WO2021093271A1

WO2021093271A1 - Beta cypermethrin nano aqueous agent, preparation method therefor and use thereof

Info

Publication number: WO2021093271A1
Application number: PCT/CN2020/085763
Authority: WO
Inventors: 高瑞花; 陈叶青; 邢刚; 洪鹏; 张宝俊
Original assignee: 南京华洲药业有限公司
Priority date: 2019-11-12
Filing date: 2020-04-21
Publication date: 2021-05-20
Also published as: CN110973152A

Abstract

The present invention relates to the technical field of pesticides, and discloses a beta cypermethrin nano aqueous agent, the nano aqueous agent using beta cypermethrin, surfactant, and water as raw materials and not containing any organic solvent, and being made by means of a surfactant micelle solubilisation method; in the nano aqueous agent, the mass percentage of beta cypermethrin is 0.5-5%, the mass percentage of surfactant is 5-25%, and the remainder is water. The present invention uses a surfactant micelle solubilisation technique to make the nano aqueous agent, having excellent stability compared to common pesticide types, remaining stable after cold storage at 0℃ for 7 days and hot storage at 54℃ for 14 days respectively; the beta cypermethrin does not precipitate, facilitating storage and having a longer shelf life; the nano aqueous agent of the present invention has lower production costs, better quick-acting and lasting performance, will not produce adverse reactions such as pesticide damage, and is more suitable for dosage by an unmanned aerial vehicle.

Description

High-efficiency cypermethrin nano-aqueous agent, preparation method and application thereof

Technical field

The invention belongs to the technical field of pesticide production and processing, and specifically relates to a new formulation of beta-cypermethrin and a preparation method and application thereof.

Background technique

Beta cypermethrin, chemical name: 2,2-Dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid-α-cyano-(3-phenoxy)benzyl ester. Molecular formula: C ₂₂ H ₁₉ C _L2 NO ₃ . Beta-cypermethrin is a broad-spectrum insecticide with high insecticidal activity against many kinds of pests. It can be applied to a variety of fruit trees, a variety of vegetables, grains, cotton, oil tea and other crops and a variety of forests. For tobacco caterpillar, cotton bollworm, diamondback moth, beet armyworm, Spodoptera litura, tea looper, red bollworm, aphids, Liriomyza, beetles, stink bugs, psyllids, thrips, heartworms, Leaf rollers, caterpillars, spiny moths, citrus leaf miners, red wax scales and other pests have good killing effects.

Lambda-cypermethrin is hardly soluble in water, and its solubility in water is 93.4μg/L at 25°C. Currently, the pesticide formulations developed with lambda-cypermethrin as the original drug are mainly emulsifiable concentrates and water emulsions. However, both emulsifiable concentrates and water emulsions contain a large amount of organic solvents. During use, 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; reduce organic solvents The use and development of aqueous formulations are the inevitable way for the development of beta-cypermethrin formulations.

With the continuous improvement of users' awareness of environmental protection and the rapid growth of demand for sanitary drugs, the existing formulations of beta-cypermethrin have been unable to meet the demand for use. In order to ensure that under the premise of safety and environmental protection, accelerate the promotion and use of high-efficiency cypermethrin products, it is particularly necessary to develop a new formulation that is friendly to humans, animals and the environment, and facilitates the application of aerial plant protection technologies and equipment such as drones.

Summary of the invention

The present invention provides a high-efficiency cypermethrin nano-aqueous agent and its preparation method and application in view of the above-mentioned technical problems; this application adopts surfactant micellar solubilization technology, without organic solvents, and uses surfactants to form The nano-scale micellar solution carries the insoluble pesticide ingredient beta-cypermethrin, and then forms a new type of nano-aqueous agent. Different from conventional pesticide water formulations, the effective ingredients in the nano water formulations of the present invention are insoluble in water and cannot form a true true solution, but are wrapped by nano-scale surfactant micelles and uniformly dispersed in water to form a true solution .

The purpose of the present invention can be achieved through the following technical solutions:

A high-efficiency cypermethrin nano-aqueous agent, the nano-aqueous agent is made of high-efficiency cypermethrin, surfactant and water as raw materials, does not contain any organic solvents, and is made by using surfactant micellar solubilization technology; wherein, the nano-aqueous agent The mass percentage of beta-cypermethrin is 0.5-5%, the mass percentage of surfactant is 5-25%, and the balance is water.

Preferably, the mass percentage of the beta-cypermethrin is 1-4.5%, the mass percentage of the surfactant is 5-20%, and the balance is water.

The surfactant is selected from the group consisting of tristyryl phenol polyoxyethylene ether phosphate, sodium alcohol ether succinate monoester sulfonate, styryl phenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether phosphate, alkyl Any one or more of phenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether, sorbitan fatty acid ester polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, preferably 1 to 4 Kind.

Another object of the present invention is to provide a method for preparing the high-efficiency cypermethrin nano-aqueous agent. Firstly, the high-efficiency cypermethrin and the surfactant are mixed, and then water is added and stirred to form a surfactant micellar solution, which is a nano-cypermethrin aqua solution.

Specifically, the preparation method of the lambda cypermethrin nano-aqueous agent includes the following steps:

Step (1), at room temperature (10-35°C), the beta-cypermethrin is mixed with the surfactant, and stirred, so that the beta-cypermethrin is uniformly dispersed in the surfactant;

In step (2), water is added and stirred evenly to form a surfactant micellar solution, which is the beta-cypermethrin nano-aqueous agent.

Preferably, in the step (1), the stirring speed is 60-100 revolutions per second, and the stirring time is generally 0.5 h. The technician can adjust the time so that the beta-cypermethrin is uniformly dispersed in the surfactant.

Preferably, in the step (2), the stirring speed is 60-100 revolutions per second, and the stirring time is 0.5-1 h.

Different from conventional pesticide water formulations, the active ingredients in the nano-aqueous formulations of the present invention are not soluble in water and cannot form a true true solution. Instead, they are coated by nano-scale surfactant micelles and uniformly dispersed in water to form a "true" solution. Solution".

The high-efficiency cypermethrin nano-aqueous agent of the present invention is a light yellow transparent liquid, and the average particle size of the surfactant micelles is nanometer level; after entering water, it can quickly dissolve with water to form a completely transparent solution, and the dilution stability is qualified.

Compared with the prior art, the beneficial effects of the present invention are:

1. The high-efficiency cypermethrin nano-aqueous formulation 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.

2. Because the active ingredients of the present invention are carried by nano-sized micelles, it can form a "true solution", and the preparation 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 cypermethrin does not precipitate and is convenient for storage. Shelf life is longer.

3. 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.

4. 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.

5. The high-efficiency cypermethrin nano-aqueous agent of the present invention has low production cost, simple processing technology, and very good economic efficiency.

Description of the drawings

Figure 1 shows the state of the 2.5% beta-cypermethrin nano-aqueous preparation prepared in Example 4 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 2.5% beta-cypermethrin aqueous solution prepared at room temperature in Comparative Example 3 after being placed at low temperature (0°C) for 1-2 days and then heated to room temperature.

Detailed ways

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.

The particle size detection method of nano-aqueous agent:

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).

Example 1

Preparation method: Weigh 10g of lambda cypermethrin (based on active ingredients, the same below) and 70g of fatty alcohol polyoxyethylene ether phosphate, mix and stir for 0.5h at 90 rpm, and add 940g under stirring. Water, continue to stir for 1 hour to obtain 1% beta-cypermethrin nano-aqueous agent.

The nano-aqueous agent of this embodiment is a light yellow transparent liquid with a viscosity of 85 mPa·s and an average particle size of 13.0 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.

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.

Example 2

The preparation method is the same as that of Example 1, and 1.5% lambda-cypermethrin nano-aqueous agent is prepared.

The appearance of the nano-aqueous agent of this embodiment is a light yellow transparent liquid, a viscosity of 100 mPa·s, and an average particle size of 16.5 nanometers.

Example 3

The preparation method is the same as that in Example 1, and 2% lambda cypermethrin nano-aqueous agent is prepared.

The appearance of the nano-aqueous agent of this embodiment is a light yellow transparent liquid, a viscosity of 92 mPa.s, and an average particle size of 18.0 nanometers.

Example 4

The preparation method is the same as that of Example 1, and 2.5% lambda cypermethrin nano-aqueous agent is prepared.

The appearance of the nano-aqueous agent of this embodiment is a light yellow transparent liquid, the viscosity is 88 mPa.s, and the average particle size is 22.5 nanometers.

In this implementation, the nano-aqueous agent can quickly dissolve with water after entering water to form a completely transparent solution, and the dilution stability is qualified.

Example 5

The preparation method is the same as that in Example 1, and 3% lambda cypermethrin nano-aqueous agent is prepared.

The appearance of the nano-aqueous agent of this embodiment is a light yellow transparent liquid, a viscosity of 75 mPa.s, and an average particle size of 24.5 nanometers.

Example 6

The preparation method is the same as that in Example 1, and the 3.5% beta-cypermethrin nano-aqueous agent is prepared.

The appearance of the nano-aqueous agent of this embodiment is a light yellow transparent liquid, a viscosity of 77 mPa.s, and an average particle size of 18.5 nanometers.

Example 7

The preparation method is the same as that of Example 1, and 4% lambda cypermethrin nano-aqueous agent is prepared.

The appearance of the nano-aqueous agent of this embodiment is a light yellow transparent liquid, the viscosity is 78 mPa.s, and the average particle size is 18.7 nanometers.

Example 8

The preparation method is the same as in Example 1, and the 4.5% beta-cypermethrin nano-aqueous agent is prepared.

The appearance of the nano-aqueous agent of this embodiment is a light yellow transparent liquid, a viscosity of 85 mPa.s, and an average particle size of 21.3 nanometers.

Comparative example 1-4

Using the auxiliary agent (wetting agent) currently used on the water agent, the preparation experiment of the water agent is carried out, and the specific formula is shown in Table 1.

Table 1. Formulations of Comparative Examples 1-4

The preparation method is the same as in Example 1.

In Comparative Examples 1 and 2, with the addition of additives, the beta-cypermethrin still could not be completely dissolved in water and could not form a qualified aqueous solution.

Comparative Examples 3 and 4 can be prepared to obtain aqueous solutions at room temperature (10-35°C), but when the aqueous solution is placed under low temperature (below 0°C) conditions, the lambda cypermethrin technical drug will continue to precipitate and cannot be recovered after heating, indicating that the use is not essential. The surfactant in the present invention or the surfactant used in the conventional water agent other than the surfactant composition cannot be used to formulate a qualified lambda cypermethrin water agent.

Comparing the 2.5% beta-cypermethrin nano-aqueous agent of Example 4 with the 2.5% beta-cypermethrin aqueous agent of the comparative example, see Figure 1 and Figure 2. Figure 1 shows the 2.5%-beta-cypermethrin nano-aqueous solution prepared in Example 4 at low temperature. (0℃) After standing for 1-2 days and then warming to normal temperature; Figure 2 shows the 2.5% lambda cypermethrin aqueous solution prepared at normal temperature in Comparative Example 3 after being placed at low temperature (0°C) for 1-2 days and then warming to normal temperature State; It can be seen from the figure that the beta-cypermethrin nano-aqueous agent of the present application is still stable after being placed for 1-2 days, and the solution is clear and transparent, while the solution of the comparative example is turbid and has foaming phenomenon.

Example 9 Biological Activity Comparison

Field efficacy test one:

Test agent: the lambda cypermethrin nano-aqueous agent of Example 1-8.

Control agent: 4.5% beta-cypermethrin EC (commercially available).

Control object: cotton bollworm.

Test method: The normal field usage of beta-cypermethrin (active ingredient) is used, and the test plots are arranged in random blocks. The area of each plot is 667m ² , and the drone is used for spraying, and the drug load is 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.

Table 2 Field test results of cotton bollworm

It can be seen from the above table that the high-efficiency cypermethrin nano-aqueous agent has shown excellent quick-acting and lasting effect in the control of cotton bollworm, 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.

Field efficacy test two:

Test agent: the lambda cypermethrin nano-aqueous agent of Example 1-8.

Control agent: 4.5% beta-cypermethrin EC (commercially available).

Control object: cotton aphids.

experiment method:

The normal field dosage (active ingredient) of beta-cypermethrin is used, and the dosage treatment is set for three repetitions, and the random block arrangement is repeated. Each repetition is set with an area of 20m ^{2. The} knapsack sprayer is used for routine spraying. The number of aphids larvae was investigated for 7 days, 15 days, 30 days, 45 days, and 60 days. The method and statistical analysis of the data were carried out in accordance with the relevant standards of GB/T17980.75-2004.

Table 3 Field test results of cotton aphids

It can be seen from the above table that the high-efficiency cypermethrin nano-aqueous agent has shown excellent quick-acting and lasting effect in the control of cotton 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.

Field efficacy test three:

Test agents: 8 kinds of beta-cypermethrin nano-aqueous agents in Examples 1-8.

Control agent: 4.5% beta-cypermethrin EC (commercially available).

Control object: Chinese cabbage borer.

experiment method:

The normal field dosage of beta-cypermethrin (active ingredient) is used, and the dosage treatment is set for three repetitions, and the random block arrangement is repeated. Each repetition is set with an area of 20m ² , and the sprayer is used for routine spraying, respectively, 1 day, 3 days after treatment. 7 days, 15 days, 30 days, 45 days, 60 days to investigate the number of cabbage borer larvae, methods and statistical analysis of data were carried out in accordance with the relevant standards of GB/T17980.14-2000.

Table 4 Field test results of Chinese cabbage borer

It can be seen from the above table that the high-efficiency cypermethrin nano-aqueous agent has shown excellent quick-acting and sustained-effectiveness in the control of 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.

The protection content of the present invention is not limited to the above embodiment. Without departing from the spirit and scope of the inventive concept, changes and advantages that can be imagined by those skilled in the art are all included in the present invention, and the appended claims are the protection scope.

Claims

A high-efficiency cypermethrin nano-aqueous agent, characterized in that the nano-aqueous agent is made of high-efficiency cypermethrin, a surfactant and water as raw materials, and is made by a surfactant micellar solubilization method; wherein, the nano-aqueous agent is The mass percentage of beta-cypermethrin is 0.5-5%, the mass percentage of surfactant is 5-25%, and the balance is water.
The lambda-cypermethrin nano-aqueous formulation according to claim 1, wherein the mass percentage of lambda-cypermethrin is 1-4.5%.
The high-efficiency cypermethrin nano-aqueous agent according to claim 1, wherein the surfactant is selected from the group consisting of tristyryl phenol polyoxyethylene ether phosphate, sodium alcohol ether succinate monoester sulfonate, and styryl phenol Polyoxyethylene ether, fatty alcohol polyoxyethylene ether phosphate, alkylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether, sorbitan fatty acid ester polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene Any 1 to 4 types of vinyl ether.
The preparation method of the lambda-cypermethrin nano-aqueous agent according to claim 1, wherein the lambda-cypermethrin is first mixed with a surfactant, and then water is added and stirred to form a surfactant micellar solution, which is the lambda-cypermethrin nano-aqueous agent.
The preparation method of lambda cypermethrin nano-aqueous agent according to claim 4, characterized in that it comprises the following steps:

Step (1), at room temperature, the beta-cypermethrin is mixed with the surfactant, and stirred, so that the beta-cypermethrin is uniformly dispersed in the surfactant;

In step (2), water is added and stirred evenly to form a surfactant micellar solution, which is the beta-cypermethrin nano-aqueous agent.
The preparation method of the high-efficiency cypermethrin 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.