Insecticide composition as well as preparation method and application thereof

Abstract

The invention relates to the technical field of insecticides, in particular to an insecticide composition and a preparation method and application thereof.The insecticide composition is prepared from, by weight, 5-25 parts of neonicotinoid insecticides, 2-15 parts of 4-trifluoromethyl nicotinamide, 2-5 parts of microbial insecticides, 2-20 parts of botanical insecticides and 2-10 parts of sulfonated modified graphene nano powder. 5-15 parts of silicon dioxide-titanium oxide composite powder particles; the microbial insecticide is prepared from bacillus thuringiensis and metarhizium anisopliae; the botanical insecticide is prepared from azadirachtin, veratrine and celastrus angulatus. By matching and combining the raw materials, the prepared insecticide composition can improve the insecticidal effect while reducing the use of neonicotinoid insecticides, and reduces the influence on the farmland environment.

Description

Technical Field

[0001] This application relates to the technical field of insecticides, and specifically relates to an insecticide composition, a preparation method thereof, and an application thereof. Background Art

[0002] Various pests and diseases will occur during the cultivation process of agricultural plants, such as peach aphids, melon aphids, cabbage aphids, and radish aphids of the aphid category, Tetranychus cinnabarinus, Tetranychus truncatus, and Tetranychus urticae Koch of the spider mite category, etc. These are all the main pests that harm cucurbit and vegetable crops. Pests and diseases are the natural enemies of crops, and eliminating crop pests and diseases is a key problem in achieving increased grain production. The emergence of insecticides has played a great role in curbing various crop pests and diseases, ensuring a bumper harvest of agriculture.

[0003] Neonicotinoid insecticides are a type of nitroguanidine systemic insecticides used globally. They can protect plant seedlings from leaf-eating pests and can also effectively control various piercing-sucking mouthpart pests, as well as some Lepidoptera and Coleoptera pests on field crops, vegetables, and fruit trees. Due to their novel mode of action, strong selective toxicity, high efficiency, broad spectrum, and good environmental compatibility, neonicotinoid insecticides have greatly enhanced the resistance of crops to pests and diseases and are widely used worldwide. However, their toxicity to non-target organisms and various residue problems have also received extensive attention.

[0004] Reducing the negative impact of neonicotinoid insecticides while maintaining high efficiency in killing pests has become an urgent problem in the field of insecticides. Summary of the Invention

[0005] This application aims to at least overcome one of the defects of the prior art, and provides an insecticide composition, a preparation method thereof, and an application thereof. Through the combination of various raw materials, the prepared insecticide composition can improve the insecticidal effect while reducing the use of neonicotinoid insecticides and reduce the impact on the farmland environment.

[0006] In a first aspect, an embodiment of this application provides an insecticide composition, which is achieved through the following technical solutions:

[0007] An insecticide composition, comprising the following raw materials for preparation in parts by weight:

[0008] 5-25 parts of neonicotinoid insecticide, 2-15 parts of 4-trifluoromethyl nicotinamide, 2-5 parts of microbial insecticide, 2-20 parts of plant-derived insecticide, 2-10 parts of sulfonated modified graphene nanopowder, and 5-15 parts of silica-titania composite powder particles;

[0009] The microbial insecticide is composed of Bacillus thuringiensis and Metarhizium anisopliae;

[0010] The plant-derived insecticide is composed of azadirachtin, veratridine, and celangulin.

[0011] The insecticide composition according to the embodiments of the present application has at least the following beneficial effects:

[0012] By mixing and using, the insecticide composition of the present application mixes a neonicotinoid insecticide with other environmentally friendly insecticides, giving play to their respective advantages. It can improve the insecticidal effect while reducing the use of neonicotinoid insecticides, and reduce the impact on the farmland environment.

[0013] The sulfonated modified graphene nanopowder of the present application has a large specific surface area and strong adsorption capacity. It can adsorb the active ingredients of the insecticide, and at the same time adhere to the body surface of pests to enhance the insecticidal effect. As a carrier, graphene can slowly release the active ingredients and extend the duration of the insecticide. In addition, the efficient adsorption and slow-release characteristics of graphene can reduce the usage amount of the insecticide, lower the cost, and reduce the negative impact on the environment. Graphene itself has antibacterial and antiviral properties, which can enhance the comprehensive effect of the insecticide. After sulfonation modification, the dispersibility and compatibility of graphene nanopowder are improved, further enhancing the insecticidal effect of the insecticide.

[0014] The silica-titania composite powder particles of the present application use titania powder and silica powder in combination, which can combine the characteristics of both and produce a synergistic effect. The photocatalytic effect of titania can destroy the cell structure of pests, while silica powder has a high specific surface area and porous structure, which can adsorb more titania and insecticide on the surface of pests, providing more contact opportunities for the photocatalytic reaction of titania and improving the insecticidal efficiency. Silica powder can be used as a carrier to prevent the agglomeration of titania particles and improve its dispersibility, thereby increasing the active sites of the photocatalytic reaction. The addition of silica powder can protect titania powder from photocorrosion and extend its photocatalytic activity. Silica can also slowly release the photocatalytic active ingredients of titania and the active ingredients of the insecticide, extending the insecticidal effect.

[0015] 4-Trifluoromethyl nicotinamide of the present application exerts its effect by inhibiting nicotinamidase. By inhibiting the nicotinamidase activity of pests, it causes the accumulation of nicotinamide in the pests, and then over-activates the ion channels, resulting in poisoning symptoms in the pests and ultimately death. This target is specific in the insect nervous system and does not exist in vertebrates. Therefore, it has a high safety for non-target organisms and can be used to control aphids, brown planthoppers, and whiteflies.

[0016] As a microbial low-toxicity insecticide, the Bacillus thuringiensis of the present application can produce two major types of toxins: endotoxin and exotoxin. The endotoxin causes pests to stop feeding and die of starvation, while the exotoxin acts slowly and mainly plays a role during the molting and metamorphosis of pests. These two periods are the peak periods of RNA synthesis. The exotoxin can inhibit DNA-dependent RNA polymerase, leading to the poisoning and death of pests. Metarhizium anisopliae is a broad-spectrum insecticide that can directly kill pests by invading their bodies through contact. The combination of Bacillus thuringiensis and Metarhizium anisopliae can enhance their respective bactericidal effects, with complementary mechanisms of action to expand the control range and improve the insecticidal efficiency.

[0017] The azadirachtin of the present application is a plant-derived insecticide extracted from neem trees. It exerts its effects through antifeedant action, interference with egg laying and metamorphosis, and inhibition of growth and development. It is easily degraded in the environment without residue, is friendly to the ecological environment, and is not prone to generating drug resistance. Veratridine is a natural substance extracted from Chinese herbal medicines. It exerts its effects through contact toxicity and stomach toxicity, mainly acting on the nervous system of pests. First, it inhibits the sensory nerve endings of the insect body, and then inhibits the central nervous system, resulting in the paralysis, antifeeding, and rolling of pests until they die. The drug effect is persistent, safe, and reliable. Celangulin is a plant-derived insecticide with multiple modes of action such as anesthesia, antifeedant, stomach toxicity, and contact toxicity. It has the characteristics of high efficiency, long persistence, low toxicity, and harmlessness, and is easy to degrade. The combination of azadirachtin, veratridine, and celangulin can produce a synergistic effect, with a more diverse mechanism of action on pests, thereby enhancing the insecticidal effect and having stronger adaptability to deal with more types of pests.

[0018] According to some embodiments of the present application, the preparation of the silica-titania composite powder particles includes the following steps: Prepare a suspension with a mass concentration of 1.5% from 35-45 parts by weight of nano-titania powder, add 1-2 parts of sodium hexametaphosphate for dispersion, perform ultrasonic oscillation for 30-40 min, heat to 120-200 °C, and simultaneously dropwise add 40-50 parts of sodium silicate and 30-40 parts of dilute sulfuric acid, adjust the pH value to 8-10, keep warm and age for 1-2 h, dry at 100-110 °C for 0.5-1 h, calcine, and grind to obtain the silica-titania composite powder particles.

[0019] Furthermore, the calcination includes pre-calcination and formal calcination. The pre-calcination in the two-stage calcination is for pre-activation first, and the formal calcination is for activation. Through the two-stage calcination, the crystal lattice is gradually destroyed, making it easier to form amorphous active materials and improving the adsorption effect of the silica-titania composite powder particles.

[0020] Even further, the pre-calcination is carried out at a temperature of 200-220 °C for 30-40 min.

[0021] Even further, the formal calcination is carried out at a temperature of 500-600 °C for 20-30 min.

[0022] Further, the grinding makes the particle size of the silica-titania composite powder reach more than 100 mesh. Grinding to more than 100 mesh can make the silica-titania composite powder particles smaller, enhance the dispersibility, facilitate rapid and uniform mixing with other components during the subsequent preparation of the insecticide, and at the same time increase the fineness of the prepared insecticide, making it convenient for application.

[0023] According to some embodiments of the present application, the preparation of the sulfonated modified graphene nanopowder includes the following steps: uniformly mixing the nano-graphene powder and Na2SO3 at a weight ratio of (3 - 5):(2 - 3), adding a NaOH solution with a mass fraction of 15%, and reacting at a temperature of 150 - 200 °C for 3 - 5 h to obtain the sulfonated modified graphene nanopowder.

[0024] According to some embodiments of the present application, the weight ratio of Bacillus thuringiensis to Metarhizium anisopliae in the microbial insecticide is (2 - 3):1.

[0025] According to some embodiments of the present application, the weight ratio of azadirachtin, veratridine, and celangulin in the botanical insecticide is (1 - 2):1:(2 - 3).

[0026] According to some embodiments of the present application, the neonicotinoid insecticide includes at least two of imidacloprid, thiacloprid, thiamethoxam, clothianidin, dinotefuran, sulfoxaflor, triflumezopyrim, and dichlorothiopyrimidine. When multiple neonicotinoid insecticides are used in combination, the sensitivities of different neonicotinoid insecticides to pests are different. The combined use can cover a wider range of pest species, enhance the interference with the nervous system of pests through different metabolic pathways, has multiple action sites, can improve the insecticidal speed, and is more likely to achieve control of all insect stages.

[0027] Further, the neonicotinoid insecticide is composed of imidacloprid, thiamethoxam, and triflumezopyrim mixed in a weight ratio of (3 - 5):(2 - 3):(1 - 2).

[0028] In a second aspect, the embodiments of the present application provide a preparation method of the above-mentioned insecticide composition, which is achieved through the following technical solutions:

[0029] A preparation method of an insecticide composition includes the following steps:

[0030] Mix the microbial insecticide and the sulfonated modified graphene nanopowder by weight, add 10 - 20 parts of a 20% by mass sugar water and stir for 20 min - 30 min, then add the neonicotinoid insecticide, 4-trifluoromethylnicotinamide, the botanical insecticide, and the silica-titania composite powder particles, and continue to stir for 1 - 2 h to obtain the insecticide composition.

[0031] The preparation method of the insecticide composition according to the embodiments of the present application has at least the following beneficial effects:

[0032] The preparation method of the present application has simple steps, does not require complex production equipment, has low cost, no pollution in the manufacturing process, no emission of toxic substances, does not harm the health of operators, and is suitable for industrial production.

[0033] According to some embodiments of the present application, the rotation speeds of both stirrings are 1000 - 2000 r / min.

[0034] In a third aspect, the embodiments of the present application provide the application of the above-mentioned insecticide composition in the preparation of insecticide formulations.

[0035] The formulations include at least one of wettable powders, water-dispersible granules, suspensions, and suspoemulsions. Detailed implementation manners

[0036] To make the objectives, technical solutions, and advantages of the present application clearer, the following will be further described in detail with reference to specific embodiments. The embodiments described herein are only a part of the embodiments of the present application and should not be construed as limiting the protection scope of the present application.

[0037] Example 1

[0038] Preparation of the insecticide composition: Select raw materials by weight: 15 parts of neonicotinoid insecticides, 8 parts of 4-trifluoromethylnicotinamide, 4 parts of microbial insecticides, 10 parts of plant-derived insecticides, 6 parts of sulfonated modified graphene nanopowders, and 10 parts of silica-titania composite powder particles; the microbial insecticide is composed of Bacillus thuringiensis and Metarhizium anisopliae in a weight ratio of 2.5:1; the plant-derived insecticide is composed of azadirachtin, veratridine, and celangulin in a weight ratio of 1.5:1:2.5; the neonicotinoid insecticide is composed of imidacloprid, thiamethoxam, and triflumezopyrim in a weight ratio of 4:2.5:1.5;

[0039] Mix the microbial insecticide and sulfonated modified graphene nanopowders by weight, add 15 parts of sugar water with a mass concentration of 20% and stir at a rotation speed of 1500 r / min for 25 min, then add the neonicotinoid insecticides, 4-trifluoromethylnicotinamide, plant-derived insecticides, and silica-titania composite powder particles, and continue to stir at a rotation speed of 1500 r / min for 1.5 h to obtain the insecticide composition;

[0040] Among them, the preparation method of the silica-titania composite powder particles is as follows: 40 parts of nano-titania powder is formulated into a suspension with a mass concentration of 1.5% according to weight, 1.5 parts of sodium hexametaphosphate is added for dispersion, ultrasonic oscillation is carried out for 35 min, heated to 160 °C, and at the same time 45 parts of sodium silicate and 35 parts of dilute sulfuric acid are added dropwise, the pH value is adjusted to 8-10, aged at a constant temperature for 1.5 h, dried at 105 °C for 0.8 h, pre-calcined at a temperature of 210 °C for 35 min, calcined at a temperature of 550 °C for 25 min, and ground to more than 100 mesh to obtain silica-titania composite powder particles;

[0041] The preparation method of the sulfonated modified graphene nano powder is as follows: nano-graphene powder and Na2SO3 are mixed evenly according to a weight ratio of 4:2.5, and a NaOH solution with a mass fraction of 15% is added, and the reaction is carried out at a temperature of 180 °C for 4 h to obtain sulfonated modified graphene nano powder.

[0042] Example 2

[0043] Preparation of the insecticide composition: The raw materials are selected according to weight: 25 parts of neonicotinoid insecticide, 2 parts of 4-trifluoromethyl nicotinamide, 5 parts of microbial insecticide, 2 parts of plant-derived insecticide, 10 parts of sulfonated modified graphene nano powder, 5 parts of silica-titania composite powder particles; The microbial insecticide is composed of Bacillus thuringiensis and Metarhizium anisopliae according to a weight ratio of 3:1; The plant-derived insecticide is composed of azadirachtin, veratridine and celangulin according to a weight ratio of 1:1:3; The neonicotinoid insecticide is composed of imidacloprid, thiamethoxam and triflumezopyrim according to a weight ratio of 3:3:1;

[0044] The microbial insecticide and the sulfonated modified graphene nano powder are mixed according to weight, 20 parts of sugar water with a mass concentration of 20% is added and stirred at a speed of 1000 r / min for 30 min, and the neonicotinoid insecticide, 4-trifluoromethyl nicotinamide, plant-derived insecticide, and silica-titania composite powder particles are added, and stirring is continued at a speed of 1000 r / min for 2 h to obtain the insecticide composition;

[0045] Among them, the preparation method of the silica-titania composite powder particles is as follows: 35 parts of nano-titania powder is formulated into a suspension with a mass concentration of 1.5% according to weight, 2 parts of sodium hexametaphosphate is added for dispersion, ultrasonic oscillation is carried out for 30 min, heated to 200 °C, and at the same time 40 parts of sodium silicate and 40 parts of dilute sulfuric acid are added dropwise, the pH value is adjusted to 8-10, aged at a constant temperature for 1 h, dried at 110 °C for 0.5 h, pre-calcined at a temperature of 220 °C for 30 min, calcined at a temperature of 600 °C for 20 min, and ground to more than 100 mesh to obtain silica-titania composite powder particles;

[0046] The preparation method of the sulfonated modified graphene nanopowder is as follows: Mix the nano graphene powder and Na2SO3 evenly according to a weight ratio of 5:2, add a NaOH solution with a mass fraction of 15%, react at a temperature of 200 °C for 3 h to obtain the sulfonated modified graphene nanopowder.

[0047] Example 3

[0048] Preparation of the insecticide composition: Select raw materials by weight: 5 parts of neonicotinoid insecticide, 15 parts of 4-trifluoromethyl nicotinamide, 2 parts of microbial insecticide, 20 parts of plant-derived insecticide, 2 parts of sulfonated modified graphene nanopowder, and 15 parts of silica-titania composite powder particles; The microbial insecticide is composed of Bacillus thuringiensis and Metarhizium anisopliae according to a weight ratio of 2:1; The plant-derived insecticide is composed of azadirachtin, veratridine, and celangulin according to a weight ratio of 2:1:2; The neonicotinoid insecticide is composed of imidacloprid, thiamethoxam, and triflumezopyrim according to a weight ratio of 5:2:2;

[0049] Mix the microbial insecticide and the sulfonated modified graphene nanopowder by weight, add 10 parts of sugar water with a mass concentration of 20%, stir at a speed of 2000 r / min for 20 min, add the neonicotinoid insecticide, 4-trifluoromethyl nicotinamide, plant-derived insecticide, and silica-titania composite powder particles, and continue to stir at a speed of 2000 r / min for 1 h to obtain the insecticide composition;

[0050] Among them, the preparation method of the silica-titania composite powder particles is as follows: Prepare a suspension with a mass concentration of 1.5% from 45 parts of nano titanium oxide powder by weight, add 1 part of sodium hexametaphosphate for dispersion, perform ultrasonic oscillation for 40 min, heat to 120 °C, and simultaneously dropwise add 50 parts of sodium silicate and 30 parts of dilute sulfuric acid, adjust the pH value to 8-10, keep warm and age for 2 h, dry at 100 °C for 1 h, pre-calcine at a temperature of 200 °C for 40 min, calcine formally at a temperature of 500 °C for 30 min, and grind to more than 100 meshes to obtain the silica-titania composite powder particles;

[0051] The preparation method of the sulfonated modified graphene nanopowder is as follows: Mix the nano graphene powder and Na2SO3 evenly according to a weight ratio of 3:3, add a NaOH solution with a mass fraction of 15%, react at a temperature of 150 °C for 5 h to obtain the sulfonated modified graphene nanopowder.

[0052] Example 4

[0053] Preparation of the insecticide composition: The raw materials are selected by weight parts: 15 parts of neonicotinoid insecticides, 6 parts of 4-trifluoromethylnicotinamide, 3 parts of microbial insecticides, 8 parts of plant-derived insecticides, 7 parts of sulfonated modified graphene nanopowder, and 9 parts of silica-titania composite powder particles; The microbial insecticide is composed of Bacillus thuringiensis and Metarhizium anisopliae in a weight ratio of 3:1; The plant-derived insecticide is composed of azadirachtin, veratridine, and celangulin in a weight ratio of 2:1:3; The neonicotinoid insecticide is a mixture of imidacloprid, thiamethoxam, and triflumezopyrim in a weight ratio of 4:3:1;

[0054] Mix the microbial insecticide and the sulfonated modified graphene nanopowder by weight parts, add 15 parts of sugar water with a mass concentration of 20%, stir at a speed of 1500 r / min for 25 min, add the neonicotinoid insecticide, 4-trifluoromethylnicotinamide, plant-derived insecticide, and silica-titania composite powder particles, and continue to stir at a speed of 1500 r / min for 1.5 h to obtain the insecticide composition;

[0055] Among them, the preparation method of the silica-titania composite powder particles is as follows: Prepare a suspension with a mass concentration of 1.5% from 40 parts of nano-titania powder by weight parts, add 1.5 parts of sodium hexametaphosphate for dispersion, ultrasonically oscillate for 35 min, heat to 150 °C, and simultaneously dropwise add 45 parts of sodium silicate and 35 parts of dilute sulfuric acid, adjust the pH value to 8-10, keep warm and age for 1.5 h, dry at 110 °C for 0.8 h, pre-calcine at a temperature of 210 °C for 35 min, officially calcine at a temperature of 550 °C for 25 min, and grind to more than 100 meshes to obtain the silica-titania composite powder particles;

[0056] The preparation method of the sulfonated modified graphene nanopowder is as follows: Mix the nano-graphene powder and Na2SO3 evenly according to a weight ratio of 4:3, add a NaOH solution with a mass fraction of 15%, and react at a temperature of 180 °C for 4 h to obtain the sulfonated modified graphene nanopowder.

[0057] Comparative Example 1

[0058] Preparation of the insecticide composition: The raw materials are selected by weight parts: 15 parts of neonicotinoid insecticides, 8 parts of 4-trifluoromethylnicotinamide, 4 parts of microbial insecticides, 10 parts of plant-derived insecticides, 6 parts of sulfonated modified graphene nanopowder; The microbial insecticide is composed of Bacillus thuringiensis and Metarhizium anisopliae in a weight ratio of 2.5:1; The plant-derived insecticide is composed of azadirachtin, veratridine, and celangulin in a weight ratio of 1.5:1:2.5; The neonicotinoid insecticide is a mixture of imidacloprid, thiamethoxam, and triflumezopyrim in a weight ratio of 4:2.5:1.5;

[0059] Mix the microbial insecticide and sulfonated modified graphene nanopowder by weight parts, add 15 parts of sugar water with a mass concentration of 20%, stir at a speed of 1500 r / min for 25 min, add neonicotinoid insecticide, 4-trifluoromethyl nicotinamide, and plant-derived insecticide, and continue to stir at a speed of 1500 r / min for 1.5 h to obtain an insecticide composition;

[0060] Among them, the preparation method of the sulfonated modified graphene nanopowder is as follows: Mix the nano-graphene powder and Na2SO3 evenly according to a weight ratio of 4:2.5, add a NaOH solution with a mass fraction of 15%, and react at a temperature of 180 °C for 4 h to obtain the sulfonated modified graphene nanopowder.

[0061] Comparative Example 2

[0062] Preparation of the insecticide composition: Select raw materials by weight parts: 15 parts of neonicotinoid insecticide, 8 parts of 4-trifluoromethyl nicotinamide, 4 parts of microbial insecticide, 10 parts of plant-derived insecticide, and 10 parts of silica-titania composite powder particles; The microbial insecticide is composed of Bacillus thuringiensis and Metarhizium anisopliae according to a weight ratio of 2.5:1; The plant-derived insecticide is composed of azadirachtin, veratridine, and celangulin according to a weight ratio of 1.5:1:2.5; The neonicotinoid insecticide is composed of imidacloprid, thiamethoxam, and triflumezopyrim according to a weight ratio of 4:2.5:1.5;

[0063] Mix the microbial insecticide by weight parts, add 15 parts of sugar water with a mass concentration of 20%, stir at a speed of 1500 r / min for 25 min, add neonicotinoid insecticide, 4-trifluoromethyl nicotinamide, plant-derived insecticide, and silica-titania composite powder particles, and continue to stir at a speed of 1500 r / min for 1.5 h to obtain an insecticide composition;

[0064] Among them, the preparation method of the silica-titania composite powder particles is as follows: Prepare a suspension with a mass concentration of 1.5% of 40 parts of nano-titanium oxide powder by weight parts, add 1.5 parts of sodium hexametaphosphate for dispersion, ultrasonically oscillate for 35 min, heat to 160 °C, and simultaneously dropwise add 45 parts of sodium silicate and 35 parts of dilute sulfuric acid, adjust the pH value to 8-10, keep warm and age for 1.5 h, dry at 105 °C for 0.8 h, pre-calcine at a temperature of 210 °C for 35 min, calcine formally at a temperature of 550 °C for 25 min, and grind to more than 100 meshes to obtain the silica-titania composite powder particles.

[0065] Comparative Example 3

[0066] Preparation of the insecticide composition: Raw materials are selected by weight parts: 15 parts of neonicotinoid insecticide, 8 parts of 4-trifluoromethyl nicotinamide, 4 parts of microbial insecticide, 10 parts of plant-derived insecticide, 6 parts of sulfonated modified graphene nanopowder, and 10 parts of silica-titania composite powder particles; the microbial insecticide is Bacillus thuringiensis; the plant-derived insecticide is composed of azadirachtin, veratridine, and celangulin in a weight ratio of 1.5:1:2.5; the neonicotinoid insecticide is mixed by imidacloprid, thiamethoxam, and triflumezopyrim in a weight ratio of 4:2.5:1.5;

[0067] Mix the microbial insecticide and the sulfonated modified graphene nanopowder by weight parts, add 15 parts of sugar water with a mass concentration of 20% and stir at a speed of 1500 r / min for 25 min, then add the neonicotinoid insecticide, 4-trifluoromethyl nicotinamide, plant-derived insecticide, and silica-titania composite powder particles, and continue to stir at a speed of 1500 r / min for 1.5 h to obtain the insecticide composition;

[0068] Among them, the preparation method of the silica-titania composite powder particles is as follows: Prepare a suspension with a mass concentration of 1.5% from 40 parts of nano-titania powder by weight parts, add 1.5 parts of sodium hexametaphosphate for dispersion, perform ultrasonic oscillation for 35 min, heat to 160 °C, and simultaneously dropwise add 45 parts of sodium silicate and 35 parts of dilute sulfuric acid, adjust the pH value to 8-10, keep warm and age for 1.5 h, dry at 105 °C for 0.8 h, pre-calcine at a temperature of 210 °C for 35 min, officially calcine at a temperature of 550 °C for 25 min, and grind to more than 100 meshes to obtain the silica-titania composite powder particles;

[0069] The preparation method of the sulfonated modified graphene nanopowder is as follows: Mix the nano-graphene powder and Na2SO3 evenly according to a weight ratio of 4:2.5, add a NaOH solution with a mass fraction of 15%, and react at a temperature of 180 °C for 4 h to obtain the sulfonated modified graphene nanopowder.

[0070] Comparative Example 4

[0071] Preparation of the insecticide composition: Raw materials are selected by weight parts: 15 parts of neonicotinoid insecticide, 8 parts of 4-trifluoromethyl nicotinamide, 4 parts of microbial insecticide, 10 parts of plant-derived insecticide, 6 parts of sulfonated modified graphene nanopowder, and 10 parts of silica-titania composite powder particles; the microbial insecticide is composed of Bacillus thuringiensis and Metarhizium anisopliae in a weight ratio of 2.5:1; the plant-derived insecticide is composed of azadirachtin and celangulin in a weight ratio of 1.5:2.5; the neonicotinoid insecticide is mixed by imidacloprid, thiamethoxam, and triflumezopyrim in a weight ratio of 4:2.5:1.5;

[0072] Mix the microbial insecticide and sulfonated modified graphene nanopowder by weight parts, add 15 parts of sugar water with a mass concentration of 20%, stir at a speed of 1500 r / min for 25 min, add neonicotinoid insecticide, 4-trifluoromethyl nicotinamide, plant-derived insecticide, and silica-titania composite powder particles, and continue to stir at a speed of 1500 r / min for 1.5 h to obtain an insecticide composition;

[0073] Among them, the preparation method of the silica-titania composite powder particles is as follows: Prepare a suspension with a mass concentration of 1.5% from 40 parts of nano-titania powder by weight parts, add 1.5 parts of sodium hexametaphosphate for dispersion, ultrasonically oscillate for 35 min, heat to 160 °C, and simultaneously dropwise add 45 parts of sodium silicate and 35 parts of dilute sulfuric acid, adjust the pH value to 8-10, keep warm and age for 1.5 h, dry at 105 °C for 0.8 h, pre-calcine at a temperature of 210 °C for 35 min, officially calcine at a temperature of 550 °C for 25 min, and grind to more than 100 meshes to obtain silica-titania composite powder particles;

[0074] The preparation method of the sulfonated modified graphene nanopowder is as follows: Mix nano-graphene powder and Na2SO3 evenly according to a weight ratio of 4:2.5, add a NaOH solution with a mass fraction of 15%, and react at a temperature of 180 °C for 4 h to obtain sulfonated modified graphene nanopowder.

[0075] Form the insecticide compositions prepared in Examples 1-4 and Comparative Examples 1-4 into wettable powders, and apply them to the wheat farmland with pests and diseases of the same variety of wheat planted in the same village respectively. Test the relevant data of pests and diseases in the farmland. The photosynthetic rate of the leaves is tested with a portable photosynthesis measuring instrument. The tested leaves are healthy leaves at similar parts of the plants, and the average value of different plants in the same farmland is used as the test result.

[0076] The test data are shown in Table 1 below:

[0077] Table 1

[0078]

[0079] It can be seen from Table 1 that the insecticide compositions prepared in Examples 1-4 of the present application can significantly enhance the insecticidal effect, improve the photosynthetic rate of wheat leaves, and increase the wheat yield.

[0080] Silica-titania composite powder particles were not used in the raw materials of Comparative Example 1, and the rest were the same as in Example 1. The pest lethality rate of the insecticide composition prepared in Comparative Example 1 decreased, and at the same time, the photosynthesis rate of the leaves also decreased significantly. The wheat yield was lower than that of Example 1, indicating that the silica-titania composite powder particles of the present application combine the use of titanium oxide powder and silica powder, which can combine the characteristics of both and produce a synergistic effect. The photocatalytic effect of titanium oxide can destroy the cell structure of pests, while silica powder has a high specific surface area and a porous structure, which can adsorb more titanium oxide and insecticide on the surface of pests, providing more contact opportunities for the photocatalytic reaction of titanium oxide and improving the insecticidal efficiency. Silica powder can be used as a carrier to prevent the agglomeration of titanium oxide particles and improve its dispersibility, thereby increasing the active sites of the photocatalytic reaction. The addition of silica powder can protect titanium oxide powder from photocorrosion and extend its photocatalytic activity; silica can also slowly release the photocatalytic active ingredients of titanium oxide and the insecticide active ingredients, prolonging the insecticidal effect.

[0081] Sulfonated modified graphene nanopowder was not used in the raw materials of Comparative Example 2, and the rest were the same as in Example 1. The pest lethality rate of the insecticide composition prepared in Comparative Example 2 decreased, and at the same time, the photosynthesis rate of the leaves also decreased significantly. The wheat yield was lower than that of Example 1, indicating that the sulfonated modified graphene nanopowder of the present application has a large specific surface area and strong adsorption ability, can adsorb insecticide active ingredients, and at the same time adhere to the body surface of pests to improve the insecticidal effect. As a carrier, graphene can slowly release active ingredients and prolong the duration of the insecticide; in addition, the high-efficiency adsorption and slow-release characteristics of graphene can reduce the usage amount of the insecticide, reduce costs, and reduce the negative impact on the environment. Graphene itself has antibacterial and antiviral properties, which can enhance the comprehensive effect of the insecticide; after sulfonated modification, the dispersibility and compatibility of graphene nanopowder are improved, further enhancing the insecticidal effect of the insecticide.

[0082] Metarhizium anisopliae was not contained in the microbial insecticide in the raw materials of Comparative Example 3, and the rest were the same as in Example 1. The pest lethality rate of the insecticide composition prepared in Comparative Example 3 decreased, and at the same time, the photosynthesis rate of the leaves also decreased significantly. The wheat yield was lower than that of Example 1, indicating that the Metarhizium anisopliae of the present application is a broad-spectrum insecticide, which can directly kill pests by invading into the pests through contact; the combination of Bacillus thuringiensis and Metarhizium anisopliae can enhance their respective bactericidal effects, and the complementary action mechanisms can expand the control range and improve the insecticidal efficiency.

[0083] The plant-derived insecticide in the raw materials of Comparative Example 4 does not contain veratridine, and the rest are the same as those in Example 1. The pest lethality rate of the insecticide composition prepared in Comparative Example 4 decreased, and at the same time, the photosynthesis rate of the leaves also decreased significantly. The wheat yield was lower than that in Example 1, indicating that the veratridine in this application is a natural substance extracted from Chinese herbal medicine, which exerts its effects through contact poisoning and stomach poisoning, mainly acting on the nervous system of pests. First, it inhibits the sensory nerve endings of the insect body, and then inhibits the central nerve, resulting in paralysis, refusal to eat, rolling until death of the pests. The drug effect is long-lasting, safe and reliable; the combination of azadirachtin, veratridine and celangulin can produce a synergistic effect, and the mechanism of action on pests is more diverse, thus enhancing the insecticidal effect, and at the same time, it has stronger adaptability and can deal with more types of pests.

[0084] Although the embodiments of the present application have been shown and described, those of ordinary skill in the art can understand that various changes, modifications, substitutions or variations can be made to these embodiments without departing from the principle and spirit of the present application, and the technical solutions after these changes, modifications, substitutions or variations will fall within the protection scope of the present application.

Claims

1. An insecticide composition, characterized in that: The preparation comprises the following raw materials in parts by weight: 5-25 parts of neonicotinoid insecticide, 2-15 parts of 4-trifluoromethylnicotinamide, 2-5 parts of microbial insecticide, 2-20 parts of botanical insecticide, 2-10 parts of sulfonated modified graphene nanopowder, 5-15 parts of silicon dioxide-titanium oxide composite powder particles; The microbial insecticide is composed of Bacillus thuringiensis and Metarhizium anisopliae; The plant-based insecticide consists of azadirachtin, veratridine and celangulin.

2. The insecticide composition according to claim 1, characterized in that: The preparation of the silicon dioxide-titanium oxide composite powder particles comprises the following steps: preparing 35-45 parts of nano titanium oxide powder into a suspension with a mass concentration of 1.5% by weight, adding 1-2 parts of sodium hexametaphosphate for dispersion, ultrasonically oscillating for 30-40 minutes, heating to 120-200° C., while dropwise adding 40-50 parts of sodium silicate and 30-40 parts of dilute sulfuric acid, adjusting the pH value to 8-10, heat-insulating and aging for 1-2 hours, drying at 100-110° C. for 0.5-1 hour, roasting, and grinding to obtain the silicon dioxide-titanium oxide composite powder particles.

3. An insecticide composition according to claim 2, characterized in that: The calcination includes pre-calcination and formal calcination; the pre-calcination is carried out at a temperature of 200-220° C. for 30-40 minutes, and the formal calcination is carried out at a temperature of 500-600° C. for 20-30 minutes.

4. The insecticide composition according to claim 2, characterized in that: The grinding is performed so that the particle size of the silica-titanium oxide composite powder particles reaches above 100 meshes.

5. The insecticide composition according to claim 1, characterized in that: The preparation of the sulfonated modified graphene nanopowder comprises the following steps: mixing the nanographene powder and Na2SO3 in a weight ratio of (3-5):(2-3) uniformly, adding a NaOH solution with a mass fraction of 15%, reacting at a temperature of 150-200°C for 3-5h, and obtaining the sulfonated modified graphene nanopowder.

6. The insecticide composition according to claim 1, characterized in that: The weight ratio of Bacillus thuringiensis to Metarhizium anisopliae in the microbial insecticide is (2-3):

1.

7. The insecticide composition according to claim 1, characterized in that: The weight ratio of azadirachtin, veratridine and celangulin in the botanical insecticide is (1-2):1:(2-3).

8. The insecticide composition according to claim 1, characterized in that: The neonicotinoid insecticides include at least two of imidacloprid, thiacloprid, thiamethoxam, clothianidin, dinotefuran, sulfoxaflor, trifluanid, and dichlorothiapyrim.

9. A method for preparing a pesticide composition according to any one of claims 1 to 8, characterized in that: The following steps are involved: The microbial insecticide and the sulfonated modified graphene nanopowder are mixed according to weight parts, 10-20 parts of white sugar water with a mass concentration of 20% are added and stirred for 20 min-30 min, neonicotinoid insecticide, 4-trifluoromethylnicotinamide, botanical insecticide, and silica-titanium oxide composite powder particles are added, and stirring is continued for 1-2 h to obtain an insecticide composition.

10. Use of the insecticide composition according to any one of claims 1 to 8 in the preparation of an insecticide formulation, wherein the insecticide formulation comprises at least one of a wettable powder, a water dispersible granule, a suspension concentrate, and a suspoemulsion.

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