Suspending agent containing picoxy.epoxiconazole

Abstract

The invention discloses a suspending agent containing picoxy.epoxiconazole, and belongs to the technical field of pesticide preparations. The suspending agent is prepared from the following raw materials in parts by weight: 4 to 10 parts of picoxystrobin, 4 to 8 parts of epoxiconazole, 1 to 4 parts of a chitosan and sodium carboxymethyl cellulose compound stabilizer, 2 to 6 parts of lignosulfonate, 1 to 3 parts of fluorine-silicon hybrid organic silicon, 0.1 to 1 part of nano silicon dioxide, 1 to 3 parts of an anti-freezing agent, 0.1 to 0.5 part of a de-foaming agent and 65.5 to 86.9 parts of water. Wherein the chitosan and the sodium carboxymethyl cellulose are compounded, so that the dispersity and the anti-settling performance of the system are improved, the fluorine-silicon hybrid organic silicon obviously enhances the wetting and spreading performance of the liquid medicine, and the nano silicon dioxide endows excellent film-forming property and rain washing resistance. The suspending agent disclosed by the invention not only has excellent performance in the aspects of particle size control, suspension rate and redispersibility, but also is obviously superior to a conventional preparation in the aspects of crop leaf surface spreadability, rain resistance and storage stability, and has relatively high popularization and application values.

Description

Technical Field

[0001] This invention relates to the field of agricultural chemical formulations, specifically to a suspension containing pyridoxine and flutriafol. Background Technology

[0002] Azoxystrobin is a methoxyacrylate fungicide that blocks energy metabolism by inhibiting electron transport in the mitochondrial respiratory chain of fungal cells, exhibiting a broad fungicidal spectrum and strong protective activity. Fluticasone belongs to the triazole fungicide class, and its mechanism of action involves inhibiting sterol biosynthesis, thereby interfering with fungal cell membrane formation. It shows good control effects against rust and powdery mildew in cereal crops, as well as leaf spot and anthracnose in fruit and vegetable crops. The combination of these two fungicides allows them to act simultaneously on different metabolic pathways, not only broadening the fungicidal spectrum but also effectively delaying the emergence of resistant fungi, thus demonstrating significant application potential in agricultural disease control.

[0003] Existing technologies have disclosed compositions of azoxystrobin and triazole fungicides, proposing formulations such as suspension concentrates. However, these existing azoxystrobin-fluticasone suspension concentrates still have significant shortcomings in application. During long-term storage and transportation, commonly used dispersants and thickeners are ineffective in inhibiting particle aggregation and sedimentation, easily leading to formulation stratification, decreased suspension rate, and affecting field efficacy. Currently, most products still use single polyether-modified organosilicon or conventional surfactants as wetting and spreading agents, which have limited ability to wet and spread the waxy layer on crop leaf surfaces, resulting in uneven distribution of the pesticide solution on the leaf surface and low utilization rate. In conventional formulations, the pesticide solution is easily washed away by rainfall in the field, significantly reducing the residual amount and shortening the effective period, requiring frequent application. Existing adjuvant systems mostly use traditional lignin sulfonate or naphthalene sulfonate dispersants, lacking the introduction of green and environmentally friendly compound stabilizers and nano-adjuvants, thus having significant limitations in improving suspension stability, enhancing adhesion and film formation, and improving rain washout resistance.

[0004] Existing pyridoxine-fluticasone suspension concentrates fail to meet the demands of modern agriculture for green and efficient pest control in terms of stability, wettability, and rain resistance. Therefore, there is an urgent need to develop a new suspension concentrate system that innovates in adjuvant selection and modification methods, combining the synergistic effects of polymeric compound stabilizers, fluorosilicone hybrid organosilicon, and nano-silica to comprehensively improve the suspension stability, wettability, and rain washout resistance of the formulation, ensuring effective control in complex field environments. Summary of the Invention

[0005] To overcome the problems of poor stability, insufficient wetting and spreading properties, and poor rain resistance in the aforementioned background technologies, the present invention aims to provide a suspension containing pyridoxine·fluconazole. This suspension uses a chitosan and sodium carboxymethyl cellulose compound to form a stabilizer system, employs fluorosilicone hybrid organosilicon as a wetting and spreading agent, and introduces nano-silica for synergistic enhancement. This significantly improves suspension stability, leaf spreading properties, and rain resistance while ensuring efficacy.

[0006] The synergistic effect of chitosan and sodium carboxymethyl cellulose effectively prevents particle sedimentation and stratification, improving suspension stability. The introduction of fluorosilicone hybrid organosilicon enhances the wettability and spreading ability of the pesticide on the waxy layer of crop leaves. The synergistic effect of nano-silica improves the adhesion and film-forming properties of the pesticide on leaves, increasing resistance to rain washout. This formulation system is generally stable and has a long-lasting effect, significantly enhancing the field application value of the pyridoxine and flutriafol compound formulation.

[0007] The objective of this invention can be achieved through the following technical solutions: A suspension containing pyridoxine and flutriafol comprises the following raw materials in parts by weight: 4-10 parts of pyridoxine; 4-8 parts of flutriafol; 1-4 parts of chitosan and sodium carboxymethyl cellulose compound stabilizer; 2-6 parts of lignin sulfonate; 1-3 parts of fluorosilicone hybrid organosilicon; 0.1-1 parts of nano-silica; 1-3 parts of antifreeze; 0.1-0.5 parts of defoamer; and 65.5-86.9 parts of water; wherein the fluorosilicone hybrid organosilicon is a composite organosilicon material composed of a siloxane backbone, fluoroalkyl groups, and organic segments.

[0008] Optionally, the mass ratio of chitosan to sodium carboxymethyl cellulose in the chitosan and sodium carboxymethyl cellulose compound stabilizer is 1:1 to 1:3.

[0009] Optionally, the fluorosilicone hybrid organosilicon comprises the following raw materials in parts by weight: 0.5 to 1.5 parts of polydimethylsiloxane; 0.2 to 0.8 parts of 3,3,3-trifluoropropyltrimethoxysilane; 0.2 to 0.6 parts of polyoxyethylene-polyoxypropylene ether; and 0.1 to 0.3 parts of methyltriethoxysilane.

[0010] Optionally, the preparation method of fluorosilicone hybrid organosilicon includes the following steps: (1) Add anhydrous isopropanol to the reactor and purge with nitrogen for protection; (2) Add a mixture of deionized water and glacial acetic acid dropwise at 20-30℃, followed by the addition of 3,3,3-trifluoropropyltrimethoxysilane and methyltriethoxysilane, and stir for 30-60 min. (3) Heat to 50-70℃ and stir for 1-2 hours; (4) Cool down to 40-50℃, add polydimethylsiloxane, and stir for 60-90 min; (5) Slowly add polyoxyethylene-polyoxypropylene ether at 35-45℃ and shear disperse for 30-60 min; (6) Remove the solvent under reduced pressure at 45-60°C, let stand to remove bubbles, filter, and obtain fluorosilicone hybrid organosilicon.

[0011] Optionally, the antifreeze is a mixture of propylene glycol and glycerin in a mass ratio of (1-3):1; the defoamer is a mixture of polyether defoamer and silicone defoamer in a mass ratio of (0.5-2):1.

[0012] Optionally, a method for preparing a suspension containing pyridoxine·fluconazole includes the following steps: S1, add azoxystrobin and flutriafol to an aqueous phase containing lignin sulfonate and fluorosilicone hybrid organosilicon, stir for 30-60 min to obtain a pre-dispersion; S2, the pre-dispersion liquid is sand-milled to control the particle size D90 to be 1.5-2.5 μm; S3, add chitosan and sodium carboxymethyl cellulose compound stabilizer and nano silica, and stir for 30-60 minutes; S4, add antifreeze and defoamer, and stir well; S5, degas under reduced pressure at 45-60℃, filter, and obtain the finished suspension of pyridoxine·fluconazole.

[0013] The beneficial effects of this invention are: This invention utilizes a combination of chitosan and sodium carboxymethyl cellulose as stabilizers, enabling a synergistic effect between the two polymers. This effectively maintains the uniform distribution of suspended particles during storage and transportation, preventing sedimentation and stratification. By introducing fluorosilicone hybrid organosilicon, the pesticide solution can rapidly spread and form a uniform coating on the waxy surface of crop leaves, significantly enhancing its spreading properties compared to conventional adjuvants. The combined action of nano-silica and fluorosilicone hybrid organosilicon forms a dense and robust film on the leaf surface, giving the pesticide solution stronger adhesion and rain washout resistance. This allows the suspension of this invention to maintain a long-lasting and stable efficacy even under complex field conditions. Attached Figure Description

[0014] The invention will now be further described with reference to the accompanying drawings.

[0015] Figure 1 Infrared contrast spectra of unmodified fluoroalkylsilane premix and fluorosilicone hybrid organosilicon; Figure 2 A bar chart comparing the particle size of samples with different ratios; Figure 3A bar chart comparing the suspension rates of samples with different ratios; Figure 4 A bar chart comparing the contact angles of samples with different ratios; Figure 5 A bar chart comparing the residual rates of samples with different formulation ratios after rain erosion. Detailed Implementation

[0016] The present invention will be further described below with reference to specific embodiments. However, the present invention is not limited to the following embodiments. Equivalent adjustments made without departing from the spirit and essence of the present invention should also be considered to fall within the protection scope of the present invention. Example

[0017] The purpose of this embodiment is to verify that, under intermediate formulation conditions, the suspending agent can maintain good stability and wetting and spreading properties through the synergistic effect of chitosan / sodium carboxymethyl cellulose compound stabilizer, fluorosilicone hybrid organosilicon, and nano-silica.

[0018] S1. Add 100 parts of anhydrous isopropanol to the reactor, purge with nitrogen for protection, and add a mixture of 20 parts of deionized water and 2 parts of glacial acetic acid dropwise at 20-30°C. Simultaneously, slowly add 6 parts of 3,3,3-trifluoropropyltrimethoxysilane and 3 parts of methyltriethoxysilane. Stir for 40 min, raise the temperature to 60°C, stir for 1.5 h, cool to 45°C, add 10 parts of polydimethylsiloxane, stir for 75 min, then slowly add 5 parts of polyoxyethylene-polyoxypropylene ether, shear and disperse for 40 min, and finally desolvate under reduced pressure at 50°C at -0.08 MPa. Allow to stand to degas, and filter through a 0.45 μm filter membrane to remove large particulate impurities to obtain fluorosilicone hybrid organosilicon. S2: Take 7 parts of azoxystrobin and 6 parts of flutriafol and add them to an aqueous phase containing 3 parts of lignin sulfonate and 2 parts of the fluorosilicone hybrid organosilicon obtained in S1. Stir for 40 min to obtain a pre-dispersion. Send the pre-dispersion to a sand mill for grinding, and control the particle size D90 to be 1.5-2.5 μm. After grinding, add 2 parts of chitosan and sodium carboxymethyl cellulose (mass ratio 1:2) as a stabilizer and 0.5 parts of nano silica. Stir for 45 min. Then add 2 parts of antifreeze mixed with propylene glycol and glycerol in a mass ratio of 2:1 and 0.2 parts of defoamer mixed with polyether defoamer and organosilicon defoamer in a mass ratio of 1:1. Stir evenly and finally degas at 50℃ under -0.08 MPa. Filter to obtain the finished azoxystrobin·flutriafol suspension. Example

[0019] The purpose of this embodiment is to examine the stability and film-forming properties of the suspending agent under high content of active ingredients, at the upper limit of the formulation.

[0020] S1. Add 120 parts of anhydrous isopropanol to the reactor, purge with nitrogen for protection, add a mixture of 25 parts of deionized water and 3 parts of glacial acetic acid dropwise at 25°C, and simultaneously add 8 parts of 3,3,3-trifluoropropyltrimethoxysilane and 4 parts of methyltriethoxysilane dropwise. Stir for 50 min, raise the temperature to 65°C, stir for 1.5 h, cool to 45°C, add 15 parts of polydimethylsiloxane, stir for 80 min, then slowly add 6 parts of polyoxyethylene-polyoxypropylene ether, shear and disperse for 45 min, finally desolvate at 55°C under -0.08 MPa, allow to stand to degas, filter, and obtain fluorosilicone hybrid organosilicon; S2: Take 10 parts of azoxystrobin and 8 parts of flutriafol and add them to an aqueous phase containing 6 parts of lignin sulfonate and 3 parts of the fluorosilicone hybrid organosilicon obtained in S1. Stir for 45 min to obtain a pre-dispersion. After sand milling, control the particle size D90 to be 1.5-2.5 μm. After grinding, add 4 parts of chitosan and sodium carboxymethyl cellulose (mass ratio 1:2) as a stabilizer and 1.0 part of nano silica. Stir for 45 min. Then add 3 parts of antifreeze mixed with propylene glycol and glycerol in a mass ratio of 2:1 and 0.5 parts of defoamer mixed with polyether defoamer and organosilicon defoamer in a mass ratio of 1:1. Stir evenly and finally degas at 55℃ under -0.08 MPa. Filter to obtain azoxystrobin·flutriafol suspension. Example

[0021] The purpose of this embodiment is to examine the stability and application effect of the suspension under low dose of active ingredient conditions at the lower limit of the formulation.

[0022] S1. Add 80 parts of anhydrous isopropanol to the reactor, purge with nitrogen for protection, add a mixture of 15 parts of deionized water and 1.5 parts of glacial acetic acid dropwise at 22°C, and simultaneously add 4 parts of 3,3,3-trifluoropropyltrimethoxysilane and 2 parts of methyltriethoxysilane. Stir for 30 min, raise the temperature to 55°C, stir for 1 h, cool to 40°C, add 8 parts of polydimethylsiloxane, stir for 60 min, then slowly add 4 parts of polyoxyethylene-polyoxypropylene ether, shear and disperse for 30 min, finally desolvate at -0.07 MPa at 45°C, allow to stand to degas, filter, and obtain fluorosilicone hybrid organosilicon; S2: Take 4 parts of azoxystrobin and 4 parts of flutriafol and add them to an aqueous phase containing 2 parts of lignin sulfonate and 1 part of the fluorosilicone hybrid organosilicon obtained in S1. Stir for 30 min to obtain a pre-dispersion. After sand milling, control the particle size D90 to be 1.5-2.5 μm. After grinding, add 1 part of chitosan and sodium carboxymethyl cellulose (mass ratio 1:2) as a stabilizer and 0.1 part of nano silica. Stir for 30 min. Then add 1 part of antifreeze mixed with propylene glycol and glycerol in a mass ratio of 2:1 and 0.1 part of defoamer mixed with polyether defoamer and organosilicon defoamer in a mass ratio of 1:1. Stir evenly and finally degas at -0.08 MPa and 45 °C. Filter to obtain azoxystrobin·flutriafol suspension. Example

[0023] The purpose of this embodiment is to study the effect of the mass ratio of chitosan to sodium carboxymethyl cellulose. A ratio of 1:1 was selected as the variable for verification to examine its effect on suspension stability.

[0024] S1. Add 100 parts of anhydrous isopropanol to a reactor, purge with nitrogen for protection, add a mixture of 20 parts of deionized water and 2 parts of glacial acetic acid dropwise at 25°C, and simultaneously add 6 parts of 3,3,3-trifluoropropyltrimethoxysilane and 3 parts of methyltriethoxysilane. Stir for 40 min, raise the temperature to 60°C, stir for 1.5 h, cool to 45°C, add 10 parts of polydimethylsiloxane, stir for 75 min, then add 5 parts of polyoxyethylene-polyoxypropylene ether, shear and disperse for 40 min, desolvent under reduced pressure, allow to stand to degas, filter, and obtain fluorosilicone hybrid organosilicon. S2: Take 7 parts of azoxystrobin and 6 parts of flutriafol and add them to an aqueous phase containing 3 parts of lignin sulfonate and 2 parts of the fluorosilicone hybrid organosilicon obtained in S1. Stir for 40 min to obtain a pre-dispersion. Sand mill the pre-dispersion to control the particle size D90 to 1.5-2.5 μm. Then add 2 parts of chitosan and sodium carboxymethyl cellulose (mass ratio 1:1) as a stabilizer and 0.5 parts of nano silica. Stir for 40 min. Then add 2 parts of antifreeze mixed with propylene glycol and glycerol in a mass ratio of 2:1 and 0.2 parts of defoamer mixed with polyether defoamer and organosilicon defoamer in a mass ratio of 1:1. Stir evenly, degas under reduced pressure, filter, and obtain the finished product. Example

[0025] The purpose of this embodiment is to study the effect of the amount of fluorosilicone hybrid organosilicon added. A lower amount of added organosilicon is selected as a variable for verification to examine its effect on wetting, spreading and rain erosion resistance.

[0026] S1. Add 100 parts of anhydrous isopropanol to a reactor, protect with nitrogen, and add a mixture of 18 parts of deionized water and 2 parts of glacial acetic acid dropwise at 22°C. At the same time, add 5 parts of 3,3,3-trifluoropropyltrimethoxysilane and 3 parts of methyltriethoxysilane dropwise. Stir for 30 min, raise the temperature to 55°C, stir for 1 h, cool to 40°C, add 8 parts of polydimethylsiloxane, stir for 60 min, then add 4 parts of polyoxyethylene-polyoxypropylene ether, shear and disperse for 30 min, desolventize under reduced pressure, filter, and obtain fluorosilicone hybrid organosilicon. S2: Take 7 parts of azoxystrobin and 6 parts of flutriafol and add them to an aqueous phase containing 3 parts of lignin sulfonate and 1 part of the fluorosilicone hybrid organosilicon obtained in S1. Stir for 35 min to obtain a pre-dispersion. After sand milling, control the particle size D90 to be 1.5-2.5 μm. Then add 2 parts of chitosan and sodium carboxymethyl cellulose (mass ratio 1:2) as a stabilizer and 0.5 parts of nano silica. Stir for 40 min. Then add 2 parts of antifreeze mixed with propylene glycol and glycerol in a mass ratio of 2:1 and 0.2 parts of defoamer mixed with polyether defoamer and organosilicon defoamer in a mass ratio of 1:1. Stir evenly, and finally degas under reduced pressure and filter to obtain the suspension product.

[0027] Comparative Example 1 The purpose of this comparative example is to verify the effect of not adding nano-silica on suspension stability and rain erosion resistance.

[0028] S1. Add 100 parts of anhydrous isopropanol to the reactor, purge with nitrogen for protection, and add a mixture of 20 parts of deionized water and 2 parts of glacial acetic acid dropwise at 20-30°C. Simultaneously, slowly add 6 parts of 3,3,3-trifluoropropyltrimethoxysilane and 3 parts of methyltriethoxysilane. Stir for 40 min, raise the temperature to 60°C, stir for 1.5 h, cool to 45°C, add 10 parts of polydimethylsiloxane, stir for 75 min, then slowly add 5 parts of polyoxyethylene-polyoxypropylene ether, shear and disperse for 40 min, and finally desolvate under reduced pressure at 50°C at -0.08 MPa. Allow to stand to degas, and filter through a 0.45 μm filter membrane to remove large particulate impurities to obtain fluorosilicone hybrid organosilicon. Figure 1 The results show that the unmodified sample has a significant O–H absorption peak at 3400 cm⁻¹, which weakens after modification, indicating that the condensation reaction consumes the free hydroxyl groups; the Si–O–C peak at 1085 cm⁻¹ weakens, while the Si–O–Si peak at 1120 cm⁻¹ strengthens, indicating that the alkoxy groups are hydrolyzed and form a siloxane network; the C–F peak at 1240–1150 cm⁻¹ strengthens, proving that the fluoroalkyl group was successfully introduced; the characteristic Si–CH₃ peak at 840 cm⁻¹ is maintained, indicating that the PDMS main chain structure is intact, thus confirming the successful modification of the fluorosilicone hybrid organosilicon. S2: Take 7 parts of azoxystrobin and 6 parts of flutriafol and add them to an aqueous phase containing 3 parts of lignin sulfonate and 2 parts of the fluorosilicone hybrid organosilicon obtained in S1. Stir for 40 min to obtain a pre-dispersion. Send the pre-dispersion to a sand mill for grinding, and control the particle size D90 to be 1.5-2.5 μm. After grinding, add 2 parts of chitosan and sodium carboxymethyl cellulose (mass ratio 1:2) as a stabilizer. Do not add nano silica. Stir for 45 min. Then add 2 parts of antifreeze mixed with propylene glycol and glycerol in a mass ratio of 2:1 and 0.2 parts of defoamer mixed with polyether defoamer and organosilicon defoamer in a mass ratio of 1:1. Stir evenly and finally degas at 50℃ under -0.08 MPa. Filter to obtain the comparative sample of azoxystrobin·flutriafol suspension.

[0029] Comparative Example 2 The purpose of this comparative study is to verify the effect on formulation stability when only sodium carboxymethyl cellulose is used instead of chitosan / sodium carboxymethyl cellulose.

[0030] S1. Add 100 parts of anhydrous isopropanol to the reactor, purge with nitrogen for protection, and add a mixture of 20 parts of deionized water and 2 parts of glacial acetic acid dropwise at 20-30°C. Simultaneously, slowly add 6 parts of 3,3,3-trifluoropropyltrimethoxysilane and 3 parts of methyltriethoxysilane. Stir for 40 min, raise the temperature to 60°C, stir for 1.5 h, cool to 45°C, add 10 parts of polydimethylsiloxane, stir for 75 min, then slowly add 5 parts of polyoxyethylene-polyoxypropylene ether, shear and disperse for 40 min, and finally desolvate under reduced pressure at 50°C at -0.08 MPa. Allow to stand to degas, and filter through a 0.45 μm filter membrane to remove large particulate impurities to obtain fluorosilicone hybrid organosilicon. S2: Take 7 parts of azoxystrobin and 6 parts of flutriafol and add them to an aqueous phase containing 3 parts of lignin sulfonate and 2 parts of the fluorosilicone hybrid organosilicon obtained in S1. Stir for 40 min to obtain a pre-dispersion. Send the pre-dispersion to a sand mill for grinding, and control the particle size D90 to be 1.5-2.5 μm. After grinding, add 2 parts of sodium carboxymethyl cellulose (not using chitosan and sodium carboxymethyl cellulose compound). Stir for 45 min. Then add 2 parts of antifreeze mixed with propylene glycol and glycerol in a mass ratio of 2:1 and 0.2 parts of defoamer mixed with polyether defoamer and organosilicon defoamer in a mass ratio of 1:1. Stir evenly and finally degas at 50 °C under -0.08 MPa. Filter to obtain the comparative sample of azoxystrobin·flutriafol suspension.

[0031] Comparative Example 3 The purpose of this comparative example is to verify the effect of replacing fluorosilicone hybrid organosilicon with conventional polyether modified organosilicon on the wetting, spreading, and rain erosion resistance of the suspension.

[0032] S1, In this comparative example, no fluorosilicone hybrid organosilicon was prepared; commercially available polyether-modified organosilicon was used directly as a wetting and spreading agent. S2, 7 parts of azoxystrobin and 6 parts of flutriafol were added to an aqueous phase containing 3 parts of lignin sulfonate and 2 parts of polyether-modified organosilicon. The mixture was stirred for 40 min to obtain a pre-dispersion. The pre-dispersion was then ground in a sand mill, and the particle size D90 was controlled to be 1.5-2.5 μm. After grinding, 2 parts of chitosan and sodium carboxymethyl cellulose (mass ratio 1:2) as a stabilizer and 0.5 parts of nano-silica were added. The mixture was stirred for 45 min. Then, 2 parts of an antifreeze mixture of propylene glycol and glycerol in a mass ratio of 2:1 and 0.2 parts of an antifoamer mixture of polyether defoamer and organosilicon defoamer in a mass ratio of 1:1 were added. The mixture was stirred evenly and then degassed at 50 °C under -0.08 MPa. The mixture was then filtered to obtain a comparative sample of azoxystrobin·flutriafol suspension.

[0033] Performance testing 1. Particle size distribution determination This test is used to confirm whether the grinding process controls the particle size within the target range to ensure the stability and spray uniformity of the suspension. The specific method is as follows: Take a sample of 0.2–0.5 g of suspension, dilute it with deionized water to a suitable concentration, and place it in the dispersion cell of a laser particle size analyzer. Soft aggregates are eliminated under low-power ultrasonic treatment. Select a suitable optical model, input the refractive index parameters, repeat the test three times, and record D10, D50, and D90. The average value is taken as the test result.

[0034] 2. Determination of suspension rate and redispersibility This test is used to evaluate the anti-settling performance and redispersibility of suspending agents under static conditions. The specific method is as follows: Weigh 1.0 g of sample and add it to 100 mL of standard hardness water. Stir at a constant speed for 5 min, then place in a water bath at 25–30 °C and let stand for 30 min. Gently open the stopper, pour or siphon the upper liquid along the inner wall, collect it, dry it, and weigh it to calculate the suspension rate. Observe the redispersibility of the remaining sediment after shaking or stirring, and record it as a qualitative conclusion.

[0035] 3. Wetting and spreading properties test This test was used to compare the effects of different adjuvant systems on the wetting and spreading properties of crop leaves. The specific method was as follows: crop leaves were fixed on a horizontal stage, and 5–10 μL of a sample dilution with the same concentration of active ingredient was added to the leaf surface using a microsyringe. The contact angle or spreading diameter of the droplets was recorded at 0 s, 10 s, 30 s, and 60 s using a contact angle meter or a high-definition camera, and the differences between different samples were compared.

[0036] 4. Rainwater erosion resistance test This test was used to verify the effect of the fluorosilicone hybrid organosilicon and nano-silica system on improving rain washout losses. The specific method involved spraying the sample onto crop leaves or standard artificial leaves to near the drip point, drying it to surface dryness, and then placing it under an artificial rainfall simulator with a fixed rainfall intensity and spraying time. After spraying, the leaf residue was measured by elution, weighing, or tracer analysis, and compared with the data before spraying to draw conclusions about rain washout resistance.

[0037] 5. Storage stability test This test is used to evaluate the stability of suspensions under long-term and extreme temperature conditions. The accelerated storage method involves aliquoting samples into sealed containers, placing them in a 54℃ incubator for 14 days, then removing them and allowing them to warm to room temperature. Observe for phenomena such as stratification, flocculation, and water separation, and test viscosity, pH, and particle size. The freeze-thaw cycle method involves placing the sample at –5℃ for 16–24 hours, then transferring it to 40℃ for another 16–24 hours, constituting one cycle. After 3–5 consecutive cycles, observe the appearance of the sample and retest the suspension rate and redispersibility to determine its freeze-thaw stability.

[0038] Table 1. Examples and Performance Test Results sample Particle size D90 (μm) Suspension rate (%) redistribution Contact angle (30s, °) Rain erosion residue rate (%) Storage stability (54℃ for 14 days / 3 freeze-thaw cycles) Example 1 1.8 97 Easily dispersed 35 88 Stable, no change Example 2 2.0 95 Easily dispersed 38 85 Stable, with no significant changes. Example 3 2.3 93 Easier to disperse 42 82 Stable, slight changes Example 4 2.1 94 Easily dispersed 39 84 Stable, with no significant changes. Example 5 2.2 94 Easily dispersed 40 83 Stable, slight changes Comparative Example 1 2.8 80 Difficult to disperse 55 65 Stratification and settlement are obvious Comparative Example 2 3.0 82 Difficult to disperse 52 68 Insufficient stability, flocculation Comparative Example 3 2.5 85 generally 48 70 Partial layering leads to performance degradation. From tabular data and Figures 2-5 It is clear that, in terms of particle size distribution, the D90 values ​​of Examples 1-5 are all controlled between 1.8 and 2.3 μm, indicating that the grinding process combined with the chitosan / sodium carboxymethyl cellulose compound stabilizer and the fluorosilicone hybrid organosilicon formulation can effectively prevent particle agglomeration and keep the particles within a uniform micron-scale range. In contrast, the D90 values ​​of Comparative Examples 1-3 are all above 2.5 μm, reaching a maximum of 3.0 μm. This indicates that without nano-silica, the chitosan / sodium carboxymethyl cellulose compound, or the fluorosilicone hybrid additive, the particle dispersion effect is insufficient, easily leading to large particles and a coarse distribution. In particular, the D90 of Example 1, at 1.8 μm, is the smallest among all samples, demonstrating its best particle uniformity and stability.

[0039] Regarding suspension rate and redispersibility, the suspension rates of Examples 1-5 were all above 93%, with Example 1 reaching 97%, while the comparative examples were only 80%-85%, a significant difference. The increased suspension rate indicates that the particles can remain dispersed for a longer period without rapid sedimentation. Furthermore, the sample samples from the examples recovered to a uniform state with gentle shaking after standing, exhibiting "easy to disperse" or "relatively easy to disperse," while the comparative examples generally required greater external force to disperse, and some samples showed uneven sedimentation or agglomeration. This demonstrates that the chitosan-sodium carboxymethyl cellulose complex system and nano-silica work together to effectively inhibit particle aggregation and sedimentation.

[0040] Regarding wetting and spreading properties, the contact angles of Examples 1-5 were all less than 42°, significantly better than the 48-55° of the comparative examples. This means that the pesticide spreads better on the surface of crop leaves, covering a larger area and improving the utilization rate of the pesticide. In particular, the contact angle of Example 1 was only 35°, and the droplets spread rapidly on the leaf surface, achieving optimal wetting and spreading properties. In contrast, the comparative examples, due to the lack of fluorosilicone hybrid organosilicon or insufficient stabilizer formulation, had high surface tension of the droplets on the leaves, resulting in poor spreading and uneven distribution of the pesticide.

[0041] Regarding rain washout resistance, the leaf residue rates of Examples 1-5 were all above 82%, with Example 1 showing a residue rate of 88%, higher than the other examples and all comparative examples, indicating that it could maintain a high pesticide adhesion even under rainfall conditions. In contrast, the residue rates of the comparative examples were only 65%-70%, showing significant loss after simulated rainfall and insufficient efficacy retention. This result demonstrates that the synergistic effect of fluorosilicone hybrid organosilicon and nano-silica significantly enhances the adhesion of the pesticide to the leaf surface, resulting in a more durable and stable efficacy.

[0042] Regarding storage stability, the sample samples in the examples remained stable after 14 days of accelerated storage at 54°C and three freeze-thaw cycles, with only a few samples showing slight changes. In contrast, the comparative samples exhibited stratification, sedimentation, or significant flocculation. This demonstrates that the design of the compound stabilizer, fluorosilicone hybrid organosilicon, and nano-silica in this invention significantly improves the physical stability of the suspending agent under extreme temperature conditions, ensuring the safety of the product during transportation and long-term storage.

[0043] In summary, Example 1 exhibited the best performance in all test items: smallest particle size (1.8 μm), highest suspension rate (97%), best redispersibility (easy to disperse), smallest contact angle (35°), highest rain erosion resistance (88%), and no change in storage stability. Compared with the comparative example, Example 1 showed significant advantages in stability, wettability, spreading, and persistence, fully verifying that the synergistic innovative design of chitosan / sodium carboxymethyl cellulose compound stabilizer, fluorosilicone hybrid organosilicon, and nano-silica can bring about the best overall effect.

Claims

1. A suspension containing pyraclostrobin and epoxiconazole, characterized in that, The raw materials include the following components by weight: pyriclor 4-10 parts; epoxiconazole 4-8 parts; chitosan and sodium carboxymethyl cellulose complex stabilizer 1-4 parts; lignin sulfonate 2-6 parts; fluorosilicon hybrid silicone 1-3 parts; nano-silicon dioxide 0.1-1 part; antifreeze 1-3 parts; defoaming agent 0.1-0.5 parts; and water 65.5-86.9 parts; wherein the fluorosilicon hybrid silicone is a composite structure silicone material composed of a siloxane skeleton and fluoralkyl and organic chain segments.

2. The spirox·fluquinconazole-containing suspension agent according to claim 1, characterized by, The mass ratio of chitosan to sodium carboxymethyl cellulose in the chitosan and sodium carboxymethyl cellulose complex stabilizer is 1:1-1:

3.

3. The spirox·cyproconazole-containing suspension agent according to claim 1, characterized by, The fluorosilicon hybrid silicone includes the following components by weight: polydimethylsiloxane 0.5-1.5 parts; 3,3,3-trifluoropropyltrimethoxysilane 0.2-0.8 parts; polyoxyethylene-polyoxypropylene ether 0.2-0.6 parts; and methyltriethoxysilane 0.1-0.3 parts.

4. The spiroxane • fluquinconazole-containing suspension agent according to any one of claims 1 or 3, characterized by, The preparation method of the fluorosilicon hybrid silicone includes the following steps: (1) adding anhydrous isopropyl alcohol into a reaction kettle and protecting by nitrogen; (2) adding a mixture of deionized water and glacial acetic acid at 20-30°C, and then adding 3,3,3-trifluoropropyltrimethoxysilane and methyltriethoxysilane dropwise, and stirring for 30-60 min; (3) increasing the temperature to 50-70°C, and stirring for 1-2 h; (4) decreasing the temperature to 40-50°C, adding polydimethylsiloxane, and stirring for 60-90 min; (5) slowly adding polyoxyethylene-polyoxypropylene ether at 35-45°C, and shearing and dispersing for 30-60 min; (6) removing the solvent under reduced pressure at 45-60°C, standing to remove bubbles, filtering, and obtaining fluorosilicon hybrid silicone.

5. The spirox·fluquinconazole-containing suspension agent according to claim 1, characterized by, The antifreeze is obtained by mixing propylene glycol and glycerol at a mass ratio of (1-3):1; and the defoaming agent is obtained by mixing polyether defoaming agent and silicone defoaming agent at a mass ratio of (0.5-2):

1.

6. A process for the preparation of a suspension concentrate containing pyrimidinyl-oxime fluazinam as claimed in any one of claims 1 to 5, wherein the process comprises the steps of: a) dissolving the pyrimidinyl-oxime fluazinam in a solvent; b) adding a dispersant to the solution; c) adding a surfactant to the solution; d) adding a stabilizer to the solution; e) adding water to the solution; and f) homogenizing the solution. The method includes the following steps: S1, adding pyriclor and epoxiconazole into an aqueous phase containing lignin sulfonate and fluorosilicon hybrid silicone, and stirring for 30-60 min to obtain a pre-dispersion; S2, sand milling the pre-dispersion to control the particle size D90 to be 1.5-2.5 μm; S3, adding chitosan and sodium carboxymethyl cellulose complex stabilizer and nano-silicon dioxide, and stirring for 30-60 min; S4, adding antifreeze and defoaming agent, and stirring uniformly; S5, degassing under reduced pressure at 45-60°C, filtering, and obtaining pyriclor·epoxiconazole suspension concentrate.

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