2020085561-appb-000004
制备方法同实施例1，制得2.5％高效氯氟氰菊酯纳米水剂。
本实施例纳米水剂外观透明无色，粘度102mPa.s，平均粒径为15.8纳米。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。
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。
实施例5
Figure PCTCN2020085561-appb-000005
制备方法同实施例1，制得3％高效氯氟氰菊酯纳米水剂。
本实施例纳米水剂外观透明无色，粘度78mPa.s，平均粒径为22.3纳米。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。
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。
实施例6
Figure PCTCN2020085561-appb-000006
Figure PCTCN2020085561-appb-000007
制备方法同实施例1，制得3.5％高效氯氟氰菊酯纳米水剂。
本实施例纳米水剂外观透明无色，粘度89mPa.s，平均粒径为19.5纳米。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。
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。
实施例7
Figure PCTCN2020085561-appb-000008
制备方法同实施例1，制得4％高效氯氟氰菊酯纳米水剂。
本实施例纳米水剂外观透明无色，粘度86mPa.s，平均粒径为24.5纳米。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。
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。
实施例8
Figure PCTCN2020085561-appb-000009
制备方法同实施例1，制得4.5％高效氯氟氰菊酯纳米水剂。
本实施例纳米水剂外观透明无色，粘度92mPa.s，平均粒径为18.7纳米。 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。
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。
实施例9
Figure PCTCN2020085561-appb-000010
制备方法同实施例1，制得5％高效氯氟氰菊酯纳米水剂。
本实施例纳米水剂外观透明无色，粘度102mPa.s，平均粒径为20.4纳米。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。
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。
对比例1-4
采用目前水剂上采用的助剂(润湿剂)，进行该水剂的配制实验，具体配方如表1所示。
表1对比例1-对比例4配方
Figure PCTCN2020085561-appb-000011
制备方法同实施例1。
按照对比例1和对比例2，在添加助剂的情况下，高效氯氟氰菊酯仍然无法完全溶解在水中，不能形成合格的水溶液。
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，高效氯氟氰菊酯会析出，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高效氯氟氰菊酯纳米水剂。
将实施例8的4.5％高效氯氰菊酯纳米水剂和对比例的4.5％高效氯氰菊酯水剂进行对比，参见图1和图2，图1为实施例8制得的4.5％高效氯氟氰菊酯纳米水剂在低温(0℃)放置1-2d后再升温至常温后的状态；图2为对比例4常温制得的4.5％高效氯氟氰菊酯水剂在低温(0℃)放置1-2d后再升温至常温后的状态。由图中可以看出，本申请的高效氯氰菊酯纳米水剂在放置1-2d后仍然稳定，溶液澄清透明，而对比例的溶液变得浑浊粘稠，高效氯氟氰菊酯析出。
实施例10生物活性对比
田间药效试验一：
供试药剂：实施例1～实施例9的高效氯氟氰菊酯纳米水剂。
对照药剂：2.5％高效氯氟氰菊酯乳油(市售)。
防除对象：棉花棉铃虫。试验方法：采用高效氯氟氰菊酯正常田间使用量(有效成分)，试验小区采用随机区组排列，每个小区设置面积为667m 2，采用无人机进行喷雾，载药量10L。设置飞行高度1.5m，喷药宽度4.1m，飞行速度5m/s，兑水喷药量0.9L/亩，分别处理后1天、3天、7天、15天、30天、45天、60天调查棉铃虫幼虫数量，方法及数据统计分析参照GB/T17980.5-2000相关标准进行。
表2棉花棉铃虫的田间试验效果
Figure PCTCN2020085561-appb-000012
Figure PCTCN2020085561-appb-000013
由上表可见，高效氯氟氰菊酯纳米水剂在棉花棉铃虫的防治上表现了优良的速效性和持效性，持效期长达一个月以上。在试验过程中，没有发现药害等不良反应，具有实际推广应用价值。
田间药效试验二：
供试药剂：实施例1～9中的9种高效氯氟氰菊酯纳米水剂。
对照药剂：2.5％高效氯氟氰菊酯乳油(市售)。
防除对象：小麦蚜虫。
试验方法：采用高效氯氟氰菊酯正常田间使用剂量(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20m 2,用背负式喷雾器进行常规喷雾，分别处理后1天、3天、7天、15天、30天、45天、60天调查蚜虫幼虫数量，方法及数据统计分析参照GB/T17980.79-2004相关标准进行。
表3小麦蚜虫的田间试验效果
Figure PCTCN2020085561-appb-000014
Figure PCTCN2020085561-appb-000015
由上表可见，高效氯氟氰菊酯纳米水剂在小麦蚜虫的防治上表现了优良的速效性和持效性，持效期长达一个月以上。在试验过程中，没有发现药害等不良反应，具有实际推广应用价值。
田间药效试验三：
供试药剂：实施例1～9中的9种高效氯氟氰菊酯纳米水剂。
对照药剂：2.5％高效氯氟氰菊酯乳油(市售)。
防除对象：青菜菜螟。
试验方法：采用高效氯氟氰菊酯正常田间使用剂量(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20m 2,用背负式喷雾器进行常规喷雾，分别处理后1天、3天、7天、15天、30天、45天、60天调查菜螟幼虫数量，方法及数据统计分析参照GB/T17980.14-2000相关标准进行。
表4青菜菜螟的田间试验效果
Figure PCTCN2020085561-appb-000016
Figure PCTCN2020085561-appb-000017
由上表可见，高效氯氟氰菊酯纳米水剂在青菜菜螟的防治上表现了优良的速效性和持效性，持效期长达一个月以上。在试验过程中，没有发现药害等不良反应，具有实际推广应用价值。
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。

Claims (6)

  1. 一种高效氯氟氰菊酯纳米水剂，其特征在于所述的纳米水剂以高效氯氟氰菊酯、表面活性剂和水为原料，采用表面活性剂胶束增溶方法制成；其中，所述的纳米水剂中高效氯氟氰菊酯的质量百分含量为0.5-10％，表面活性剂的质量百分含量为5-20％，余量为水。
  2. 根据权利要求1所述的高效氯氟氰菊酯纳米水剂，其特征在于高效氯氟氰菊酯的质量百分含量为1-5％。
  3. 根据权利要求1所述的高效氯氟氰菊酯纳米水剂，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、三苯乙烯基苯酚聚氧乙烯醚磷酸酯、脂肪醇聚氧乙烯醚磷酸酯、烷基酚聚氧乙烯醚磷酸酯、脂肪酸甲酯磺酸钠中的任意1种或多种。
  4. 权利要求1所述的高效氯氟氰菊酯纳米水剂制备方法，其特征在于先将高效氯氟氰菊酯与表面活性剂混合，再加入水，搅拌形成表面活性剂胶束溶液，即为高效氯氟氰菊酯纳米水剂。
  5. 权利要求4所述的高效氯氟氰菊酯纳米水剂的制备方法，其特征在于包括以下步骤：
    步骤(1)，在常温下，将高效氯氟氰菊酯与表面活性剂混合，搅拌，使高效氯氟氰菊酯均匀分散在表面活性剂中；
    步骤(2)，加入水，持续搅拌均匀，形成表面活性剂胶束溶液，即为含高效氯氟氰菊酯的纳米水剂。
  6. 根据权利要求5所述的高效氯氟氰菊酯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。
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