CN111296420A

CN111296420A - Diatomite-neonicotinoid original drug composition with specific structure and application thereof

Info

Publication number: CN111296420A
Application number: CN202010101338.1A
Authority: CN
Inventors: 樊惠
Original assignee: Guangzhou Huiyu Agricultural Development Co ltd
Current assignee: Guangzhou Huiyu Agricultural Development Co ltd
Priority date: 2020-02-19
Filing date: 2020-02-19
Publication date: 2020-06-19

Abstract

The invention relates to the technical field of pesticides, and particularly relates to a diatomite-neonicotinoid original drug composition with a specific structure and application thereof. A diatomite-neonicotinoid original drug composition with a specific structure is characterized in that the mass ratio of the diatomite with the specific structure to the neonicotinoid original drug is (1: 60) - (400: 1); the diatomite with the specific structure is diatomite with silicon dioxide with a specific sawtooth-shaped honeycomb structure. According to the invention, the diatomite with the specific saw-tooth honeycomb structure silicon dioxide is mixed with the neonicotinoid raw pesticide, so that the co-toxicity coefficient is higher, the pesticide dosage can be obviously reduced, and the environmental pollution is reduced; the diatomite with the specific sawtooth-shaped honeycomb structure silicon dioxide is a natural component and is particularly suitable for organic agricultural application; the invention reduces the surface tension of the system by adding specific dispersant, wetting agent and filler, is beneficial to spreading, adhesion and permeation of the liquid medicine, improves the heat storage stability of the water, improves the suspension rate of the product and better exerts the drug effect.

Description

Diatomite-neonicotinoid original drug composition with specific structure and application thereof

Technical Field

The invention relates to the technical field of pesticides, and particularly relates to a diatomite-neonicotinoid original drug composition with a specific structure and application thereof.

Background

At present, chemical agents are mainly used for preventing and treating pests at home and abroad, and a large amount of pest damage is saved. However, the long-term use of chemical agents has serious problems of agent residue, environmental pollution, pest resistance, pest rampant and the like. Therefore, it is an urgent task to reduce the use and gradually eliminate chemical pesticides with toxic and side effects, develop efficient pesticides with no toxicity, no harm, no harmful residue, or low toxicity, and explore new methods for pest control.

Acetamiprid, belonging to chloronicotinyl compounds, having the common English name of acetamiprid and the chemical name of N- (N-cyano-ethylimino) -N-methyl-2-chloropyridine-5-methylamine, is a novel pesticide; the appearance is white crystal, the melting point is 101.0-103.3 ℃, and the vapor pressure is>1.33×10^-6Pa (25 deg.C); the solubility in water at 25 ℃ is 4200 mg/l, and the compound is soluble in acetone, methanol, ethanol, dichloromethane, chloroform, acetonitrile, tetrahydrofuran, etc., and is stable in water at pH 7, and gradually hydrolyzed at 45 ℃ at pH 9, and is stable in sunlight. Clothianidin is a chemical substance with molecular formula of C₆H₈ClN₅O₂S, clothianidin is an insecticide in neonicotinoids, is a novel insecticide with high efficiency, safety and high selectivity, has the similar action to a nicotine acetylcholine receptor, and has contact poisoning, stomach toxicity and systemic activity; the pesticide is mainly used for preventing and controlling hemiptera, coleopteran, dipteran and certain lepidopteran pests such as aphids, leafhoppers, thrips, plant hoppers and the like on rice, vegetables, fruit trees and other crops, has the advantages of high efficiency, broad spectrum, low dosage, low toxicity, long efficacy duration, no phytotoxicity to the crops, safe use, no cross resistance with conventional pesticides and the like, has excellent systemic and osmotic effects, and is another variety for replacing high-toxicity organophosphorus pesticides; the pesticide has novel and special structure and more excellent performance compared with the traditional nicotine pesticide, and is likely to become a worldwide large-scale pesticide variety. Nitenpyram, the foreign language name nitenpyram, the chemical name of (E) -N- (6-chloro-3-picolyl) -N-ethyl-N' -methyl-2-nitroethylenediamine, nicotinimides, is a novel product developed after imidacloprid and acetamiprid in Japan, and has excellent systemic propertyThe pesticide has the advantages of osmosis, broad insecticidal spectrum, safety and no phytotoxicity; is a regeneration product for preventing and controlling pests with piercing-sucking mouthparts, such as whitefly, aphid, pear psylla, leafhopper and thrips.

The natural diatomite, silicon dioxide and other components with conventional crystal structures are mainly adsorbed on the body surface of insects to achieve the purpose of insect disinfestation, and can not form good synergistic interaction with any functional component of acetamiprid, nitenpyram and clothianidin.

Disclosure of Invention

In view of the above technical problems, the first aspect of the present invention provides a specific-structure diatomaceous earth-neonicotinoid original drug composition, wherein the mass ratio of the specific-structure diatomaceous earth to the neonicotinoid original drug is (1: 60) - (400: 1); the diatomite with the specific structure is diatomite with silicon dioxide with a specific sawtooth-shaped honeycomb structure.

As a preferable technical scheme, the neonicotinoid original drug is any one selected from imidacloprid, acetamiprid, thiacloprid, thiamethoxam, clothianidin, dinotefuran, nitenpyram, imidaclothiz, mepiquat chloride and cycloxaprid.

As a preferable technical scheme, the neonicotinoid original drug is acetamiprid, and the mass ratio of the diatomite with the specific structure to the acetamiprid is (1: 40) - (200: 1); the neonicotinoid original drug is clothianidin, and the mass ratio of the diatomite with the specific structure to the clothianidin is (1: 60) - (400: 1); the neonicotinoid original drug is nitenpyram, and the mass ratio of the diatomite with the specific structure to the nitenpyram is (1: 40) - (100: 1).

The invention provides a diatomite-neonicotinoid pesticide with a specific structure, which comprises the diatomite-neonicotinoid raw pesticide composition with the specific structure and an auxiliary agent; the content of the auxiliary agent is 5-20 wt% of the diatomite-neonicotinoid original drug composition with the specific structure; the auxiliary agent at least comprises any one of a dispersing agent, a wetting agent and a filler.

As a preferable technical scheme, the formulation of the diatomite-neonicotinoid pesticide with the specific structure is selected from any one of missible oil, suspending agent, wettable powder, water dispersible granules, poison bait, mother liquor and mother powder.

In a preferred embodiment, the dispersant is an anionic high molecular surfactant.

In a preferred embodiment, the anionic polymeric surfactant is a polycarboxylate.

As a preferred technical solution, the wetting agent is sulfonate.

As a preferable technical scheme, the sulfonate is a compound of naphthalene sulfonate and sodium dodecyl sulfate.

The third aspect of the invention provides an application of the diatomite-neonicotinoid pesticide with the specific structure, wherein the diatomite-neonicotinoid pesticide with the specific structure is applied to control one or more of citrus red spider, scale insects, frankliniella occidentalis, whitefly, leaf miner, prodenia litura, tea leafhopper, tea yellow thrips, tea geometrid, green plant bug and grape aphid.

Has the advantages that: the invention provides a diatomite-neonicotinoid original drug composition with a specific structure, which is prepared by mixing diatomite with silicon dioxide with a specific saw-tooth honeycomb structure and neonicotinoid original drug acetamiprid, clothianidin or nitenpyram, has a higher co-toxicity coefficient, can obviously reduce the pesticide dosage and reduce the environmental pollution; the diatomite with the specific sawtooth-shaped honeycomb structure silicon dioxide is a natural component, is particularly suitable for organic agriculture application, and adsorbs/destroys a waxy layer on the body surface of an insect; the invention reduces the surface tension of the system by adding specific dispersant, wetting agent and filler, is beneficial to spreading, adhesion and permeation of the liquid medicine, improves the heat storage stability of the water, improves the suspension rate of the product and better exerts the drug effect.

Drawings

Fig. 1 is an optical microscope photograph of diatomaceous earth having specific saw-toothed honeycomb-structured silica in example 1 of the present invention.

FIG. 2 is an electron microscope image of diatomaceous earth having silica with a specific saw-toothed honeycomb structure in example 1 of the present invention.

Detailed Description

The technical features of the technical solutions provided by the present invention will be further clearly and completely described below with reference to the specific embodiments, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

It will be understood by those skilled in the art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

The words "preferred", "preferably", "more preferred", and the like, in the present invention, refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.

In order to solve the technical problems, the invention provides a diatomite-neonicotinoid original drug composition with a specific structure, wherein the mass ratio of the diatomite with the specific structure to the neonicotinoid original drug is (1: 60) - (400: 1); the diatomite with the specific structure is diatomite with silicon dioxide with a specific sawtooth-shaped honeycomb structure.

In the present invention, the term "composition" means that the components of the composition are packaged in combination or separately and used together when used. In the invention, the 'diatomite-neonicotinoid with a specific structure' means that the diatomite-neonicotinoid with the specific structure can be mixed and packaged together and used together when in use; also comprises a specific structure of diatomite-neonicotinoid separately packaged, and when in use, the diatomite-neonicotinoid is mixed together according to a proportion.

In some embodiments, the mass ratio of the diatomaceous earth with a specific structure to the neonicotinoid raw pesticide is (1: 1) - (400: 1).

In some embodiments, the diatomaceous earth having a particular saw-tooth honeycomb structure silica is available under the trade designation Celite610, purchased from the gareli stone, france. As shown in FIGS. 1 and 2, under an optical microscope and an electron microscope, Celite610 can be seen to have a clear saw-toothed honeycomb structure.

On one hand, the diatomite with the specific structure has a larger specific surface area due to the saw-tooth-shaped honeycomb structure, and is favorable for being better adsorbed on a wax layer on the body surface of the insect, so that the insect body is quickly dehydrated. On the other hand, due to the zigzag honeycomb structure, the composition is beneficial to causing damage to a wax layer on the surface of the insect body, tearing the surface of the insect body, rapidly permeating into the insect body and causing fatal damage to the insect, thereby improving the lethality of the composition.

In some embodiments, the neonicotinoid prodrug is selected from any one of imidacloprid, acetamiprid, thiacloprid, thiamethoxam, clothianidin, dinotefuran, nitenpyram, imidaclothiz, mepiquat chloride and cycloxaprid.

In some preferred embodiments, the neonicotinoid prodrug is selected from any one of acetamiprid, clothianidin and nitenpyram.

Acetamiprid

In the invention, the Acetamiprid is named as Acetaaminoprid in English, and the Acetamiprid is named as N- (N-cyano-ethylimino) -N-methyl-2-chloropyridine-5-methylamine in chemical name. Its pure product is colorless crystal, its melting point is 98.9 deg.C, density is 1.330(20 deg.C), and its vapor pressure is 1.33X 10^-6Pa, higher polarity. Solubility in water at 25 ℃ of 4200mg L^-1And can be dissolved in acetone, methanol, ethanol, dichloromethane, chloroform, acetonitrile, tetrahydrofuran, etc. The acetamiprid has an effective absorption light wave of 215-248 nm, is stable in water with pH 7, and is gradually hydrolyzed at 45 ℃ when the pH is 9, and is stable in sunlight.

The molecular structural formula of the acetamiprid is as follows:

the action mechanism of the acetamiprid mainly acts on a nicotine acetylcholine receptor of a postsynaptic membrane of an insect nervous system in the modes of contact poisoning, stomach toxicity, penetration, systemic absorption and the like to generate a nerve blocking effect, so that the insect is finally paralyzed until death, and the acetamiprid has obvious effects on various pests such as homoptera, lepidoptera, coleoptera and total thysanoptera. The acetamiprid has the characteristics of high efficiency, low toxicity, environmental friendliness and the like, has smaller lethality to human beings, livestock and natural enemies of pests due to the larger difference of the action mechanism and the traditional pesticide, is widely suitable for pest control of various crops such as fruit trees, vegetables and the like, and has reports of using the acetamiprid for controlling underground pests.

Clothianidin

In the invention, the clothianidin is a chemical substance with the molecular formula of C₆H₈ClN₅O₂And S. Chemical name: (E) -1- (2-chloro-1, 3-thiazol-5-ylmethyl) -3-methyl-2-2-nitroguanidine. Clothianidin is an insecticide in neonicotinoids, is a novel efficient, safe and high-selectivity insecticide, has similar action to nicotinic acetylcholine receptors, and has contact poisoning, stomach toxicity and systemic activity. The pesticide is mainly used for preventing and controlling hemiptera, coleopteran, dipteran and certain lepidopteran pests such as aphids, leafhoppers, thrips, plant hoppers and the like on rice, vegetables, fruit trees and other crops, has the advantages of high efficiency, broad spectrum, low dosage, low toxicity, long efficacy duration, no phytotoxicity to the crops, safe use, no cross resistance with conventional pesticides and the like, has excellent systemic and osmotic effects, and is another variety for replacing high-toxicity organophosphorus pesticides. The pesticide has novel and special structure and more excellent performance compared with the traditional nicotine pesticide, and is likely to become a worldwide large-scale pesticide variety.

The molecular structural formula of the acetamiprid is as follows:

nitenpyram

In the invention, the nitenpyram, also called imidacloprid, is a second generation neonicotinoid insecticide behind imidacloprid; acetamiprid (Acetamiprid), also known as Acetamiprid, was developed by japan Caoda corporation and is an excellent chloronicotinyl insecticide following imidacloprid and nitenpyram. The English common name is Nitenpyram, and the chemical name is (E) -N- (6-chloro-3-picolyl) -N-ethyl-N' -methyl-2-nitroethylenediamine. The pure product is light yellow crystal, the melting point is 83-84 ℃, the density is 1.40(26 ℃), and the vapor pressure: 1.1X 10^-9Pa (25 ℃ C.). Solubility in each solvent (20 ℃): water (pH 7)840g L^-1Chloroform 700g L^-1Acetone 290g L^-1Xylene 4.5g L^-1。

The molecular structural formula of the nitenpyram is as follows:

the nitenpyram is essentially an agonist of a nicotinic acetylcholine receptor, can effectively inhibit the activity of acetylcholinesterase after acting on the nerve of an insect, has a nerve blocking effect on a neural axis synaptic receptor of the insect, and has remarkable effects of preventing and treating various sucking-mouth pests such as aphids, whiteflies and the like. Nitenpyram also has good insecticidal activity to other pests which have drug resistance to traditional pesticides, and also has the characteristics of low toxicity, systemic property, short half-life period, no cross resistance with traditional pesticides and the like, so that nitenpyram is widely applied to crops such as vegetables, fruits, tea leaves, rice and the like and gardening.

In some embodiments, the neonicotinoid original drug is acetamiprid, and the mass ratio of the diatomite with the specific structure to the acetamiprid is (1: 40) - (200: 1); the neonicotinoid original drug is clothianidin, and the mass ratio of the diatomite with the specific structure to the clothianidin is (1: 60) - (400: 1); the neonicotinoid original drug is nitenpyram, and the mass ratio of the diatomite with the specific structure to the nitenpyram is (1: 40) - (100: 1).

In some embodiments, the neonicotinoid original drug is acetamiprid, and the mass ratio of the diatomite with the specific structure to the acetamiprid is (1: 40) - (200: 1).

In some preferred embodiments, the mass ratio of the diatomite with the specific structure to the acetamiprid is (1: 20) - (200: 1).

In some more preferred embodiments, the mass ratio of the diatomite with the specific structure to the acetamiprid is (1: 1) - (200: 1).

In some embodiments, the neonicotinoid is clothianidin, and the mass ratio of the diatomite with the specific structure to the clothianidin is (1: 60) - (400: 1).

In some preferred embodiments, the mass ratio of the diatomite with the specific structure to the clothianidin is (1: 30) - (400: 1).

In some more preferred embodiments, the mass ratio of the diatomaceous earth with a specific structure to clothianidin is (1: 1) - (400: 1).

In some more preferred embodiments, the mass ratio of the diatomaceous earth with a specific structure to clothianidin is (1: 200) - (400: 1).

In some embodiments, the neonicotinoid original drug is nitenpyram, and the mass ratio of the diatomite with the specific structure to the nitenpyram is (1: 40) - (100: 1).

In some preferred embodiments, the mass ratio of the diatomite with the specific structure to the nitenpyram is (50: 1) - (100: 1).

The inventor unexpectedly discovers that when the diatomite with the specific saw-tooth honeycomb-structure silicon dioxide is compounded with a neonicotinoid original drug which is any one of acetamiprid, nitenpyram and clothianidin, the neonicotinoid original drug has a high co-toxicity coefficient particularly for citrus red spiders, citrus scale insects, frankliniella occidentalis, whiteflies, liriomyza sativae, prodenia litura, tea leafhopper, tea leaf tea yellow thrips, tea leaf tea geometrid, green plant bugs and grape aphids, and the compound of the diatomite with the specific saw-tooth honeycomb-structure silicon dioxide and the neonicotinoid original drug has a remarkable synergistic effect. The inventor thinks that the reason is probably because the diatomite with the specific sawtooth-shaped honeycomb-structure silicon dioxide not only adsorbs and destroys the wax coat on the body surface of the insect, but also can promote the permeation speed of the neonicotinoid raw pesticide into the insect body, so that the neonicotinoid raw pesticide enters the insect body, the nicotinic acetylcholine receptor of the postsynaptic membrane of the insect nervous system is promoted, the nerve blocking effect is generated, and the diatomite with the specific sawtooth-shaped honeycomb-structure silicon dioxide is more beneficial to the paralysis and death of the insect caused by the neonicotinoid raw pesticide in the modes of contact killing, stomach toxicity, permeation, systemic absorption and the like, so that the quick-acting performance of the composition is improved. Under the synergistic action of diatomite with specific saw-tooth honeycomb structure silicon dioxide and any one of acetamiprid, nitenpyram and clothianidin, the control efficiency of the composition on pests is obviously improved, and the composition has high quick-acting property and lethality and obvious synergistic action.

In some embodiments, the adjuvant is present in an amount of 5-20 wt% of the structured diatomaceous earth-neonicotinoid prodrug composition.

In some preferred embodiments, the adjuvant is present in an amount of 10-15 wt% of the specific structure diatomaceous earth-neonicotinoid prodrug composition.

In a most preferred embodiment, the adjuvant is present in an amount of 13 wt% of the structured diatomaceous earth-neonicotinoid prodrug composition.

In some embodiments, the adjuvant includes at least any one of a dispersant, a wetting agent, and a filler.

In some preferred embodiments, the adjuvants include dispersants, wetting agents, and fillers.

In some preferred embodiments, the auxiliary agent comprises 12-30 parts by weight of dispersing agent, 5-20 parts by weight of wetting agent and 50-80 parts by weight of filler.

In some more preferred embodiments, the auxiliary agent comprises 24 parts of dispersing agent, 12 parts of wetting agent and 65 parts of filler by weight.

Dispersing agent

In some embodiments, the dispersant is selected from one or more of naphthalene sulfonate formaldehyde condensate, alkylphenol polyoxyethylene ether formaldehyde condensate sulfate, sodium lignosulfonate, polycarboxylate, EO/PO block polyether, alkylphenol polyoxyethylene ether phosphate.

The naphthalene sulfonate formaldehyde condensates include, but are not limited to: any one of sodium methylenedinaphthalenesulfonate, a formaldehyde condensate of sodium methylnaphthalenesulfonate, and a formaldehyde condensate of benzylnaphthalenesulfonic acid.

The alkyl phenol polyoxyethylene ether formaldehyde condensate sulfates include, but are not limited to: sodium nonylphenol polyoxyethylene ether formaldehyde sulfate.

The sodium lignosulfonate includes, but is not limited to: HMK-D1009.

The polycarboxylates include, but are not limited to: HMK-D1008, HMK-D1003 and GY-D180.

The EO/PO block polyethers include, but are not limited to: propylene glycol polyoxyethylene polyoxypropylene ether.

The alkylphenol ethoxylate phosphates include, but are not limited to: any one of APE-4P, APE-6P, APE-8P, APE-10P.

In some preferred embodiments, the dispersant is an anionic polymeric surfactant.

In some preferred embodiments, the anionic polymeric surfactant is sodium lignosulfonate and/or polycarboxylate.

In some preferred embodiments, the anionic polymeric surfactant is a polycarboxylate.

In some preferred embodiments, the polycarboxylate is selected from one or more of HMK-D1008, HMK-D1003, GY-D180.

In a more preferred embodiment, the polycarboxylate is GY-D180, available from Guangyaomai agricultural chemical, Inc. of Beijing.

Wetting agent

In some embodiments, the wetting agent is selected from one or more of a sulfate, a sulfonate, and a polyoxyethylene ether.

The sulfates include, but are not limited to: one or more of alkyl sulfate and polyoxyethylene ether sulfate.

The alkyl sulfates may be exemplified by: sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium hexadecyl sulfate.

The polyoxyethylene ether sulfates may be exemplified by: sodium lauryl polyoxyethylene ether sulfate.

The sulfonate salts include, but are not limited to: one or more of alkyl sulfonate, alkyl benzene sulfonate, naphthalene sulfonate, alkenyl sulfonate, alkyl amido taurate.

The alkylsulfonic acid salts include, for example: sodium dodecyl sulfonate, sodium tetradecyl sulfonate, and sodium hexadecyl sulfonate.

As the alkylbenzene sulfonates, there can be exemplified: sodium dodecyl benzene sulfonate, sodium tetradecyl benzene sulfonate and sodium hexadecyl benzene sulfonate.

The naphthalene sulfonates may be exemplified by: sodium dibutylnaphthalenesulfonate, sodium diisopropylnaphthalenesulfonate, sodium 2-naphthalenesulfonate, sodium 1-naphthalenesulfonate, and sodium 2-hydroxy-7-naphthalenesulfonate.

As the alkenyl sulfonate, α -sodium alkenyl sulfonate and diisooctyl succinate sodium sulfonate can be exemplified.

As the alkylamido taurates, there can be exemplified: sodium methyl myristoyl taurate, sodium cocoyl-N-methyltaurate.

In some preferred embodiments, the wetting agent is a sulfonate.

In some preferred embodiments, the sulfonate is a combination of naphthalene sulfonate and sodium lauryl sulfate.

In some preferred embodiments, the naphthalene sulfonate is selected from one or more of HMK-DF100, HMK-D1009, GY-D10, HMK-D1002.

In a more preferred embodiment, the naphthalene sulfonate is GY-D10, available from Guangyaomai agricultural chemical, Inc. of Beijing.

In some preferred embodiments, the mass ratio of the sodium dodecyl sulfate to the GY-D10 is 1: (1.3-1.8).

In some preferred embodiments, the mass ratio of the sodium dodecyl sulfate to the GY-D10 is 1: 1.5.

the invention adopts the dispersant, has good dispersion effect on any one of the raw pesticide acetamiprid, nitenpyram and clothianidin, and is suitable for both wettable powder and water dispersible grain size. The inventor unexpectedly discovers in the research process that when the dispersant is polycarboxylate GY-D800, the flowability and the suspensibility of the pesticide composition can be remarkably improved. The reason the inventor believes is probably that the comb-shaped structure of the polycarboxylate GY-D800 provides electrostatic repulsion and steric hindrance effect after adsorbing the dispersed particles, and has good dispersing and suspending effect on the original medicine. Surprisingly, when the polycarboxylate GY-D800 and the wetting agent act together, and the wetting agent is naphthalene sulfonate GY-D10 and sodium dodecyl sulfate, the wetting spreadability and pest control effect of the pesticide are best. The reason that the inventor thinks is probably that the naphthalene ring in the naphthalene sulfonate GY-D10 is very easy to be adsorbed on the surface of pesticide particles due to the conjugation effect of the naphthalene ring, so that the hydrophilic group of the naphthalene sulfonate GY-D10 is easy to form a hydrogen bond with water to generate association, and the association with the polycarboxylate GY-D800 and the sodium dodecyl sulfate forms a stable water film on the surface of the pesticide particles, so that the wetting and spreading performance of the pesticide is improved, and target pests are fully wetted; meanwhile, the ionized ion structure of the polycarboxylate GY-D800 can promote penetration of the technical material to insects and improve the pest control effect. However, in the process of research, the inventor finds that the sodium dodecyl sulfate has strong foaming, and the dispersion stability and the heat storage stability of the pesticide are influenced. The inventor unexpectedly finds that when the wetting agent is sodium dodecyl sulfate, the mass ratio of GY-D10 is 1: (1.3-1.8) and the mass ratio of the polycarboxylate GY-D800 wetting agent is (1.5-2.4): the dispersion stability and heat storage stability of the pesticide became the best at 1. The inventor thinks that the reason is probably that the ionic structure ionized by the polycarboxylate GY-D800 is beneficial to the adsorption between the ionic structure ionized by the polycarboxylate GY-D800 and the diatomite, the thickness of the foam layer can be reduced by the zigzag honeycomb structure of the diatomite, the chemical structure of the naphthalene sulfonate GY-D10 can be adjusted, a liquid film formed by foam by the sodium dodecyl sulfonate can be gradually thinned, the dispersibility of the diatomite of the technical product and the silicon dioxide with the specific zigzag honeycomb structure is improved under the combined action of the polycarboxylate GY-D800, the sodium dodecyl sulfonate and the naphthalene sulfonate GY-D10, the pesticide is ensured to have proper surface tension and contact angle, target pests are fully wetted, and the dispersion stability and the heat storage stability of the pesticide are improved.

Filler material

In some embodiments, the filler is selected from one or more of kaolin, talc, precipitated calcium carbonate, bentonite, diatomaceous earth, attapulgite, white carbon, straw ash.

In some preferred embodiments, the filler is attapulgite and/or straw ash.

In some preferred embodiments, the attapulgite is dopamine modified attapulgite.

In one embodiment, the method for preparing the dopamine-modified attapulgite comprises the following steps: adding 10g of attapulgite into 500ml of an Tris-HCl (pH 8.5, 10mmol/L) buffer solution, magnetically stirring for 30min, adding 1g of dopamine hydrochloride, and continuously stirring for 12h in the dark; after the reaction is finished, collecting black precipitates through a series of centrifugation-washing-centrifugation processes, and then drying in vacuum to obtain the dopamine-modified attapulgite;

the attapulgite with the mesh number of 150-.

In some preferred embodiments, the dopamine-modified attapulgite and straw ash are mixed in a mass ratio of 1: (1.2-1.6).

In some more preferred embodiments, the dopamine-modified attapulgite and straw ash are present in a mass ratio of 1: 1.4.

in some more preferred embodiments, the straw ash is straw ash containing 45 wt% silica, having an average particle size of 10 μm, available from Kedy electric energy Co., Wuhan, China.

The attapulgite adopted by the invention is a hydrous magnesium-rich silicate clay mineral with a layer chain structure, has good thickening effect, cation exchangeability, water absorption, adsorption decoloration property, large specific surface area and the like, is often used as a filler of pesticides, but the natural attapulgite is agglomerated into a rod-shaped structure due to the existence of Van der Waals force, so that the dispersing performance of the attapulgite is limited. The inventor unexpectedly discovers in the research process that the dispersibility and the loading capacity of the pesticide can be improved when the attapulgite is modified by dopamine. The inventor believes that the reason is that the affinity is obviously improved because the surface of the dopamine modified attapulgite is rough and has an obvious interface, and the hydroxyl and the amino on the surface of the dopamine modified attapulgite are favorable for interacting with the neonicotinoid raw pesticide through hydrogen bonds, so that the loading capacity of the pesticide is improved; meanwhile, a structure with positive charges is formed on the surface of the dopamine-modified attapulgite, and under the combined action of the polycarboxylate GY-D800, the sodium dodecyl sulfate and the naphthalene sulfonate GY-D10, the van der Waals force of the attapulgite is destroyed, the dopamine-modified attapulgite is in a fibrous structure, and the dispersibility of the attapulgite is improved. However, dopamine modified attapulgite has strong hydrophilicity, and the pesticide loaded on the attapulgite is not favorable for long-term stability. In the further research process, the inventor unexpectedly discovers that when dopamine modified attapulgite and straw ash are compounded to be used as a filler, the straw ash is straw ash containing 45 wt% of silicon dioxide, and the average particle size of the straw ash is controlled to be 10 micrometers, the adhesive force of pesticides can be improved, and the loss rate of the pesticides can be reduced. The reason considered by the inventor is probably that the straw ash has a micro-nano pore structure, a large surface area, strong surface activity and negative surface charge, and the positive charge on the surface of the dopamine-modified attapulgite interacts with the negative charge on the surface of the straw ash, so that particles of the dopamine-modified attapulgite enter the microporous structure of the straw ash, and the dispersion and suspension capacity of the attapulgite can be improved; meanwhile, the straw ash containing 10% of carbon and 45% of silicon dioxide adsorbs neonicotinoid raw pesticide through hydrogen bonds, electrostatic adsorption and other modes, so that the adhesive force of the raw pesticide is improved, the original structure of the attapulgite is collapsed to form a film-like structure, the migration resistance of pesticide molecules is reduced, the pesticide release amount is improved, and the contact chance of pesticide and harmful organisms is increased.

In some embodiments, the adjuvant may further include one or more of a disintegrant, a binder, a synergist, an antioxidant, an adsorbent.

Such disintegrants include, but are not limited to: sodium sulfate, ammonium sulfate, urea, polyvinylpyrrolidone, sodium chloride, potassium chloride and microcrystalline cellulose.

Such binders include, but are not limited to: sodium carboxymethylcellulose, carboxymethyl starch, hydroxypropyl methylcellulose, starch, glucose, sucrose, polyvinyl alcohol, polyethylene glycol, and polyvinylpyrrolidone.

Such synergists include, but are not limited to: anhydrous fast T-1, super penetrants TT-1, 319D, GreenwetBP, organic silicon QS-302-NP50, organic silicon GC, 100LQ, Agrospred101, Agrospred prime, and boleton S240.

The antioxidants include, but are not limited to: 2, 6-di-tert-butyl-p-cresol and butyl hydroxy anisole.

The adsorbents include, but are not limited to: white carbon black.

In some embodiments, the formulation of the structurally specific diatomaceous earth-neonicotinoid pesticide is selected from any one of emulsifiable concentrate, suspension concentrate, wettable powder, water dispersible granule, poison bait, mother liquor and mother powder.

In some preferred embodiments, the formulation of the diatomite-neonicotinoid pesticide composition with a specific structure is wettable powder and/or water dispersible granules.

Wettable powder

Wettable powder (wetteapowder, abbreviated as WP) is a pesticide preparation which is prepared by mixing raw pesticide, auxiliary agent and filler to a certain fineness and is diluted with water for use. The wettable powder has the following advantages: (1) the raw medicine which is insoluble in water can be processed into WP, the content of the WP can be higher than that of the suspending agent, and the WP can be mixed with water for spraying. (2) The original medicine which is unstable to water can be prepared into wettable powder to improve the stability. (3) Does not contain organic solvent, has good environmental compatibility and is convenient for storage and transportation. (4) The physical stability is higher than the suspension rate, and the conditions of caking, precipitation and the like can not occur. (5) The production cost is low, and the production technology and the production equipment are mature. Meanwhile, wettable powders also have some disadvantages: (1) there is some dust pollution in the process. (2) The particle size is relatively large and the effect is relatively reduced. (3) The formula auxiliary dosage is relatively less, and the performances of wetting, spreading and the like of crops and targets after dilution are relatively poor. In summary, wettable powders as one of the four basic formulations of pesticide formulations have problems in practical use, and these problems can be overcome by adding appropriate functional additives.

In one embodiment, the formulation of the structurally specific diatomaceous earth-neonicotinoid pesticide is a wettable powder.

In one embodiment, the preparation method of the diatomite-neonicotinoid wettable powder with the specific structure comprises the following steps: the auxiliary agent and the neonicotinoid original drug are subjected to high-speed universal grinding and are uniformly mixed; and adding diatomite with the specific sawtooth-shaped honeycomb structure silicon dioxide, shaking by using a self-sealing bag, transferring into a flask, stirring and mixing for 30min by using a stirrer, and fully and uniformly mixing to obtain the diatomite-neonicotinoid wettable powder with the specific structure.

In order to avoid the destruction of the diatomaceous earth structure of the specific saw-toothed honeycomb-structure silica, mechanical pulverization is not used, but stirring and mixing are adopted.

Water dispersible granule

Water Dispersible Granules (WDG) are composed of raw pesticide, wetting agent, dispersing agent, isolating agent, stabilizing agent, adhesive, filler or carrier. When the water dispersible granule is used, the water dispersible granule can be quickly disintegrated and dispersed to form a highly suspended solid-liquid dispersion system. The preparation has the advantages that: (1) no dust pollution is caused during use; (2) the content of the active ingredients is generally between 50 percent and 90 percent, and more than 70 percent, and the packaging, storage and transportation are convenient and safe; (3) no water is contained, so the storage stability of the preparation is high; (4) the dispersibility in water is good, and the suspension rate is high; (5) good fluidity, convenient metering and easy processing of the packing materials.

In one embodiment, the formulation of the diatomite-neonicotinoid pesticide with a specific structure is a water dispersible granule.

In one embodiment, the preparation method of the diatomite-neonicotinoid water dispersible granule with the specific structure comprises the following steps: the auxiliary agent and the neonicotinoid original drug are subjected to high-speed universal grinding and are uniformly mixed; and adding diatomite with the specific saw-tooth honeycomb structure silicon dioxide, shaking by using a self-sealing bag, transferring into a flask, stirring and mixing for 30min by using a stirrer, fully and uniformly mixing, and then granulating to obtain the diatomite-neonicotinoid water dispersible granule with the specific structure.

In the present invention, the diatomaceous earth-neonicotinoid agricultural chemicals having a specific structure are formulated into a wettable powder and a water dispersible powder, and the two formulations are diluted with water or the like and applied to plants, water surfaces or soil. In addition, the preparation can also be used in combination with other bactericides, herbicides, insecticides, fertilizers, soil conditioners, and the like.

The present invention is described in detail below with reference to examples, which are provided for the purpose of further illustration only and are not to be construed as limiting the scope of the present invention, and the insubstantial modifications and adaptations thereof by those skilled in the art based on the teachings of the present invention will still fall within the scope of the present invention.

Examples

Example 1

Example 1 provides a diatomaceous earth-neonicotinoid technical composition of a specific structure, comprising acetamiprid, diatomaceous earth with silica of a specific saw-tooth honeycomb structure; the mass ratio of the diatomite with the specific structure to the acetamiprid is 200: 1; the diatomaceous earth having a particular saw-tooth honeycomb structure silica is available under the trade name Celite610, purchased from the gareli stone company, france.

Example 2

Example 2 the same as example 1, except that the mass ratio of Celite610 to acetamiprid is 100: 1.

example 3

Example 3 the same as example 1, except that the mass ratio of Celite610 to acetamiprid is 1: 1.

example 4

Example 4 the same as example 1, except that the mass ratio of Celite610 to acetamiprid is 1: 20.

example 5

Example 5 the same as example 1, except that the mass ratio of Celite610 to acetamiprid is 1: 40.

example 6

Example 6 the same as example 1, except that there is no Celite 610.

Example 7

Example 7 is the same as example 1 except that no acetamiprid was present.

Example 8

Example 8 the same as example 1, except that acetamiprid was replaced by clothianidin, and the mass ratio of Celite610 to clothianidin was 400: 1.

example 9

Example 9 is the same as example 8 except that the mass ratio of Celite610 to clothianidin is 200: 1.

example 10

Example 10 is the same as example 8 except that the mass ratio of Celite610 to clothianidin is 1: 1.

example 11

Example 11 is the same as example 8 except that the mass ratio of Celite610 to clothianidin is 1: 30.

example 12

Example 12 is the same as example 8 except that the mass ratio of Celite610 to clothianidin is 1: 60.

example 13

Example 13 is the same as example 8 except that Celite610 is not present.

Example 14

Example 14 the same as example 1, except that acetamiprid was replaced by nitenpyram, and the mass ratio of Celite610 to nitenpyram was 100: 1.

example 15

Example 15 is the same as example 14, except that the mass ratio of Celite610 to nitenpyram is 50: 1.

example 16

Example 16 is the same as example 14, except that the mass ratio of Celite610 to nitenpyram is 1: 1.

example 17

Example 17 is the same as example 14, except that the mass ratio of Celite610 to nitenpyram is 1: 20.

example 18

Example 18 is the same as example 14, except that the mass ratio of Celite610 to nitenpyram is 1: 40.

example 19

Example 19 is the same as example 14 except that Celite610 is not present.

Example 20

Embodiment 1 provides a diatomite-neonicotinoid water dispersible granule with a specific structure, which comprises a diatomite-neonicotinoid original drug composition with the specific structure and an auxiliary agent; the content of the auxiliary agent is 13 wt% of the diatomite-neonicotinoid original drug composition with the specific structure;

the diatomite-neonicotinoid original drug composition with the specific structure comprises clothianidin and diatomite with silicon dioxide with a specific sawtooth-shaped honeycomb structure; the mass ratio of the diatomite with the specific structure to the clothianidin is 400: 1; the diatomaceous earth having a particular saw-tooth honeycomb structure silica is available under the trade designation Celite610, purchased from the gareli stone company, france;

the auxiliary agent comprises 24 parts of dispersing agent, 12 parts of wetting agent and 65 parts of filler in parts by weight; the dispersant is GY-D180; the wetting agent is sodium dodecyl sulfate, GY-D10 with the mass ratio of 1: 1.5 of a compound; the filler is dopamine-modified attapulgite, and the mass ratio of straw ash is 1: 1.4; the straw ash is straw ash containing 45 wt% of silicon dioxide, and the average particle size is 10 mu m; in one embodiment, the method for preparing the dopamine-modified attapulgite comprises the following steps: adding 10g of attapulgite into 500mL of Tris-HCl (pH 8.5, 10mmol/L) buffer solution, magnetically stirring for 30min, adding 1g of dopamine hydrochloride, and continuously stirring for 12h in the dark; after the reaction is finished, collecting black precipitates through a series of centrifugation-washing-centrifugation processes, and then drying in vacuum to obtain the dopamine-modified attapulgite; the mesh number of the attapulgite is 150-200 meshes;

the preparation method of the diatomite-neonicotinoid water dispersible granule with the specific structure comprises the following steps: the dispersing agent, the wetting agent, the filler and the acetamiprid raw pesticide are subjected to high-speed universal grinding and are uniformly mixed; and adding Celite610, shaking by using a self-sealing bag, transferring into a flask, stirring and mixing for 30min by using a stirrer, fully and uniformly mixing, and then granulating to obtain the diatomite-neonicotinoid water dispersible granule with the specific structure.

Example 21

Example 21 differs from example 20 in that the filler is free of dopamine modified attapulgite.

Example 22

Example 22 the same as example 20, except that the attapulgite was not dopamine modified attapulgite.

Example 23

Example 23 is the same as example 20 except that the filler is free of straw ash containing 45% silica.

Example 24

Example 24 is the same as example 20 except that GY-D800, a polycarboxylate salt, is not present.

Example 25

Example 25 example 20 is the same as example 20 except that polycarboxylate GY-D800 is replaced with alkylphenol ethoxylate phosphate ester APE-4P, which is purchased from Wuhana white Chemicals, Inc.

Example 26

Example 26 is the same as example 20 except that there is no naphthalene sulfonate GY-D10.

Example 27

Example 27 the same as example 20 except that the naphthalene sulfonate GY-D10 was replaced with sodium lauryl sulfate.

Performance testing

Firstly, screening by a co-toxicity coefficient method (CTC): taking the diatomite-neonicotinoid original drug composition with the specific structure described in the examples 1-19 to carry out combined toxicity determination on pests; the co-toxicity coefficient (CTC) of each mixed combination is determined by a Sun & Johnson (1960) co-toxicity coefficient method (CTC) according to a raw test standard method NY/T1154.7-2006. Generally, a co-toxicity coefficient greater than 120 indicates a synergistic effect, less than 80 indicates an antagonistic effect, and between 80 and 120 indicates an additive effect. The co-toxicity coefficient is calculated as follows

The Theoretical Toxicity Index (TTI) of the mixture is the toxicity index of the agent A x the percent (%) of the agent A + the toxicity index of the agent B x the percent (%) of the agent B

1. And (3) measuring the combined virulence of citrus red spiders: taking the diatomite-neonicotinoid original drug composition with the specific structure disclosed in the embodiment 1-15, and adopting a blade spraying method according to a method in NY/T1154.13-2008 standard; cleaning and wiping flat citrus leaves with consistent sizes, sticking the leaves onto wet sponge with the leaf surfaces facing upwards, enclosing the peripheries of the leaves by wet small cotton slivers to prevent tested mites from escaping, putting the wet sponge into a culture dish with the diameter of 9cm, adding water into the culture dish, and slightly lowering the water level to be lower than the height of the sponge; inoculating indoor bred nymphs to leaves, wherein each leaf is not less than 30 heads; placing the culture dish on a bottom plate of a Potter spraying tower for spraying, wherein the spraying amount is 1mL, taking out the culture dish after the liquid medicine is settled for 1min, and transferring the culture dish to a breeding condition for breeding; each treatment was repeated 4 times and a blank control was run. After 48h, the death condition of the test insects is checked under a dissecting mirror, and the death condition is recorded; the judgment standard of the death of the test insects is as follows: death was counted as no response when the test insects were gently touched by tweezers.

TABLE 1 toxicity test results of blending Celite610 and acetamiprid to citrus red spider

TABLE 2 toxicity test results of Celite610 and clothianidin mixture against citrus red spider

2. And (3) determining the combined virulence of the citrus coccid: taking the diatomite-neonicotinoid original drug composition with the specific structure disclosed in the embodiment 1-19, and adopting an insect soaking method according to a method in NY/T1154.6-2006 standard; dipping the trimmed citrus leaves with citrus arrowhead scales in a test solution for 10 seconds, taking out the citrus leaves, absorbing redundant liquid medicine around the leaves and the insects by using filter paper, putting the citrus leaves and the insects into a culture dish (the diameter is 90mm) filled with moisturizing filter paper, wrapping petioles by using wet cotton balls for moisturizing, repeating the steps for 4 times per concentration, covering the dish cover after the treatment is finished, and putting the dish cover into an observation room for culture; after 72d, checking the death condition of the test insects by using a dissecting mirror, and recording, wherein the death judgment standard of the test insects is fresh and alive, and the test insects are regarded as live insects in yellow or light yellow; the dead insects are considered to be dead insects if the body of the insects is shriveled and the color is dark.

Table 3 toxicity test results of Celite610 and acetamiprid mixed to Chimonarda citricola

Table 4 toxicity test results of Celite610 and clothianidin mixture against Chimonanthi citrea

TABLE 5 toxicity test results of Celite610 and nitenpyram mixture against Chimonanthia citrea

3. Combined virulence determination of frankliniella occidentalis: taking the diatomite-neonicotinoid original drug composition with the specific structure disclosed in the examples 1-19, and adopting a leaf soaking disc method according to a standard method NY/T1154.14-2008 for biological test; beating the leaves into leaf disks by using a puncher with the diameter of 18mm, soaking the leaf disks in a test reagent solution for 10 seconds, putting the leaf disks into a culture dish (with the diameter of 90mm) padded with moisturizing filter paper, putting 5 leaf disks into each dish, naturally drying, then selecting the Frankliniella occidentalis adults into the culture dish, sealing the mouth of each dish by using a preservative film, pricking a needle head on the film to ventilate, repeating the treatment for 4 times, and placing the treated dishes in an observation room for culture after the treatment is finished; and (4) after 72h, checking and recording the death condition of the test insects, wherein the death judgment standard of the test insects is that the test insects are dead as the result of no response when the pointed writing brush is lightly contacted with the test insects.

TABLE 6 toxicity test results of mixing Celite610 and acetamiprid for Frankliniella occidentalis

TABLE 7 toxicity test results of Celite610 and clothianidin mixture on Frankliniella occidentalis

TABLE 8 toxicity test results of Celite610 and nitenpyram mixture on Frankliniella occidentalis

4. Combined virulence determination of trialeurodes vaporariorum: taking the diatomite-neonicotinoid original drug composition with the specific structure disclosed in the embodiment 1-19, and adopting a leaf soaking method according to a method in NY/T1154.14-2008 standard; heating agar (1%) solution to dissolve, sucking into a beaker with the volume of 20mL to 200mL, and condensing at normal temperature for later use; soaking the leaves in a test solution for 10 seconds, taking out, naturally drying, sticking the leaves on the surface of the solidified agar solution, wrapping petioles with wet cotton balls, putting 3-4 leaves in each beaker, inoculating adult trialeurodes vaporariorum, covering 15 heads of each beaker with a preservative film, tying some small holes on the film with needles for ventilation, repeating the treatment for 4 times, and placing the beaker in an observation room for cultivation after the treatment is finished; and (4) after 72h, detecting the death condition of the test insects, and recording, wherein the death judgment standard of the test insects is that no response is calculated when the tweezers lightly contact the test insects.

TABLE 9 toxicity test results of blending Celite610 and acetamiprid to Bemisia alba

TABLE 10 toxicity test results of Celite610 and clothianidin mixture against Bemisia alba

TABLE 11 toxicity test results of Celite610 and nitenpyram mixture against Bemisia tabaci

5. Joint virulence determination of liriomyza sativae: taking the diatomite-neonicotinoid original drug composition with the specific structure disclosed in the examples 1-19, and adopting a spraying method according to a method in NY/T1154.13-2008 standard; transplanting potted cowpea pest-free seedlings into pest cages, inoculating a certain amount of mated adult liriomyza nanmeriae, taking out bean seedlings with liriomyza nanmeriae eggs after 6h, placing the bean seedlings in another pest cage, continuously breeding to larvae of 2 years (ensuring that each plate contains no less than 80 larvae of 2 years), then carrying out spraying treatment, naturally air drying, and transferring to an artificial climate box for continuous breeding; repeating every 4 times, and setting blank control; and (3) cutting bean seedlings from roots at the later stage of 3-year-old larvae, moisturizing the tail ends by using soaked cotton balls, putting the bean seedlings into plastic basins in an artificial climate box, pupating the bean seedlings, and counting the quantity of pupae in each dish.

TABLE 12 toxicity test results of Celite610 and acetamiprid mixed Palaenopsis invicta

TABLE 13 toxicity assay results of Celite610 and clothianidin in combination for Liriomyza sativae

TABLE 14 toxicity assay results of Celite610 and nitenpyram mixed for Liriomyza sativae

6. Combined virulence determination of spodoptera litura: taking the diatomite-neonicotinoid original drug composition with the specific structure disclosed in the embodiment 1-15, and adopting a leaf soaking disc method according to a method in NY/T1154.14-2008 standard; beating cabbage leaves into leaf disks by using a puncher with the diameter of 18mm, soaking the leaf disks in a reagent solution for 10 seconds, putting the leaf disks into culture dishes (the diameter is 90mm) filled with moisturizing filter paper, putting 6 leaf disks into each dish, naturally drying, selecting 3-year-old larvae of spodoptera litura hungry for 4 hours into the culture dishes, repeating the steps for 4 times, covering the culture dishes with a dish cover, and culturing in an observation room; and (4) after 72h, detecting the death condition of the test insects, and recording, wherein the death judgment standard of the test insects is that no response is calculated when the tweezers lightly contact the test insects.

TABLE 15 toxicity test results of mixing Celite610 and acetamiprid against spodoptera litura

TABLE 16 toxicity test results of mixing Celite610 and clothianidin to Spodoptera litura

7. Determining the combined toxicity of the tea leafhoppers: taking the diatomite-neonicotinoid original drug composition with the specific structure disclosed in the embodiment 1-19, and adopting an impregnation method according to a method in NY/T1154.11-2008 standard; selecting 3 fresh tea tree sprouts, soaking in a test liquid for 30 seconds, taking out, naturally drying, wrapping the base parts of the sprouts with wet absorbent cotton to preserve moisture, sealing absorbent cotton balls with a preservative film, and placing in a glass test tube (phi 200 x 30mm) with the concentration repeated for 4 times; then, 3-year-old nymphs of tea lesser leafhoppers subjected to ether mild anesthesia treatment are inoculated into a brush pen, 15 +/-2 heads of each tube are used, and the mouth of each tube is sealed by white gauze. After the treatment is finished, placing the film in an observation chamber; and (4) after 72h, detecting the death condition of the test insects, and recording, wherein the death judgment standard of the test insects is that no response is calculated when the tweezers lightly contact the test insects.

TABLE 17 toxicity test results of mixture of Celite610 and acetamiprid on tea leafhopper

TABLE 18 toxicity test results of mixture of Celite610 and clothianidin for tea leafhopper

TABLE 19 toxicity test results of mixture of Celite610 and nitenpyram on tea leafhopper

8. The combined toxicity determination of tea leaf tea thrips tabaci: taking the diatomite-neonicotinoid original drug composition with the specific structure disclosed in the examples 1-19, and adopting a leaf soaking method according to a standard method NY/T1154.14-2008 for biological detection; selecting fresh 3 tea tree sprout shoots with a certain amount of tea thrips (no less than 20) and soaking in the test liquid medicine for 10 seconds, taking out and naturally drying, wrapping the base parts of the sprout shoots with wet absorbent cotton to preserve moisture, sealing the absorbent cotton balls with a preservative film, and placing in a glass test tube (phi 200 x 30mm) for 4 times of repetition at each concentration. The mouth of the test tube is sealed by a preservative film, and the small holes are punched for ventilation; after the treatment is finished, placing the film in an observation chamber; and after 72h, examining the death condition of the test insects under a dissecting mirror, and recording, wherein the death judgment standard of the test insects is that the test insects die because the test insects are not reacted when the pointed writing brush is lightly contacted with the test insects.

TABLE 20 toxicity test results of mixture of Celite610 and acetamiprid on tea leaf thrips

TABLE 21 toxicity test results of mixture of Celite610 and clothianidin for tea leaf thrips

TABLE 22 toxicity test results of mixture of Celite610 and nitenpyram on tea leaf thrips

9. And (3) measuring the combined toxicity of tea geometrid: taking the diatomite-neonicotinoid original drug composition with the specific structure disclosed in the embodiment 1-15, and adopting a leaf soaking method according to a method in NY/T1154.14-2008 standard; selecting 3 fresh tea tree sprouts, soaking in a test liquid medicine for 30 seconds, taking out, naturally drying, wrapping the bases of the sprouts with wet absorbent cotton to preserve moisture, sealing absorbent cotton balls with a preservative film, and placing in a can bottle, wherein the process is repeated for 4 times per concentration; then inoculating 2-year nymphs of tea geometrid which are consistent in size, alive and healthy with a writing brush, sealing 15 +/-2 heads of each pot by using white gauze; after the treatment is finished, placing the film in an observation chamber; and (4) after 72h, detecting the death condition of the test insects, and recording, wherein the death judgment standard of the test insects is that no response is calculated when the tweezers lightly contact the test insects.

TABLE 23 toxicity test results of mixing Celite610 and acetamiprid to tea leaf geometrid

TABLE 24 toxicity test results of mixing of Celite610 and clothianidin to tea leaf geometrid

10. Joint virulence determination of lygus lucorum: taking the diatomite-neonicotinoid original drug composition with the specific structure, which is obtained in the embodiment 1-19, and referring to a method in NY/T1154.11-2008 standard, disinfecting, cleaning and airing fresh kidney beans by adopting an impregnation method, cutting the kidney beans into 2-3 cm segments, soaking the kidney beans in liquid medicines with different concentrations for 30 seconds, airing the kidney beans under natural conditions, and then putting the kidney beans into transparent plastic boxes (6 cm in diameter and 7cm in height) with smooth air, wherein each box comprises two segments; inoculating healthy and consistent 3-year-old nymphs of lygus lucorum, repeating for 4 times about 15 heads per box, and setting blank control; placing the plastic box into a light incubator for culture; and after 48h, the death condition of the test insects in each box is checked, the bodies of the lygus lucorum are lightly touched by the brush tips, and the death judgment standard of the test insects is that no response is calculated when the tweezers lightly touch the test insects.

TABLE 25 toxicity test results of blending Celite610 and acetamiprid to green plant bug

TABLE 26 toxicity assay results of Celite610 and clothianidin blending against lygus lucorum

TABLE 27 toxicity test results of blending of Celite610 and nitenpyram to green plant bug

11. Combined virulence determination of grape aphids: taking the diatomite-neonicotinoid original drug composition with the specific structure disclosed in the embodiment 1-19, and adopting an insect soaking method according to a method in NY/T1154.6-2006 standard; cutting leaves with a certain amount of grape aphids, putting the leaves into liquid medicine to be tested, soaking for 10 seconds, taking out, absorbing the liquid medicine around the insect body by using water absorption filter paper, putting the liquid medicine into a culture dish padded with moisturizing filter paper, moisturizing by using a wet cotton ball, and covering the culture dish by using wet gauze; repeating for 4 times every 30 aphids, and setting the treatment without medicament (including solvent and emulsifier) as blank control; transferring to an observation room for culture after the treatment; and (3) detecting the death condition of the test insects after 48h, and recording, wherein the judgment standard of the death of the test insects is as follows: the aphids were lightly touched with a writing brush, and the body was judged dead.

TABLE 28 toxicity test results of mixture of Celite610 and acetamiprid on grape aphid

TABLE 29 toxicity assay results of mixture of Celite610 and clothianidin against grape aphid

TABLE 30 toxicity assay results of Celite610 and nitenpyram mixture on grape aphid

Secondly, measuring the wetting time: the diatomite-neonicotinoid water dispersible granules with the same mass and the specific structures described in the examples 20-27 are poured into a beaker containing a certain amount of standard hard water from the specified height and the complete wetting time is measured according to the measurement of the GB/T5451-2001 method, and the experimental results are shown in the table 31.

Thirdly, measuring the suspension rate: according to the measurement of the GB/T14825-2006 method, the diatomite-neonicotinoid water dispersible granules with the same structure and the same quality as those in the examples 20-27 are prepared into suspension with the proper and same concentration by using the standard hard water with the same volume; standing in a measuring cylinder for a certain time under the specified conditions, measuring the mass fraction of the effective components in the suspension at one tenth of the bottom, and calculating the suspension rate, wherein the experimental results are shown in Table 31.

Fourthly, heat storage stability: the same mass of the diatomite-neonicotinoid water dispersible granules with the specific structures described in examples 20-27 is taken to prepare a pesticide solution with a proper concentration by using the same volume of standard hard water, and the pesticide solution is placed in an environment at 50 ℃ to observe whether layering occurs or not, and the experimental results are shown in table 31.

TABLE 31 results of Performance testing

The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.

Claims

1. The diatomite-neonicotinoid original drug composition with the specific structure is characterized in that the mass ratio of the diatomite with the specific structure to the neonicotinoid original drug is (1: 60) - (400: 1); the diatomite with the specific structure is diatomite with silicon dioxide with a specific sawtooth-shaped honeycomb structure.

2. The diatomite-neonicotinoid prodrug composition of claim 1, wherein the neonicotinoid prodrug is selected from any one of imidacloprid, acetamiprid, thiacloprid, thiamethoxam, clothianidin, dinotefuran, nitenpyram, imidaclothiz, meperidine and cycloxaprid.

3. The diatomite-neonicotinoid prodrug composition with the specific structure as claimed in claim 1, wherein the neonicotinoid prodrug is acetamiprid, and the mass ratio of the diatomite with the specific structure to the acetamiprid is (1: 40) - (200: 1); the neonicotinoid original drug is clothianidin, and the mass ratio of the diatomite with the specific structure to the clothianidin is (1: 60) - (400: 1); the neonicotinoid original drug is nitenpyram, and the mass ratio of the diatomite with the specific structure to the nitenpyram is (1: 40) - (100: 1).

4. The diatomite-neonicotinoid pesticide with a specific structure is characterized by comprising the diatomite-neonicotinoid pesticide with the specific structure and an auxiliary agent according to claim 1; the content of the auxiliary agent is 5-20 wt% of the diatomite-neonicotinoid original drug composition with the specific structure; the auxiliary agent at least comprises any one of a dispersing agent, a wetting agent and a filler.

5. The diatomite-neonicotinoid pesticide with a specific structure as claimed in claim 4, wherein the formulation of the diatomite-neonicotinoid pesticide with a specific structure is selected from any one of emulsifiable concentrate, suspending agent, wettable powder, water dispersible granules, poison bait, mother liquor and mother powder.

6. The diatomaceous earth-neonicotinoid pesticide of claim 4, wherein the dispersant is an anionic high molecular surfactant.

7. The diatomaceous earth-neonicotinoid pesticide of claim 6, wherein the anionic polymeric surfactant is a polycarboxylate.

8. The structurally specified diatomaceous earth-neonicotinoid pesticide of claim 4, wherein said wetting agent is a sulfonate.

9. The diatomaceous earth-neonicotinoid pesticide of claim 8, wherein the sulfonate is a combination of naphthalene sulfonate and sodium lauryl sulfate.

10. The application of the diatomite-neonicotinoid pesticide with the specific structure as claimed in any one of claims 4 to 9, wherein the diatomite-neonicotinoid pesticide with the specific structure is applied to control one or more of citrus red spider, scale insects, frankliniella occidentalis, whitefly, liriomyza sativae, prodenia litura, tea leafhopper, tea yellow thrips, tea looper, green plant bug and grape aphid.