Low-irritation cyhalothrin as well as preparation method and application thereof

Abstract

The invention discloses low-irritation cyhalothrin and a preparation method and application thereof, and belongs to the technical field of pesticide preparations, the low-irritation cyhalothrin comprises silicon dioxide nanoparticles with the surfaces grafted with amphiphilic copolymers, cyhalothrin and an anti-allergic drug, the silicon dioxide nanoparticles with the surfaces grafted with the amphiphilic copolymers are dispersed in a solvent, and the anti-allergic drug is added to the silicon dioxide nanoparticles with the surfaces grafted with the amphiphilic copolymers to prepare the low-irritation cyhalothrin. The preparation method comprises the following steps: taking porous silicon dioxide nanoparticles as a carrier, modifying a layer of amphiphilic polymer on the surface of silicon dioxide in situ, then adding cyhalothrin and an anti-allergic drug, continuously stirring, and drying the obtained product to obtain the low-irritation cyhalothrin. The cyhalothrin and the anti-allergic drug are loaded in silicon dioxide pore channels, and the anti-allergic agent is used in cooperation, so that the skin irritation of the cyhalothrin is reduced. The cyhalothrin with low irritation provided by the invention is simple in preparation method, can be used as a cyhalothrin insecticide raw medicine, and has relatively great market application potential.

Description

Technical Field

[0001] The present invention belongs to the technical field of pesticide formulations, and particularly relates to lambda-cyhalothrin with low irritation, its preparation method and application. Background Art

[0002] Insecticides, as a key means for controlling agricultural pests, account for up to 40% of the total amount of pesticides used, and are undoubtedly the core force to ensure the stability and harvest of agricultural production. Pyrethroid insecticides have emerged among many insecticide categories with their unique advantages and have become new insecticides that have attracted much attention.

[0003] These insecticides have extremely remarkable characteristics. First of all, their insecticidal spectrum is extremely wide, and they can effectively cope with the threats of various different types of pests. Whether it is common Lepidoptera pests or Coleoptera pests, they can achieve good control effects. Secondly, pyrethroid insecticides have stable chemical properties, which enables them to maintain activity for a long time in the natural environment and have a long residual period, thus providing long-term protection for crops, reducing the cost and labor consumption of frequent pesticide application, and occupying an indispensable important position in the insecticide market.

[0004] Lambda-cyhalothrin, deltamethrin, bifenthrin, etc. are the main representative varieties of pyrethroid insecticides. There is also a problem that cannot be ignored with these insecticides: they have strong skin irritation. Once the human skin comes into contact with these insecticides, it will stimulate skin tissue cells to release excessive histamine, and then cause long-term and intolerable skin itching symptoms. For production workers engaged in the preparation of technical materials and formulations, long-term contact may lead to skin allergies, redness and other discomforts; for pesticide users, they will also be troubled by skin itching during the pesticide application process, which seriously affects their work comfort and quality of life.

[0005] To solve this problem, currently two main coping strategies are mainly adopted. One is to prepare low-content emulsifiable concentrates (3%), oil formulations (5%), aerosols (6%) and other dosage forms by adjusting the formulation. This method aims to reduce the content of pyrethroids in the formulation and reduce the direct contact between users and high-concentration pyrethroids, thereby reducing skin irritation. However, this method has obvious limitations. It cannot avoid the potential harm of pyrethroid technical materials (96%) to workers during the formulation production process, and because the content of the active ingredient is reduced, to a certain extent, it will weaken the insecticidal effect of the formulation and it is difficult to achieve the ideal control level.

[0006] Second, the pyrethroid technical drug is embedded by using the polymer microsphere technology, and the direct contact between the medicament and the skin is isolated through physical wrapping. This method can theoretically effectively reduce skin irritation, but in practical applications, it faces many challenges. The preparation process of polymer microspheres is complex. It not only requires high-precision equipment but also has extremely high requirements for the technical level of operators, which increases the production cost and technical threshold. In addition, the encapsulation rate of polymer microspheres is unstable, resulting in ineffective encapsulation of some pyrethroid technical drugs and affecting the actual application effect.

[0007] These problems seriously restrict the further promotion and development of pyrethroid insecticides in the fields of formulation production and application. Therefore, the research and development of a new type of pyrethroid pesticide with both low skin irritation, high content of technical drug, and a simple preparation method has become a key topic that the current pesticide industry urgently needs to break through. This is not only of great significance for improving agricultural production efficiency and ensuring the quality and safety of agricultural products but also will promote the entire pesticide industry to develop in a more green and sustainable direction. Summary of the Invention

[0008] The purpose of the present invention is to provide a lambda-cyhalothrin with low irritation, its preparation method and application, so as to solve the problem of high skin irritation of lambda-cyhalothrin insecticides.

[0009] The purpose of the present invention can be achieved through the following technical solutions:

[0010] In the first aspect, the present application proposes a lambda-cyhalothrin with low irritation, which includes silica nanoparticles grafted with amphiphilic copolymers on the surface, lambda-cyhalothrin, and an anti-allergy drug. The mass ratio of the silica nanoparticles grafted with amphiphilic copolymers on the surface, lambda-cyhalothrin, and the anti-allergy drug is 1-2:0.01-10:0.01-10.

[0011] In some possible implementation manners, the anti-allergy drug is at least one of chlorpheniramine, promethazine, diphenhydramine, cetirizine, loratadine, ebastine, azelastine, fexofenadine, desloratadine, levocetirizine, and menthol.

[0012] In the first aspect, the present application proposes a preparation method of a lambda-cyhalothrin with low irritation, including the following steps: dispersing silica nanoparticles grafted with amphiphilic copolymers on the surface in a solvent, then adding lambda-cyhalothrin and an anti-allergy drug, and continuing to stir. After drying the obtained product, a lambda-cyhalothrin with low irritation is obtained.

[0013] In some possible implementation manners, the silica nanoparticles grafted with amphiphilic copolymers are obtained by atom transfer radical polymerization (ATRP) of glycidyl bromoisobutyrate, tris(2-dimethylaminoethyl)amine, and cuprous chloride to initiate surface amination of silica nanoparticles, hydrophobic monomers, and hydrophilic monomers. The hydrophobic monomer is an acrylate monomer; the hydrophilic monomer is a polyethylene glycol methacrylate monomer.

[0014] In some possible implementation manners, the dosage ratio of glycidyl bromoisobutyrate, tris(2-dimethylaminoethyl)amine, cuprous chloride, surface-aminated silica nanoparticles, hydrophobic monomers, and hydrophilic monomers is 2-10 g: 50-150 μL: 10-50 mg: 1-4 g: 1-10 g: 2-20 g;

[0015] The temperature of the atom transfer radical polymerization reaction is 90 °C, and the reaction time is 24-72 h.

[0016] In some possible implementation manners, the acrylate monomer includes at least one of methyl methacrylate, 2-hydroxyethyl methacrylate, and butyl acrylate.

[0017] In some possible implementation manners, the molecular weight of the polyethylene glycol methacrylate monomer is between 100 and 5000.

[0018] In some possible implementation manners, the surface-aminated silica nanoparticles are obtained by hydrolysis and condensation of an amino silane coupling agent on the surface of silica nanoparticles, introducing amino groups on the surface of silica nanoparticles, and serving as the starting point for subsequent radical polymerization.

[0019] In some possible implementation manners, the amino silane coupling agent is at least one of 3-aminopropyltriethoxysilane (APTES, KH-550), 3-aminopropyltrimethoxysilane (A-1110), 3-aminopropyltrimethoxysilane (A-1110), and N-β-(aminoethyl)-γ-aminopropyltriethoxysilane (A-1130).

[0020] In some possible implementation manners, the present application proposes an application of pyrethrum with low irritation, using the pyrethrum with low irritation as the insecticide technical material. When the pyrethrum with low skin irritation is used in the form of dry powder / compound solution / emulsion, it will not cause skin irritation such as itching when contacting human skin.

[0021] The beneficial effects of the present invention:

[0022] The silica nanoparticles loaded with beta-cypermethrin in a stable manner in the present invention have amphiphilicity, and this property enables the silica and the loaded drug to be uniformly and stably dispersed in organic / inorganic solvents. Its carrier and the modified polymer are of low toxicity and pollution-free, and are a material with very high safety.

[0023] The beta-cypermethrin with low skin irritation provided by the present invention has a stable structure, strong practicability, and high market application potential. Brief Description of the Drawings

[0024] The present invention will be further described below in conjunction with the drawings.

[0025] Figure 1 are (a) transmission electron microscope images (TEM, Hitachi HT7700) and (b) dynamic light scattering spectra (DLS, Malvern Mastersizer 3000) of the silica nanoparticles grafted with active radical polymerization initiators on the surface prepared in Example 1 of the present invention;

[0026] Figure 2 are (a) transmission electron microscope images (TEM, Hitachi HT7700) and (b) dynamic light scattering spectra (DLS, Malvern Mastersizer 3000) of the beta-cypermethrin with low skin irritation prepared in Example 1 of the present invention;

[0027] Figure 3 is a control chart for detecting the skin histamine concentration of rats after administration of the beta-cypermethrin with low skin irritation prepared in Example 1 of the present invention and the control group;

[0028] Figure 4 is a control chart for detecting the serum histamine concentration of rats after administration of the beta-cypermethrin with low skin irritation prepared in Example 1 of the present invention and the control group. Detailed Description of the Invention

[0029] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts shall fall within the protection scope of the present invention.

[0030] Obviously, the following description is only some examples or embodiments of the present application. For those of ordinary skill in the art, without creative efforts, the present application can also be applied to other similar scenarios. In addition, it can also be understood that although the efforts made in this development process may be complex and lengthy, for those of ordinary skill in the art related to the content disclosed in the present application, some design, manufacturing or production changes based on the technical content disclosed in the present application are only conventional technical means and should not be understood as the content disclosed in the present application being insufficient.

[0031] However, there will be cases where unnecessary details are omitted. For example, there are cases where the detailed description of well-known matters is omitted and the repeated description of actually identical structures is omitted. This is to avoid the following description becoming unnecessarily lengthy and to facilitate the understanding of those skilled in the art. In addition, the following description is provided for those skilled in the art to fully understand the present application and is not intended to limit the subject matter recited in the claims.

[0032] If there is no special instruction, all embodiments and optional embodiments of the present application can be combined with each other to form new technical solutions, and all technical features and optional technical features of the present application can be combined with each other to form new technical solutions.

[0033] In the first aspect of the embodiments of the present application, a beta-cypermethrin with low irritation is provided, which includes silica nanoparticles grafted with amphiphilic copolymers on the surface, beta-cypermethrin, and an anti-allergy drug. The mass ratio of the silica nanoparticles grafted with amphiphilic copolymers on the surface, beta-cypermethrin, and the anti-allergy drug is 1-2:0.01-10:0.01-10. The silica nanoparticles stably loaded with beta-cypermethrin of the present invention have amphiphilicity, and this property can make silica and the loaded drug uniformly and stably dispersed in organic / inorganic solvents.

[0034] In some embodiments, the anti-allergy drug is at least one of chlorpheniramine, promethazine, diphenhydramine, cetirizine, loratadine, ebastine, azelastine, fexofenadine, desloratadine, levocetirizine, and menthol.

[0035] In the second aspect of the embodiments of the present application, a preparation method of a beta-cypermethrin with low irritation is provided, which includes the following steps: dispersing silica nanoparticles grafted with amphiphilic copolymers on the surface in a solvent, then adding beta-cypermethrin and an anti-allergy drug, continuing to stir, and drying the obtained product to obtain a beta-cypermethrin with low irritation.

[0036] In some embodiments, the silica nanoparticles grafted with amphiphilic copolymers are obtained by atom transfer radical polymerization (ATRP) of glycidyl bromoisobutyrate, tris(2-dimethylaminoethyl)amine, and copper chloride to initiate surface amination of silica nanoparticles, hydrophobic monomers, and hydrophilic monomers. The hydrophobic monomer is an acrylate monomer; the hydrophilic monomer is a polyethylene glycol methacrylate monomer.

[0037] In some embodiments, the dosage ratios of glycidyl bromoisobutyrate, tris(2-dimethylaminoethyl)amine, copper chloride, surface-aminated silica nanoparticles, hydrophobic monomers, and hydrophilic monomers are 2 - 10 g : 50 - 150 μL : 10 - 50 mg : 1 - 4 g : 1 - 10 g : 2 - 20 g;

[0038] The temperature of the atom transfer radical polymerization reaction is 90 °C, and the reaction time is 24 - 72 h.

[0039] In some embodiments, the acrylate monomer includes at least one of methyl methacrylate, 2-hydroxyethyl methacrylate, and butyl acrylate.

[0040] In some embodiments, the molecular weight of the polyethylene glycol methacrylate monomer is between 100 and 5000.

[0041] In some embodiments, the surface-aminated silica nanoparticles are obtained by hydrolysis and condensation of an amino silane coupling agent on the surface of silica nanoparticles, introducing amino groups on the surface of silica nanoparticles as the starting point for subsequent radical polymerization.

[0042] In some embodiments, the amino silane coupling agent is at least one of 3-aminopropyltriethoxysilane (APTES, KH-550), 3-aminopropyltrimethoxysilane (A-1110), 3-aminopropyltrimethoxysilane (A-1110), and N-β-(aminoethyl)-γ-aminopropyltriethoxysilane (A-1130).

[0043] In the third aspect of the embodiments of the present application, a low-irritation application of fenvalerate is provided, using the low-irritation fenvalerate as an insecticide technical material. When the low-skin-irritation fenvalerate is used in the form of dry powder / compound solution / emulsion, it will not cause skin irritation such as itching when contacting human skin.

[0044] Example 1

[0045] This example provides a low-irritation fenvalerate, which is prepared by the following steps:

[0046] Step S1: 10 g of tetraethyl orthosilicate and 20 mL of ammonia water are dispersed in 300 mL of anhydrous ethanol, argon gas is introduced for protection, and the temperature is kept at 50° C. for 1 h, and then 2 g of silane coupling agent KH-550 is added, and then the temperature is raised to 90° C., and condensed and refluxed for 24 h. The obtained product is separated by high-speed centrifugation, washed with anhydrous ethanol for 3 times, and dried to obtain surface-amino-silica nanoparticles;

[0047] Step S2: 1 g of the surface-aminated silica nanoparticles obtained in step S1 is ultrasonically dispersed in 50 mL of water, placed in a single-mouth bottle, stirred for 1 h, and then 2 g of glycidyl bromide isobutyrate is added, reacted at room temperature for 24 h, and the obtained product is centrifuged, washed with anhydrous ethanol three times and dried to obtain silica nanoparticles with a surface-grafted active free radical polymerization initiator;

[0048] Step S3: 1 g of the silica nanoparticles with the surface grafted active free radical polymerization initiator obtained in step S2 is dispersed in 10 mL of anisole and placed in a polymerization bottle, and then 1 g of a hydrophobic monomer, 2 g of a hydrophilic monomer, and 10 mg of cuprous chloride are added, fully dissolved, and argon gas is introduced for protection. After three freeze-thaw cycles, 50 μL of tris(2-dimethylaminoethyl)amine is injected through a microsyringe to start polymerization, and the reaction is carried out at 90° C. for 24 h. The obtained product is precipitated in methanol and vacuum dried to obtain silica nanoparticles with the surface grafted amphiphilic copolymer;

[0049] Step S4: 1 g of the silica nanoparticles with the amphiphilic copolymer grafted on the surface obtained in step S3 is dispersed in 20 mL of dimethyl sulfoxide and placed in a single-mouth bottle, and then 6 g of cypermethrin and 1 g of an antiallergic drug (chlorpheniramine) are added at room temperature and stirred for 2 h. The obtained product is precipitated in methanol and vacuum dried to obtain silica nanoparticles stably loaded with cypermethrin, i.e., cypermethrin with low skin irritation;

[0050] In step S3, the hydrophobic monomer is butyl methacrylate; and the hydrophilic monomer is polyethylene glycol methacrylate (molecular weight 360).

[0051] (a) Transmission electron microscopy (TEM, Hitachi HT7700) and (b) dynamic light scattering (DLS, Malvern Mastersizer 3000) of the silica nanoparticles with surface grafted active free radical polymerization initiator prepared in Example 1. It can be seen that the silica nanoparticles are monodisperse and evenly distributed with a size of about 60 nanometers.

[0052] Figure 2Transmission electron microscope images (TEM, Hitachi HT7700) and (b) dynamic light scattering spectra (DLS, Malvern Mastersizer 3000) of the beta-cypermethrin with low skin irritation prepared in Example 1 of the present invention. It can be seen that the silica nanoparticles stably loaded with beta-cypermethrin are in a monodisperse structure, and the nanoparticles are evenly distributed. Due to the surface modification with amphiphilic block copolymers and the internal loading of beta-cypermethrin and anti-allergy drugs, the size of the silica composite nanoparticles is about 90 nanometers.

[0053] To test the anti-skin itching and irritation function of the silica composite nanoparticles stably loaded with beta-cypermethrin, after anesthetizing adult male SD rats, a hair removal machine was used to remove the hair on the back. The rats were divided into 3 groups, with 10 rats in each group. Among them, the first group of rats received no treatment on the back and was named the normal rat group; the second group had the silica nanoparticles stably loaded with beta-cypermethrin (100 mg) dispersed in water and then applied to the depilated area on the back of the rats, and was named the low skin irritation beta-cypermethrin group; the third group had beta-cypermethrin (75 mg) dispersed in water and then applied to the depilated area on the back of the rats, and was named the beta-cypermethrin raw drug group. The three groups of rats were anesthetized for 1 h in the same environment and then awakened simultaneously, and the skin itching and irritation stress responses of each group of rats were observed. After observing the stress responses of the rats, each group of rats was sacrificed, and the skin at the drug application site and the rat serum were taken to analyze the histamine expression levels in the skin and serum. As Figure 3 shown, the histamine concentration in the skin tissue of normal rats was 25 ng / mL, and at this time the rats showed no skin irritation; the histamine concentration in the skin tissue of the low skin irritation beta-cypermethrin group of rats was about 26 ng / mL, and the histamine expression level was almost the same as that of normal rats. At this time, the rats showed no obvious irritation reaction; the histamine concentration in the skin tissue of the beta-cypermethrin raw drug group of rats reached 35 ng / mL. At this time, the rats showed obvious itching on the back and scratching phenomenon. This shows that the low skin irritation beta-cypermethrin has the function of reducing skin histamine secretion and inhibiting skin irritation. In addition, an experiment with a mass ratio of 6:1 of beta-cypermethrin and an anti-allergy drug (chlorpheniramine) was also set up, and the result was the same as that of the third group. The reason is that when beta-cypermethrin and the anti-allergy drug are directly mixed, the dispersion effect is poor. In addition, the contact area between beta-cypermethrin and the skin is also larger, and the anti-allergy drug cannot play a role, resulting in the same result as the third group without adding the anti-allergy drug.

[0054] To further analyze the inhibitory function of the low skin irritation beta-cypermethrin on histamine secretion, the histamine expression levels in the sera of the 3 groups of rats were analyzed. As Figure 4As shown. It can be seen that the histamine concentration in the serum of normal rats is 25ng / mL; the histamine concentration in the serum of rats in the low skin irritation cypermethrin group is also around 25ng / mL, which is almost the same as that of normal rats. At this time, the rats showed no obvious irritation reaction; the histamine concentration in the serum of rats in the cypermethrin original drug group reached 30ng / mL, and the rats showed the most obvious irritation and stress at this time. This shows that low skin irritation cypermethrin has the function of reducing the secretion of histamine in the blood and inhibiting irritation.

[0055] Therefore, the cypermethrin with low skin irritation of the present invention can effectively reduce the skin irritation of cypermethrin original drug and has great practical application potential.

[0056] Example 2

[0057] This embodiment provides a low-irritation chrysanthemum ester, which is prepared by the following steps:

[0058] Step S1: 15 g of tetraethyl orthosilicate and 30 mL of ammonia water are dispersed in 400 mL of anhydrous ethanol, argon gas is introduced for protection, and the temperature is kept at 45° C. for 1 hour, and then 2 g of silane coupling agent KH-550 is added, and then the temperature is raised to 90° C., and condensed and refluxed for 18 hours. The obtained product is separated by high-speed centrifugation, washed with anhydrous ethanol for 3 times, and dried to obtain surface-aminated silica nanoparticles;

[0059] Step S2: 2 g of the surface-aminated silica nanoparticles obtained in step S1 are ultrasonically dispersed in 60 mL of water, placed in a single-mouth bottle, stirred for 2 h, and then 2 g of glycidyl bromide isobutyrate is added, reacted at room temperature for 24 h, and the obtained product is centrifuged, washed with anhydrous ethanol three times and dried to obtain silica nanoparticles with a surface-grafted active free radical polymerization initiator;

[0060] Step S3: 1.5 g of the silica nanoparticles with the surface grafted active free radical polymerization initiator obtained in step S2 was dispersed in 10 mL of anisole and placed in a polymerization bottle, and then 5 g of a hydrophobic monomer, 10 g of a hydrophilic monomer, and 25 mg of cuprous chloride were added, fully dissolved, and argon gas was introduced for protection. After three freeze-thaw cycles, 80 μL of tris(2-dimethylaminoethyl)amine was injected through a microsyringe to start polymerization, and the reaction was carried out at 90° C. for 24 h. The obtained product was precipitated in methanol and vacuum dried to obtain silica nanoparticles with the surface grafted amphiphilic copolymer;

[0061] Step S4: 2 g of the silica nanoparticles with the amphiphilic copolymer grafted on the surface obtained in step S3 are dispersed in 40 mL of dimethyl sulfoxide and placed in a single-mouth bottle, and then 10 g of cypermethrin and 1 g of an antiallergic drug (chlorpheniramine) are added at room temperature and stirred for 2 h. The obtained product is precipitated in methanol and vacuum dried to obtain silica nanoparticles stably loaded with cypermethrin, i.e., cypermethrin with low skin irritation;

[0062] In step S3, the hydrophobic monomer is methyl methacrylate; and the hydrophilic monomer is polyethylene glycol methacrylate (molecular weight is 300).

[0063] Example 3

[0064] This embodiment provides a low-irritation chrysanthemum ester, which is prepared by the following steps:

[0065] Step S1: 20 g of tetraethyl orthosilicate and 50 mL of ammonia water are dispersed in 500 mL of anhydrous ethanol, argon gas is introduced for protection, and the temperature is kept at 50° C. for 1 hour, and then 5 g of silane coupling agent KH-550 is added, and then the temperature is raised to 90° C., and condensed and refluxed for 24 hours. The obtained product is separated by high-speed centrifugation, washed with anhydrous ethanol for 3 times, and dried to obtain surface-amino-silica nanoparticles;

[0066] Step S2: 4 g of the surface-aminated silica nanoparticles obtained in step S1 were ultrasonically dispersed in 80 mL of water, placed in a single-mouth bottle, stirred for 2 h, and then 10 g of glycidyl bromide isobutyrate was added, reacted at room temperature for 12 h, and the obtained product was centrifuged, washed with anhydrous ethanol for 3 times and dried to obtain silica nanoparticles with a surface-grafted active free radical polymerization initiator;

[0067] Step S3: 1 g of the silica nanoparticles with the surface grafted active free radical polymerization initiator obtained in step S2 was dispersed in 10 mL of anisole, and then placed in a polymerization bottle, and then 10 g of a hydrophobic monomer, 5 g of a hydrophilic monomer, and 10 mg of cuprous chloride were added, and fully dissolved, and argon gas was introduced for protection. After three freeze-thaw cycles, 50 μL of tris(2-dimethylaminoethyl)amine was injected through a microsyringe to start polymerization, and the reaction was carried out at 90° C. for 24 h. The obtained product was precipitated in methanol and vacuum dried to obtain silica nanoparticles with the surface grafted amphiphilic copolymer;

[0068] Step S4: 1 g of the silica nanoparticles with the amphiphilic copolymer grafted on the surface obtained in step S3 is dispersed in 20 mL of dimethyl sulfoxide and placed in a single-mouth bottle, and then 8 g of cypermethrin and 1 g of an antiallergic drug (chlorpheniramine) are added at room temperature and stirred for 2 h. The obtained product is precipitated in methanol and vacuum dried to obtain silica nanoparticles stably loaded with cypermethrin, i.e., cypermethrin with low skin irritation;

[0069] In step S3, the hydrophobic monomer is tert-butyl methacrylate; the hydrophilic monomer is polyethylene glycol methacrylate (with a molecular weight of 360).

[0070] Example 4

[0071] Compared with Example 1, in this example, the addition amount of the anti-allergy drug is adjusted to 2 g, and the other raw materials and the preparation process are the same as those in Example 1.

[0072] Example 5

[0073] Compared with Example 1, in this example, the addition amount of the anti-allergy drug is adjusted to 3 g, and the other raw materials and the preparation process are the same as those in Example 1.

[0074] Example 6

[0075] Compared with Example 1, in this example, the addition amount of the anti-allergy drug is adjusted to 4 g, and the other raw materials and the preparation process are the same as those in Example 1.

[0076] Example 7

[0077] Compared with Example 1, in this example, the addition amount of the anti-allergy drug is adjusted to 5 g, and the other raw materials and the preparation process are the same as those in Example 1.

[0078] Example 8

[0079] Compared with Example 1, in this example, the addition amount of the anti-allergy drug is adjusted to 6 g, and the other raw materials and the preparation process are the same as those in Example 1.

[0080] Proved by transmission electron microscope images (TEM, Hitachi HT7700) and dynamic light scattering spectra (DLS, Malvern Mastersizer 3000), similar to Example 1, for the pyrethrum with low skin irritation prepared in Examples 2 - 8, the sizes of the silica nanoparticles without polymer modification and without drug loading are all significantly increased.

[0081] It should be noted that in this article, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the term "comprising", "including" or any other variant thereof is intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements not only includes those elements, but also includes other elements not explicitly listed, or further includes elements inherent to this process, method, article or device.

[0082] Although embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A beta-cypermethrin with low irritation, characterized in that, Silica nanoparticles grafted with amphiphilic copolymers, beta-cyfluthrin, and an anti-allergy drug, where the mass ratio of the silica nanoparticles grafted with amphiphilic copolymers, beta-cyfluthrin, and the anti-allergy drug is 1 to 2: 0.01 to 10: 0.01 to 10.

2. A kind of beta-cypermethrin with low irritation according to claim 1, characterized in that, The anti-allergy drug is at least one of chlorpheniramine, promethazine, diphenhydramine, cetirizine, loratadine, ebastine, azelastine, fexofenadine, desloratadine, levocetirizine, and menthol.

3. A preparation method of beta-cypermethrin with low irritation as described in claim 1 or 2, characterized in that, It includes the following steps: Disperse the silica nanoparticles grafted with amphiphilic copolymers in a solvent, then add beta-cyfluthrin and the anti-allergy drug, continue stirring, and dry the resulting product to obtain a beta-cyfluthrin with low irritation.

4. The preparation method of a beta-cypermethrin with low irritation according to claim 3, characterized in that, The silica nanoparticles grafted with amphiphilic copolymers are obtained by surface amination of silica nanoparticles initiated by glycidyl bromoisobutyrate, tris(2-dimethylaminoethyl)amine, and copper chloride, followed by atom transfer radical polymerization of a hydrophobic monomer and a hydrophilic monomer. The hydrophobic monomer is an acrylate monomer; the hydrophilic monomer is a polyethylene glycol methacrylate monomer.

5. The preparation method of pyrethrum ester with low irritation according to claim 4, characterized in that, The dosage ratio of glycidyl bromoisobutyrate, tris(2-dimethylaminoethyl)amine, copper chloride, surface-aminated silica nanoparticles, hydrophobic monomer, and hydrophilic monomer is 2 to 10 g: 50 - 150 μL: 10 to 50 mg: 1 to 4 g: 1 to 10 g: 2 to 20 g.

6. The preparation method of pyrethrum ester with low irritation according to claim 4, characterized in that, The temperature of the atom transfer radical polymerization reaction is 90 °C, and the reaction time is 24 to 72 h.

7. The preparation method of a kind of permethrin with low irritation according to claim 4, characterized in that, The acrylate monomer includes at least one of methyl methacrylate, 2-hydroxyethyl methacrylate, and butyl acrylate; the molecular weight of the polyethylene glycol methacrylate monomer is between 100 and 5000.

8. The preparation method of a kind of beta-cypermethrin with low irritation according to claim 4, characterized in that, The surface-aminated silica nanoparticles are obtained by hydrolysis and condensation of an amino silane coupling agent on the surface of silica nanoparticles.

9. The preparation method of a beta-cypermethrin with low irritation according to claim 8, characterized in that, The amino silane coupling agent is at least one of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, and N-β-(aminoethyl)-γ-aminopropyltriethoxysilane.

10. The application of beta-cypermethrin with low irritation as described in claim 1 or 2, characterized in that, Use this beta-cyfluthrin with low irritation as the original pesticide drug.

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