CN111567567A

CN111567567A - Nano material copolymerized mineral and plant extract insecticidal bactericide and preparation method thereof

Info

Publication number: CN111567567A
Application number: CN202010419523.5A
Authority: CN
Inventors: 苏斌; 苏文雯; 苏文锦
Original assignee: Beijing Jinxiu New Technology Development Co ltd
Current assignee: Beijing Jinxiu New Technology Development Co ltd
Priority date: 2020-05-18
Filing date: 2020-05-18
Publication date: 2020-08-25

Abstract

The invention relates to an insecticidal bactericide of a nano material copolymerized mineral and a plant extract and a preparation method thereof. The composite nano photocatalytic material and the plant extract are jointly immobilized on the mineral soil through a specific method, and the insecticidal bactericide has the advantages of realization of standardized production, small dosage, quick drug effect, small spraying frequency, stability, no influence of regional environment, no reduction of night efficacy and cost advantage. The insecticidal bactericide is non-toxic and harmless and is environment-friendly, and the insecticidal bactericide is aqueous or aqueous dispersion, and can be prepared into powder or aqueous dispersion.

Description

Nano material copolymerized mineral and plant extract insecticidal bactericide and preparation method thereof

Technical Field

The invention relates to an insecticidal bactericide, in particular to an insecticidal bactericide of a nano material copolymerized mineral and a plant extract, which has spectral insecticidal and bactericidal effects and belongs to the field of pollution-free environment-friendly physical and biological pesticides.

Background

In 2005, China surpassed the United states and became the first major agricultural chemical producing nation in the world, most of domestic agricultural chemical enterprises in China currently produce imitation products with expired patents of multinational companies, and the number of the varieties created in China is less than 10%. The structure innovation and the parent innovation are few, and the group reformation is carried out on the existing products. Mainly comprises kresoxim-methyl, fluoride ether bacteria amide, fluxapyrozole activated ester, flumorph, pyrisoxazole, dimethomorph, kresoxim-methyl, enestroburin, coumoxystrobin, shenqinmycin, thiediazole copper, cyhalothrin, Dufulin, clopicolinate, thiazole zinc, pyraoxystrobin, meperidine, cycloxaprid, sulfur-fluorine oxime ether, fluroxypyr-methyl, pyrimorph, pyraclostrobin, methidathioluramine, triflumilast, thifluzamide, pyraclostrobin, fenoxaprop-ethyl, thiaclopramide, SYP-12194, H-0909, SIOC0426, ZJ1835, HNPC-A9092, HNPC-A8169, WL-2004-L-13 and the like which take chemical pesticides as main components. The chemical pesticide has high toxicity and causes pollution to grains and vegetables, and long-term consumption of the polluted vegetable and grain is an important reason for diseases such as cancer, arteriosclerosis, cardiovascular diseases, fetal deformity, stillbirth, premature death, premature senility and the like. Safe, efficient, economic and convenient-to-use pesticide products will become mainstream products in the market in the future, the environment protection is the requirement of pesticide industry development, and the high efficiency, low toxicity and low residue are the development direction of the pesticide industry.

Nano-pesticides, biological (extract) pesticides and physical pesticides are currently available in the market.

Firstly, the pesticides generally have single performance, the nano materials have a sterilization function, but the insecticidal function is not strong, and the control effect on pests such as cabbage caterpillar, cabbage aphid, cotton bollworm, cotton red spider, prodenia litura, liriomyza sativae, wheat aphid, rice planthopper, rice stem borer, greenhouse whitefly, black tail leafhopper and the like is poor; the biological pesticide has obvious insecticidal effect, but has weak sterilization and antibacterial performance, and has almost no effect on bacteria such as maggots, rhizoctonia, root rot and the like.

At present, the nano pesticide mostly adopts the pesticide grain diameter nanocrystallization technology of a preparation or the technology of mixing with nano materials; the nano particles are novel nano particle drug delivery systems, the particle size of the nano particles is generally defined to be 1-100 nm, and the researched nano particles comprise polymer nanocapsules, nanospheres, pharmacosome, lipid nanospheres, nanoemulsion, polymer capsules, nano powder, suspending agents and microcapsules; the pesticide has relatively single function, is not easy to control in single amount, has poor synergistic effect, can generate precipitation and deterioration after long-term storage, and cannot fundamentally solve the problems of broad spectrum, stability and target insensitivity of the pesticide so that pests have resistance to the pesticide.

Secondly, the biopesticide generally has the defects of slow pesticide effect, poor control effect, poor stability, high price and the like, is rich in plant resources, is prepared from local materials, is convenient to use, is easy to degrade, has light pollution and is safe to crops; the botanical pesticide has the advantages of less environmental pollution, less resistance of pests, high selectivity, low toxicity to human, livestock and natural enemies and relatively low development and use cost.

The plant source pesticide has the following defects: most natural product compounds have complex structures and are not easy to synthesize or have high synthesis cost; the active ingredients are easy to decompose, the preparation ingredients are complex and difficult to standardize; most botanical insecticides have slow drug action, so that some farmers think that the used insecticides have no effect; the spraying times are many, the residual period is short, and the pesticide is not easy to be accepted by farmers; due to the regional distribution of plants, the selection of processing sites is limited by a plurality of factors, the collection of plants is seasonal, and the like. The botanical pesticide is generally an aqueous agent, is easy to decompose under the action of sunlight or microorganisms, has short half-life period and fast residual degradation, is poor in enrichment mechanism after being eaten by animals, has different targets for different pesticides, and is limited in use because the single target is a biological pesticide. For the insect with thick wax layer, the crustacean pests can not do the best. Especially, the difficult and complicated diseases such as maggots and root nematodes of Chinese chives, scallion and the like and anthracnose and root rot can not be solved.

Thirdly, physical pesticide insecticides rely on physical principles, such as physical shape penetration to inhibit insects, and the insecticides have poor bactericidal performance and single function. The physical pesticide (insecticide) is a bacteriostatic agent, has limited functions and large consumption, and has undesirable effect when being used alone.

The three pesticides are used independently, and function loss exists commonly. The fertilizer is used separately and alternately, the using amount is large, the labor cost is high, the spraying interval time is long, and the fertilizer does not accord with the growth cycle of plants; and the three pesticides can not be effectively compounded due to specific physical and chemical properties, and the defects that the biological pesticide, namely the plant extract pesticide active ingredient is easy to decompose, is easy to decompose after being acted by sunlight or microorganisms, has short half-life period and quick residue degradation and is poor in enrichment mechanism after being eaten by animals can not be fundamentally solved by adopting a simple mixing mode.

Target-based insensitivity is a mechanism by which pests develop resistance to pesticides that is of paramount importance, particularly in connection with high levels of resistance in pests. With the growing emphasis on the problem of pest resistance to different types of pesticides, many means of resistance have been developed, ranging from the development of new pesticides to the planting of transgenic plants. The single strategy has the potential to repudiate and exacerbate the resistance problem, thereby presenting problems such as toxicant residues and outbreaks of secondary pests. The drug resistance is an evolutionary response to the stress of the pesticide, and can only delay the uncontrollable state and not increase the use amount of the pesticide or continuously change the toxicity of the pesticide. The use amount of the pesticide must be strictly controlled and reduced. Therefore, the control of pests needs to be solved by adopting a new material cross-border technology by adopting a new technology, and the pesticide returns to the basic principle of the material, the synergistic action and the composite principle.

By combining the above, how to adopt the synergistic compound principle of multiple materials to prepare the insecticidal bactericide with broad-spectrum insecticidal and bactericidal functions, stable product, durable pesticide effect, no toxicity, no harm, environmental friendliness and standardized preparation process.

Disclosure of Invention

The invention aims to solve the technical problem of providing the insecticidal bactericide of the nanometer material copolymerized mineral and the plant extract.

The technical scheme for solving the technical problems is as follows: an insecticidal bactericide of nano-material copolymerized mineral and plant extract comprises mineral soil, composite nano-photocatalytic material and plant extract, wherein the composite nano-photocatalytic material and the plant extract are jointly immobilized on the mineral soil.

The invention has the beneficial effects that: the composite nano photocatalytic material and the plant extract are jointly immobilized on the mineral soil through a specific method, and the insecticidal bactericide has the advantages of realization of standardized production, small dosage, quick drug effect, small spraying frequency, stability, no influence of regional environment, no reduction of night efficacy and cost advantage. The insecticidal bactericide is non-toxic and harmless and is environment-friendly, and the insecticidal bactericide is aqueous or aqueous dispersion, and can be prepared into powder or aqueous dispersion.

On the basis of the technical scheme, the invention can be further improved as follows.

The invention relates to the nano-material copolymerized mineral and the insecticidal bactericide of the plant extract, wherein the mineral soil comprises rare earth and one or more than two of diatomite, attapulgite, bentonite, kaolin and pottery clay, and the fineness is 5000-10000 meshes.

The rare earth (RE ═ Ce4+, La3+, Nd3+, Sm3+, Zr3+, Er3+, Eu3+ and Y3+) contains a plurality of noble metals and transition metals, and the unique outer-layer electronic structure of the rare earth ions enables the rare earth ions to easily absorb the excitation of near ultraviolet light after forming organic or inorganic compounds, thereby emitting visible fluorescence emission corresponding to central ions; the rare earth is implanted into the insecticidal and bactericidal agent system, the high absorption of the rare earth to ultraviolet light and the high luminous efficiency of rare earth ions are utilized, and the rare earth organic complex is dispersed into the insecticidal and bactericidal agent system, so that the limitation of the insecticidal effect of the plant extract immobilized on mineral soil on the performance of light at night is solved (most of plant extracts obtained from plants are photosensitive compounds, namely, the insecticidal activity of the plant extracts can be promoted under the condition of light, the plants are protected from being damaged by insects in a unique mode), and the performance of the composite nano photocatalytic material for photocatalytic decomposition of organic matters is greatly improved.

Meanwhile, the rare earth elements can improve the chlorophyll content of plants, enhance photosynthesis, promote root development and increase nutrient absorption of roots. The rare earth can also promote seed germination, improve the seed germination rate and promote seedling growth. Besides the main functions, the fertilizer also has the capability of enhancing disease resistance, cold resistance and drought resistance of certain crops. The rare earth can effectively promote photosynthesis and root development of crops, and improve the nutrient absorption capacity of the root system. Can improve the protection function of crop cells, enhance the stress resistance of crops to drought, high temperature, low humidity and salt and alkali, simultaneously enhance the oxidase activity of plants in crop metabolism, decompose and remove pathogenic bacteria, and improve the disease and insect resistance of crops. But also can promote the propagation of beneficial bacteria in the soil, inhibit the activity of harmful microorganisms and improve the fertility of the soil. In addition, the biological activity of crops can be promoted, the quality of agricultural products is improved, the contents of starch and protein in grain crops are increased, and the sugar degree, the coloring degree and the freshness retaining degree of fruit and vegetable crops are increased.

The processing fineness of the diatomite, the attapulgite, the bentonite, the kaolin and the argil is 5000-10000 meshes, the diatomite, the attapulgite, the bentonite, the kaolin and the argil have rich pore channel structures and large specific surface areas, have strong adsorbability and stable chemical properties, can provide more active sites for photocatalytic reaction by introduction, and are convenient for the recovery and the reutilization of a catalyst; the diatomite, the attapulgite, the bentonite, the kaolin and the argil have good performances of rheology, adsorption, catalysis, decoloration and the like, and the natural mineral soil is a carrier of the composite nano photocatalytic material, so that on one hand, particles of the composite nano photocatalytic material can be immobilized on the natural mineral soil to inhibit self agglomeration of nano particles; on the other hand, the concentration of the pests and bacteria on the surface of the catalyst can be improved, the charges carried by the charged composite nano photocatalytic material are utilized to destroy protein and phospholipid bilayers of the pests and bacteria, so that the pests are killed, the material is non-toxic and harmless, and the efficiency of degrading the bacteria by the photocatalysis of the composite nano photocatalytic material is improved.

The invention controls the fineness of rare earth, diatomite, attapulgite, bentonite, kaolin and pottery clay to be 5000-10000 meshes so as to ensure the stability of the system.

The invention relates to an insecticidal bactericide of nano material co-polymer mineral and plant extract, further, the composite nano photocatalytic material comprises one or more than two of nano titanium dioxide and nano graphene, nano zinc oxide, nano copper oxide, nano aluminum trioxide, nano calcium carbonate, nano tin antimony, nano indium tin, nano cerium oxide, nano cobalt oxide, nano tungsten oxide or nano tourmaline.

The nano titanium dioxide can be preferably anatase type TiO 2; under the irradiation of ultraviolet and visible light, the nano titanium dioxide converts light energy into chemical energy and promotes the decomposition of organic matters, when the light energy is equal to or exceeds the band gap energy of the nano titanium dioxide, electrons are excited from a Valence Band (VB) to a Conduction Band (CB) to form photon-generated carriers (electron-hole pairs), the valence band holes are strong oxidants, and the conduction band electrons are strong reducing agents; anatase TiO2 requires an energy of 3.2eV for excitation, corresponding to a wavelength around 380 nm. The photocatalytic activity is high (strong ultraviolet light absorption performance, large energy gap, strong reducibility of photoproduction electrons and strong oxidizability of holes); due to the limitation of the wavelength, the invention compounds other types of photocatalysis nano materials, and further improves the photocatalysis efficiency of the oxidation reduction of the nano titanium dioxide.

The particle size of the nano photocatalytic material is 1-10nm, on one hand, due to quantum size effect and energy level splitting, the energy gap is increased, the energy level of a conduction band is moved towards the negative direction, the energy level of a valence band is moved towards the positive direction, so that the potential of the conduction band is more negative, the potential of the valence band is more positive, and the TiO semiconductor photocatalyst is enhanced₂The oxidation-reduction capability of the photocatalyst improves the photocatalytic activity. On the other hand, the smaller the particle, e_cb ^-And h_vb ⁺Can diffuse and migrate to the surface of the particle to participate in the reaction more quickly. Meanwhile, the smaller the particle size, the larger the specific surface area, the more the light energy is absorbed, the higher the density of the electron-hole pair generated, the more the reaction substance the particle adsorbs, and the higher the concentration of the oxidized or reduced substance, so the photocatalytic activity will be higher and the stability of the whole insecticidal and bactericidal agent system will be maintained.

The invention also provides a nano material copolymerized mineral and plant extract insecticidal bactericide, which comprises the steps of (1) carrying out surface modification on mineral soil by adopting alcohols to obtain a mineral soil modification dispersion liquid; preparing the composite nano photocatalytic material into composite nano dispersion liquid; preparing the plant extract into plant extract nano dispersion liquid;

adding the mineral soil modified dispersion liquid into a reaction kettle, dropwise adding the composite nano dispersion liquid, adjusting the pH value, slowly dropwise adding the plant extract modified dispersion liquid, stirring for reaction and homogenization, filtering after homogenization, washing, drying, and cooling to obtain insecticidal bactericide powder; the mineral soil modification dispersion liquid comprises the following components: composite nano dispersion liquid: the volume ratio of the plant extract nano dispersion liquid is (1: 1.5: 5) - (1: 1.5: 7.5).

According to the method, the mineral soil is subjected to surface modification by adopting alcohols to obtain the mineral soil modification dispersion liquid, so that the hydroxyl groups in the mineral soil can be improved, and the more the hydroxyl groups in the mineral soil are, the better the adsorption performance is; the hydroxyl can be converted under the heat treatment condition, so that the adsorption performance of the mineral soil is changed; the hydroxyl groups have certain activity and can react with or form bonds with other substances to change the adsorption property of the mineral soil; the mineral soil modification dispersion liquid is adopted: composite nano dispersion liquid: the volume ratio of the plant extract nano dispersion liquid is mixed, homogenized, filtered, washed, dried and cooled to obtain the insecticidal and bactericidal agent powder, which can be prepared into stable water dispersion liquid, and the composite nano photocatalytic material has high solid carrying rate, good adsorptivity of the plant extract, small dosage, quick drug effect, less spraying times and stability without being influenced by regional environment.

The preparation method of the insecticidal and bactericidal agent of the nanomaterial co-polymineral and the plant extract further comprises the following steps of (1):

step (11), adding mineral soil and deionized water into a reaction vessel according to the solid-liquid mass percentage of 10-50%, stirring and mixing uniformly, adding organic acid and/or inorganic acid containing hydroxyl, the mass of which is 1-10% of the total mass of the mineral soil and the deionized water, fully stirring and reacting at the water bath temperature of 50-150 ℃, performing suction filtration after reaction, and drying to obtain refined mineral soil; the preferred bath temperature is 100 ℃.

The reason for adopting organic acid containing hydroxyl (organic acid can be one or more of formic acid, tartaric acid, citric acid, tannic acid, acetic acid, oxalic acid, malic acid, mugineic acid, succinic acid, punicic acid, vanillic acid, benzoic acid, salicylic acid, coumaric acid, ferulic acid, syringic acid, citric acid, caffeic acid, benzoic acid, stearic acid, oleic acid, linoleic acid, linolenic acid and the like) or inorganic acid to treat in the step is that: because the mineral soil particles have certain electronegativity, the surface of the mineral soil is negatively charged in most pH value ranges, but under an acidic condition, because the hydroxyl groups on the surface of the mineral soil are protonated and positively charged, the isoelectric points of the mineral soil (such as diatomite) can be moved by grafting functional groups on the surface of the mineral soil, and the more the hydroxyl groups in the mineral soil are, the better the adsorption performance is; the hydroxyl can be converted under the heat treatment condition to change the adsorption performance of the mineral soil, so that the purity of the mineral soil can be improved, the density of the mineral soil is reduced, the pore volume, the specific surface area and the like are increased, and the pore structure is obviously improved.

And (12) mixing and stirring the fine mineral soil and the alcohol aqueous solution according to the mass ratio of 1.0-10.0%, wherein the mixing and stirring can be performed for about 10 minutes, then respectively adding a dispersing agent accounting for 0.1-0.4% of the total weight of the fine mineral soil and the alcohol aqueous solution and a wetting agent accounting for 0.1-0.4% of the total weight of the fine mineral soil and the alcohol aqueous solution, uniformly stirring to obtain a mineral soil mixture, then dropwise adding a non-alcohol surface modifier accounting for 0.1-0.5% of the total weight of the mineral soil mixture, performing ultrasonic dispersion for 15 minutes, ensuring that the mineral soil mixture is fully dispersed, homogenizing, and optionally placing the homogenized mixture in a homogenizer for homogenizing for 10 minutes to form the mineral soil modified dispersion liquid.

Alcohol solvent is selected to process the fine mineral soil, so that the water solubility and the solubility of the system are ensured, and the plant extracts are usually prepared by water extraction or alcohol extraction, so that the solubility of the final product can be ensured; based on the treatment of the alcohol solvent and the non-alcohol surface modifier, the polarity of the mineral soil is mainly improved, the acting force between the mineral soil and other materials in the whole preparation system is stronger, the alcohol is generally a good solvent, and the prepared product has low pollution and meets the requirement of environmental protection; the aggregation of the material is avoided, and the surface groups and functional groups of the material are changed, so that the dispersibility, solubility and associativity, compatibility, surface tension and stability of the material are changed; meanwhile, the surface modification is carried out by adopting an alcohol solvent, so that the hydroxyl in the mineral soil is improved, and the more the hydroxyl is, the better the adsorption performance is.

The preparation method of the insecticidal bactericide of the nano material copolymerized mineral and the plant extract further comprises the step (11) of using one or more of phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid, boric acid and the like as the inorganic acid; according to the invention, the mineral soil is treated by adopting a medium-strong acid leaching method, and the medium-strong acid is found to dissolve impurities such as A12O3, Fe2O3, CaO, MgO and the like and also dissolve a certain amount of amorphous SiO2 along with the increase of the acid concentration and the acid leaching time, the existence of the amorphous SiO2 can cause the system to be unstable, and the medium-strong acid can dissolve the impurities such as A12O3, Fe2O3, CaO, MgO and the like in the mineral soil to generate salts.

The preparation method of the insecticidal and bactericidal agent of the nanomaterial co-polymineral and the plant extract further comprises the following steps of (2) obtaining the composite nano dispersion liquid:

step (21), dispersing a first nano photocatalytic material with the particle size of 1-10nm in an ammonium salt solution according to the mass volume concentration of 50g-100g/L, dropwise adding an inorganic compound solution, and performing ultrasonic dispersion for 15 minutes optionally to obtain a nano mixed dispersion liquid A; the volume ratio of the ammonium salt solution to the inorganic compound solution is 3: 1-1: 3; the first nanometer photocatalytic material can be semiconductor nanometer material, and the semiconductor nanometer material can be nanometer titanium dioxide; the inventor tests and finds that the mass volume concentration of the first nano photocatalytic material dispersed in the ammonium salt solution and the volume ratio of the ammonium salt solution to the inorganic compound solution are necessarily controlled within the above range, if the first nano photocatalytic material forms impurities which influence the subsequent reaction; but too little results in insufficient solid loading to affect the photocatalytic effect; the maximum solid loading and the particle size distribution (the particle size distribution is in the range of 50 nm) of the nano photocatalytic material are ensured within the range of the reaction parameters, and the formation of impurities or the uneven particle size distribution is avoided.

In the step, ammonium salt is selected, because sufficient chemical reaction cannot be guaranteed, and sodium ions and potassium ions of targets can be exchanged for the mineral soil as an exchanger in the environment of the composite nano photocatalytic material by using a proper excessive amount of ammonium salt. The ion channel is a protein pore canal embedded in a cell membrane, consists of transmembrane protein macromolecules-channel protein, has a highly selective hydrophilic channel, controls the permeability of sodium, potassium, calcium and chlorine plasmas, and plays an important role in nerve impulse conduction.

Step (22), dispersing a second nano photocatalytic material in deionized water according to the mass volume concentration of 50g-100g/L, adding a dispersing agent and a wetting agent, and performing high-speed dispersion stirring, wherein the high-speed dispersing agent can be adopted for dispersion stirring to obtain a nano mixed dispersion liquid B; the dosage of the dispersant and the wetting agent is 0.1 to 0.4 percent of the total weight of the second composite nano photocatalytic material and the deionized water; the second nano photocatalytic material can be any one or more than two of nano graphene, nano zinc oxide, nano copper oxide, nano aluminum trioxide, nano calcium carbonate, nano tin antimony, nano indium tin, nano cerium oxide, nano cobalt oxide, nano tungsten oxide or nano tourmaline.

Dropwise adding the nano mixed dispersion liquid B into the nano mixed dispersion liquid A, ensuring the stability of reaction and the uniformity of particle size and distribution, homogenizing by a homogenizer for 10 minutes to obtain a composite nano dispersion liquid; the volume ratio of the nano mixed dispersion liquid A to the nano mixed dispersion liquid B is 1: 1-2: 1.

the invention adopts the second nano photocatalytic material for compounding and carrying, can ensure the compounding amount to the maximum degree, can also ensure the uniformity of particle size and distribution, simultaneously expands the wavelength range of the first nano photocatalytic material, ensures the redox capability of the first nano photocatalytic material, and improves the photocatalytic activity.

The addition of the nano photocatalytic material has a relatively obvious influence on the catalytic performance of the material, because the capability of capturing electrons and holes is insufficient when the addition of the nano material is too small, the photoproduction electrons and holes can not be effectively separated, and the catalytic activity is reduced. The invention adds the second nanometer photocatalysis material, selects the diameter of the added nanometer photocatalysis material between 5nm and 10nm through selecting the dispersant and the wetting agent, and has enough activity to compound the first nanometer photocatalysis material (semiconductor nano particles), the method also has the defect that when the adding amount of the second nanometer photocatalysis material exceeds a certain amount, the surplus second nanometer photocatalysis material appears in the form of crystals, and the existence of the second nanometer photocatalysis material crystals can destroy the highly dispersed state of the second nanometer photocatalysis material on the surface of the first nanometer photocatalysis material particles, thus leading to certain reduction of the catalytic performance and uneven particle size distribution of the composite nanometer material, therefore, the volume ratio of the nanometer mixed dispersion liquid A and the nanometer mixed dispersion liquid B must be strictly controlled.

The preparation method of the insecticidal bactericide of the nano material copolymerized minerals and the plant extracts further comprises the step (21) of controlling the concentration of the ammonium salt solution to be 0.5 mol/L; the concentration of the inorganic compound solution is 0.5 mol/L. The concentration meets the requirement of the reaction stability of the system, and the solution concentration has larger difference on the reaction temperature condition and the subsequent treatment temperature condition, thereby greatly influencing the stability and the preparation cost of the whole reaction system.

The preparation method of the insecticidal and bactericidal agent containing the nanomaterial co-polymer minerals and the plant extracts further comprises the step (21) of using one or more of urea, ammonium nitrate, ammonium sulfate, ammonium carbonate, ammonium bicarbonate, dodecyl ammonium chloride, ammonium bisulfate, ammonium fluoride, ammonium bromide, ammonium iodide, dioctadecyl dimethyl ammonium bromide, dodecyl dimethyl benzyl ammonium chloride or quaternary ammonium salts as the ammonium salt in the ammonium salt solution. The quaternary ammonium salt has a general formula R4NX, wherein four hydrocarbyl groups R can be the same or different, X is more than one halogen anion (F, CI, Br, I), and can also be one or more than two acid radicals (such as HSO, RCOO, etc.).

The preparation method of the insecticidal and bactericidal agent of the nanomaterial copolymerized mineral substance and the plant extract further comprises the steps that the dispersing agent and the wetting agent in the steps (12) and (22) are the same, and are two or more than two of alkylphenol ethoxylate phosphate, aryl phenol polyether phosphate, octadecyl phosphate, phosphate dispersing agent BYK110, NP10/TX10 phosphate, nonyl phenol polyether phosphate, 600 phosphate, TSP phosphate and fatty alcohol ether phosphate; the wetting agent is one or more of dodecyl polyoxyethylene ether, polyoxyethylene alkylphenol ether, polyoxyethylene fatty alcohol ether, polyoxyethylene polyoxypropylene block ester and the like, and alkylphenol polyoxyethylene ether, alkylaryl polyoxyethylene ether, polyaryl nuclear polyoxyethylene ether, calcium dodecylbenzene sulfonate, glycerol, polyethylene glycol 200-400 and tween.

The dispersant is adopted in the step (12) and the step (22), so that the stability of a system is stabilized, the acetylcholinesterase blocking performance is achieved, and the insecticidal effect is improved. Insect-based membrane receptor activation channels (ligand-gated channels), the nicotinic acetylcholine receptors (nachrs) of insects are localized to the central nervous system and are abundantly expressed on ganglia. Firstly, the membrane receptor is activated by some substance outside the membrane, and secondly, the chemical information can be converted into an electric signal. The acetylcholine receptor is the main target action site of the pesticide, and the organic phosphate ester has the performance of blocking acetylcholinesterase.

The wetting agent is mainly obtained by the addition reaction of hydrophobic compounds containing-OH groups, such as alcohol or phenol, and ethylene oxide or propylene oxide, and the polymerization reaction is adopted, the molecular number of the ethylene oxide or the propylene oxide can be artificially adjusted, and the hydrophilic-lipophilic balance of the surfactant is controlled; meanwhile, the surfactant auxiliary agent can inhibit the growth of bacteria, viruses and nematodes to a certain extent; therefore, the selection of the wetting agent is directly related to the success or failure of the whole preparation system, and is crucial to the binding, compatibility, stability and functionality of the whole system materials.

The preparation method of the insecticidal and bactericidal agent containing the nanomaterial co-polymer mineral and the plant extract further comprises the step (21) of adding one or more inorganic compounds selected from copper carbonate, copper sulfate, magnesium sulfate, zinc sulfate, copper nitrate, aluminum sulfate, zinc nitrate, magnesium nitrate, zinc chloride, aluminum chloride, copper chloride and the like into the inorganic compound solution. Acid radical ions of the inorganic compound in the step need to be the same as those of the inorganic acid in the step (11), so that disorder of a reaction system is avoided.

The preparation method of the insecticidal and bactericidal agent of the nanomaterial co-polymineral and the plant extract further comprises the following steps of:

step (31) preparation of a plant extract modified dispersion

Dispersing plant extract into alcohol aqueous solution, wherein the mass volume concentration of the plant extract and the alcohol aqueous solution is 2.00g/L-10.00g/L, and uniformly stirring to obtain extract mixed solution; dripping non-alcohol surface modifier which accounts for 0.1-1.5% of the total weight of the plant extract mixed liquor into the plant extract mixed liquor, uniformly mixing and stirring, optionally mixing and stirring for 10 minutes, homogenizing, optionally homogenizing in a homogenizer for 10 minutes to form plant extract modified dispersion liquid; the method for surface modification of the plant extract is a precondition for ensuring the formation of plant extract nanoparticles with certain sizes.

Step (32) preparation of a plant extract nanodispersion

(321) Dissolving natural high molecular organic sugar carrier in organic acid to prepare C solution with mass concentration of 0.1-8.0 g/L, namely natural high molecular organic sugar solution; organic acid is adopted to further activate the activity of the plant extract, ensure the stability of the whole system and obtain the plant extract nano dispersion liquid.

(322) Dissolving a natural high molecular compound with carboxymethyl or hydroxymethyl in deionized water to prepare a solution with the mass concentration of 0.1-7.0 g/L D, namely a carboxymethyl or hydroxymethyl high molecular solution;

(323) and (3) mixing the solution C and the solution D according to the volume ratio of 1:1, mixing, namely dropwise adding and mixing under the stirring condition to obtain a solution E;

(324) dissolving soluble calcium salt in deionized water under stirring to prepare a cross-linking agent solution with calcium ion concentration of 1.0-10.0 g/L;

(325) and under the condition of stirring, respectively and sequentially dripping plant extract modified dispersion liquid into the solution D, dripping the mixed solution E, dripping the solution C, dripping the cross-linking agent solution, after dripping is finished, adjusting the pH, continuously stirring, and homogenizing to obtain the plant extract nano-dispersion liquid. When the cross-linking agent solution and the natural polymer organic sugar solution are added under the stirring condition, through the interaction of amino and carboxyl between two macromolecular chains and the interaction of divalent ions and carboxyl, the originally extended carboxymethyl or hydroxymethyl polymer random coil is cross-linked and contracted to form spherical nano particles; on the other hand, the plant extract modified dispersion liquid is added into the carboxymethyl or hydroxymethyl macromolecule solution at the same time, the plant extract modified dispersion liquid is quickly mixed and dissolved with water, and the plant extract is separated out in the form of tiny grains; the size of the plant extract crystal particles depends on the amount of mixed water and the stirring and dripping speed, the existence of a large amount of water enables the plant extract crystal particles to form nanometer crystal particles with smaller particle sizes, the two processes are simultaneously carried out, and the plant extract nanometer crystal particles are immobilized on the spherical nanometer particles to generate the plant extract nanometer particles.

Plant extract nanodispersion: the long-chain anions and the carboxylation modification are adopted to cause the plant extract nano dispersion liquid to have negative charges; the mineral soil modified dispersion liquid is modified to be positively charged, so that the plant extract nano dispersion liquid is negatively charged, the intermolecular binding force is stronger, the phase separation is not easy to generate, and the relative content of two interaction groups is controlled, so that the plant extract is fixedly loaded on the mineral soil through the attraction between the charges. Therefore, the amount of charge in the system, i.e., the proportional relationship of the reactions of the respective raw materials, is important. The selection of the organic acid or the inorganic acid containing hydroxyl is directly related to the stability of the whole preparation system, and is important for the compatibility among various materials of the whole system, the stability and the functionality of the system.

The preparation method of the insecticidal bactericide of the nanomaterial co-polymineral and the plant extract further comprises the step (12) and the step (31), wherein the alcohol aqueous solution consists of an alcohol solvent and deionized water, and the mass ratio of the alcohol solvent to the deionized water is 1: 1-1: 5.

the preparation method of the insecticidal bactericide of the nano material copolymerized mineral and the plant extract further comprises the steps of (12) and (31) enabling the alcohol solvent and the non-alcohol surface modifier to be the same and to be one or more of methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol or propanol; the non-alcoholic surface modifier is KH550, KH560, KH570, silicone oil, methyl silicone oil, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, and sodium alkyl benzene sulfonate.

The alcohol solvent and the non-alcohol surface modifier in the steps (12) and (31) are the same, so that the compatibility among the components and the stability of the whole system are mainly ensured, and the toxicity and the pollution of the product can be effectively reduced by adopting the alcohol solvent.

The invention further provides a preparation method of the insecticidal bactericide of the nano material copolymerized minerals and the plant extracts, wherein the plant extracts are two or more of nicotine, camptothecin, stemonine, veratrine, matrine, wilfordine, ficolin, tetrandrine, aloperine, allicin, cnidium lactone, celastrol, pyrethrin, aetheroyl speranskia herb, steroids such as achyranthes bidentata sterone, lycoside, toosendanin, tea saponin, celastrol, rhododendrin, rotenone and rotenone.

Pesticides have different targets based on different plant extracts. The targets of most plant extract insecticides are important receptors or enzymes in the insect nervous system, and neurotoxicity can lead to rapid paralysis or death of the insect. Three central targets of commonly used pesticides are ligand-gated ion channels, voltage-gated ion channels, acetylcholinesterase. Ligand-gated ion channels are also known as neurotransmitter-gated ion channels, among which are more nicotinic acetylcholine receptor channels, gamma-aminobutyric acid (CABA) receptor channels, glycine receptor channels, and glutamate receptor channels. Ligand-gated ion channels receive chemical signal neurotransmitters, such as acetylcholine or r-aminobutyric acid (CABA), which can be converted into electrical signals by opening the ion channel within them. Unlike ligand-gated ion channels, voltage-gated ion channels are turned on by changes in membrane potential rather than changes in neurotransmitter concentration. Insect voltage-gated sodium ion channels are sites of action for DDT and pyrethroid insecticides. Acetylcholinesterase (AChE) is the site of action of organophosphorus and carbamate insecticides, breaking down the neurotransmitter choline. Inhibition of AChE by insecticides can lead to accumulation of acetylcholine at synapses, where excess acetylcholine causes depolarizing blockages, and inhibition of normal nerve conduction in insects eventually leads to death of the insect. According to the synergistic action of the materials and the material compounding principle, two or more plant extract insecticides are compounded to form a multi-target insecticidal system with synergistic action.

The preparation method of the insecticidal bactericide of the nano material copolymerized mineral and the plant extract, further, the solution D: plant extract modified dispersion: e, mixing liquid: solution C: the volume ratio of the cross-linking agent solution is 40: 2: 2:1:1.

The preparation method of the insecticidal and bactericidal agent of the nanomaterial co-polymer mineral and the plant extract further comprises the step (4) and the step (325) of adjusting the pH value to 7, wherein the pH value adjusting agent is one or more of ammonia water, ethanolamine, hexamethylenetetramine, AMP-95, 2-amino-2-methyl-1-propanol, 2-amino-2-ethyl-1, 3-propanediol, diethanolamine, triethanolamine, N-methylethanolamine, dimethylethanolamine, monoethanolamine, butylethanolamine, and N-aminopropyl-methylethanolamine. The invention is based on the selection of ammonia, amino and amine pH regulators, and mainly considers the continuity, compatibility, stability (such as no unnecessary chemical reaction or precipitation) and influence on plant extracts of the whole pesticide system.

The preparation method of the insecticidal and bactericidal agent of the nanomaterial co-polymer mineral and the plant extract further comprises the step (321), wherein the natural polymer organic sugar carrier can be one or more than two of sucrose, arabinose, trehalose, chitosan, lactose, oligosaccharide, glucose, maltose, N-acetyl carboxyl sugar, polygalactomannose, fructose, carboxyl agarose, ferric carboxyl maltose, konjac glucomannan and the like.

The organic acid can be one or more selected from formic acid, tartaric acid, citric acid, tannic acid, acetic acid, oxalic acid, malic acid, mugineic acid, succinic acid, punicic acid, vanillic acid, benzoic acid, salicylic acid, coumaric acid, ferulic acid, syringic acid, citric acid, caffeic acid, benzoic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, etc.

The carboxymethyl or hydroxymethyl polymer can be selected from one or more of hydroxypropyl methylcellulose, hydroxyethyl cellulose, hydroxypropyl starch, carboxymethyl cellulose, carboxymethyl starch, carboxymethyl dextrin, carboxymethyl pachyman, carboxymethyl chitosan, carboxymethyl fructose, carboxymethyl chitose, carboxymethyl inulin, amino acid, carboxymethyl glucose, and carboxymethyl chitosan oligosaccharide;

the crosslinking agent can be one or more selected from calcium nitrate, calcium dihydrogen phosphate, calcium carbonate, calcium acetate, calcium formate, calcium gluconate, calcium lactate, calcium citrate, L-threonine calcium carbonate, and calcium oxalate.

In the preparation method of the nano material copolymerized mineral and the insecticidal and bactericidal agent of the plant extract, further, the acid radical of the organic acid or the inorganic acid containing the hydroxyl in the step (11) is the same as the acid radical ion of the cross-linking agent in the cross-linking agent solution.

The dropwise addition involved in the process of the present invention is generally selected from 0.5 to 3 hours, preferably from 1 to 2 hours.

The preparation of the plant extract nano dispersion liquid is based on that natural high molecular organic sugar and carboxymethyl or hydroxymethyl polymer are used as carrier materials, and the interaction between a functional group with positive charge on a molecular chain of the natural high molecular organic sugar and a carboxyl functional group with negative charge on a molecular chain of the carboxymethyl or hydroxymethyl polymer is utilized to control the mass concentration and the dosage of the solution, so that the nano particles of the immobilized plant extract dispersed in water can be prepared.

The natural high molecular organic sugar and the carboxymethyl or hydroxymethyl polymer not only can be carrier materials, but also can play a role in biological activity, the plant extract nano particles are formed on the premise that the types of polar groups after the surfaces of the natural high molecular organic sugar and the carboxymethyl or hydroxymethyl polymer solution, the carboxymethyl or hydroxymethyl polymer solution and the plant extract are modified, the mass concentration and the dosage of the solution and the necessary modification on the surface of the plant extract are controlled, and the selection of the alcohol solvent and the non-alcohol surface modifier has a remarkable effect on the stability and the compatibility of the whole system in consideration of the solubility and the compatibility of the carboxymethyl or hydroxymethyl polymer and the modifier.

The semiconductor current carrier in the composite nano photocatalytic material has high recombination rate and low quantum yield, and has poor spectral response to visible light, so that the application of the composite nano photocatalytic material is greatly limited; the mineral soil is used as a carrier of the nano photocatalytic material, so that the nano photocatalytic material is firmly combined with the mineral soil, the performance of the nano photocatalytic material is more stable and durable, and the photodegradation quantum efficiency and the photocatalytic efficiency are improved; the mineral soil-supported composite nano photocatalytic material can improve the photocatalytic performance of the material under visible light by means of the adsorption effect of the mineral soil and the photocatalytic effect of the composite nano photocatalytic material, so that the insecticidal and bactericidal capability is improved, and the composite material has a certain insecticidal and bactericidal function particularly at night, and has high efficiency and cost controllability because the amount of the titanium reagent consumed by the composite material is much smaller than that of a pure photocatalyst.

The invention finally obtains the mineral soil and simultaneously carries the composite nano photocatalytic material and the plant extract to simultaneously realize spectral disinsection and sterilization, and has no environmental pollution and good stability.

The plant extract of the invention comprises alkaloids, terpenoids, flavonoids and essential oils.

(1) Alkaloids

The substance has the strongest toxicity to insects, and has various action modes on the insects: such as poison, avoidance, food refusal, anesthesia, growth and development inhibition, etc. At present, more than 6000 kinds of alkaloids are found, and the main alkaloids which are proved to have the effect of killing pests mainly comprise nicotine, camptothecin, stemonine, veratrine, matrine, wilfordine, ficuline, tetrandrine, aloperine and the like.

(2) Terpenes as intermediates

Such compounds include pinene, monoterpenes, sesquiterpenes, diterpenes, triterpenes. The substances have antifeedant, systemic, anesthetic, repellent, growth and development inhibiting, pest information transmission and mating destroying, contact killing and stomach poisoning effects, and mainly comprise azadirachtin, toosendanin, tea saponin, celastrus angulatus, rhododendrin, etc.

(3) Flavonoid compounds

The ketone compounds are present in the form of glycoside or aglycone, diglucoside or trisaccharide, and mainly comprise rotenone, etc. with the function of preventing and treating pests. The action mode is antifeedant and toxic action.

(4) Essential oils

Essential oils are plant secondary metabolites with small molecular weight, which not only have the effects of poisoning, fumigating, avoiding or inducing, antifeedant, inhibiting growth and development, but also have the effect of inducing insect sex pheromone, and are mainly used for preventing warehouse pests, such as chrysanthemum oil, peppermint oil, thyme oil, cinnamon essential oil, turpentine oil, ruta essential oil, turnip essential oil and the like.

The nano-material copolymerized mineral and plant extract insecticidal bactericide is non-toxic and harmless, is a broad-spectrum, high-efficiency, low-toxicity, easily-degradable and residue-free insecticide, and does not produce the unique insecticidal bactericidal effect of drug resistance.

The insecticidal and bactericidal agent has the effect of repelling and killing almost all plant pests, indoor bedbugs, fleas, flies, mosquitoes and the like, and has no pollution to people, livestock and surrounding environment. Has antibacterial and antifungal activity, can be used for preventing and treating or repelling pests such as flies, mosquitoes, locusts and the like in rooms, vegetable gardens, gardens and lawns, and ticks, big flies, gadflies, midges, bed bugs, fleas, mosquitoes and the like on pets, cattle, sheep and other livestock, and has strong poisoning and killing effects on roundworms, pinworms and hookworms.

The insecticidal mechanism is probably shown in that the insecticidal composition inhibits the acetylcholinesterase of insects, influences the nervous system, causes the non-functional contraction of muscles of pests, and finally dies due to exhaustion. Or inhibiting calcium ion absorption, affecting thallus growth and spore germination, preventing thallus cell wall chitin deposition, or blocking nerve center conduction after pests eat and contact, destroying midgut tissue and various detoxification enzyme systems and respiratory metabolism, affecting digestion and absorption, losing taste function of food, and killing pests due to improper growth and development caused by antifeedant. Inhibiting chitin deposition on insect body wall and fungal cell wall to express pesticidal and bacteriostatic activity, or dissolving wax layer in the surface of insect, and allowing the bioactive matter to enter cuticle layer to increase the space between cells and reduce defense capacity, so that the bioactive matter can enter insect body quickly. The contact administration of the insect epidermis overcomes the defect that the natural absorption of liquid medicine by the insect body takes effect slowly or no stomach toxicity is generated due to refusal of feeding of insects, and the insects die due to the contact administration only when contacting the medicine, and can also inhibit the generation, germination, adhesion, invasion and bud canal elongation of pathogenic bacteria and act on the nervous system of pests.

Therefore, when only 100mL of stock solution is used for spraying per 667 square meters, the control effect on plant diseases and insect pests can reach 85% -95%, and the effect is equivalent to that of chemical pesticides. Breaks through the environmental protection but not high efficiency of the prior biological pesticide.

The villi of the spodoptera exigua egg masses are mainly made of chitin, and the effect of the insecticidal bactericide on the spodoptera exigua egg masses is likely to dissolve the villi on the spodoptera exigua egg masses, reduce the adhesiveness of egg granules and cause the reduction of the hatching rate.

Detailed Description

The principles and features of this invention are described in conjunction with the following embodiments, which are given by way of illustration only and are not intended to limit the scope of the invention.

The loading rate of the plant extract in the embodiment of the invention is the percentage ratio of the amount of the plant extract adsorbed on the final product to the amount of the plant extract added in the system.

Example 1

The nano-material copolymerized mineral and plant extract insecticidal bactericide comprises rare earth and kaolin, a titanium dioxide-copper oxide composite photocatalytic material and plant extracts of matrine and stemonine, wherein the titanium dioxide-copper oxide composite photocatalytic material and the plant extracts of matrine and stemonine are jointly immobilized on the rare earth and the kaolin.

Example 1 insecticidal and fungicidal composition of nanomaterial co-minerals and plant extracts was obtained by the following method:

1. pretreatment of rare earth and kaolin

Mixing 40g of rare earth with the fineness of 8000 meshes with 10g of kaolin with the fineness of 8000 meshes, dispersing the mixture in 1000mL of deionized water, stirring and uniformly mixing, and then adding 20g of phosphoric acid. The mixed solution is fully stirred in the reaction kettle for reaction for 2 hours under the condition that the water bath temperature is kept at 100 ℃. And then filtering, drying and calcining the materials to obtain the purified refined rare earth and kaolin clay mixed soil.

2. Surface modification of rare earth and kaolin

50g of refined rare earth composite kaolin and 200mL of isopropanol are uniformly mixed and stirred for 10 min. Adding 4 g of 600# phosphate and 6 g of polyoxyethylene fatty alcohol ether, dispersing in 800mL of deionized water, stirring and dropwise adding 2 g of KH550, performing ultrasonic dispersion for 15min to ensure full dispersion, placing in a homogenizer, and homogenizing for 10min to form the fine rare earth and kaolin dispersion liquid.

3. Preparation of nano titanium dioxide-nano copper oxide composite dispersion liquid

Dispersing 100g of nano-material titanium dioxide in 1000mL of ammonium carbonate solution with the concentration of 0.5mol/L, dropwise adding 1000mL of 0.5mol/L copper nitrate solution, and performing ultrasonic dispersion for 15min to obtain a nano-zinc oxide mixed dispersion liquid A. Dispersing 50g of nano copper oxide into 1000mL of deionized water, adding 5g of 600 phosphate, and stirring for 30min by a high-speed dispersion machine to obtain nano copper oxide mixed dispersion liquid B. And (3) taking 2000mL of nano zinc oxide mixed dispersion liquid A, dropwise adding and mixing 1000mL of nano copper oxide mixed dispersion liquid B, and homogenizing for 10min by using a homogenizer to obtain the titanium dioxide and copper oxide composite nano dispersion liquid.

4. Matrine and stemonine surface modification

Dispersing 50g of each matrine and stemonine in 1000mL of isopropanol, stirring and mixing, sequentially dropwise adding 10g of sodium dodecyl benzene sulfonate and 3 g of KH550, stirring for 10min, placing in a homogenizer, and homogenizing for 10min to form matrine and stemonine mixed modified dispersion liquid.

5. Matrine and stemonine nano dispersion liquid

(1) 20g of konjac glucomannan and 10g of carboxymethyl chitosan are dissolved in 4000mL of oxalic acid solution to prepare a solution C. A solution D was prepared by dissolving 25g of carboxymethyl starch and 20g of hydroxypropyl methylcellulose in 9000mL of deionized water. 1000mL of the solution C was added dropwise to 1000mL of the solution D under stirring, and the solution E was prepared by adjusting pH to 7-8 with 10mL of an AMP-95 neutralizer.

(2) And under the stirring condition, taking 6000mL of the solution D, dropwise adding 300mL of the modified dispersion liquid mixed by the matrine and the stemonine, dropwise adding 300mL of the mixed solution E, and dropwise adding 300mL of the solution C. After the dropwise addition, stirring for 5min, ultrasonically dispersing for 10min, and placing in a homogenizer for homogenizing for 10min to obtain matrine and stemonine nanometer dispersion.

6. Kaolin and rare earth composite nano titanium dioxide-copper oxide and matrine and stemonine insecticidal bactericide stock solution

Adding 1000mL of fine rare earth and kaolin dispersion liquid into a reaction kettle, stirring 3000mL of composite nano zinc oxide and copper oxide dispersion liquid, adjusting the pH value to 7-8 by adopting 5mL of AMP-95 neutralizing agent, and slowly dropwise adding 6000mL of matrine and stemonine nano dispersion liquid. Stirring by a high-speed dispersion machine, reacting for 2h at 90 ℃, placing in a homogenizer, and homogenizing for 10min to obtain 10000mL of mineral soil-supported nano titanium dioxide-copper oxide matrine and stemonine nano stock solution. Filtering, washing, drying and calcining the stock solution at 220 ℃ for 2h, and cooling to room temperature to obtain kaolin and rare earth composite nano titanium dioxide-copper oxide and matrine stemonine insecticidal bactericide powder.

The kaolin, rare earth composite nano titanium dioxide-copper oxide and matrine stemonine insecticidal bactericide powder has the particle size of about 20-50nm, the surface of the powder is positively charged with PDI of about 0.5, the Zeta potential value is about 67mV, and the matrine stemonine loading rate can reach 60 percent by adopting a dynamic light scattering nano particle size analyzer.

In the aspect of insect killing: lepidoptera larvae such as cabbage caterpillar, armyworm, tea geometrid, aphid, oriental tobacco budworm, mites such as rust mite and red spider, and pear psylla. Effectively preventing and controlling various crop aphids, tea plant tea lesser leafhopper, rice planthopper, cotton aphid, vegetable trialeurodes vaporariorum and other piercing-sucking pests and lepidoptera pests such as cabbage caterpillar, cotton bollworm and the like.

And (3) sterilization: rice: bacterial leaf streak of rice, bacterial leaf blight of rice, basal rot of rice, bacterial brown streak of rice, bacterial brown spot of rice, bacterial wilt of cassava, root canker of apple, black rot of radish, bacterial soft rot of onion, soft rot of beet, bacterial root canker of beet, bacterial tail rot of beet (root tail rot), bacterial spot blight of beet, bacterial wilt of mulberry, bacterial black blight of mulberry, and blight of mulberry.

Example 2

The nano-material copolymerized mineral and plant extract insecticidal bactericide comprises attapulgite and rare earth, a nano-titanium dioxide-nano zinc oxide composite photocatalytic material, plant extract osthole and pirrine, wherein the nano-titanium dioxide-nano zinc oxide composite photocatalytic material, the plant extract osthole and the pirrine are jointly immobilized on the attapulgite and the rare earth.

Example 2 insecticidal and fungicidal composition comprising nanomaterial co-minerals and plant extracts obtained by the following method:

1. pretreatment of attapulgite and rare earth

30g of attapulgite with the fineness of 8000 meshes, 10g of rare earth with the fineness of 8000 meshes are dispersed in 1000mL of deionized water, 10g of concentrated sulfuric acid is added after stirring and mixing uniformly, and the mixed solution is stirred and reacted in a reaction kettle for 2 hours fully under the condition of keeping the temperature at 100 ℃. And then filtering, drying and calcining the material to obtain purified fine attapulgite and rare earth composite soil.

2. Surface modification of attapulgite and rare earth

Taking 40g of fine attapulgite, 40g of rare earth and 200mL of absolute ethyl alcohol, and uniformly mixing and stirring for 10 min. Adding 6 g of nonylphenol polyether phosphate and 4 g of polyoxyethylene fatty alcohol ether, dispersing in 800mL of deionized water, stirring and dropwise adding 3 g of KH570, performing ultrasonic dispersion for 15min to ensure full dispersion, placing in a homogenizer, and homogenizing for 10min to form the attapulgite and rare earth dispersion.

3. Preparation of composite nano titanium dioxide-nano zinc oxide dispersion liquid

Dispersing 100g of nano-material titanium dioxide in 1000mL of ammonium carbonate solution with the concentration of 0.5mol/L, dropwise adding 1000mL of 0.5mol/L zinc sulfate solution into the solution, and ultrasonically dispersing for 15min to obtain a nano-titanium dioxide mixed dispersion liquid A. Dispersing 50g of nano zinc oxide into 1000mL of deionized water, adding 5g of fatty alcohol ether phosphate and 5g of polyoxyethylene fatty alcohol ether high-speed dispersion machine, and stirring for 30min to obtain nano zinc oxide mixed dispersion liquid B. And (3) taking 2000mL of the nano titanium dioxide mixed dispersion liquid A, dropwise adding and mixing 1000mL of the nano zinc oxide mixed dispersion liquid B, and homogenizing for 15min by using a homogenizer to obtain the composite nano titanium dioxide and nano zinc oxide dispersion liquid.

4. Osthole and pirrine surface modification

Dispersing 70g of osthole and 30g of pirroline in 1000mL of absolute ethanol, mixing and stirring, sequentially dropwise adding 8 g of sodium dodecyl sulfate, dropwise adding 2 g of KH570, continuously stirring for 10min, placing in a homogenizer, and homogenizing for 10min to obtain osthole and pirroline dispersion liquid.

5. Osthole and pirrine nano dispersion liquid

(1) 10g of carboxymethyl chitose, 10g of oligosaccharide and 10g of carboxymethyl glucose are dissolved in 4000mL of acetic acid solution to prepare a solution C. A solution D was prepared by dissolving 30g of carboxymethyl cellulose and 15 g of hydroxypropyl methyl cellulose in 9000mL of deionized water. 1000mL of the solution C was added dropwise to 1000mL of the solution D under stirring, and pH was adjusted to 7-8 with 4mL of 25% aqueous ammonia to obtain a solution E.

(2) And under the stirring condition, taking 6000mL of the solution D, dropwise adding 300mL of osthole and pirrine alcohol dispersion liquid, dropwise adding 300mL of the mixed solution E, and dropwise adding 300mL of the solution C. After the dropwise addition, 8mL of 25% ammonia water is used for adjusting the pH value to 7-8, stirring is continued for 5min, ultrasonic dispersion is carried out for 10min, the obtained product is placed in a homogenizer, and homogenization is carried out for 10min, so that the osthole and pyritrine nano dispersion liquid is obtained.

6. Adding 1000mL of rare earth dispersion liquid into attapulgite, rare earth composite nano titanium dioxide-zinc oxide and osthole pirrine insecticidal bactericide stock solution in a reaction kettle, stirring 3000mL of composite nano zinc oxide and copper oxide dispersion liquid, adjusting the pH to 7 by using 25% ammonia water, and slowly dropwise adding 6000mL of osthole and pirrine nano dispersion liquid. Stirring by a high-speed dispersion machine, reacting for 2h at 70 ℃, placing in a homogenizer, and homogenizing for 10min to obtain 10000mL of mineral soil-immobilized titanium dioxide-zinc oxide and osthole pirrine nano stock solution. Filtering, washing, drying and calcining the stock solution at 200 ℃ for 2h, and cooling to room temperature to obtain attapulgite and rare earth composite nano titanium dioxide-zinc oxide and osthole pirrine insecticidal bactericide powder.

The attapulgite, rare earth composite nano titanium dioxide-zinc oxide and osthole pirrine insecticidal bactericide powder is analyzed by a dynamic light scattering nano particle size analyzer to be about 10-15nm in particle size, the surface of the powder has positive charge with PDI of about 0.5, the Zeta potential value is about 63mV, and the osthole pirrine load rate can reach 65 percent at most.

In the aspect of insect killing: it has effects on cabbage worm, diamondback moth, aphid and spodoptera exigua egg mass, and can almost prevent and kill all kinds of pests.

And (3) sterilization: the plant pathogenic fungi such as powdery mildew of cucumber, plasmopara viticola, phytophthora capsici, fusarium graminearum and the like have obvious inhibiting effect. The bacterial wilt of potatoes, soft rot of potatoes, black shank of potatoes, ring rot of potatoes, blast of sweet potatoes, stem rot of corn, black glume of wheat, bacterial wilt of cassava, canker of citrus (including navel orange, shaddock, pomelo, lemon, kumquat, bitter orange, trifoliate orange and the like), canker of Shatian pomelo, pear root cancer, pear fire blight, peach bacterial perforation (including plum, apricot, nectarine, cherry and the like), apple root cancer, pineapple heart rot, loquat bud blight, loquat cancer, walnut black spot, kiwi canker, mango bacterial black spot, fruit tree bacterial root cancer (including peach, pear, apple, Chinese chestnut, plum, apricot, grape and the like), bacterial green rot of watermelons, bacterial fruit rot of watermelons, vegetable green blight of solanaceae (tomato, eggplant, hot pepper) soft rot, scab, bacterial angular leaf spot of cucumbers, brown spot, sore, hot spot of cucumbers, brown rot of cucumbers, black spots of cucumbers, melons, melon, Muskmelon and luffa), cruciferous vegetable soft rot, bacterial black spot (Chinese cabbage, radish, cauliflower, etc.), bean bacterial angular leaf spot (kidney bean, hyacinth bean, cowpea, mung bean, etc.), bean bacterial blight (kidney bean, hyacinth bean, cowpea, mung bean), ginger blast (ginger rot ), melon bacterial wilt, pepper bacterial spot (pepper scab), pepper bacterial leaf spot, taro bacterial spot, taro rot (taro soft rot, taro rot), onion bacterial soft rot, soybean bacterial leaf burn, soybean bacterial spot, soybean bacterial leaf eruption, rape black rot, rape bacterial black spot, beet soft rot, beet bacterial root canker, beet tail rot (root rot), beet bacterial spot, beet bacterial rot, beet bacterial leaf spot, beet bacterial leaf rot, beet bacterial leaf spot, beet leaf rot, rape black rot, rape seed rot, beet bacterial black rot, Tobacco bacterial wilt, tobacco angular leaf spot, tobacco soft rot (hollow stem), bacterial diseases of medicinal materials and bacterial diseases of flowers.

Example 3

The nano-material copolymerized mineral and plant extract insecticidal bactericide comprises diatomite, bentonite and rare earth, a nano-titanium dioxide-nano aluminum oxide composite photocatalytic material, a plant extract toosendanin and a cortex meliae extract, wherein the nano-titanium dioxide-nano zinc oxide composite photocatalytic material, the plant extract cnidium lactone and pirrine are jointly immobilized on the diatomite, the bentonite and the rare earth.

Example 3 insecticidal and fungicidal composition of nanomaterial co-minerals and plant extracts, obtained by the following method:

1. pretreatment of diatomite, bentonite and rare earth

32 g of diatomite with the fineness of 8000 meshes, 8 g of rare earth with the fineness of 8000 meshes and 5g of bentonite with the fineness of 8000 meshes are mixed and dispersed in 1000mL of deionized water, 12 g of concentrated hydrochloric acid is added after stirring and mixing uniformly, and the mixed solution is fully stirred and reacts for 2 hours in a reaction kettle under the condition of keeping the temperature at 100 ℃. And then filtering, drying and calcining the material to obtain purified fine diatomite, bentonite and rare earth composite soil.

2. Surface modification of diatomite, bentonite and rare earth

40g of fine compound soil and 200mL of absolute ethyl alcohol are uniformly mixed and stirred for 10 min. Adding 5g of TSP phosphate and 5g of alkylaryl polyoxyethylene ether, dispersing in 800mL of deionized water, stirring and dropwise adding 2.5 g of KH560, dispersing for 15min by ultrasonic wave to ensure full dispersion, placing in a homogenizer, and homogenizing for 10min to form the diatomite, bentonite and rare earth dispersion.

3. Preparation of composite nano titanium dioxide-nano alumina dispersion liquid

Dispersing 120 g of nano-material titanium dioxide into 1000mL of 0.5mol/L ammonium bicarbonate solution, dropwise adding 1000mL of 0.5mol/L aluminum sulfate solution, and performing ultrasonic dispersion for 15min to obtain a nano-titanium dioxide mixed dispersion liquid A. Dispersing 60g of nano-alumina in 1000mL of deionized water, adding 5g of TSP phosphate and 5g of alkylaryl polyoxyethylene ether, and stirring for 30min by a high-speed dispersion machine to obtain nano-zinc oxide mixed dispersion liquid B. And (3) taking 2000mL of the nano titanium dioxide mixed dispersion liquid A, dropwise adding and mixing 1000mL of the nano alumina mixed dispersion liquid B, and homogenizing for 20min by using a homogenizer to obtain the composite nano titanium dioxide-nano zinc oxide dispersion liquid.

4. Surface modification of toosendanin and cortex Meliae extract

Dispersing 45g of toosendanin and 45g of cortex meliae extract in 600mL of absolute ethanol, mixing and stirring, sequentially dropwise adding 10g of 12-alkyl sodium sulfate, dropwise adding 2.5 g of KH560, continuously stirring for 10min, placing in a homogenizer, and homogenizing for 10min to obtain toosendanin and cortex meliae dispersion.

5. Toosendanin, chinaberry bark extract nano dispersion liquid and celastrus angulatus emulsion

(1) 5g of carboxymethyl chitose, 20g of chitosan and 5g of carboxymethyl glucose were dissolved in 4000mL of acetic acid solution to prepare a solution C. A solution D was prepared by dissolving 30g of carboxymethyl cellulose, 10g of carboxymethyl starch, and 5g of hydroxypropyl methyl cellulose in 9000mL of deionized water. 1000mL of the solution C was added dropwise to 1000mL of the solution D under stirring, and 5mL of triethanolamine was added to adjust the pH to 7 to 8, followed by mixing to obtain a solution E.

(2) Under the condition of stirring, 6000mL of D solution is taken, 300mL of toosendanin and chinaberry bark extract alcohol dispersion liquid is added dropwise, 300mL of E mixed solution is added dropwise, and 300mL of C solution is added dropwise. After the dropwise addition, regulating the pH value to 7-8 by 9mL of triethanolamine, continuously stirring for 5min, ultrasonically dispersing for 10min, placing in a homogenizer, and homogenizing for 10min to obtain toosendanin and cortex meliae extract nano dispersion liquid.

(3) Celastrus angulatus extract emulsion

According to the published formula: 10g of celastrus angulatus original drug, 25g of N, N-dimethylformamide, 75 g of glycol, 2.5 g of sodium dodecyl sulfate, 3.5 g of fatty alcohol-polyoxyethylene ether and 383 g of deionized water. And g. The operation is as follows: dissolving celastrus angulatus original drug partially with N, N-dimethylformamide, adding ethylene glycol after celastrus angulatus is completely dissolved, adding sodium dodecyl sulfate and alkylphenol polyoxyethylene (OP-15), heating to 45 ℃, stirring uniformly, adding deionized water, continuing stirring for 30 minutes, and cooling after stirring to obtain celastrus angulatus microemulsion. Ultrasonically dispersing for 20min, placing in a homogenizer, and homogenizing for 10min to obtain celastrus angulatus nano microemulsion.

6. Mineral soil composite nano titanium dioxide-alumina, toosendanin cortex meliae extract and kurarinone insecticidal bactericide stock solution

1000mL of diatomite, bentonite and rare earth dispersion liquid are added into a reaction kettle, 3000mL of composite nano zinc oxide and copper oxide dispersion liquid is stirred, 7mL of triethanolamine is adopted to adjust the pH value to 7, and 5500mL of toosendanin and chinaberry bark extract nano dispersion liquid is slowly dripped. Stirring by a high-speed dispersion machine, reacting for 2h at 85 ℃, cooling to normal temperature, and dropwise adding 500mL celastrus angulatus nano microemulsion. Placing in a homogenizer, homogenizing for 10min to obtain mineral soil-supported titanium dioxide-aluminum oxide and toosendanin cortex Meliae extract and Celastrus angulatus nanometer stock solution 10000 mL. Filtering, washing, oven drying at 180 deg.C, calcining for 2 hr, and cooling to room temperature to obtain mineral soil composite nanometer titanium dioxide-aluminum oxide, toosendanin cortex Meliae extract and Celastrus angulatus insecticidal and bactericidal agent powder.

The particle size of the dynamic light scattering nanometer particle size analyzer is about 15-20nm, the PDI is about 0.5, the surface of the analyzer is positively charged, the Zeta potential value is about 57mV, and the highest load rate of the plant extract can reach 65%.

In the aspect of insect killing: it has broad spectrum for pests with thick wax layer and crustacean pests, and can be used for killing cabbage caterpillar, diamondback moth and aphid in vegetable crops. Has stomach poisoning effect on insects such as black cutworm, cabbage looper, and cotton bollworm. The composition has special effects on asparagus caterpillar and prodenia litura, has high efficiency on rice leaf roller, sesamia inferens, chilo suppressalis and tryporyza incertulas, and has a lasting period of 30 days. Preventing and treating lepidoptera pests such as cabbage caterpillar, budworm, beet armyworm and the like. Preventing and treating various aphids, spider mites, whiteflies on kidney beans and liriomyza on kidney beans. Has strong toxic action on ascaris, pinworm and hookworm

And (3) sterilization: the broad-spectrum bactericide has obvious inhibiting effect on all plant pathogenic fungi and the like. Various diseases and pestilences of potatoes such as potato; various bacterial viral diseases of field crops; various bacterial viral diseases of forest trees and fruit trees; bacterial viral diseases for almost all fruit and vegetables; bacterial diseases of medicinal materials and bacterial diseases of flowers.

Example 4

The nano-material copolymerized mineral and plant extract insecticidal bactericide comprises diatomite and rare earth, a nano-titanium dioxide-tourmaline composite photocatalytic material and plant extracts of rotenone and triptolide, wherein the nano-titanium dioxide-tourmaline composite photocatalytic material and the plant extracts of rotenone and triptolide are jointly immobilized on the diatomite and the rare earth.

Example 4 insecticidal and fungicidal composition of nanomaterial co-minerals and plant extracts, obtained by the following method:

1. diatomite and rare earth pretreatment

37 g of diatomite with the fineness of 8000 meshes and 8 g of rare earth with the fineness of 8000 meshes are mixed and dispersed in 1000mL of deionized water, 10g of concentrated sulfuric acid is added after stirring and mixing uniformly, and the mixed solution is stirred and reacted in a reaction kettle for 2 hours fully under the condition of keeping the temperature at 100 ℃. And then filtering, drying and calcining the material to obtain purified fine diatomite and rare earth composite soil.

2. Surface modification of fine diatomite and rare earth

40g of fine compound soil and 200mL of absolute ethyl alcohol are uniformly mixed and stirred for 10 min. Adding 6 g of TX10 phosphate and 5g of dodecyl polyoxyethylene ether, dispersing in 800mL of deionized water, stirring and dropwise adding 2.5 g of KH570, dispersing for 15min by ultrasonic waves to ensure full dispersion, placing in a homogenizer, and homogenizing for 10min to form the diatomite, bentonite and rare earth dispersion liquid.

3. Preparation of composite nano titanium dioxide-nano tourmaline dispersion liquid

Dispersing 110 g of nano-material titanium dioxide into 1000mL of ammonium carbonate solution with the concentration of 0.5mol/L, dropwise adding 1000mL of 0.5mol/L zinc sulfate solution into the solution, and ultrasonically dispersing for 15min to obtain a nano-titanium dioxide mixed dispersion liquid A. Dispersing 55g of nano tourmaline into 1000mL of deionized water, adding 5g of TX10 phosphate and 5g of dodecyl polyoxyethylene ether, and stirring for 30min by a high-speed dispersion machine to obtain nano tourmaline mixed dispersion liquid B. And (3) taking 2000mL of the nano titanium dioxide mixed dispersion liquid A, dropwise adding and mixing 1000mL of the nano alumina mixed dispersion liquid B, and homogenizing for 20min by adopting a homogenizer to obtain the composite nano titanium dioxide and nano tourmaline dispersion liquid.

4. Rotenone and tripterygium wilfordii alkali surface modification

Dispersing 45g of rotenone and 45g of triptolide in 800mL of isopropanol, mixing and stirring, sequentially dropwise adding 10g of 12-alkyl sodium sulfate, dropwise adding 2.5 g of KH570, continuously stirring for 10min, placing in a homogenizer, and homogenizing for 10min to obtain a rotenone and triptolide dispersion.

5. Rotenone and tripterygium wilfordii alkali nano dispersion liquid

(1) 10g of carboxymethyl chitose and 30g of chitosan were dissolved in 4000mL of acetic acid solution to prepare a solution C. A solution D was prepared by dissolving 40g of carboxymethyl cellulose and 5g of hydroxypropyl methyl cellulose in 9000mL of deionized water. 1000mL of the solution C was added dropwise to 1000mL of the solution D under stirring, and 5mL of triethanolamine was added to adjust the pH to 7-8, followed by mixing to obtain a solution E.

(2) And under the stirring condition, 6000mL of the solution D is taken, 300mL of the rotenone and triptolide dispersion liquid is dropwise added, 300mL of the mixed solution E is dropwise added, and 300mL of the solution C is dropwise added. After the dropwise addition, 9mL of diethanolamine is used for adjusting the pH value to 7-8, stirring is continuously carried out for 5min, ultrasonic dispersion is carried out for 10min, and the mixture is placed in a homogenizer for homogenization for 10min, so as to obtain the rotenone and triptolide nano dispersion liquid.

6. Mineral soil composite nano titanium dioxide-tourmaline and rotenone and tripterygium wilfordii alkali insecticidal bactericide stock solution

Adding 1000mL of diatomite, bentonite and rare earth dispersion into a reaction kettle, stirring 3000mL of composite nano zinc oxide and copper oxide dispersion, adjusting the pH to 7 by adopting 7mL of triethanolamine, and slowly dropwise adding 6000mL of rotenone and tripterygium wilfordii alkali nano dispersion. Stirring with a high-speed dispersion machine, reacting at 85 ℃ for 2h, cooling to normal temperature, placing in a homogenizer, and homogenizing for 10min to obtain 10000mL of mineral soil composite nano titanium dioxide-tourmaline and rotenone and triptolide insecticidal bactericide stock solution. Filtering, washing, drying and calcining the stock solution at 200 ℃ for 2h, and cooling to room temperature to obtain powder.

The particle size of the mineral soil composite nano titanium dioxide-tourmaline, rotenone and triptolide insecticidal and bactericidal agent powder is about 10-20nm by adopting a dynamic light scattering nano particle size analyzer, and the highest load rate of the plant extract can reach 65%.

Tourmaline is capable of permanently generating micro-current, which can break down bacteria and some insects. The tourmaline has piezoelectricity, pyroelectric property and far infrared radiation, micron-sized tourmaline powder is added to obtain a catalyst with smaller particle size, the loading capacity and the catalytic activity of the catalyst are improved, and the tourmaline has a weak electric field which can inhibit the recombination of electrons and holes and promote photocatalytic oxidation. The tourmaline contains transition metal ions, and can generate electron 2 hole pairs when irradiated by excitation light to promote generation of OH free radicals, and the generation of the OH free radicals has the same photocatalytic activation effect as that of nano semiconductor. The broad-spectrum insecticidal bactericide has the effect of killing all bacterial diseases. Especially has good killing effect on maggots and root nematodes such as Chinese chives and scallions, and other difficult and complicated diseases such as anthracnose and root rot, replaces the prior chemical pesticide and biological pesticide, does not generate drug resistance, and does not pollute the environment.

The insecticidal bactericide of the embodiment 4 of the invention has strong contact poisoning and stomach poisoning effects on almost all insects, particularly cabbage butterfly larvae, diamondback moths and aphids. Tourmaline has piezoelectricity, pyroelectric property, far infrared radiation and weak electric field property, and can kill pests in thick wax layer and crustacean, without affecting killing effect at night and in cloudy days. The action mechanism mainly influences the respiration of insects and mainly acts on a certain component between NADH dehydrogenase and coenzyme Q. The tourmaline-loaded nano plant extract insecticidal bactericide enables the electron transfer chain of pest cells to be inhibited, so that ATP level in organisms is reduced, and finally pests cannot be supplied with energy, and then slowly die due to action retardation and paralysis. Mitochondria, NADH dehydrogenase, succinic acid, mannitol, and other substances in many biological cells are sensitive to rotenone. The electron transfer from NADPH to NADH in the mitochondria of Setayria cervi is highly inhibited by the biocide, and the activity of the fumarate reductase system in the mitochondrial granules of the filarial parasite Setariadigitata is sensitive to the biocide. The insecticidal bactericide can inhibit electromotive force EMT of Trypanosoma brucei brucei mitochondrial inner membrane, thereby indirectly influencing the activity of NADH dehydrogenase. The insecticidal bactericide can also inhibit the activity of reductase from NADH to cytochrome C and from NADH to coenzyme Q in respiratory chain of mitochondria of Trypanosoma brucei, and the inhibition rate is up to 80-90%.

The field test control effects of insect killing and sterilization of examples 1 to 4 of the invention

The insecticidal and bactericidal agent stock solutions of examples 1 to 4 have field control effects on cabbage caterpillar, armyworm, tea geometrid, aphid, tobacco budworm, rust mite, red spider, diamond back moth, black cutworm, rice leaf roller, sesamia inferens and whitefly of more than 89%, and control effects on cabbage caterpillar, armyworm, tea geometrid, aphid, tobacco budworm, rust mite and diamond back moth of up to 98%.

Examples 1 to 4 the stock solutions of the insecticidal and bactericidal agents had field control effects on powdery mildew and downy mildew of cucumber, phytophthora capsici, fusarium graminearum, ralstonia solanacearum, corn stalk rot, citrus grandis canker, walnut black spot, bean bacterial blight, pepper bacterial leaf spot, taro bacterial spot, onion bacterial soft rot, soybean bacterial leaf burn, rape soft rot, rape bacterial black spot, beet soft rot, beet bacterial root cancerosis, beet bacterial leaf blight, tobacco bacterial wilt of more than 92%, and the control effects on powdery mildew of cucumber, grapevine mildew, phytophthora capsici, bean bacterial blight, and pepper bacterial leaf spot of up to 100%.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims

1. The insecticidal bactericide of the nano material copolymerized mineral and the plant extract is characterized by comprising mineral soil, a composite nano photocatalytic material and the plant extract, wherein the composite nano photocatalytic material and the plant extract are jointly and fixedly carried on the mineral soil.

2. The insecticidal and bactericidal agent of nanomaterial co-polymineral and plant extract as claimed in claim 1, wherein the mineral soil comprises one or more of rare earth and diatomite, attapulgite, bentonite, kaolin and china clay, and the fineness is 5000-10000 mesh.

3. The insecticidal and bactericidal agent of nanomaterial co-polymer minerals and plant extracts as claimed in claim 1, wherein the composite nano photocatalytic material comprises any one or more of nano titanium dioxide and nano graphene, nano zinc oxide, nano copper oxide, nano aluminum trioxide, nano calcium carbonate, nano tin antimony, nano indium tin, nano cerium oxide, nano cobalt oxide, nano tungsten oxide, or nano tourmaline.

4. A method for preparing insecticidal bactericide of nanometer material copolymerized mineral and plant extract comprises (1) surface modifying mineral soil with alcohol to obtain mineral soil modified dispersion; preparing the composite nano photocatalytic material into composite nano dispersion liquid; preparing the plant extract into plant extract nano dispersion liquid;

5. The method for preparing the nano-material co-minerals and plant extracts as claimed in claim 4, wherein the mineral soil modification dispersion liquid in step (1) is obtained by the following method:

step (11), adding mineral soil and deionized water into a reaction vessel according to the solid-liquid mass percentage of 10-50%, stirring and mixing uniformly, adding organic acid or inorganic acid containing hydroxyl, the mass of which is 1-10% of the total mass of the mineral soil and the deionized water, fully stirring and reacting at the water bath temperature of 50-150 ℃, performing suction filtration after reaction, and drying to obtain refined mineral soil;

and (12) mixing and stirring the fine mineral soil and the alcohol aqueous solution according to the mass ratio of 1.0-10.0%, then respectively adding a dispersing agent accounting for 0.1-0.4% of the total weight of the fine mineral soil and the alcohol aqueous solution and a wetting agent accounting for 0.1-0.4% of the total weight of the fine mineral soil and the alcohol aqueous solution, uniformly stirring to obtain a mineral soil mixture, then dropwise adding a non-alcohol surface modifier accounting for 0.1-0.5% of the total weight of the mineral soil mixture, and performing ultrasonic dispersion and homogenization to form the mineral soil modified dispersion liquid.

6. The method for preparing nano-material co-minerals and plant extracts as claimed in claim 5, wherein the inorganic acid in step (11) is one or more selected from phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid, boric acid, etc.

7. The method for preparing the nano-material co-polymineral and plant extract insecticidal and bactericidal agent according to any one of claims 5 to 6, wherein the composite nano-dispersion liquid in the step (2) is obtained by the following method:

step (21), dispersing a first nano photocatalytic material with the particle size of 1-10nm in an ammonium salt solution according to the mass volume concentration of 50g-100g/L, dropwise adding an inorganic compound solution, and performing ultrasonic dispersion to obtain a nano mixed dispersion liquid A; the volume ratio of the ammonium salt solution to the inorganic compound solution is (3: 1) - (1: 3);

step (22), dispersing a second nano photocatalytic material in deionized water according to the mass volume concentration of 50g-100g/L, adding a dispersing agent and a wetting agent, and dispersing and stirring at a high speed to obtain a nano mixed dispersion liquid B; the dosage of the dispersant and the wetting agent is 0.1 to 0.4 percent of the total weight of the second composite nano photocatalytic material and the deionized water;

dropwise adding the nano mixed dispersion liquid B into the nano mixed dispersion liquid A, and homogenizing by adopting a homogenizer to obtain a composite nano dispersion liquid; the volume ratio of the nano mixed dispersion liquid A to the nano mixed dispersion liquid B is (1: 1) - (2: 1).

8. The method for preparing nano-material co-minerals and plant extracts as claimed in claim 7, wherein the concentration of the ammonium salt solution in step (21) is 0.5 mol/L; the concentration of the inorganic compound solution is 0.5 mol/L.

9. The method as claimed in claim 7, wherein the ammonium salt in the ammonium salt solution in step (21) is one or more of urea, ammonium nitrate, ammonium sulfate, ammonium carbonate, ammonium bicarbonate, dodecylammonium chloride, ammonium bisulfate, ammonium fluoride, ammonium bromide, ammonium iodide, dioctadecyldimethylammonium bromide, dodecyldimethylbenzylammonium chloride or quaternary ammonium salt.

10. The method for preparing pesticides and fungicides containing nanomaterial co-minerals and plant extracts as claimed in claim 7, wherein said dispersing agent and said wetting agent in steps (12) and (22) are the same, and are two or more of alkylphenol ethoxylate phosphate, aryl phenol polyether phosphate, octadecyl phosphate, phosphate dispersing agent BYK110, NP10/TX10 phosphate, nonyl phenol polyether phosphate, 600 phosphate, TSP phosphate, and fatty alcohol ether phosphate; the wetting agent is one or more of dodecyl polyoxyethylene ether, polyoxyethylene alkylphenol ether, polyoxyethylene fatty alcohol ether, polyoxyethylene polyoxypropylene block ester and the like, and alkylphenol polyoxyethylene ether, alkylaryl polyoxyethylene ether, polyaryl nuclear polyoxyethylene ether, calcium dodecylbenzene sulfonate, glycerol, polyethylene glycol 200-400 and tween.

11. The method as claimed in claim 7, wherein the inorganic compound in the inorganic compound solution in step (21) is one or more selected from copper carbonate, copper sulfate, magnesium sulfate, zinc sulfate, copper nitrate, aluminum sulfate, zinc nitrate, magnesium nitrate, zinc chloride, aluminum chloride, and copper chloride.

12. The method for preparing the nano-material co-polymineral and plant extract insecticidal and bactericidal agent according to any one of claims 5 to 6 and 8 to 11, wherein the plant extract nano-dispersion in the step (3) is obtained by the following steps:

step (31) preparation of a plant extract modified dispersion

Dispersing plant extract into alcohol aqueous solution, wherein the mass volume concentration of the plant extract and the alcohol aqueous solution is 2.00g/L-10.00g/L, and uniformly stirring to obtain extract mixed solution; dripping non-alcohol surface modifier which accounts for 0.1-1.5% of the total weight of the plant extract mixed liquor into the extract mixed liquor, uniformly mixing, stirring and homogenizing to form plant extract modified dispersion liquid;

step (32) preparation of a plant extract nanodispersion

(321) Dissolving natural polymer organic sugar carrier in organic acid to prepare C solution with mass concentration of 0.1-8.0 g/L;

(322) dissolving a natural high molecular compound with carboxymethyl or hydroxymethyl in deionized water to prepare a solution with the mass concentration of 0.1-7.0 g/L D;

(325) and under the condition of stirring, respectively and sequentially dripping plant extract modified dispersion liquid into the solution D, dripping the mixed solution E, dripping the solution C, dripping the cross-linking agent solution, after dripping is finished, adjusting the pH, continuously stirring, and homogenizing to obtain the plant extract nano-dispersion liquid.

13. The method for preparing nano-material co-minerals and plant extracts as claimed in claim 12, wherein the alcohol aqueous solution in steps (12) and (31) comprises alcohol solvent and deionized water, and the mass ratio of the alcohol solvent to the deionized water is 1: 1-1: 5.

14. the method for preparing nano-material co-minerals and plant extracts as claimed in claim 12, wherein the alcoholic solvent and the non-alcoholic surface modifier in steps (12) and (31) are the same and are one or more of methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and propanol; the non-alcoholic surface modifier is KH550, KH560, KH570, silicone oil, methyl silicone oil, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, and sodium alkyl benzene sulfonate.

15. The method of claim 12, wherein the plant extract is selected from the group consisting of nicotine, camptothecin, stemonine, veratrine, matrine, wilfordine, ficolinine, tetrandrine, aloperine, allicin, cnidium lactone, celastrol, pyrethrin, etorphine, phytoalexin, steroids such as cortexolone, lycoside, toosendanin, theasaponin, celastrol, rhodojaponin, rotenone, and rotenone.

16. The method for preparing a nano-material co-polymineral and plant extract insecticidal and bactericidal agent as claimed in claim 12, wherein the ratio of D solution: plant extract modified dispersion: e, mixing liquid: solution C: the volume ratio of the cross-linking agent solution is 40: 2: 2:1:1.

17. The method for preparing a pesticidal and fungicidal agent containing a nanomaterial co-mineral and a plant extract according to claim 12, wherein the pH is adjusted to 7 in the steps (4) and (325).

18. The method for preparing an insecticidal/fungicidal agent comprising a nanomaterial as claimed in claim 12, wherein in step (321), the natural polymer organic sugar carrier is one or more of sucrose, arabinose, trehalose, chitosan, lactose, oligosaccharide, glucose, maltose, N-acetylcarboxyl sugar, polygalactomannose, fructose, carboxysepharose, ferricarboxymaltose, and konjac glucomannan; the organic acid is one or more of formic acid, tartaric acid, citric acid, tannic acid, acetic acid, oxalic acid, malic acid, mugineic acid, succinic acid, punicic acid, vanillic acid, benzoic acid, salicylic acid, coumaric acid, ferulic acid, syringic acid, citric acid, caffeic acid, benzoic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, etc.; the carboxymethyl or hydroxymethyl macromolecule is one or more than two of hydroxypropyl methyl cellulose, hydroxyethyl cellulose, hydroxypropyl starch, carboxymethyl cellulose, carboxymethyl starch, carboxymethyl dextrin, carboxymethyl pachyman, carboxymethyl chitosan, carboxymethyl fructose, carboxymethyl chitose, carboxymethyl inulin, amino acid, carboxymethyl glucose, carboxymethyl chitosan oligosaccharide, etc.; the crosslinking agent is one or more of calcium nitrate, calcium dihydrogen phosphate, calcium carbonate, calcium acetate, calcium formate, calcium gluconate, calcium lactate, calcium citrate, L-threonine calcium carbonate, and calcium oxalate.

19. The method for preparing a pesticide-bactericide of nanomaterial co-minerals and plant extracts according to claim 12, wherein the acid group of the organic acid or inorganic acid containing a hydroxyl group in step (11) is the same as the acid group ion of the cross-linking agent in the cross-linking agent solution.