CN117918344A - A soluble solid nanometer preparation of high-efficiency cyhalothrin and preparation method thereof - Google Patents

Abstract

The invention relates to the technical field of nano pesticides, and discloses a high-efficiency cyhalothrin soluble solid nano preparation and a preparation method thereof; the nanometer preparation comprises 1-30 high-efficiency cyhalothrin, 0.1-15 wetting agent, 0.1-15 dispersing agent, 0.1-3 preservative and 0.1-37 water; compared with the prior art, the high-efficiency cyhalothrin soluble solid nano preparation overcomes the defects of poor water dispersibility and slow dissolution rate of insoluble pesticides, the particle size of the drug particles is smaller than 300nm, the specific surface area is obviously increased, the dispersion performance of the drug particles is improved, the spreading and wetting performance of the drug liquid on the surfaces of the blades are enhanced, and the control effect of the drug liquid on target pests in the blades in unit area is further improved. In addition, the preparation method is simple and feasible, and the prepared high-efficiency cyhalothrin soluble solid nano preparation has stable physical and chemical properties, is convenient to store and transport, does not contain an organic solvent, has high drug loading capacity and safety, and can be produced in a large scale.

Description

A soluble solid nanometer preparation of high-efficiency cyhalothrin and preparation method thereof

Technical Field

The invention relates to the technical field of nano pesticides, and in particular to a highly effective cyhalothrin soluble solid nano preparation and a preparation method thereof.

Background technique

High-efficiency cyhalothrin is a synthetic pyrethroid insecticide with contact and stomach poison effects, a wide insecticide spectrum, rapid knockdown, and a long lasting effect. It can prevent and control cotton boll weevils, cotton bollworms, corn borers, cotton spider mites, vegetable yellow flea beetles, diamondback moths, cabbage worms, Spodoptera litura, potato aphids, potato beetles, etc., and is also effective against sanitary pests such as mosquitoes, flies, and cockroaches. At present, the commonly used dosage forms of high-efficiency cyhalothrin are mainly low-concentration emulsions, water emulsions, suspensions, and wettable powders. Among them, emulsions contain a large amount of organic solvents, and water emulsions contain chemical solvents, which have serious residual pollution. Dust drift will occur in the production and use of wettable powders, and the actual effective utilization rate of pesticides is not high. The drug particles in the suspension have a large dispersion, and stability problems such as sedimentation and precipitation are prone to occur, which is not convenient for storage and transportation.

At present, with the rapid development of nanotechnology in the agricultural field, the processing of new pesticide formulations through nanomaterials and nanopreparation technology has become a hot spot in the current dosage form processing. Soluble solid nanoformulations are new pesticide formulations created by efficiently combining the original drug, carrier and adjuvant through nanotechnology or methods.

Summary of the invention

The invention provides a soluble solid nanometer preparation of high-efficiency cyhalothrin, which can solve the problems of poor water dispersibility and slow dissolution of high-efficiency cyhalothrin, make up for the defects of traditional dosage forms and improve its effective utilization rate.

The present invention provides a highly effective cyhalothrin soluble solid nano preparation, which comprises, by weight percentage:

1-30 of cyhalothrin, 0.1-15 of wetting agent, 0.1-15 of dispersant, 0.1-3 of preservative and 0.1-37 of water.

Further, the wetting agent is one or more of a nonionic surfactant, a sulfonate anionic surfactant, a phosphate anionic surfactant, a carboxylate anionic surfactant and an oligomeric surfactant;

Further, the nonionic surfactant is one or more of alkylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, fatty amine polyoxyethylene ether, alkyl polyglycoside, polyarylphenol polyoxyethylene ether, castor oil polyoxyethylene ether, polyoxyethylene fatty acid ester, ethylene oxide/propylene oxide block copolymer, sorbitan ester ether and polyglycerol fatty acid ester;

The sulfonate anionic surfactant is selected from one or more of alkylbenzene sulfonate, sodium α-olefin sulfonate, polyoxyethylene ether sulfate, polycyclic aromatic hydrocarbon formaldehyde condensate sulfonate or alkyl aromatic hydrocarbon sulfonate, sodium alkyl succinate sulfonate, polyoxyethylene ether monosuccinate sulfonate, fatty alcohol sulfate, and fatty amide N-methyl taurine sodium salt;

The phosphate anionic surfactant is one or more of polyoxyethylene ether phosphate, alkyl alcohol phosphate and alcohol ether carboxylate.

Furthermore, the dispersant is one or more of anionic dispersants, nonionic dispersants, anionic and nonionic dispersants, polymer dispersants and cationic dispersants.

Further, the anionic dispersant is one or more of naphthaldehyde condensate sulfonate, alkylnaphthaldehyde condensate sulfonate and lignin sulfonate;

and/or, the anionic nonionic dispersant is one or more of a phosphate dispersant, a sulfate dispersant and a succinate sulfonate;

And/or, the nonionic dispersant is one or more of fatty alcohol polyoxypropylene polyoxyethylene ether and polyoxyethylene polypropylene ether block copolymer.

Furthermore, it is characterized in that the preparation method of the highly effective cyhalothrin soluble solid nano preparation is:

(1) dispersing the highly effective cyhalothrin in water and heating it until the whole is in a molten state to obtain a molten phase;

(2) dissolving a wetting agent, a dispersant, and a preservative in water, and stirring until transparent to obtain a dispersed phase;

(3) mixing the dispersed phase and the molten phase at high temperature, and dispersing and emulsifying the phase under high shear until the emulsion is uniform to obtain an emulsion;

(4) adding a water-soluble carrier material to the emulsion and stirring to obtain a uniform emulsion mixture, and drying to obtain a soluble solid nano-preparation of highly effective chlorfenapyr.

Furthermore, in the step (1), the highly effective cyhalothrin is dispersed in water and heated to 80° C.;

And/or, in step (3), the high temperature is 80°C;

And/or, in step (4), the water-soluble carrier material is one or more of polyethylene glycol, povidone, tartaric acid, succinic acid, chitosan, glucose, galactose, sucrose, lactose, mannitol, sorbitol, xylitol, hydroxypropyl cellulose and hydroxypropyl methylcellulose.

Furthermore, in the step (3), the shear rate of the high shear dispersion emulsification is 1000-30000 rpm/min; the shear time of the high shear dispersion emulsification machine is 0.05-1h;

And/or, in step (3), the stirring speed is 100-1000 rpm/min;

And/or, in step (4), the drying is drying or freeze drying.

Furthermore, the drying temperature is 40°C and the drying time is 2-8h;

The pre-freezing temperature of the freeze-drying is -80°C, the pre-freezing time is 1-6 hours, and the freeze-drying time is 12-72 hours.

The present invention also provides a method for preparing any of the above-mentioned highly effective cyhalothrin soluble solid nanoformulations, comprising:

(1) dispersing the highly effective cyhalothrin in water and heating it until the whole is in a molten state to obtain a molten phase;

(2) dissolving a wetting agent, a dispersant, and a preservative in water, and stirring until transparent to obtain a dispersed phase;

(3) mixing the dispersed phase and the molten phase at high temperature, and dispersing and emulsifying the phase under high shear until the emulsion is uniform to obtain an emulsion;

(4) adding a water-soluble carrier material to the emulsion and stirring to obtain a uniform emulsion mixture, and drying to obtain a soluble solid nano-preparation of highly effective chlorfenapyr.

Compared with the prior art, the invention has the following beneficial effects:

The invention provides a method for preparing a soluble solid nanometer preparation of high-efficiency cyhalothrin, which solves the problem of poor water solubility and dispersibility of high-efficiency cyhalothrin, significantly enhances the spreading and wetting effect of the drug solution on the leaf surface, thereby improving the control effect of the drug solution on target pests and significantly improving the effective utilization rate of the pesticide.

The drug particles prepared by the present invention have uniform size distribution and an average particle size of about 10-300nm, which significantly increases the specific surface area of the drug particles, increases the contact area between the active components of the pesticide and pests, enhances the pest control effect, reduces the amount of pesticide used and thus reduces environmental pollution.

The highly effective chlorfenapyr soluble solid nano-preparation uses a small amount of surfactant and eliminates organic solvents, thus greatly reducing toxicity and increasing non-target biological safety, and can be used as an environmentally friendly formulation.

The highly effective chlorfenapyr soluble solid nano-preparation has a high content of pesticide compounds, a high drug loading capacity, a simple preparation process, and can be scaled up for use in production processes.

Other features and advantages of the present invention will be described in the following description, and partly become obvious from the description, or be understood by practicing the present invention. The main purpose and other advantages of the present invention can be realized and obtained by the schemes particularly pointed out in the description.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG1 is a process flow chart of the highly effective cyhalothrin soluble solid nanoformulation prepared by the present invention;

FIG2 is a scanning electron microscope characterization image of the 10% highly efficient cyhalothrin soluble solid nanoformulation of the present invention in Example 1;

FIG3 is a scanning electron microscope characterization image of the 15% highly effective cyhalothrin soluble solid nanoformulation of Example 2 of the present invention;

FIG. 4 is a scanning electron microscope characterization image of the 20% highly efficient chlorfenapyr soluble solid nanoformulation of Example 3 of the present invention.

Detailed ways

The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

FIG. 1 is a process flow chart of the highly effective cyhalothrin soluble solid nanoformulation prepared by the present invention.

Example 1

A 10% highly effective cyhalothrin soluble solid nano preparation comprises the following steps:

(1) Weigh 5 g of high-efficiency cyhalothrin technical drug and disperse it in water, place it in a water bath and heat it to 80° C. until the whole is in a molten state to obtain a molten phase;

(2) Weigh 1.0 g of polyoxyethylene sorbitan fatty acid ester and 0.5 g of castor oil polyoxyethylene ether and dissolve them in deionized water, and stir them thoroughly until they become transparent to obtain a dispersed phase;

(3) At 80°C, the dispersed phase was added dropwise to the molten phase, and dispersed and emulsified in a high shear dispersing emulsifier for a period of time until the emulsion was uniform. The shear rate was 8000 rpm and the shear time was 5 min.

(4) After the emulsion was taken out after emulsification and dispersion, 43.5 g of sucrose was added and stirred continuously at a stirring speed of 300 rpm to obtain a uniform emulsion. A 10% highly efficient chlorfenapyr soluble solid nanoformulation was obtained by freeze drying.

The present invention prepares a 10% soluble solid nanometer preparation of highly effective cyhalothrin, which is dispersed in water to form a uniform and stable solution with a particle size of about 90 nm. The scanning electron microscope characterization result is shown in FIG2 .

Example 2

A 15% highly effective cyhalothrin soluble solid nano preparation comprises the following steps:

(1) Weigh 10 g of high-efficiency cyhalothrin technical drug, disperse it in water, place it in a water bath and heat it to 80° C., until the whole is in a molten state to obtain a molten phase;

(2) Weigh 1.5 g of fatty alcohol polyoxyethylene ether and 1.0 g of polyethylene glycol and dissolve them in deionized water, and stir them thoroughly until they become transparent to obtain a dispersed phase;

(3) At 80°C, the dispersed phase was added dropwise to the molten phase, and dispersed and emulsified in a high shear dispersing emulsifier for a period of time until the emulsion was uniform. The shear rate was 10,000 rpm and the shear time was 10 min.

(4) After the emulsion was taken out after emulsification and dispersion, 34.2 g of sucrose and 20 g of mannitol were added and stirred continuously at a stirring speed of 300 rpm to obtain a uniform emulsion. A 15% highly efficient chlorfenapyr soluble solid nanoformulation was obtained by freeze drying.

The present invention prepares a 15% soluble solid nanometer preparation of highly effective cyhalothrin, which is dispersed in water to form a uniform and stable solution with a particle size of about 150 nm. The scanning electron microscope characterization result is shown in FIG3 .

Example 3

A 20% highly efficient cyhalothrin soluble solid nano preparation comprises the following steps:

(1) Weigh 10 g of high-efficiency cyhalothrin technical drug, disperse it in water, place it in a water bath and heat it to 80° C., until the whole is in a molten state to obtain a molten phase;

(2) Weigh 2 g of fatty alcohol polyoxyethylene ether, 2 g of ethylene oxide/propylene oxide block copolymer, and 0.5 g of sodium dodecyl sulfate, dissolve them in deionized water, and stir them thoroughly until they become transparent to obtain a dispersed phase;

(3) At 80°C, the dispersed phase was added dropwise to the molten phase, and dispersed and emulsified in a high shear dispersing emulsifier for a period of time until the emulsion was uniform. The shear rate was 12000 rpm and the shear time was 10 min.

(4) After the emulsion was taken out after emulsification and dispersion, 35.5 g of xylitol was added and stirred continuously at a stirring speed of 300 rpm to obtain a uniform emulsion. A 20% highly efficient chlorfenapyr soluble solid nanoformulation was obtained by freeze drying.

The present invention prepares a 20% soluble solid nanometer preparation of highly effective cyhalothrin, which is dispersed in water to form a uniform and stable solution with a particle size of about 240 nm. The scanning electron microscope characterization result is shown in FIG4 .

Comparative Example

The control group of the comparative example is a commercially available cyhalothrin wettable powder with a drug concentration of 5%.

The suspension rate analysis experiment is to examine the dispersion performance of the active components of pesticide formulations after being dispersed with water, and is one of the important means to evaluate the dispersion performance of pesticide formulations.

First, accurately measure 5.0mL of pesticide formulation and transfer it to a 200mL beaker containing 50mL of standard hard water. Shake the beaker in a circular motion for 2min (120 times/min), place it in a water bath at 30±1℃ for 13min, transfer it to a 250mL measuring cylinder with standard hard water, add it dropwise to the scale line, plug it with a stopper, and turn it upside down 30 times (1min). Open the stopper and let it stand in a constant temperature water bath at 30±1℃ for 30min. Finally, remove the upper 225mL suspension, ensuring that the time is controlled within 10-15s, ensuring that the sediment at the bottom of the measuring cylinder is not stirred, and ensuring that the solution is absorbed a few millimeters below the liquid surface. Finally, the initial active ingredient content _m0 of the initial suspension and the active ingredient content _m1 in the 225mL suspension are measured by liquid chromatography, and the suspension rate (Suspensibility, S) is calculated according to the following formula:

Table 1 Suspension rate of pesticide preparations

As shown in Table 1, the suspension rate of different concentrations of highly effective chlorfenapyr soluble solid nanoformulations is significantly better than that of the control group, that is, after the preparation is diluted with water, the active ingredients of the drug can be evenly suspended and dispersed in the liquid medicine. After the drug particles are nanosized, the particle size is significantly reduced, and the drug particles disperse faster per unit time. At the same time, the Brownian motion of the particles becomes more intense as the particle size decreases, which accelerates the dispersion of the particles. The higher the suspension rate, the better the dispersion performance of the drug particles, and the particles of the active ingredients can be evenly suspended in the liquid medicine for a long time. The liquid medicine ensures a consistent concentration during spraying and is evenly deposited on the target, thereby increasing the control effect of the liquid medicine on the target pests.

Indoor biological activity test

According to the "Guidelines for Indoor Bioassay Tests of Pesticides" (NY/T 1154.10-2008), firstly, the soluble solid nanometer preparation of high-efficiency cyhalothrin and the experimental control group were diluted into 5 series of concentrations in equal proportions, and each concentration was repeated 4 times, and the same volume of deionized water was used as a control. Aphids were used as target pests and raised in a constant temperature incubator. Finally, the number of aphid deaths in each concentration gradient culture dish was counted, and the half-lethal concentration (LC ₅₀ ) and its 95% confidence interval were calculated.

Table 2 Indoor biological activity test of high-efficiency cyhalothrin preparations against aphids

As shown in Table 2, the toxicity effect of different concentrations of soluble solid nano-preparations of high-efficiency cyhalothrin is significantly higher than that of the control group, and has a better insecticidal effect. After the high-efficiency cyhalothrin drug particles are nano-processed, the smaller the particle size, the larger the unit specific surface area, the greater the adhesion of the drug particles on the leaf surface, and thus the contact area with the surface of crop pests is increased, and the active components are easier to act on biological targets. At the same time, the dispersibility and wetting properties of the soluble solid nano-preparation of high-efficiency cyhalothrin are significantly enhanced, and the drug solution can be evenly dispersed on the crop leaf surface, thereby improving the effectiveness of the preparation and the control effect on pests and diseases.

The above description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. The high-efficiency cyhalothrin soluble solid nano preparation is characterized by comprising the following components in percentage by weight:

1-30 high-efficiency cyhalothrin, 0.1-15 wetting agent, 0.1-15 dispersing agent, 0.1-3 preservative and 0.1-37 water.

2. The lambda-cyhalothrin-soluble solid nano-formulation of claim 1, wherein the wetting agent is one or more of a non-ionic surfactant, a sulfonate-type anionic surfactant, a phosphate-type anionic surfactant, a carboxylate-type anionic surfactant, and an oligomeric surfactant.

3. The lambda-cyhalothrin soluble solid nano-formulation of claim 2, wherein the non-ionic surfactant is one or more of alkylphenol ethoxylates, fatty alcohol ethoxylates, fatty amine ethoxylates, alkyl glycosides, polyarylphenol ethoxylates, castor oil ethoxylates, polyoxyethylene fatty acid esters, ethylene oxide/propylene oxide block copolymers, sorbitol ethers and polyglycerin fatty acid esters;

The sulfonate anionic surfactant is selected from one or more of alkylbenzene sulfonate, alpha-alkenyl sodium sulfonate, polyoxyethylene ether sulfate, polycyclic aromatic hydrocarbon formaldehyde condensate sulfonate or alkyl aromatic hydrocarbon sulfonate, sodium alkyl succinic sulfonate, polyoxyethylene ether monosuccinate sulfonate, fatty alcohol sulfate and fatty amide N-methyl taurate sodium salt;

the phosphate anionic surfactant is one or more of polyoxyethylene ether phosphate, alkyl alcohol phosphate and alcohol ether carboxylate.

4. The lambda-cyhalothrin-soluble solid nano-formulation of claim 2, wherein the dispersant is one or more of an anionic dispersant, a nonionic dispersant, an anionic nonionic dispersant, a polymeric dispersant, and a cationic dispersant.

5. The lambda-cyhalothrin soluble solid nano-formulation of claim 4, wherein the anionic dispersant is one or more of naphthalene formaldehyde condensate sulfonate, alkyl naphthalene formaldehyde condensate sulfonate and lignin sulfonate;

And/or the anionic non-ionic dispersant is one or more of phosphate dispersant, sulfate dispersant and succinate sulfonate;

and/or the nonionic dispersant is one or more of fatty alcohol polyoxypropylene polyoxyethylene ether and polyoxyethylene polypropylene ether block copolymers.

6. The efficient cyhalothrin-soluble solid nano-formulation of any one of claims 1-5, wherein the method of preparing the efficient cyhalothrin-soluble solid nano-formulation is:

(1) Dispersing the high-efficiency cyhalothrin in water, heating, and obtaining a molten phase in a molten state;

(2) Dissolving a wetting agent, a dispersing agent and a preservative in water, and stirring to a transparent state to obtain a dispersed phase;

(3) Mixing the disperse phase with the melt phase at high temperature, and emulsifying the mixture by high-shear dispersion until the emulsion is uniform to obtain emulsion;

(4) And adding a water-soluble carrier material into the emulsion, stirring to obtain a uniform emulsion mixture, and drying to obtain the high-efficiency cyhalothrin soluble solid nano preparation.

7. The lambda-cyhalothrin-soluble solid nano-formulation of claim 6, wherein in step (1), the lambda-cyhalothrin is dispersed in water and heated to 80 ℃;

and/or, in the step (3), the high temperature is 80 ℃;

And/or in the step (4), the water-soluble carrier material is one or more of polyethylene glycol, povidone, tartaric acid, succinic acid, chitosan, glucose, galactose, sucrose, lactose, mannitol, sorbitol, xylitol, hydroxypropyl cellulose and hydroxypropyl methylcellulose.

8. The lambda-cyhalothrin-soluble solid nano-formulation according to claim 7, wherein in step (3), the shear rate of the high shear dispersion emulsification is 1000-30000rpm/min; the shearing time of the high shearing dispersion emulsifying machine is 0.05-1h;

and/or, in the step (3), the stirring speed is 100-1000rpm/min;

and/or, in the step (4), the drying is drying or freeze drying.

9. The lambda-cyhalothrin soluble solid nano-formulation of claim 8, wherein the temperature of the drying is 40 ℃ and the time of the drying is 2-8 hours;

The pre-freezing temperature of the freeze drying is-80 ℃, the pre-freezing time is 1-6h, and the freeze drying is 12-72h.

10. A method of preparing the lambda-cyhalothrin-soluble solid nano-formulation as claimed in any one of claims 1-9, comprising:

(1) Dispersing the high-efficiency cyhalothrin in water, heating, and obtaining a molten phase in a molten state;

(2) Dissolving a wetting agent, a dispersing agent and a preservative in water, and stirring to a transparent state to obtain a dispersed phase;

(3) Mixing the disperse phase with the melt phase at high temperature, and emulsifying the mixture by high-shear dispersion until the emulsion is uniform to obtain emulsion;

(4) And adding a water-soluble carrier material into the emulsion, stirring to obtain a uniform emulsion mixture, and drying to obtain the high-efficiency cyhalothrin soluble solid nano preparation.