Pesticide suspending agent containing tembotrione-triclopyr butoxyethyl ester-ametryn and application thereof

Abstract

The invention relates to the technical field of pesticides, in particular to a pesticide suspending agent containing tembotrione, triclopyr butoxyethyl ester and ametryn and application thereof.According to the pesticide suspending agent, the tembotrione is subjected to hydroxylation, microencapsulation and charcoal loading and is compounded with an organic silicon auxiliary, the triclopyr butoxyethyl ester is subjected to nanocrystallization modification, and the ametryn is prepared. The ametryn is subjected to ion exchange resin modification and is combined with the synergist to prepare the pesticide suspending agent. Compared with the prior art, the suspending agent is wide in weeding spectrum and can effectively prevent and remove various weeds in sugarcane fields; the lasting period is long, and the pesticide application frequency is reduced; the pesticide is safe to sugarcanes and is not easy to generate phytotoxicity; the weeding composition has the advantages that the pesticide leaching in soil and the pollution risk to the environment are reduced, all the components have a synergistic effect, the weeding activity is improved, an efficient, safe and sustainable solution is provided for sugarcane field weeding, and the weeding composition has a wide application prospect.

Description

Technical Field

[0001] The invention relates to the technical field of pesticides, and in particular to a pesticide suspension containing tembotrione-butoxyethyl triclopyrazone-ametryn and application thereof. Background Art

[0002] As an extremely important sugar crop in the world, sugarcane plays a key role in providing the main raw materials for the sugar industry, and its sugar production accounts for a relatively high proportion of the total sugar production. At the same time, with the continuous exploration and development of the energy field, sugarcane, as an efficient energy crop, has also shown great potential in the production of biofuels. For example, the production of ethanol by fermentation of sugarcane provides a new way to alleviate the energy crisis.

[0003] However, in the process of sugarcane cultivation, the growth of weeds is a long-term and thorny problem. Weeds compete with sugarcane for nutrients, water and light resources in the soil. In terms of nutrient competition, weeds will quickly absorb key nutrients such as nitrogen, phosphorus and potassium in the soil, resulting in insufficient nutrient supply for sugarcane during growth, resulting in short plants and yellow leaves, affecting the normal growth and development of sugarcane. In terms of water, weeds have a well-developed root system and strong water absorption, which will reduce the available water for sugarcane. This effect is particularly obvious in the dry season. In severe cases, it may even cause sugarcane to wither and die due to lack of water. In terms of light competition, weeds grow rapidly. Weeds that are too high and dense will block the sunlight, making it impossible for sugarcane to fully photosynthesize, thereby affecting its sugar accumulation and yield formation. According to relevant studies, in a weedy sugarcane field, the quality loss of sugarcane can reach 20%-50%. At the same time, because weeds affect the normal growth of sugarcane, its sugar content will also decrease, seriously affecting the quality of sugarcane.

[0004] At present, in the weeding operation of sugarcane fields, although the commonly used herbicides can control the growth of weeds to a certain extent, there are many disadvantages. The weed control spectrum of some herbicides is relatively narrow, and they can only work on specific types of weeds. They cannot achieve comprehensive and effective control of the wide variety of weeds in sugarcane fields. For example, some herbicides have a good control effect on grass weeds, but are powerless against broad-leaved weeds, resulting in changes in the weed community in sugarcane fields. Some weeds that were not originally dominant may multiply in large numbers because they are not effectively suppressed. At the same time, the effective period of these commonly used herbicides is generally short. Often, weeds can be seen to be controlled to a certain extent in a short period of time after application, but as time goes by, weeds will soon grow again, requiring frequent application of pesticides. Frequent application of pesticides not only increases the investment of manpower, material resources and financial resources, but may also have adverse effects on the soil environment and ecosystem. In addition, many commonly used herbicides are prone to cause phytotoxicity to sugarcane during use. Since sugarcane has low tolerance to some herbicides, if the dosage is not properly controlled or the application time is inappropriate during the application process, it will cause symptoms of pesticide damage such as burns and deformities on the sugarcane leaves, seriously affecting the growth and yield of sugarcane, and may even lead to a complete loss of sugarcane harvest.

[0005] Therefore, according to the above-mentioned related technologies, it is urgent to develop a pesticide suspension containing tembotrione-butoxyethyl triclopyrazone-ametryn and its application. Summary of the invention

[0006] In view of this, the object of the present invention is to provide a pesticide suspension containing tembotrione-butoxyethyl triclopyrazone-ametryn and its application, so as to provide a highly effective, safe and long-lasting sugarcane field herbicide.

[0007] Based on the above purpose, the present invention provides a pesticide suspension containing tembotrione-butoxyethyl triclopyrazone-ametryn and its application.

[0008] A pesticide suspension containing tembotrione-butoxyethyl triclopyr-ametryn is prepared from the following raw materials in parts by mass: 5-10 parts of modified tembotrione, 10-16 parts of modified butoxyethyl triclopyr, 15-18 parts of modified ametryn, 5-5.8 parts of dispersant, 3-3.4 parts of wetting agent, 0.3-0.5 parts of thickener, 5-6 parts of antifreeze agent, 0.5-0.8 parts of defoamer and 56-62 parts of water;

[0009] The modified tembotrione is a tembotrione suspension;

[0010] The modified triclopyr butoxyethyl ester is polyvinyl pyrrolidone modified triclopyr butoxyethyl ester;

[0011] The modified ametryn is ion exchange resin modified ametryn.

[0012] Preferably, the preparation process of the tembotrione suspension is as follows:

[0013] Step A1. Hydroxylation of tembotrione to obtain hydroxylated tembotrione;

[0014] Step A2. Microencapsulation of hydroxylated tembotrione to obtain microencapsulated tembotrione;

[0015] Step A3. Loading of microcapsules with tambara to obtain carbon-loaded tambara;

[0016] Step A4. Compounding of carbon-supported tembotrione to obtain a tembotrione suspension.

[0017] Preferably, the hydroxylation process of tembotrione in step A1 is as follows:

[0018] In a 250 mL three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, add tampronone and then add anhydrous ethanol as an organic solvent, cool the reaction system to 0-5°C, add chloroethanol dropwise, and control the dropping time to be 30-45 min. After the dropping is completed, raise the reaction temperature to 50-60°C, stir and react for 6-8 hours. After the reaction is completed, pour the reaction solution into ice water, filter, wash and dry solids to obtain hydroxylated tampronone;

[0019] The dosage ratio of tamponic acid ketone, anhydrous ethanol and chloroethanol is 9-13g:95-115mL:2-4g.

[0020] After the introduction of the hydrophilic group hydroxyl, the molecular polarity of cyclosulfuron is enhanced and its solubility in water is significantly improved. This allows cyclosulfuron to be more evenly dispersed in the aqueous phase when formulated into a pesticide suspension, avoiding agglomeration. During the spraying process, the agent can cover the surface of weeds more evenly, increasing the contact area with the weeds and improving the weed control effect. At the same time, the enhancement of hydrophilicity may change the migration behavior of cyclosulfuron in the soil, reduce its leaching loss, and improve its stability in the soil.

[0021] Preferably, the microencapsulation process of the hydroxylated tembotrione in step A2 is as follows:

[0022] The hydroxylated cyclosulfone is dissolved in toluene to obtain an oil phase, the isocyanate and polyethylene glycol are dissolved in deionized water, and sodium dodecyl sulfate is added to obtain an aqueous phase, the aqueous phase is added to a 500mL four-necked flask equipped with a stirrer and a thermometer, stirring is started, the speed is controlled at 800-1000r / min, the oil phase is added dropwise to the aqueous phase, the dropping time is 30-35min, a stable emulsion is formed, and then the reaction temperature is increased to 60-70°C, the reaction is carried out for 3-4h, the isocyanate and the polyethylene glycol undergo polymerization reaction at the oil-water interface, and a microcapsule wall encapsulating the cyclosulfone is gradually formed, and after the reaction is completed, the reaction solution is transferred to a centrifuge tube, centrifuged at a speed of 5000-6000r / min for 15-20min, the microencapsulated cyclosulfone is separated, and the microencapsulated cyclosulfone is washed with deionized water for 3-4 times to obtain microencapsulated cyclosulfone.

[0023] Preferably, the dosage ratio of the hydroxylated cyclohexane and toluene is 5-7 g: 50-55 mL;

[0024] The usage ratio of the isocyanate, polyethylene glycol, deionized water and sodium lauryl sulfate is 2-2.8 g: 3-4 g: 100-120 mL: 0.5-0.8 g;

[0025] The microencapsulated cyclosulfuron has good sustained-release properties. In the field environment, the microcapsule wall can control the release rate of cyclosulfuron, allowing it to continue to exert its herbicidal effect for a long time and extend its effective period. At the same time, the microcapsules can protect cyclosulfuron from external environmental factors such as light and oxidation, improve the stability of the agent, and reduce the degradation of active ingredients, thereby reducing the dosage and number of applications and reducing costs.

[0026] Preferably, the loading process of microcapsule tembotrione in step A3 is as follows:

[0027] Weigh microcapsule cyclosulfuron and rice husk biochar, add them to a Tween-80 aqueous solution, transfer the mixed solution to a three-necked flask equipped with a stirrer and a thermometer, stir at 40-50°C and 300-400r / min for 6-8h to load the microcapsule cyclosulfuron on the surface and pores of the biochar, and after the reaction, separate the loaded biochar by filtration, wash with deionized water until no surfactant is detected in the washing liquid, and then dry at 60-70°C to constant weight to obtain carbon-loaded cyclosulfuron;

[0028] The dosage ratio of the microcapsule tembotrione, rice husk biochar and Tween-80 aqueous solution is 5-7 g: 10-15 g: 200-230 mL;

[0029] The mass fraction of Tween-80 in the Tween-80 aqueous solution is 0.5%-0.7%.

[0030] The adsorption performance of cyclosulfuron in soil was significantly enhanced after biochar loading. After adding rice biochar, the adsorption amount of cyclosulfuron was significantly increased, which helps to reduce the leaching of cyclosulfuron in soil and reduce the risk of pollution to groundwater and surface water. At the same time, the organic matter and surface functional groups in biochar may interact with cyclosulfuron, further affecting its release and migration behavior, making it more effective on weeds and improving the weed control effect.

[0031] Preferably, the compounding process of the carbon-supported tembotrione in step A4 is as follows:

[0032] The carbon-loaded cyclosulfone is added to deionized water, and stirred to form a suspension. Under stirring conditions, polyether-modified silicone is slowly added at a rate of 1-2 drops / second, and stirring is continued for 30-45 minutes to fully mix the silicone additive and the biochar-loaded cyclosulfone to obtain a cyclosulfone suspension;

[0033] The carbon-supported cyclohexane, deionized water and polyether-modified silicone are used in a ratio of 10-13 g: 100-115 mL: 2-2.6 g;

[0034] Silicone adjuvants have ultra-low surface tension and can significantly reduce the contact angle of the agent solution on the surface of weed leaves, enhancing wettability and spreadability. After compounding with biochar-loaded microencapsulated cyclosulfuron, silicone adjuvants can help cyclosulfuron better adhere to the surface of weeds and penetrate into the weeds. At the same time, silicone adjuvants may promote the rupture of microcapsules on the surface of weeds and the release of cyclosulfuron, thereby increasing the bioavailability of cyclosulfuron and enhancing its herbicidal activity. In addition, this compounding may also improve the dispersibility of cyclosulfuron in the soil, further improving its adsorption and effect in the soil.

[0035] After a series of modifications and compounding of cyclosulfone, a synergistic effect was generated between the steps. Hydroxylation modification improved the solubility and dispersibility of cyclosulfone, providing a better basis for subsequent microencapsulation, biochar loading and compounding with silicone adjuvants. Microencapsulation and biochar loading not only improved the stability and adsorption of cyclosulfone, but also provided better conditions for the action of silicone adjuvants. Silicone adjuvants and other modification steps synergized to further improve the herbicidal effect and performance of cyclosulfone in soil. Biochar loading significantly enhanced the adsorption of cyclosulfone in soil, reducing its leaching and environmental pollution risks. At the same time, the use of microencapsulation and silicone adjuvants reduced the dosage of cyclosulfone while improving the herbicidal effect, further reducing the potential harm to the environment. This multi-modified cyclosulfone has significantly improved herbicidal effect, duration, stability and environmental friendliness, and its comprehensive performance has been greatly improved, providing a more efficient, safe and sustainable solution for the prevention and control of annual weeds in sugarcane fields.

[0036] Preferably, the preparation process of the modified triclopyr butoxyethyl ester is as follows:

[0037] Step B1. dissolving butoxyethyl triclopyr in ethyl acetate to form an organic phase;

[0038] Step B2. dissolving polyvinyl pyrrolidone in deionized water to form an aqueous phase;

[0039] Step B3. At room temperature, the organic phase is added dropwise to the aqueous phase, and magnetic stirring is turned on at the same time. The stirring speed is set to 780-810 r / min, and the dropping time is 28-33 min to form a stable emulsion. The emulsion is transferred to a rotary evaporator, and the ethyl acetate is removed by reduced pressure evaporation at a temperature of 40-50°C. As the solvent evaporates, butoxyethyl triclopyr gradually forms nanoparticles dispersed in the aqueous phase. The evaporation process is continued for 1-2 hours until no obvious solvent is evaporated. Finally, the obtained nanoparticle suspension is centrifuged at 4800-5100 rpm for 15-18 minutes, and then washed with deionized water for 3 times to remove excess surfactant to obtain triclopyr butoxyethyl ester nanoparticles. The prepared triclopyr butoxyethyl ester nanoparticle suspension is transferred to a three-necked flask equipped with a stirrer and a thermometer, and stirred at a speed of 200-300 r / min at room temperature to uniformly disperse the nanoparticles in the suspension. The carbon-loaded cyclosulfone is weighed and added to the stirring triclopyr butoxyethyl ester nanoparticle suspension, and the addition time is controlled to be 15-20 minutes. Then, a polyvinyl alcohol dispersant is added and stirring is continued for 30-45 minutes. The mixed suspension is subjected to ultrasonic treatment for 15-20 minutes, and the ultrasonic power is set to 200-300 W and the frequency is 40-60 kHz to obtain modified triclopyr butoxyethyl ester.

[0040] Preferably, the usage ratio of triclopyr butoxyethyl ester and ethyl acetate in step B1 is 5-7 g: 50-55 mL;

[0041] The usage ratio of polyvinyl pyrrolidone and deionized water in step B2 is 1-1.5 g: 200-220 mL;

[0042] The mass ratio of the triclopyr butoxyethyl ester nanoparticles to the carbon-supported tembotrione in step B3 is 30-40:10-12;

[0043] The amount of the polyvinyl alcohol dispersant used in step B3 is 0.5%-1% of the mass of the suspension.

[0044] Preferably, the preparation process of the modified ametryn is as follows:

[0045] Step C1. Soak 001×7 strong acidic cationic resin in deionized water for 24 hours, then soak it in 5% hydrochloric acid solution for 4-6 hours, and then wash it with deionized water until it is neutral to obtain a pretreated resin;

[0046] Step C2. Add azomethine and the pretreated resin into a 250 mL three-necked flask, add deionized water, and stir at a water bath temperature of 30-40° C. and a speed of 200-300 rpm for 8-10 hours. During the reaction, certain groups in the azomethine molecule exchange with ions on the ion exchange resin to change the charge properties and molecular structure of the azomethine. After the reaction, separate the ion exchange resin from the reaction solution by filtration, wash with deionized water for 3-5 times, combine the washing solution and the reaction solution, and remove water by reduced pressure distillation or the like to obtain a crude azomethine product;

[0047] Step C3. Add the crude ametryn and tert-butylhydroquinone into a 100 mL round-bottom flask, add acetone, stir at room temperature at a speed of 150-200 rpm for 30-45 min, and then dry the product, which can be dried under vacuum at 40-50° C. for 2-3 h to obtain modified ametryn;

[0048] The usage ratio of ametryn, pre-treated resin and deionized water in step C2 is 5-7 g: 10-13 g: 150-160 mL;

[0049] In step C3, the usage ratio of the crude ametryn, tert-butylhydroquinone and acetone is 5-7 g: 1-1.4 g: 50-65 mL.

[0050] Preferably, the dispersant is any one of sodium lignin sulfonate and naphthalene sulfonate formaldehyde condensate;

[0051] The wetting agent is any one of alkylphenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether;

[0052] The thickener is any one of xanthan gum and magnesium aluminum silicate;

[0053] The antifreeze agent is any one of ethylene glycol and propylene glycol;

[0054] The defoamer is an organosilicon defoamer.

[0055] A method for preparing a pesticide suspension containing tembotrione-butoxyethyl triclopyrazone-ametryn, comprising the following steps:

[0056] Add modified cyclosulfone, modified butoxyethyl triclopyr, modified ametryn, dispersant, wetting agent, thickener, antifreeze agent and defoamer into water, stir for 15 minutes, and then grind in a sand mill for 2 hours to prepare a pesticide suspension.

[0057] Beneficial effects of the present invention:

[0058] The present invention provides a pesticide suspension containing tembotrione-butoxyethyl triclopyr-ametryn and its application. The present invention prepares the pesticide suspension by hydroxylating tembotrione, microencapsulating, loading biochar and compounding with an organosilicon adjuvant, performing nano-modification on butoxyethyl triclopyr, performing ion exchange resin modification on ametryn and combining it with a synergist. Compared with the prior art, the suspension has a wide weed control spectrum and can effectively prevent and control various weeds in sugarcane fields; has a long lasting effect and reduces the number of times of application; is safe for sugarcane and is not prone to pesticide damage; reduces the risk of pesticide leaching in the soil and pollution to the environment, and the components synergistically enhance the synergy to improve the herbicidal activity, providing an efficient, safe and sustainable solution for weed control in sugarcane fields, and has broad application prospects. DETAILED DESCRIPTION

[0059] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with specific embodiments.

[0060] Embodiment 1: A method for preparing a pesticide suspension containing tembotrione-butoxyethyl triclopyraclostrobin-ametryn, comprising the following steps:

[0061] S1. In a 250mL three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 9g of cyclosulfone was added, and then 95mL of anhydrous ethanol was added as an organic solvent. The reaction system was cooled to 0°C, and 2g of chloroethanol was added dropwise. The addition time was controlled to be 30min. After the addition was completed, the reaction temperature was raised to 50°C, and the reaction was stirred for 6h. After the reaction was completed, the reaction solution was poured into ice water. Solids were precipitated, filtered, washed and dried to obtain hydroxylated cyclosulfone;

[0062] S2. Dissolve 5g of hydroxylated cyclosulfone in 50mL of toluene to obtain an oil phase, dissolve 2g of isocyanate and 3g of polyethylene glycol in 100mL of deionized water, and add 0.5g of sodium dodecyl sulfate to obtain an aqueous phase, add the aqueous phase to a 500mL four-necked flask equipped with a stirrer and a thermometer, start stirring, control the speed at 800r / min, drop the oil phase into the aqueous phase, and the dropping time is 30min to form a stable emulsion, then increase the reaction temperature to 60°C, react for 3h, allow the isocyanate and polyethylene glycol to undergo polymerization at the oil-water interface, and gradually form a microcapsule wall that wraps the cyclosulfone. After the reaction is completed, transfer the reaction solution to a centrifuge tube, centrifuge at a speed of 5000r / min for 15min, separate the microencapsulated cyclosulfone, and wash it 3 times with deionized water to obtain microencapsulated cyclosulfone;

[0063] S3. Weigh 5g of microcapsule cyclosulfuron and 10g of rice husk biochar, add them to 200mL of 0.5% Tween-80 aqueous solution, transfer the mixture to a three-necked flask equipped with a stirrer and a thermometer, stir at 40°C and 300r / min for 6h to load the microcapsule cyclosulfuron on the surface and pores of the biochar, and after the reaction, separate the loaded biochar by filtration, wash with deionized water until no surfactant is detected in the washing liquid, and then dry at 60°C to constant weight to obtain carbon-loaded cyclosulfuron;

[0064] S4. Add 10g of carbon-loaded cyclosulfone to 100mL of deionized water, stir evenly to form a suspension, slowly add 2g of polyether-modified silicone at a rate of 1 drop / second under stirring, continue stirring for 30min, so that the silicone additive and the biochar-loaded cyclosulfone are fully mixed to obtain a cyclosulfone suspension, wherein the preparation process of the polyether-modified silicone is as follows: add 100g of hydrogenated silicone oil and 50g of polyether monomer to a three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, then add 150mL of toluene, start stirring, and allow the original The materials are fully mixed, and 0.05 g of a 2% isopropanol solution of chloroplatinic acid is added dropwise to the mixed solution. Stirring is maintained during the dropping process. Note that the dropping speed should not be too fast to avoid excessive reaction. The reaction system is slowly heated to 80°C and reacted at this temperature for 4 hours. After the reaction is completed, the reaction solution is cooled to room temperature, and then the toluene solvent is removed by reduced pressure distillation. The remaining product is washed 3 times with an appropriate amount of anhydrous ethanol to remove unreacted raw materials and catalysts. The washed product is vacuum dried at 50°C for 2 hours to obtain polyether-modified silicone;

[0065] S5. Dissolve 5 g of butoxyethyl triclopyr in 50 mL of ethyl acetate to form an organic phase;

[0066] S6. Dissolve 1 g of polyvinyl pyrrolidone in 200 mL of deionized water to form an aqueous phase;

[0067] S7. At room temperature, the organic phase was added dropwise to the aqueous phase, and magnetic stirring was turned on at the same time. The stirring speed was set to 780 r / min, and the dropping time was 28 min to form a stable emulsion. The emulsion was transferred to a rotary evaporator, and ethyl acetate was removed by reduced pressure evaporation at a temperature of 40°C. As the solvent evaporated, butoxyethyl triclopyr gradually formed nanoparticles dispersed in the aqueous phase. The evaporation process lasted for 1 h until no obvious solvent was evaporated. Finally, the obtained nanoparticle suspension was centrifuged at 4800 rpm for 15 min, and then washed with deionized water 3 times to remove excess surfactant to obtain butoxyethyl triclopyr nanoparticles. 30 g of preparation The good suspension of butoxyethyl triclopyr is transferred to a three-necked flask equipped with a stirrer and a thermometer, and stirred at a speed of 200 r / min at room temperature to uniformly disperse the nanoparticles in the suspension, 10 g of carbon-supported cyclohexane is weighed, and added to the stirring suspension of butoxyethyl triclopyr nanoparticles, and the addition time is controlled to be 15 min, and then a polyvinyl alcohol dispersant is added, and the amount of the polyvinyl alcohol dispersant is 0.5% of the mass of the suspension, and stirring is continued for 30 min. The mixed suspension is subjected to ultrasonic treatment for 15 min, and the ultrasonic power is set to 200 W and the frequency is 40 kHz to obtain modified butoxyethyl triclopyr;

[0068] S8. The 001×7 strong acid cation resin was soaked in deionized water for 24 hours, then soaked in 5% hydrochloric acid solution for 4 hours, and then washed with deionized water until neutral to obtain a pretreated resin;

[0069] S9. 5 g of amethoxazole and 10 g of pretreated resin were added to a 250 mL three-necked flask, and 150 mL of deionized water was added. The mixture was stirred at 200 rpm at a water bath temperature of 30° C. for 8 h. During the reaction, certain groups in the amethoxazole molecule exchanged with ions on the ion exchange resin to change the charge properties and molecular structure of the amethoxazole. After the reaction, the ion exchange resin was separated from the reaction solution by filtration, and the mixture was washed with deionized water for 3 times. The washing solution and the reaction solution were combined, and water was removed by vacuum distillation or the like to obtain a crude amethoxazole product.

[0070] S10. 5 g of crude amethoxazole and 1 g of tert-butylhydroquinone were added to a 100 mL round-bottom flask, and 50 mL of acetone was added. The mixture was stirred at 150 rpm for 30 min at room temperature. The product was then dried, which may be done by vacuum drying at 40° C. for 2 h to obtain modified amethoxazole.

[0071] S11. Add 5 g of modified cyclosulfone, 10 g of modified butoxyethyl triclopyr, 15 g of modified ametryn, 5 g of sodium lignin sulfonate, 3 g of alkylphenol polyoxyethylene ether, 0.3 g of xanthan gum, 5 g of ethylene glycol, and 0.5 g of silicone defoamer into 56 g of water, stir for 15 min, and then sand grind in a sand mill for 2 h to obtain a pesticide suspension.

[0072] Embodiment 2: A method for preparing a pesticide suspension containing tembotrione-butoxyethyl triclopyraclostrobin-ametryn, comprising the following steps:

[0073] S1. In a 250mL three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 10g of cyclosulfone was added, and then 100mL of anhydrous ethanol was added as an organic solvent. The reaction system was cooled to 1°C, and 2.5g of chloroethanol was added dropwise. The addition time was controlled at 35min. After the addition was completed, the reaction temperature was raised to 53°C, and the reaction was stirred for 6.5h. After the reaction was completed, the reaction solution was poured into ice water. Solids were precipitated, filtered, washed and dried to obtain hydroxylated cyclosulfone;

[0074] S2. Dissolve 5.5g of hydroxylated cyclosulfonyl ketone in 52mL toluene to obtain an oil phase, dissolve 2.2g of isocyanate and 3.3g of polyethylene glycol in 105mL of deionized water, and add 0.6g of sodium dodecyl sulfate to obtain an aqueous phase, add the aqueous phase to a 500mL four-necked flask equipped with a stirrer and a thermometer, start stirring, control the speed at 850r / min, drop the oil phase into the aqueous phase, and the dropping time is 32min to form a stable emulsion, then increase the reaction temperature to 63°C, react for 3.5h, allow the isocyanate and polyethylene glycol to undergo polymerization at the oil-water interface, and gradually form a microcapsule wall that wraps the cyclosulfonyl ketone, after the reaction is completed, transfer the reaction solution to a centrifuge tube, centrifuge at a speed of 5300r / min for 17min, separate the microencapsulated cyclosulfonyl ketone, and wash it 3 times with deionized water to obtain microencapsulated cyclosulfonyl ketone;

[0075] S3. Weigh 5.5g of microcapsule cyclosulfuron and 12g of rice husk biochar, add them to 210mL of Tween-80 aqueous solution with a mass fraction of 0.55%, transfer the mixture to a three-necked flask equipped with a stirrer and a thermometer, and stir at 43°C and 320r / min for 6.5h to load the microcapsule cyclosulfuron on the surface and pores of the biochar. After the reaction is completed, separate the loaded biochar by filtration, wash with deionized water until no surfactant is detected in the washing liquid, and then dry at 63°C to constant weight to obtain carbon-loaded cyclosulfuron;

[0076] S4. Add 11g of carbon-loaded cyclosulfone to 105mL of deionized water, stir evenly to form a suspension, slowly add 2.2g of polyether-modified silicone at a rate of 1 drop / second under stirring, continue stirring for 35min, so that the silicone additive and the biochar-loaded cyclosulfone are fully mixed to obtain a cyclosulfone suspension, wherein the preparation process of the polyether-modified silicone is as follows: add 100g of hydrogenated silicone oil and 50g of polyether monomer to a three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, then add 150mL of toluene, start stirring, and allow the raw materials to simmer for 30 minutes. Mix thoroughly and evenly, add 0.07 g of 2.3% isopropanol solution of chloroplatinic acid to the mixed solution, keep stirring during the dropping process, pay attention to the dropping speed should not be too fast to avoid too violent reaction, slowly heat the reaction system to 85 ° C, react at this temperature for 4.5 hours, after the reaction is completed, cool the reaction solution to room temperature, and then remove the toluene solvent by vacuum distillation, wash the remaining product with an appropriate amount of anhydrous ethanol for 3 times to remove unreacted raw materials and catalysts, and vacuum dry the washed product at 53 ° C for 2 hours to obtain polyether modified silicone;

[0077] S5. Dissolve 5.5 g of butoxyethyl triclopyr in 52 mL of ethyl acetate to form an organic phase;

[0078] S6. Dissolve 1.2 g of polyvinyl pyrrolidone in 205 mL of deionized water to form an aqueous phase;

[0079] S7. At room temperature, the organic phase was added dropwise to the aqueous phase, and magnetic stirring was turned on at the same time. The stirring speed was set to 790 r / min, and the dropping time was 29 min to form a stable emulsion. The emulsion was transferred to a rotary evaporator, and the ethyl acetate was removed by reduced pressure evaporation at a temperature of 42°C. As the solvent evaporated, butoxyethyl triclopyr gradually formed nanoparticles dispersed in the aqueous phase. The evaporation process continued for 1.5 h until no obvious solvent was evaporated. Finally, the obtained nanoparticle suspension was centrifuged at 4900 rpm for 16 min, and then washed with deionized water for 3 times to remove excess surfactant to obtain triclopyr butoxyethyl ester nanoparticles. 32 g of the prepared triclopyr butoxyethyl ester nanoparticle suspension was transferred to a three-necked flask equipped with a stirrer and a thermometer, and stirred at a speed of 220 r / min at room temperature to uniformly disperse the nanoparticles in the suspension. 11 g of carbon-supported cyclosulfone was weighed and added to the stirring triclopyr butoxyethyl ester nanoparticle suspension. The addition time was controlled at 17 min, and then a polyvinyl alcohol dispersant was added. The amount of the polyvinyl alcohol dispersant was 0.7% of the mass of the suspension. Stirring was continued for 35 min. The mixed suspension was subjected to ultrasonic treatment for 17 min, and the ultrasonic power was set to 220 W and the frequency was 45 kHz to obtain modified triclopyr butoxyethyl ester.

[0080] S8. The 001×7 strong acid cation resin was soaked in deionized water for 24 h, then soaked in 5% hydrochloric acid solution for 4.5 h, and then washed with deionized water until neutral to obtain a pretreated resin;

[0081] S9. 5.5 g of amethoxazole and 11 g of pretreated resin were added to a 250 mL three-necked flask, and 153 mL of deionized water was added. The mixture was stirred at 230 rpm at a water bath temperature of 33° C. for 8.5 h. During the reaction, certain groups in the amethoxazole molecule exchanged with ions on the ion exchange resin to change the charge properties and molecular structure of the amethoxazole. After the reaction, the ion exchange resin was separated from the reaction solution by filtration, and the mixture was washed with deionized water for 4 times. The washing solution and the reaction solution were combined, and the water was removed by vacuum distillation or the like to obtain a crude amethoxazole product.

[0082] S10. 5.5 g of crude amethoxazole and 1.1 g of tert-butylhydroquinone were added to a 100 mL round-bottom flask, and 55 mL of acetone was added. The mixture was stirred at 160 rpm for 35 min at room temperature. The product was then dried, which may be done by vacuum drying at 43 ° C for 2.5 h to obtain modified amethoxazole;

[0083] S11. Add 7 g of modified cyclosulfone, 12 g of modified butoxyethyl triclopyr, 16 g of modified azomethine, 5.2 g of naphthalenesulfonate formaldehyde condensate, 3.1 g of fatty alcohol polyoxyethylene ether, 0.35 g of magnesium aluminum silicate, 5.3 g of propylene glycol, and 0.6 g of silicone defoamer into 58 g of water, stir for 15 min, and then sand grind in a sand mill for 2 h to obtain a pesticide suspension.

[0084] Embodiment 3: A method for preparing a pesticide suspension containing tembotrione-butoxyethyl triclopyraclostrobin-ametryn, comprising the following steps:

[0085] S1. In a 250mL three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 11g of cyclosulfone was added, and then 105mL of anhydrous ethanol was added as an organic solvent. The reaction system was cooled to 2°C, and 3g of chloroethanol was added dropwise. The addition time was controlled at 40min. After the addition was completed, the reaction temperature was raised to 56°C, and the reaction was stirred for 7h. After the reaction was completed, the reaction solution was poured into ice water. Solids were precipitated, filtered, washed and dried to obtain hydroxylated cyclosulfone;

[0086] S2. 6 g of hydroxylated cyclosulfone was dissolved in 53 mL of toluene to obtain an oil phase, 2.5 g of isocyanate and 3.6 g of polyethylene glycol were dissolved in 110 mL of deionized water, and 0.7 g of sodium dodecyl sulfate was added to obtain an aqueous phase, the aqueous phase was added to a 500 mL four-necked flask equipped with a stirrer and a thermometer, stirring was started, the speed was controlled at 900 r / min, the oil phase was added dropwise to the aqueous phase, the dropping time was 33 min, a stable emulsion was formed, and the reaction temperature was then increased to 66 ° C, the reaction was carried out for 4 h, the isocyanate and polyethylene glycol were polymerized at the oil-water interface, and a microcapsule wall encapsulating the cyclosulfone was gradually formed. After the reaction was completed, the reaction solution was transferred to a centrifuge tube, centrifuged at a speed of 5500 r / min for 18 min, the microencapsulated cyclosulfone was separated, and washed 4 times with deionized water to obtain microencapsulated cyclosulfone;

[0087] S3. Weigh 6 g of microcapsule cyclosulfuron and 14 g of rice husk biochar, add them to 220 mL of a 0.6% Tween-80 aqueous solution, transfer the mixture to a three-necked flask equipped with a stirrer and a thermometer, and stir at 46°C at a speed of 350 r / min for 7 h to load the microcapsule cyclosulfuron on the surface and pores of the biochar. After the reaction is completed, separate the loaded biochar by filtration, wash with deionized water until no surfactant is detected in the washing liquid, and then dry at 65°C to constant weight to obtain carbon-loaded cyclosulfuron;

[0088] S4. 12g of carbon-loaded cyclosulfone was added to 110mL of deionized water, and stirred to form a suspension. Under stirring conditions, 2.4g of polyether-modified silicone was slowly added at a rate of 2 drops / second, and stirring was continued for 40min to fully mix the silicone additive and the biochar-loaded cyclosulfone to obtain a cyclosulfone suspension, wherein the preparation process of the polyether-modified silicone was as follows: 100g of hydrogenated silicone oil and 50g of polyether monomer were added to a three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, and then 150mL of toluene was added, stirring was started, and the original The materials were fully mixed, and 0.08 g of 2.6% isopropanol solution of chloroplatinic acid was added dropwise to the mixed solution. Stirring was maintained during the dropping process. Note that the dropping speed should not be too fast to avoid excessive reaction. The reaction system was slowly heated to 90°C and reacted at this temperature for 5 hours. After the reaction was completed, the reaction solution was cooled to room temperature, and then the toluene solvent was removed by reduced pressure distillation. The remaining product was washed 4 times with an appropriate amount of anhydrous ethanol to remove unreacted raw materials and catalysts. The washed product was vacuum dried at 55°C for 3 hours to obtain polyether-modified silicone;

[0089] S5. Dissolve 6 g of butoxyethyl triclopyr in 53 mL of ethyl acetate to form an organic phase;

[0090] S6. Dissolve 1.3 g of polyvinyl pyrrolidone in 210 mL of deionized water to form an aqueous phase;

[0091] S7. At room temperature, the organic phase was added dropwise to the aqueous phase, and magnetic stirring was turned on at the same time. The stirring speed was set to 800 r / min, and the dropping time was 32 min to form a stable emulsion. The emulsion was transferred to a rotary evaporator, and the ethyl acetate was removed by reduced pressure evaporation at a temperature of 44°C. As the solvent evaporated, butoxyethyl triclopyr gradually formed nanoparticles dispersed in the aqueous phase. The evaporation process continued for 1 hour until no obvious solvent was evaporated. Finally, the obtained nanoparticle suspension was centrifuged at 5000rpm for 17 minutes, and then washed with deionized water for 3 times to remove excess surfactant to obtain triclopyr butoxyethyl ester nanoparticles. 35g of the prepared triclopyr butoxyethyl ester nanoparticle suspension was transferred to a three-necked flask equipped with a stirrer and a thermometer, and stirred at a speed of 250r / min at room temperature to uniformly disperse the nanoparticles in the suspension. 11g of carbon-supported cyclosulfone was weighed and added to the stirring triclopyr butoxyethyl ester nanoparticle suspension. The addition time was controlled to 17min, and then a polyvinyl alcohol dispersant was added. The amount of the polyvinyl alcohol dispersant was 0.65% of the mass of the suspension. Stirring was continued for 40min, and the mixed suspension was subjected to ultrasonic treatment for 15-20min. The ultrasonic power was set to 250W and the frequency was 50kHz to obtain modified triclopyr butoxyethyl ester.

[0092] S8. The 001×7 strong acid cation resin was soaked in deionized water for 24 hours, then soaked in 5% hydrochloric acid solution for 5 hours, and then washed with deionized water until neutral to obtain a pretreated resin;

[0093] S9. 6 g of amethoxazole and 12 g of pretreated resin were added to a 250 mL three-necked flask, and 156 mL of deionized water was added. The mixture was stirred at 260 rpm at a water bath temperature of 35° C. for 9 h. During the reaction, certain groups in the amethoxazole molecule exchanged with ions on the ion exchange resin to change the charge properties and molecular structure of the amethoxazole. After the reaction, the ion exchange resin was separated from the reaction solution by filtration, and the mixture was washed with deionized water for 5 times. The washing solution and the reaction solution were combined, and the water was removed by vacuum distillation or the like to obtain a crude amethoxazole product.

[0094] S10. 6 g of crude amethoxazole and 1.2 g of tert-butylhydroquinone were added to a 100 mL round-bottom flask, and 60 mL of acetone was added. The mixture was stirred at room temperature at a speed of 170 rpm for 40 min. Then, the product was dried, which can be vacuum dried at 46 ° C for 2 h to obtain modified amethoxazole;

[0095] S11. Add 8 g of modified cyclosulfone, 14 g of modified butoxyethyl triclopyr, 17 g of modified azomethine, 5.4 g of sodium lignin sulfonate, 3.2 g of alkylphenol polyoxyethylene ether, 0.4 g of xanthan gum, 5.5 g of ethylene glycol, and 0.7 g of silicone defoamer into 60 g of water, stir for 15 min, and then sand grind in a sand mill for 2 h to obtain a pesticide suspension.

[0096] Embodiment 4: A method for preparing a pesticide suspension containing tembotrione-butoxyethyl triclopyraclostrobin-ametryn, comprising the following steps:

[0097] S1. In a 250mL three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 12g of cyclosulfone was added, and then 110mL of anhydrous ethanol was added as an organic solvent. The reaction system was cooled to 3°C, and 3.5g of chloroethanol was added dropwise. The addition time was controlled at 42min. After the addition was completed, the reaction temperature was raised to 58°C, and the reaction was stirred for 7.5h. After the reaction was completed, the reaction solution was poured into ice water. Solids were precipitated, filtered, washed and dried to obtain hydroxylated cyclosulfone;

[0098] S2. 6.5 g of hydroxylated cyclosulfone was dissolved in 54 mL of toluene to obtain an oil phase, 2.6 g of isocyanate and 3.8 g of polyethylene glycol were dissolved in 115 mL of deionized water, and 0.75 g of sodium dodecyl sulfate was added to obtain an aqueous phase, the aqueous phase was added to a 500 mL four-necked flask equipped with a stirrer and a thermometer, stirring was started, the speed was controlled at 950 r / min, the oil phase was added dropwise to the aqueous phase, the dropping time was 34 min, a stable emulsion was formed, and the reaction temperature was then increased to 68 ° C, the reaction was carried out for 3 h, the isocyanate and polyethylene glycol were polymerized at the oil-water interface, and a microcapsule wall encapsulating the cyclosulfone was gradually formed. After the reaction was completed, the reaction solution was transferred to a centrifuge tube, centrifuged at a speed of 5800 r / min for 19 min, the microencapsulated cyclosulfone was separated, and washed 3 times with deionized water to obtain microencapsulated cyclosulfone;

[0099] S3. Weigh 6.5g of microcapsule cyclosulfuron and 13g of rice husk biochar, add them to 225mL of Tween-80 aqueous solution with a mass fraction of 0.65%, transfer the mixture to a three-necked flask equipped with a stirrer and a thermometer, and stir at 48°C at a speed of 380r / min for 7.5h to load the microcapsule cyclosulfuron on the surface and pores of the biochar. After the reaction is completed, separate the loaded biochar by filtration, wash with deionized water until no surfactant is detected in the washing liquid, and then dry at 68°C to constant weight to obtain carbon-loaded cyclosulfuron;

[0100] S4. 12.5 g of carbon-loaded cyclosulfone was added to 112 mL of deionized water, and stirred to form a suspension. Under stirring conditions, 2.5 g of polyether-modified silicone was slowly added at a rate of 2 drops / second, and stirring was continued for 42 min to fully mix the silicone additive and the biochar-loaded cyclosulfone to obtain a cyclosulfone suspension, wherein the preparation process of the polyether-modified silicone was as follows: 100 g of hydrogenated silicone oil and 50 g of polyether monomer were added to a three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, and then 150 mL of toluene was added, stirring was started, and the original The materials were fully mixed, and 0.09 g of 2.8% isopropanol solution of chloroplatinic acid was added dropwise to the mixed solution. Stirring was maintained during the addition process. Note that the dropping speed should not be too fast to avoid excessive reaction. The reaction system was slowly heated to 95° C. and reacted at this temperature for 5.5 h. After the reaction was completed, the reaction solution was cooled to room temperature, and then the toluene solvent was removed by reduced pressure distillation. The remaining product was washed 4 times with an appropriate amount of anhydrous ethanol to remove unreacted raw materials and catalysts. The washed product was vacuum dried at 58° C. for 2 h to obtain polyether-modified silicone;

[0101] S5. 6.5 g of butoxyethyl triclopyr was dissolved in 54 mL of ethyl acetate to form an organic phase;

[0102] S6. Dissolve 1.4 g of polyvinyl pyrrolidone in 215 mL of deionized water to form an aqueous phase;

[0103] S7. At room temperature, the organic phase was added dropwise to the aqueous phase, and magnetic stirring was turned on at the same time. The stirring speed was set to 805 r / min, and the dropping time was 31 min to form a stable emulsion. The emulsion was transferred to a rotary evaporator, and the ethyl acetate was removed by reduced pressure evaporation at a temperature of 48°C. As the solvent evaporated, butoxyethyl triclopyr gradually formed nanoparticles dispersed in the aqueous phase. The evaporation process continued for 1.5 h until no obvious solvent was evaporated. Finally, the obtained nanoparticle suspension was centrifuged at 5050 rpm for 16 min, and then washed with deionized water for 3 times to remove excess surfactant to obtain triclopyr butoxyethyl ester nanoparticles. 38 g of the prepared triclopyr butoxyethyl ester nanoparticle suspension was transferred to a three-necked flask equipped with a stirrer and a thermometer, and stirred at a speed of 280 r / min at room temperature to uniformly disperse the nanoparticles in the suspension. 11 g of carbon-supported cyclosulfone was weighed and added to the stirring triclopyr butoxyethyl ester nanoparticle suspension. The addition time was controlled at 19 min, and then a polyvinyl alcohol dispersant was added. The amount of the polyvinyl alcohol dispersant was 0.8% of the mass of the suspension. Stirring was continued for 42 min, and the mixed suspension was subjected to ultrasonic treatment for 18 min. The ultrasonic power was set to 280 W and the frequency was 55 kHz to obtain modified triclopyr butoxyethyl ester.

[0104] S8. The 001×7 strong acid cation resin was soaked in deionized water for 24 hours, then soaked in 5% hydrochloric acid solution for 5.5 hours, and then washed with deionized water until neutral to obtain a pretreated resin;

[0105] S9. 6.5 g of amethoxazole and 11 g of pretreated resin were added to a 250 mL three-necked flask, and 158 mL of deionized water was added. The mixture was stirred at 280 rpm and reacted for 9.5 h at a water bath temperature of 38° C. During the reaction, certain groups in the amethoxazole molecule exchanged with ions on the ion exchange resin to change the charge properties and molecular structure of the amethoxazole. After the reaction, the ion exchange resin was separated from the reaction solution by filtration, and the mixture was washed with deionized water for 3 times. The washing solution and the reaction solution were combined, and water was removed by vacuum distillation or the like to obtain a crude amethoxazole product.

[0106] S10. 6.5 g of crude amethoxazole and 1.3 g of tert-butylhydroquinone were added to a 100 mL round-bottom flask, and 62 mL of acetone was added. The mixture was stirred at room temperature at a speed of 180 rpm for 42 min. Then, the product was dried, which can be vacuum dried at 48 ° C for 3 h to obtain modified amethoxazole;

[0107] S11. Add 9 g of modified cyclosulfone, 15 g of modified butoxyethyl triclopyr, 16 g of modified azomethine, 5.6 g of naphthalenesulfonate formaldehyde condensate, 3.3 g of alkylphenol polyoxyethylene ether, 0.45 g of magnesium aluminum silicate, 5.8 g of propylene glycol, and 0.65 g of silicone defoamer into 61 g of water, stir for 15 min, and then sand grind in a sand mill for 2 h to obtain a pesticide suspension.

[0108] Example 5: A method for preparing a pesticide suspension containing tembotrione-butoxyethyl triclopyraclostrobin-ametryn, comprising the following steps:

[0109] S1. In a 250mL three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 13g of cyclosulfone was added, and then 115mL of anhydrous ethanol was added as an organic solvent. The reaction system was cooled to 5°C, and 4g of chloroethanol was added dropwise. The addition time was controlled at 45min. After the addition was completed, the reaction temperature was raised to 60°C, and the reaction was stirred for 8h. After the reaction was completed, the reaction solution was poured into ice water. Solids were precipitated, filtered, washed and dried to obtain hydroxylated cyclosulfone;

[0110] S2. Dissolve 7g of hydroxylated cyclosulfone in 55mL of toluene to obtain an oil phase, dissolve 2.8g of isocyanate and 4g of polyethylene glycol in 120mL of deionized water, and add 0.8g of sodium dodecyl sulfate to obtain an aqueous phase, add the aqueous phase to a 500mL four-necked flask equipped with a stirrer and a thermometer, start stirring, control the speed at 1000r / min, drop the oil phase into the aqueous phase, and the dropping time is 35min to form a stable emulsion, then increase the reaction temperature to 70°C, react for 4h, allow the isocyanate and polyethylene glycol to undergo polymerization at the oil-water interface, and gradually form a microcapsule wall that wraps the cyclosulfone. After the reaction is completed, transfer the reaction solution to a centrifuge tube, centrifuge at 6000r / min for 20min, separate the microencapsulated cyclosulfone, and wash 4 times with deionized water to obtain microencapsulated cyclosulfone;

[0111] S3. Weigh 7g of microcapsule cyclosulfuron and 15g of rice husk biochar, add them to 230mL of Tween-80 aqueous solution with a mass fraction of 0.7%, transfer the mixture to a three-necked flask equipped with a stirrer and a thermometer, and stir at 50°C at a speed of 400r / min for 8h to load the microcapsule cyclosulfuron on the surface and pores of the biochar. After the reaction is completed, separate the loaded biochar by filtration, wash with deionized water until no surfactant is detected in the washing liquid, and then dry at 70°C to constant weight to obtain carbon-loaded cyclosulfuron;

[0112] S4. 13 g of carbon-loaded cyclosulfone was added to 115 mL of deionized water and stirred to form a suspension. Under stirring conditions, 2.6 g of polyether-modified silicone was slowly added at a rate of 2 drops / second, and stirring was continued for 45 min to fully mix the silicone additive and the biochar-loaded cyclosulfone to obtain a cyclosulfone suspension. The preparation process of the polyether-modified silicone was as follows: 100 g of hydrogenated silicone oil and 50 g of polyether monomer were added to a three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, and then 150 mL of toluene was added. Stirring was started to allow the suspension to be stirred for 3 hours. The raw materials were fully mixed, and 0.1 g of a 3% isopropanol solution of chloroplatinic acid was added dropwise to the mixed solution. Stirring was maintained during the addition process. Note that the dropping speed should not be too fast to avoid excessive reaction. The reaction system was slowly heated to 100°C and reacted at this temperature for 6 hours. After the reaction was completed, the reaction solution was cooled to room temperature, and then the toluene solvent was removed by reduced pressure distillation. The remaining product was washed 4 times with an appropriate amount of anhydrous ethanol to remove unreacted raw materials and catalysts. The washed product was vacuum dried at 60°C for 3 hours to obtain polyether-modified silicone.

[0113] S5. Dissolve 7 g of butoxyethyl triclopyr in 55 mL of ethyl acetate to form an organic phase;

[0114] S6. Dissolve 1.5 g of polyvinyl pyrrolidone in 220 mL of deionized water to form an aqueous phase;

[0115] S7. At room temperature, the organic phase was added dropwise to the aqueous phase, and magnetic stirring was turned on at the same time. The stirring speed was set to 810 r / min, and the dropping time was 33 min to form a stable emulsion. The emulsion was transferred to a rotary evaporator, and the ethyl acetate was removed by reduced pressure evaporation at a temperature of 50°C. As the solvent evaporated, butoxyethyl triclopyr gradually formed nanoparticles dispersed in the aqueous phase. The evaporation process continued for 2 hours until no obvious solvent was evaporated. Finally, the obtained nanoparticle suspension was centrifuged at 5100 rpm for 18 minutes, and then washed with deionized water for 3 times to remove excess surfactant to obtain triclopyr butoxyethyl ester nanoparticles. 40 g of the prepared triclopyr butoxyethyl ester nanoparticle suspension was transferred to a three-necked flask equipped with a stirrer and a thermometer, and stirred at a speed of 300 r / min at room temperature to uniformly disperse the nanoparticles in the suspension. 12 g of carbon-supported cyclosulfone was weighed and added to the stirring triclopyr butoxyethyl ester nanoparticle suspension. The addition time was controlled to 20 minutes. Then, a polyvinyl alcohol dispersant was added. The amount of the polyvinyl alcohol dispersant was 1% of the mass of the suspension. Stirring was continued for 45 minutes. The mixed suspension was subjected to ultrasonic treatment for 20 minutes. The ultrasonic power was set to 300 W and the frequency was 60 kHz to obtain modified triclopyr butoxyethyl ester.

[0116] S8. The 001×7 strong acid cation resin was soaked in deionized water for 24 h, then soaked in 5% hydrochloric acid solution for 6 h, and then washed with deionized water until neutral to obtain a pretreated resin;

[0117] S9. 7 g of amethoxazole and 13 g of pretreated resin were added to a 250 mL three-necked flask, 160 mL of deionized water was added, and the mixture was stirred at 300 rpm at a water bath temperature of 40° C. for 10 h. During the reaction, certain groups in the amethoxazole molecule exchanged with ions on the ion exchange resin to change the charge properties and molecular structure of the amethoxazole. After the reaction, the ion exchange resin was separated from the reaction solution by filtration, and the mixture was washed with deionized water for 5 times. The washing solution and the reaction solution were combined, and the water was removed by vacuum distillation or the like to obtain a crude amethoxazole product.

[0118] S10. 7 g of crude amethoxazole and 1.4 g of tert-butylhydroquinone were added to a 100 mL round-bottom flask, and 65 mL of acetone was added. The mixture was stirred at 200 rpm for 45 min at room temperature. The product was then dried, which may be done by vacuum drying at 50 ° C for 3 h to obtain modified amethoxazole;

[0119] S11. Add 10 g of modified cyclosulfone, 16 g of modified butoxyethyl triclopyr, 18 g of modified azomethine, 5.8 g of naphthalenesulfonate formaldehyde condensate, 3.4 g of fatty alcohol polyoxyethylene ether, 0.5 g of magnesium aluminum silicate, 6 g of propylene glycol, and 0.8 g of silicone defoamer into 62 g of water, stir for 15 min, and then sand grind in a sand mill for 2 h to obtain a pesticide suspension.

[0120] Comparative Example 1:

[0121] Compared with Example 1, this comparative example only replaces "modified cyclohexane" with "cyclohexane", and the remaining steps and parameters are the same, which will not be repeated in this comparative example, and finally a pesticide suspension is obtained.

[0122] Comparative Example 2:

[0123] Compared with Example 1, this comparative example only replaces the "modified cyclohexane" with the "carbon-supported cyclohexane", and the remaining steps and parameters are the same, which will not be repeated in this comparative example, and finally a pesticide suspension is obtained.

[0124] Comparative Example 3:

[0125] Compared with Example 1, this comparative example only replaces "modified cyclohexane" with "microcapsule cyclohexane", and the remaining steps and parameters are the same, which will not be repeated in this comparative example, and finally a pesticide suspension is obtained.

[0126] Comparative Example 4:

[0127] Compared with Example 1, this comparative example only replaces the "modified butoxyethyl triclopyr" with "butoxyethyl triclopyr nanoparticles", and the remaining steps and parameters are the same, which will not be repeated in this comparative example, and finally a pesticide suspension is obtained.

[0128] Comparative Example 5:

[0129] Compared with Example 1, this comparative example only replaces the "triclopyr butoxyethyl ester nanoparticles" with "triclopyr butoxyethyl ester", and the remaining steps and parameters are the same, which will not be repeated in this comparative example, and finally a pesticide suspension is obtained.

[0130] Comparative Example 6:

[0131] Compared with Example 1, this comparative example only replaces "modified ametryn" with "ametryn", and the remaining steps and parameters are the same, which will not be repeated in this comparative example, and finally a pesticide suspension concentrate is obtained.

[0132] Comparative Example 7:

[0133] Compared with Example 1, this comparative example only adjusts the amounts of "triclopyr butoxyethyl ester nanoparticles" and "carbon-loaded cyclosulfone" in the preparation process of "modified triclopyr butoxyethyl ester" from "30 g" and "10 g" to "10 g" and "30 g", respectively, and the remaining steps and parameters are the same, which will not be repeated in this comparative example, and finally a pesticide suspension is obtained.

[0134] Comparative Example 8:

[0135] Compared with Example 1, this comparative example only adjusts the dosage of "modified tampronone", "modified triclopyr butoxyethyl ester" and "modified ametryn" from "5g", "10g" and "15g" to "20g", "2g" and "8g", respectively, and the remaining steps and parameters are the same, which will not be repeated in this comparative example, and finally a pesticide suspension is obtained.

[0136] Performance Testing:

[0137] Weed control effect test: multiple sugarcane planting pots of the same area are set in the greenhouse, sugarcane seedlings are evenly planted in each pot, and common sugarcane field weed seeds, such as barnyard grass, crabgrass, broadleaf weeds, etc. are evenly mixed. The pesticide suspensions of Examples 1 to 5 and Comparative Examples 1 to 8 are sprayed at the same dilution multiple and spraying amount, and the blank control group is not sprayed with pesticides. After spraying, the growth of weeds is regularly observed, the mortality rate of weeds is recorded, and the weed control rate is calculated. Weed control rate = (number of weeds in the control group - number of weeds in the treatment group) / number of weeds in the control group × 100%.

[0138] Effective period test: In the above planting pots, record the time from spraying the pesticide to the time when the weeds begin to regrow and reach 10% coverage, which is taken as the effective period.

[0139] Safety test of sugarcane: observe the growth of sugarcane after spraying pesticides, including whether the leaves show symptoms of pesticide damage such as burns, deformities, and yellowing, and record the pesticide damage index. Pesticide damage index = ∑ (number of pesticide-damaged plants at each level × representative value of that level) / (total number of plants surveyed × highest representative value) × 100.

[0140] Environmental impact test: simulate rainfall conditions, conduct leaching experiments on planting pots after spraying pesticides, collect leaching solutions, test the pesticide residues in them, and evaluate the leaching risk of pesticides in the soil. At the same time, test the number and activity of microorganisms in the soil to analyze the impact of pesticides on soil microorganisms;

[0141] The results are shown in Table 1 below:

[0142] Table 1

[0143]

[0144] Data Analysis:

[0145] As can be seen from Table 1, from the weed control rate data, the weed control rate in the embodiment is relatively high, reaching 90%-93%, which is due to the synergistic effect of each component. After a series of treatments, the solubility and dispersibility of the modified cyclosulfone are improved, and it can better contact with weeds. After the modified triclopyr butoxyethyl ester is nano-sized, the specific surface area is increased and the activity is enhanced. The two are compounded, and the mechanism of action is complementary. Cyclosulfone inhibits the weed HPPD enzyme, and triclopyr butoxyethyl ester interferes with hormone balance, expands the weed control spectrum, and improves the weed control rate. As in Example 1, the two synergize to achieve a weed control rate of 90%, while the comparative example 1 is not modified and compounded, and the weed control rate is only 70%; in terms of the duration, the embodiment is 45-50 days, which is significantly longer than the comparative example. The microencapsulation of the modified cyclosulfone allows it to be slowly released and prolongs the duration of action. After the modified triclopyr butoxyethyl ester nanoparticles are compounded with the carbon-loaded cyclosulfone, the adsorption and release characteristics of the agent in the soil may be changed, further prolonging the duration. For example, the effective period of Example 3 is 50 days, while that of Comparative Example 2, which has not been effectively modified, is only 35 days. In terms of safety for sugarcane, the pesticide damage index of the embodiment is low, at 3-5. Hydroxylation and other treatments of modified cyclosulfone change its metabolism and distribution in sugarcane, reducing the risk of pesticide damage. Modified triclopyr butoxyethyl ester and modified cyclosulfone work together to optimize the selectivity of the agent between sugarcane and weeds, reducing damage to sugarcane. For example, the pesticide damage index of Example 2 is 4, while that of Comparative Example 5 is 13 because the ingredients are not reasonably modified. In terms of the relative values ​​of pesticide residues in the leaching solution and soil microbial activity, the embodiment performs better. The modified cyclosulfone biochar loading enhances adsorption and reduces leaching. The modified triclopyr butoxyethyl ester and modified cyclosulfone are compounded to reduce the inhibition of soil microorganisms. For example, the pesticide residue in the leaching solution of Example 4 is 0.45 mg / L, and the relative value of soil microbial activity is 0.86. The comparative example 6 is not reasonably modified, the pesticide residue in the leaching solution is 0.7 mg / L, and the relative value of soil microbial activity is 0.72. In general, the synergistic effect of the modified triclopyr butoxyethyl ester and the modified tampronyl is compounded, which comprehensively improves the performance of the pesticide suspension in terms of herbicidal effect, lasting effect, safety to sugarcane and environmental impact, making the various indicators of the embodiment better than those of the comparative example.

[0146] Those skilled in the art should understand that the discussion of any of the above embodiments is merely illustrative and is not intended to imply that the scope of the present invention is limited to these examples. Under the concept of the present invention, the technical features in the above embodiments or different embodiments may be combined, the steps may be implemented in any order, and there are many other variations of the different aspects of the present invention as described above, which are not provided in detail for the sake of simplicity.

[0147] The present invention is intended to cover all such substitutions, modifications and variations that fall within the broad scope of the appended claims. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A pesticide suspension containing tembotrione-butoxyethyl triclopyraclostrobin-ametryn, characterized in that: The invention is prepared from the following raw materials in parts by weight: 5-10 parts of modified tembotrione, 10-16 parts of modified butoxyethyl triclopyr, 15-18 parts of modified ametryn, 5-5.8 parts of dispersant, 3-3.4 parts of wetting agent, 0.3-0.5 parts of thickener, 5-6 parts of antifreeze agent, 0.5-0.8 parts of defoamer and 56-62 parts of water; The modified tembotrione is a tembotrione suspension; The modified triclopyr butoxyethyl ester is polyvinyl pyrrolidone modified triclopyr butoxyethyl ester; The modified ametryn is ion exchange resin modified ametryn.

2. The pesticide suspension containing tembotrione-butoxyethyl triclopyrazone-ametryn according to claim 1, characterized in that: The preparation process of the tembotrione suspension is as follows: Step A1. Hydroxylation of tembotrione to obtain hydroxylated tembotrione; Step A2. Microencapsulation of hydroxylated tembotrione to obtain microencapsulated tembotrione; Step A3. Loading of microcapsules with tambara to obtain carbon-loaded tambara; Step A4. Compounding of carbon-supported tembotrione to obtain a tembotrione suspension.

3. The pesticide suspension containing tembotrione-butoxyethyl triclopyrazone-ametryn according to claim 2, characterized in that: The hydroxylation process of tembotrione described in step A1 is as follows: In a 250 mL three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, add tampronone and then add anhydrous ethanol, cool the reaction system to 0-5°C, add chloroethanol dropwise, and control the dropping time to 30-45 min. After the dropwise addition is completed, raise the reaction temperature to 50-60°C, stir and react for 6-8 hours. After the reaction is completed, pour the reaction solution into ice water, and solid precipitates. Filter, wash and dry to obtain hydroxylated tampronone; The dosage ratio of tamponic acid ketone, anhydrous ethanol and chloroethanol is 9-13g:95-115mL:2-4g.

4. The pesticide suspension containing tembotrione-butoxyethyl triclopyrazone-ametryn according to claim 2, characterized in that: The microencapsulation process of the hydroxylated tembotrione in step A2 is as follows: The hydroxylated cyclosulfone is dissolved in toluene to obtain an oil phase, the isocyanate and polyethylene glycol are dissolved in deionized water, and sodium dodecyl sulfate is added to obtain an aqueous phase, the aqueous phase is added to a 500 mL four-necked flask equipped with a stirrer and a thermometer, stirring is started, the speed is controlled at 800-1000 r / min, the oil phase is added dropwise to the aqueous phase, the dropping time is 30-35 min, the reaction temperature is increased to 60-70° C., the reaction is carried out for 3-4 hours, after the reaction is completed, the reaction solution is transferred to a centrifuge tube, centrifuged at a speed of 5000-6000 r / min for 15-20 minutes, and washed with deionized water for 3-4 times to obtain microcapsule cyclosulfone; The dosage ratio of the hydroxylated cyclohexane and toluene is 5-7 g: 50-55 mL; The usage ratio of the isocyanate, polyethylene glycol, deionized water and sodium dodecyl sulfate is 2-2.8 g: 3-4 g: 100-120 mL: 0.5-0.8 g.

5. The pesticide suspension containing tembotrione-butoxyethyl triclopyrazone-ametryn according to claim 2, characterized in that: The loading process of microcapsule tembotrione in step A3 is as follows: Add microcapsule cyclosulfuron and rice husk biochar to a Tween-80 aqueous solution, transfer the mixture to a three-necked flask equipped with a stirrer and a thermometer, and stir at 40-50°C at a speed of 300-400 r / min for 6-8 hours. After the reaction is completed, filter and separate the loaded biochar, wash with deionized water, and then dry at 60-70°C to constant weight to obtain carbon-loaded cyclosulfuron; The dosage ratio of the microcapsule tembotrione, rice husk biochar and Tween-80 aqueous solution is 5-7 g: 10-15 g: 200-230 mL; The mass fraction of Tween-80 in the Tween-80 aqueous solution is 0.5%-0.7%.

6. The pesticide suspension concentrate containing tembotrione-butoxyethyl triclopyrazone-ametryn according to claim 2, characterized in that: The compounding process of carbon-supported tembotrione in step A4 is as follows: The carbon-supported tembotrione is added to deionized water, and stirred evenly to form a suspension. Under stirring conditions, polyether-modified silicone is added at a rate of 1-2 drops / second, and stirring is continued for 30-45 minutes to obtain a tembotrione suspension. The usage ratio of the carbon-supported cyclosulfone, deionized water and polyether-modified silicone is 10-13 g: 100-115 mL: 2-2.6 g.

7. The pesticide suspension containing tembotrione-butoxyethyl triclopyrazone-ametryn according to claim 1, characterized in that: The preparation process of the modified triclopyr butoxyethyl ester is as follows: Step B1. dissolving butoxyethyl triclopyr in ethyl acetate to form an organic phase; Step B2. dissolving polyvinyl pyrrolidone in deionized water to form an aqueous phase; Step B3. At room temperature, the organic phase is added dropwise to the aqueous phase, and magnetic stirring is turned on at the same time. The stirring speed is set to 780-810 r / min, and the dropping time is 28-33 min. The obtained emulsion is transferred to a temperature of 40-50 ° C and evaporated under reduced pressure for 1-2 h until no obvious solvent is evaporated. Finally, the obtained suspension is centrifuged at 4800-5100 rpm for 15-18 min, and then washed with deionized water 3 times to obtain triclopyr butoxyethyl ester nanoparticles. The prepared triclopyr butoxyethyl ester nanoparticle suspension is transferred to a stirring chamber A three-necked flask with a stirrer and a thermometer is placed in a room temperature at a speed of 200-300 r / min to uniformly disperse the nanoparticles in the suspension, carbon-loaded tembotrione is weighed, and added to the stirring suspension of butoxyethyl triclopyr. The addition time is controlled to be 15-20 min, and then a polyvinyl alcohol dispersant is added, and stirring is continued for 30-45 min. The mixed suspension is subjected to ultrasonic treatment for 15-20 min, and the ultrasonic power is set to 200-300 W and the frequency is 40-60 kHz to obtain modified butoxyethyl triclopyr. The usage ratio of triclopyr butoxyethyl ester and ethyl acetate in step B1 is 5-7 g: 50-55 mL; The usage ratio of polyvinyl pyrrolidone and deionized water in step B2 is 1-1.5 g: 200-220 mL; The mass ratio of the triclopyr butoxyethyl ester nanoparticles to the carbon-supported tembotrione in step B3 is 30-40:10-12; The amount of the polyvinyl alcohol dispersant used in step B3 is 0.5%-1% of the mass of the suspension.

8. The pesticide suspension concentrate containing tembotrione-butoxyethyl triclopyrazone-ametryn according to claim 1, characterized in that: The preparation process of the modified ametryn is as follows: Step C1. Soak 001×7 strong acidic cationic resin in deionized water for 24 hours, then soak it in 5% hydrochloric acid solution for 4-6 hours, and then wash it with deionized water until it is neutral to obtain a pretreated resin; Step C2. Add amethoxazole and the pretreated resin into a 250 mL three-necked flask, add deionized water, and stir at a water bath temperature of 30-40° C. and a speed of 200-300 rpm for 8-10 hours. After the reaction is completed, filter and wash with deionized water for 3-5 times, combine the washing liquid and the reaction liquid, and remove water by vacuum distillation to obtain a crude product of amethoxazole; Step C3. Add the crude ametryn and tert-butylhydroquinone into a 100 mL round-bottom flask, add acetone, stir at room temperature at a speed of 150-200 rpm for 30-45 min, remove the acetone by vacuum distillation, and dry at 40-50° C. for 2-3 h to obtain modified ametryn; The usage ratio of ametryn, pre-treated resin and deionized water in step C2 is 5-7 g: 10-13 g: 150-160 mL; In step C3, the usage ratio of the crude ametryn, tert-butylhydroquinone and acetone is 5-7 g: 1-1.4 g: 50-65 mL.

9. The pesticide suspension concentrate containing tembotrione-butoxyethyl triclopyrazone-ametryn according to claim 1, characterized in that: The dispersant is any one of sodium lignin sulfonate and naphthalene sulfonate formaldehyde condensate; The wetting agent is any one of alkylphenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether; The thickener is any one of xanthan gum and magnesium aluminum silicate; The antifreeze agent is any one of ethylene glycol and propylene glycol; The defoamer is an organosilicon defoamer.

10. The method for preparing the pesticide suspension concentrate containing tembotrione-butoxyethyl triclopyrazone-ametryn according to any one of claims 1 to 9, characterized in that: The following steps are involved: Add modified cyclosulfone, modified butoxyethyl triclopyr, modified ametryn, dispersant, wetting agent, thickener, antifreeze agent and defoamer into water, stir for 15 minutes, and then grind in a sand mill for 2 hours to prepare a pesticide suspension.

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