WO2021093267A1

WO2021093267A1 - Composite insecticidal and acaricidal nano-aqueous agent containing fenpropathrin and chlorpyrifos, and preparation method therefor and use thereof

Info

Publication number: WO2021093267A1
Application number: PCT/CN2020/085541
Authority: WO
Inventors: 杨琴; 洪鹏; 高瑞花; 张宝俊; 白杰
Original assignee: 南京华洲药业有限公司
Priority date: 2019-11-12
Filing date: 2020-04-20
Publication date: 2021-05-20
Also published as: CN110999901A

Abstract

Disclosed is a composite insecticidal and acaricidal nano-aqueous agent containing fenpropathrin and chlorpyrifos. The insecticidal composition is prepared by using fenpropathrin and chlorpyrifos as insecticidal and acaricidal active ingredients, together with a surfactant and water. Specifically, the weight percentage of fenpropathrin and chlorpyrifos is 3% to 80%, the weight percentage of the pesticide adjuvant is 5% to 20%, and the balance is water. The weight ratio of fenpropathrin to chlorpyrifos is 20:1-1:20. In the present invention, the nano-sized micelles formed by the surfactant are used to carry fenpropathrin and chlorpyrifos, which are poorly soluble in water, and the active ingredients are present in the nano-aqueous agent as nano-sized particles, facilitating the adhesion, spreading and penetration thereof on the target, and the pesticide is more resistant to being washed away in the rain. The present invention can control homopteran pests, lepidopteran pests and pest mites that occur on crops, and is especially useful for controlling rice planthoppers and citrus red spider mites, and the effect thereof is significantly higher than that of a single agent therein.

Description

Composite insecticidal and acaricidal nano-aqueous agent containing fenpropathrin and chlorpyrifos, and preparation method and application thereof

Technical field

The invention belongs to the field of pesticides, and relates to an insecticidal and acaricidal nano-aqueous agent with fenpropathrin and chlorpyrifos as main active ingredients, and a preparation method and application thereof.

Background technique

Fenpropathrin (Fenpropathrin), chemical name: 2-cyano-3-phenoxybenzyl-2,2,3,3-tetramethylcyclopropane ester. High-efficiency, broad-spectrum pyrethroids have contact and repellent effects, as well as stomach toxic effects. In addition to the general synthetic pyrethroid properties, it has good effects on spider mites of various crops, so it has the advantage of eliminating insects and mites. Effective against Lepidopteran larvae, and effective against Diptera or Hemiptera pests. It can be used to control pests on cotton, fruit trees, vegetables, tea and flowers.

Chlorpyrifos Standard, molecular formula: C ₉ H ₁₁ Cl ₃ NO ₃ PS. Chemical name: O,O-diethyl-O-(3,5,6-trichloro-2-pyridyl) phosphorothioate. Chlorpyrifos is an acetylcholinesterase inhibitor, a phosphorothioate insecticide. It has the triple effects of stomach poisoning, contact killing and fumigation. It has a good control effect on a variety of chewing and piercing-sucking mouthparts pests on rice, wheat, cotton, fruit trees, vegetables, and tea trees.

Both fenpropathrin and chlorpyrifos are difficult to dissolve in water. The solubility of fenpropathrin in water at room temperature is only 0.34mg/L, and the solubility of chlorpyrifos in water at 25°C is 2mg/L; at present, fenpropathrin and chlorpyrifos are less soluble in water. Conventional dosage forms are mainly emulsifiable concentrates, which contain a large amount of organic solvents, which pose safety hazards in production and cause serious harm to the environment in field use. Reducing the use of organic solvents and developing aqueous formulations are the inevitable way for the development of fenpropathrin and chlorpyrifos formulations.

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.

Summary of the invention

In view of the shortcomings of the existing problems, the purpose of the present invention is to provide a composite insecticidal and acaricidal nano-aqueous agent containing fenpropathrin and chlorpyrifos. The compound of fenpropathrin and chlorpyrifos in the nano-aqueous agent has a significant synergistic increase In addition, the creative discovery of certain surfactants adopts surfactant micellar solubilization technology. Without the use of organic solvents, the nano-scale micelles formed by surfactants are used to carry hardly soluble water. The active ingredients of fenpropathrin and chlorpyrifos are present in nano-sized particles as nano-sized particles, which are more convenient for their attachment, spreading and penetration on the target, more resistant to rain washing, and they do not contain organic solvents, which is safe and environmentally friendly.

The technical solutions adopted by the present invention to solve its technical problems are:

A composite insecticidal and acaricidal nano-aqueous formulation containing fenpropathrin and chlorpyrifos (hereinafter referred to as fenpropathrin·chlorpyrifos composite nano-aqueous formulation), wherein the nano-aqueous formulation has fenpropathrin and chlorpyrifos as main activities The ingredients are formulated with surfactants and water, wherein the nano-aqueous agent contains the following ingredients according to weight percentages: fenpropathrin and chlorpyrifos at 3% to 80%, and surfactants at 5 to 20%, The balance is water.

The weight ratio of fenpropathrin and chlorpyrifos is 20:1 to 1:20, preferably 1:5 to 5:1.

In the nano-aqueous agent, the weight percentage of fenpropathrin and chlorpyrifos is preferably 3% to 55%, and more preferably 3% to 21%.

The nano-aqueous agent of the present invention can only contain the active ingredients fenpropathrin and chlorpyrifos, and other components can also be added to the active ingredient during use or preparation. The effective ingredients in the nano-aqueous agent can also be synergistically effective. Exist in the composition.

Said surfactant is selected from fatty alcohol polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, styrylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether phosphate, alkylphenol polyoxyethylene ether One or more combinations of phosphoric acid ester, sodium fatty acid methyl ester sulfonate, and sodium alcohol ether succinic acid monoester sulfonate.

Wherein, the surfactant is preferably 5%-16% by weight percentage.

Another object of the present invention is to provide a method for preparing a composite insecticidal and concealing nano-aqueous agent containing fenpropathrin and chlorpyrifos, which includes:

Step (1), at room temperature (10-35°C), mix the fenpropathrin technical medicine, the chlorpyrifos technical medicine and the surfactant, and stir to make the fenpropathrin and the chlorpyrifos uniformly dispersed in the surfactant;

In step (2), water is added under stirring and evenly stirred to form a surfactant micellar solution containing fenpropathrin and chlorpyrifos, which is a transparent nano-aqueous solution of fenpropathrin and chlorpyrifos.

The fenpropathrin and chlorpyrifos nano-aqueous formulations of the present invention have a transparent appearance, and the average particle size of the surfactant micelles is at the nanometer level; after entering water, they can quickly dissolve with water to form a completely transparent solution, and the dilution stability is qualified; the performance of the nano-aqueous formulations of the present invention Stable, it is still stable after cold storage at 0°C for 7 days and 54°C hot storage for 14 days, and the effective ingredients will not precipitate, which is convenient for storage.

In step (1), the stirring speed is 60-100 revolutions per second, and the stirring time is 0.5 h. The technician can adjust the time so that the fenpropathrin and chlorpyrifos are uniformly dispersed in the surfactant.

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.

Another object of the present invention is to provide the use of the nano-aqueous agent for controlling pests and harmful mites on fruit trees, cotton and vegetables. The pest is rice planthopper, and the pest mite is citrus red spider. In the process of use, it can reduce the amount of use, delay the generation of insect pests and mite resistance, and improve the control effect, which is better than single-agent use, saving time and effort, saving costs, reducing environmental pollution, and reducing the burden on farmers.

Compared with the prior art, the present invention has the following beneficial effects: (1) This application has successfully prepared a nano aqueous formulation of fenpropathrin and chlorpyrifos by adding surfactants, which overcomes the insoluble fenpropathrin and chlorpyrifos insoluble The disadvantages of water, insoluble in water; (2) The compounding of fenpropathrin and chlorpyrifos has obvious synergistic effect, which improves the control effect on harmful mites compared with single agent alone; (3) It has quick effect at the same time. (4) The combination of two active ingredients reduces the amount of pesticides used, reduces production and use costs and environmental pollution; (5) Delays the resistance of pest mites to pesticides, and its effect is significantly higher than that of its single剂用。 Agent use.

Description of the drawings

Figure 1 shows the 12% fenpropathrin·chlorpyrifos compound nano-aqueous formulation of Example 7.

Figure 2 shows the 12% fenpropathrin·chlorpyrifos compound nano-aqueous formulation of Comparative Example 2.

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.

Example 1:

(1) Indoor toxicity test

1. The virulence of fenpropathrin, chlorpyrifos and fenpropathrin·chlorpyrifos compound nano-aqueous agent on citrus red spiders was determined by immersion slide method, each treatment was repeated 3 times, each concentration was 30, and LC _{50 was used.} The value is calculated based on Sun Yunpei’s method of co-toxicity coefficient (CTC value):

Single-dose toxicity index = standard drug LC50/a single-dose LC50×100

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

Measured Toxicity Index (ATI) = LC50 value of standard single agent/LC50 value of mixed agent×100

Co-toxicity coefficient (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 results are shown in Table 1:

Table 1 Indoor toxicity determination of fenpropathrin and chlorpyrifos compound nano-aqueous to citrus red spider

It can be seen from Table 1 that the ratio of fenpropathrin and chlorpyrifos ranges from 20:1 to 1:20, and the co-toxicity coefficient is greater than 120, which has a synergistic effect on the control of citrus red spiders, especially at 5:1 to 1 : Between 5, the co-toxicity coefficient is above 150, and the synergistic effect is significant.

2. The virulence of fenpropathrin, chlorpyrifos and fenpropathrin·chlorpyrifos composite nano-aqueous to rice planthoppers was determined by the test method of first soaking leaves and then infestation. Each treatment was repeated three times, and the LC ₅₀ value was used in accordance with Sun Yunpei Method to calculate the co-degree coefficient, the results are shown in Table 2:

Table 2 Toxicity determination of fenpropathrin and chlorpyrifos compound nano-aqueous to rice planthopper

It can be seen from Table 2 that the ratio of fenpropathrin and chlorpyrifos ranges from 20:1 to 1:20, and the co-toxicity coefficient is greater than 120, which has a synergistic effect on the control of rice planthoppers, especially at 5:1 to 1:1: Between 5, the co-toxicity coefficient is above 160, and the synergistic effect is significant.

Example 1:

Formula: 20g fenpropathrin, 1g chlorpyrifos, 10g styrylphenol polyoxyethylene ether, 6g fatty alcohol polyoxyethylene ether phosphate, add water to 100g.

Preparation method: Weigh 20g (based on active ingredients, the same below) technical fenpropathrin, 1g (based on active ingredients, the same below) technical chlorpyrifos, and 10g styrylphenol polyoxyethylene ether, 6g fatty alcohol The polyoxyethylene ether phosphate was mixed, stirred for 0.5 h at a rotation speed of 90 revolutions/sec, and kept stirring, 63 g of water was added, and stirring was continued for 1 h to obtain 21% fenpropathrin·chlorpyrifos composite nano-aqueous agent.

The nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 175 mPa·s, and an average particle size of 15.2 nanometers.

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.

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.

Example 2:

Formula: 10g fenpropathrin, 1g chlorpyrifos, 3g alkylphenol polyoxyethylene ether phosphate, 3g fatty alcohol polyoxyethylene ether, 2g alcohol ether succinic acid monoester sodium sulfonate, add water to 100g.

The preparation method is the same as in Example 1, and 11% fenpropathrin·chlorpyrifos compound nano-aqueous agent is prepared.

The nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 165.5 mPa·s, and an average particle size of 14.8 nanometers.

Example 3:

Formula: 5g fenpropathrin, 1g chlorpyrifos, 5g sodium fatty acid methyl sulfonate, 3g styrylphenol polyoxyethylene ether, add water to 100g.

The preparation method is the same as that in Example 1, and a 6% fenpropathrin·chlorpyrifos compound nano-aqueous agent is prepared.

The nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 200.5 mPa·s, and an average particle size of 17.6 nanometers.

Example 4:

Formula: 2g fenpropathrin, 1g chlorpyrifos, 5g sodium alcohol ether succinate monoester sulfonate, 3g styrylphenol polyoxyethylene ether, add water to 100g.

The preparation method is the same as that in Example 1, and a 3% fenpropathrin·chlorpyrifos composite nano-aqueous agent is prepared.

The nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 180 mPa·s, and an average particle size of 19 nanometers.

Example 5:

Formula: 2g fenpropathrin, 2g chlorpyrifos, 4g fatty alcohol polyoxyethylene ether, 8g alkylphenol polyoxyethylene ether phosphate, add water to 100g.

The preparation method is the same as that in Example 1, and a 4% fenpropathrin·chlorpyrifos composite nano-aqueous agent is prepared.

The nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 182.5 mPa·s, and an average particle size of 16.5 nanometers.

Example 6:

Formula: 3g fenpropathrin, 6g chlorpyrifos, 2g alkylphenol formaldehyde resin polyoxyethylene ether, 6g styrylphenol polyoxyethylene ether, add water to 100g. The above raw materials are prepared according to the nano-aqueous preparation method to form a fenpropathrin·chlorpyrifos composite nano-aqueous preparation with a main active ingredient content of 9% by weight.

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.

Example 7:

Formula: 2g fenpropathrin, 10g chlorpyrifos, 5g alkylphenol formaldehyde resin polyoxyethylene ether, 6g alcohol ether succinate sodium sulfonate, add water to 100g.

The preparation method is the same as that in Example 1, and a 12% fenpropathrin·chlorpyrifos composite nano-aqueous agent is prepared.

The nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 135 mPa·s, and an average particle size of 11.5 nanometers.

Example 8:

Formula: 1g fenpropathrin, 10g chlorpyrifos, 4g fatty alcohol polyoxyethylene ether, 2g alkylphenol formaldehyde resin polyoxyethylene ether, 3g alkylphenol polyoxyethylene ether phosphate, add water to 100g.

The nano-aqueous agent of this example has a transparent and slightly yellowish appearance, a viscosity of 145 mPa·s, and an average particle size of 22.0 nanometers.

Example 9:

Formula: 0.5g fenpropathrin, 10g chlorpyrifos, 3g styrylphenol polyoxyethylene ether, 3g fatty alcohol polyoxyethylene ether phosphate, add water to 100g.

The preparation method is the same as that in Example 1, and 10.5% fenpropathrin·chlorpyrifos compound nano-aqueous agent is prepared.

The nano-aqueous agent of this example has a transparent and slightly yellow appearance, a viscosity of 127.5 mPa·s, and an average particle size of 21.5 nanometers.

Comparative example 1-Comparative example 4

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.

Table 3. Formulations of Comparative Example 1-Comparative Example 4

The preparation method is the same as in Example 1.

According to the formulations of Comparative Example 1 and Comparative Example 2, with the addition of additives, fenpropathrin and chlorpyrifos still cannot be completely dissolved in water, and a qualified aqueous solution cannot be formed.

According to the formulations of Comparative Example 3 and Comparative Example 4, an aqueous solution can be prepared at room temperature (10-35°C), but when the aqueous solution is placed at a low temperature (below 0°C), the fenpropathrin and chlorpyrifos technical drugs will continue to precipitate. And it cannot be recovered after heating up. It shows that the use of surfactants other than the surfactants or conventional liquids used in the surfactant composition of the present invention cannot be used to prepare qualified fenpropathrin·chlorpyrifos composite nano-aqueous.

Example 10: Comparison of Biological Activity

Field efficacy test one

Test agent: Example 1 to Example 9 of the fenpropathrin·chlorpyrifos compound nano-aqueous agent.

Control agent: 3.5% fenpropathrin nano-aqueous, 2% chlorpyrifos nano-aqueous.

3.5% fenpropathrin nano-aqueous preparation method: weigh 3.5g (based on active ingredient) fenpropathrin technical, 7g fatty alcohol polyoxyethylene ether, 4g fatty acid methyl ester sulfonate sodium, 5g sorbitol After the three fatty acid ester polyoxyethylene ethers are mixed, they are stirred for 0.5 h at a rotation speed of 85 revolutions per second, and 80.5 g of water is added under stirring, and the stirring is continued for 1 h to obtain 3.5% fenpropathrin nano-aqueous agent.

2% chlorpyrifos nano-aqueous preparation method: weigh 2g (based on active ingredients) of chlorpyrifos original drug, 8g tristyrylphenol polyoxyethylene ether phosphate and 2g alkylphenol formaldehyde resin polyoxyethylene ether, and mix the three Then, it was stirred for 0.5 h at a rotation speed of 75 revolutions per second, 88 g of water was added under stirring, and the stirring was continued for 0.8 h to obtain 2% chlorpyrifos nano-aqueous solution.

Control object: citrus red spider.

Test method: The normal field dose (active ingredient) was used, the dose treatment was set for three repetitions, and the random block arrangement was repeated. Each repetition was set in an area of 30m ² , and the experiment was sprayed with a knapsack sprayer. Investigate the number of insect populations before application, and investigate the number of remaining live insects 3 days, 7 days, 14 days, and 30 days after application, and calculate the control effect according to the following method:

Insect population reduction rate (%) = (number of insects before application-number of insects after application) / number of insects before application × 100

Corrected control effect (%) = (Reduction rate of insect population in the treatment area-Reduction rate of insect population in the control area) / (100-Recession rate of insect population in the control area before and after control) × 100

The test results are shown in Table 4:

Table 4: Field test results of fenpropathrin·chlorpyrifos nano-aqueous on citrus red spider

The field efficacy results showed that the fenpropathrin·chlorpyrifos composite nano-aqueous agent has an excellent control effect on citrus red spiders, and the control effect is better than the direct effect of a single-dose variety.

Field efficacy test two

Control agent: 3.5% fenpropathrin nano-aqueous, 2% chlorpyrifos nano-aqueous.

Control object: rice planthopper.

Test method: The normal field dosage (active ingredient) was used, the dosage treatment was set for three repetitions, and the random block arrangement was repeated, and the area of each repetition was 50m ^{2. The} experiment used a knapsack sprayer to spray the whole cotton. Investigate the number of insect populations before application, and investigate the number of remaining live insects 3 days, 7 days, 14 days, and 30 days after application, and calculate the control effect according to the following method:

Table 5 Field test results of fenpropathrin and chlorpyrifos compound nano-aqueous on rice planthoppers

The field efficacy results showed that the fenpropathrin·chlorpyrifos composite nano-aqueous agent has an excellent control effect on rice planthopper, and the control effect is better than the direct effect of the single-agent variety.

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

Claims

A composite insecticidal and acaricide nano-aqueous agent containing fenpropathrin and chlorpyrifos, characterized in that the nano-aqueous agent uses fenpropathrin and chlorpyrifos as active ingredients, is formulated with a surfactant and water, Among them, according to the weight percentage, the content of fenpropathrin and chlorpyrifos is 3 to 80%, indicating that the active agent is 5 to 20%, and the balance is water.
The nano-aqueous formulation of claim 1, wherein the weight ratio of the fenpropathrin and chlorpyrifos is 20:1 to 1:20.
The nano-aqueous formulation of claim 2, wherein the weight ratio of the fenpropathrin and chlorpyrifos is 5:1 to 1:5.
The nano-aqueous agent according to claim 1, wherein the surfactant is selected from the group consisting of fatty alcohol polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, styrylphenol polyoxyethylene ether, fatty acid One or more combinations of alcohol polyoxyethylene ether phosphate, alkylphenol polyoxyethylene ether phosphate, sodium fatty acid methyl sulfonate, and sodium alcohol ether succinic acid monoester sulfonate.
The preparation method of nano-aqueous agent according to claim 1, characterized in that it comprises:

Step (1), at room temperature, mix the fenpropathrin original drug, chlorpyrifos original drug and the surfactant, and stir, so that the chlorpyrifos and fenpropathrin are uniformly dispersed in the surfactant;

In step (2), water is added under stirring, and the mixture is evenly stirred to form a surfactant micellar solution containing fenpropathrin and chlorpyrifos, which is a transparent nano-aqueous solution of fenpropathrin and chlorpyrifos.
The preparation method of nano-aqueous agent according to claim 5, characterized in that, in the step (1) and step (2), the stirring speed is 60-100 revolutions per second.
The use of the nano-aqueous agent according to claim 1 to control pests and mites on fruit trees, vegetables, and cotton.
The use according to claim 7, wherein the pest is rice planthopper, and the pest mite is citrus red spider.