A flutriafol carbendazim suspension agent and a preparation method thereof

Abstract

This invention discloses a flutriafol-carbendazim suspension and its preparation method, belonging to the field of pesticide formulation technology. The suspension, by weight percentage, contains 12-15% flutriafol, 10-14% carbendazim, 0.5-0.9% modified sodium bentonite, 0.8-1.4% antifreeze, 0.2-0.6% defoamer, and the balance being water. This invention uses a specific modified sodium bentonite, which is modified by intercalation with octadecyldimethylallyl ammonium chloride, combined with benzene rings and silane structures to construct a hydrophobic network. Silane and sodium bentonite are covalently bonded, and nano-zinc oxide is firmly loaded, significantly improving hydrophobicity and structural stability. Simultaneously, through the synergistic hydrophobic effect of long-chain alkyl groups and benzene rings, and the auxiliary dispersion of nano-zinc oxide, the dispersibility of the suspension is effectively improved, the suspension rate is increased, and thermal stability is enhanced, solving the problems of stratification and sedimentation during storage and use, ensuring efficacy and formulation stability.

Description

Technical Field

[0001] This invention relates to the field of pesticide formulation technology, and in particular to a flutriafol-carbendazim suspension concentrate and its preparation method. Background Technology

[0002] Fluticasone is a systemic triazole fungicide that inhibits the biosynthesis of ergosterol in the cell membrane of pathogens, thus hindering cell wall formation. It exhibits significant control effects against various fungal diseases, including wheat powdery mildew, rice false smut, and corn rust. Due to its broad-spectrum fungicidal activity and strong systemic properties, it has become one of the core agents for controlling fungal diseases in agricultural production.

[0003] Carbendazim is a broad-spectrum fungicide with the chemical name N-(2-benzimidazolyl)-methyl carbamate. It is effective against fungal diseases in a variety of crops and can be used for foliar spraying, seed treatment, and soil treatment.

[0004] In response to the call for reducing pesticide use in China, flutriafol and carbendazim are often combined and prepared as pesticide suspensions to enhance the dispersibility of flutriafol and carbendazim in pesticide formulations and ensure the effectiveness of pesticides during use. However, suspensions are not resistant to long-term storage. After being stored at high temperatures or for a long time, the suspensions often settle, resulting in a decrease in their effectiveness. Summary of the Invention

[0005] This invention provides a flutriafol-carbendazim suspension and its preparation method, which can solve the problem that in the prior art, suspensions are not resistant to long-term storage and often settle after high temperature or long-term storage, resulting in a decrease in the effectiveness of the suspension.

[0006] The objective of this invention can be achieved through the following technical solutions: In a first aspect, the present invention provides a flutriafol-carbendazim suspension, comprising, by weight percentage: 12-15% flutriafol, 10-14% carbendazim, 0.5-0.9% modified sodium bentonite, 0.8-1.4% antifreeze, 5-10% wetting agent, 0.1-0.5% thickener, 0.2-0.6% defoamer, with the balance being water.

[0007] Furthermore, the preparation method of the modified sodium-based bentonite is as follows: S1. Add dry sodium-based bentonite powder to octadecyldimethylallylammonium chloride solution, stir to react, wash, and dry to obtain organically modified sodium-based bentonite. S2. Styrene ethyltrimethoxysilane was added to anhydrous toluene, followed by the addition of organically modified sodium bentonite. The mixture was ultrasonically dispersed, and azobisisobutyronitrile was added under nitrogen protection. The mixture was heated and reacted, then centrifuged, washed, and dried to obtain highly hydrophobic composite modified sodium bentonite. S3. Add the highly hydrophobic composite modified sodium-based bentonite to an ethanol aqueous solution, heat and stir, then add nano zinc oxide, continue heating, dry, and pulverize through a 200-mesh sieve to obtain modified sodium-based bentonite.

[0008] Further, in step S1, the dried sodium-based bentonite powder is sodium-based bentonite that has passed through an 80-100 mesh sieve.

[0009] Further, in step S1, the ratio of the dry sodium bentonite powder to the octadecyl dimethyl allyl ammonium chloride solution is 10g:50mL; the concentration of the octadecyl dimethyl allyl ammonium chloride solution is 50-80mmol / L.

[0010] Furthermore, in step S1, the temperature of the stirring reaction is 40-45℃, and the time is 1-2 hours.

[0011] Further, in step S2, the ratio of styrene ethyltrimethoxysilane, anhydrous toluene, organically modified sodium bentonite, and azobisisobutyronitrile is 1.5-2g:100mL:20g:0.1-0.14g.

[0012] Furthermore, in step S2, the ultrasonic dispersion time is 30-40 minutes.

[0013] Furthermore, in step S2, the temperature of the heating reaction is 70-80℃, and the time is 3-6 hours.

[0014] Further, in step S3, the ratio of the amount of the highly hydrophobic composite modified sodium-based bentonite, the ethanol aqueous solution, and the nano zinc oxide is 10g:80-100mL:2-4g; the volume ratio of anhydrous ethanol to deionized water in the ethanol aqueous solution is 7:3.

[0015] Further, in step S3, the heating and stirring temperature is 70-80℃ and the time is 1-2 hours; the continued heating temperature is 70-80℃ and the time is 1-2 hours.

[0016] Furthermore, the antifreeze agent is any one or more of ethylene glycol, polyethylene glycol, glycerol, and benzoic acid.

[0017] Furthermore, the wetting agent is any one or more of fatty alcohol polyoxyethylene ether, lauryl alcohol polyoxyethylene ether, and isooctyl alcohol polyoxyethylene ether.

[0018] Furthermore, the thickener is either xanthan gum or hydroxypropyl cellulose ether.

[0019] Furthermore, the defoamer is an organosilicone defoamer.

[0020] Secondly, the present invention provides a method for preparing flutriafol-carbendazim suspension, comprising the following steps: Mix flutriafol, carbendazim, antifreeze, wetting agent, thickener, defoamer and water. After mixing for 3-5 minutes, add modified sodium bentonite and continue mixing for 10-16 minutes. Grind the mixture until the solid particle size is 3-5 μm, then stop grinding and cool to room temperature to obtain flutriafol-carbendazim suspension.

[0021] The beneficial effects of this invention are: 1. In the flutriafol-carbendazim suspension provided by this invention, the flutriafol content of 12-15% and the carbendazim content of 10-14% form a synergistic compound ratio, which can broaden the fungicidal spectrum and delay the development of resistance, while ensuring high fungicidal activity and low phytotoxicity risk; the modified sodium bentonite dosage of 0.5-0.9% can significantly improve the dispersibility and suspension stability of the suspension, prevent particle sedimentation, and improve the adhesion of the agent to the target surface; the antifreeze dosage of 0.8-1.4% can ensure that the formulation maintains fluidity at low temperatures. To prevent freezing and demulsification; a wetting agent dosage of 5-10% effectively reduces the surface tension of the solution, enhances spreading and penetration into crop leaves, and improves the utilization rate of the pesticide; a thickener dosage of 0.1-0.5% adjusts the viscosity of the system, prevents stratification and water separation, and prolongs storage stability; an antifoaming agent dosage of 0.2-0.6% suppresses foam generated during production and use, avoiding inaccurate measurement and waste of pesticide solution caused by foam; the remaining water serves as an environmentally friendly medium, reducing the cost of using organic solvents and environmental pollution, while also facilitating processing and safe transportation. All components work synergistically within the specified dosage range to produce a compound suspension with high suspension rate and good thermal storage stability.

[0022] 2. This invention creatively uses modified sodium-based bentonite prepared by a specific method. This modified sodium-based bentonite incorporates long-chain octadecyl cations from octadecyl dimethyl allyl ammonium chloride through intercalation into the interlayer of sodium-based bentonite. This process imbues the sodium-based bentonite with double bonds and significantly enhances its hydrophobicity, giving it a strong affinity for hydrophobic pesticide technicals such as flutriafol and carbendazim. This effectively prevents water molecule displacement and particle sedimentation, thereby significantly improving the dispersibility of solid particles in the aqueous phase and ultimately increasing the suspension rate and other properties of the suspending agent. Subsequently, the allyl double bonds copolymerize with the terminal double bonds of styrene ethyltrimethoxysilane in S2, forming a cross-linked polymer network. This network greatly inhibits the shedding or migration of the modified layer at high temperatures. The benzene ring enhances hydrophobicity and thermal stability. When it is grafted onto the surface of sodium-based bentonite together with the long-chain octadecyl group, a significant synergistic effect is achieved: the long-chain alkyl group provides a dense hydrophobic barrier, hindering water molecule penetration; the benzene ring utilizes its rigid framework to support the modified layer, inhibiting the thermal motion and rearrangement of molecular chains at high temperatures. The complementary hydrophobicity and superimposed thermal stabilization mechanisms of the two make the hydrophobicity and heat resistance of modified sodium bentonite far exceed those of single long-chain or benzene ring modification, thereby significantly improving the dispersibility, anti-settling ability and thermal storage stability of particles in the suspension from the source.

[0023] Building upon this, the silane in the highly hydrophobic composite modified sodium-based bentonite undergoes hydrolysis in an ethanol-water solution of S3, generating silanol groups. These silanol groups can undergo a condensation reaction with the hydroxyl groups on the surface of nano-zinc oxide, causing the nano-zinc oxide to be tightly bound to the surface of the modified sodium-based bentonite and the pores of the polymer network through covalent bonds. The nano-zinc oxide exhibits high heat resistance, and this chemically bonded structure further enhances the structural integrity of the modified layer at high temperatures, further improving the thermal stability of the suspending agent. Detailed Implementation

[0024] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, specific embodiments of the present invention will be described in detail below.

[0025] In a first aspect, the present invention provides a flutriafol-carbendazim suspension, comprising, by weight percentage: 12-15% flutriafol, 10-14% carbendazim, 0.5-0.9% modified sodium bentonite, 0.8-1.4% antifreeze, 5-10% wetting agent, 0.1-0.5% thickener, 0.2-0.6% defoamer, with the balance being water.

[0026] The flutriafol-carbendazim suspension provided by this invention comprises a synergistic compound of flutriafol (12-15%) and carbendazim (10-14%), which broadens the fungicidal spectrum, delays the development of resistance, and maintains high fungicidal activity and low phytotoxicity risk. Modified sodium bentonite (0.5-0.9%) significantly improves dispersibility and suspension stability, prevents particle sedimentation, and enhances target adhesion. An antifreeze agent (0.8-1.4%) ensures low-temperature fluidity and prevents freezing and demulsification. A wetting agent (5-10%) reduces surface tension, promotes spreading and penetration, and improves efficacy utilization. A thickener (0.1-0.5%) adjusts the system viscosity, prevents stratification and water separation, and prolongs storage stability. An antifoaming agent (0.2-0.6%) inhibits foam generation, avoiding inaccurate metering and waste. The remaining water serves as an environmentally friendly medium, reducing the cost of organic solvents and environmental pollution. All components work synergistically within their defined dosage ranges to produce a compound suspension with high suspension rate, good thermal storage stability, and crop safety.

[0027] In some embodiments, the modified sodium-based bentonite is prepared by: S1. Add dry sodium-based bentonite powder to octadecyldimethylallylammonium chloride solution, stir to react, wash, and dry to obtain organically modified sodium-based bentonite. The above steps involve adding dried sodium-based bentonite powder to an octadecyldimethylallylammonium chloride solution, resulting in a cation exchange reaction. The exchangeable cations between the sodium-based bentonite layers are replaced by octadecyldimethylallylammonium cations, and the long-chain octadecyl groups are inserted into the interlayer, significantly improving the hydrophobicity of the sodium-based bentonite. This gives it a strong affinity for hydrophobic pesticides such as flutriafol and carbendazim, preventing water molecule displacement and particle sedimentation. Simultaneously, the double bonds on the allyl groups reserve covalent grafting sites for subsequent polymerization reactions. This step endows the modified sodium-based bentonite with initial hydrophobicity and reactivity, fundamentally improving the dispersibility of solid particles in the suspension and increasing the suspension rate at room temperature.

[0028] S2. Styrene ethyltrimethoxysilane was added to anhydrous toluene, followed by the addition of organically modified sodium bentonite. The mixture was ultrasonically dispersed, and azobisisobutyronitrile was added under nitrogen protection. The mixture was heated and reacted, then centrifuged, washed, and dried to obtain highly hydrophobic composite modified sodium bentonite. In the above steps, styrene-ethyltrimethoxysilane is mixed with the organically modified sodium bentonite obtained in S1 in anhydrous toluene, and azobisisobutyronitrile is added to initiate free radical copolymerization. The double bonds at the ends of the silane molecules crosslink and copolymerize with the allyl double bonds on the sodium bentonite, forming a stable polymer network on the surface of the sodium bentonite; the benzene ring enhances hydrophobicity and thermal stability. This step anchors the benzene-ring-containing silane to the surface of the sodium bentonite via covalent bonds, forming a crosslinked network, which greatly inhibits the shedding or migration of the modified layer at high temperatures, and significantly improves the thermal storage stability and anti-settling ability of the suspending agent.

[0029] S3. Add the highly hydrophobic composite modified sodium-based bentonite to an ethanol aqueous solution, heat and stir, then add nano zinc oxide, continue heating, dry, and pulverize through a 200-mesh sieve to obtain modified sodium-based bentonite.

[0030] The above steps involve adding the highly hydrophobic composite modified sodium-based bentonite obtained in S2 to an ethanol-water solution. Heating causes the silanyl methoxy groups of silane to hydrolyze, generating silanol groups. These silanol groups participate in condensation with the hydroxyl groups on the surface of nano-zinc oxide, causing the nano-zinc oxide to be tightly bonded to the surface of the sodium-based bentonite and the pores of the polymer network through covalent bonds. The nano-zinc oxide, with its high specific surface area and surface defect sites, physically fills the micropores, preventing the melting adhesion and agglomeration between particles at high temperatures. This step achieves chemical integration of sodium-based bentonite and nano-zinc oxide through the hydrolysis and condensation of silane, further enhancing the thermal stability and structural integrity of the modified layer, ultimately significantly improving the dispersion uniformity, suspension rate, and anti-stratification and anti-grouting ability of the suspending agent during thermal storage.

[0031] In some embodiments, in step S1, the dried sodium-based bentonite powder is sodium-based bentonite that has passed through an 80-100 mesh sieve. This particle size range ensures sufficient contact and exchange reaction efficiency between the sodium-based bentonite and the modifying reagent, while avoiding agglomeration or filtration difficulties caused by excessively fine particle size. If the mesh size is too small (particle size too large), the specific surface area is insufficient, and ion exchange is inadequate; if the mesh size is too large (particle size too fine), agglomeration is likely and subsequent filtration will be difficult.

[0032] In some embodiments, in step S1, the ratio of the dried sodium bentonite powder to the octadecyl dimethyl allyl ammonium chloride solution is 10 g: 50 mL; the concentration of the octadecyl dimethyl allyl ammonium chloride solution is 50-80 mmol / L. This ratio ensures sufficient exchange between the long-chain alkyl ammonium cations and the interlayer cations of the sodium bentonite, imparting a suitable degree of hydrophobic modification. If the concentration is too low or the solution volume is too small, the exchange will be insufficient, resulting in inadequate hydrophobicity. If the concentration is too high or the volume is too large, multilayer adsorption may occur or raw material waste may result.

[0033] In some embodiments, in step S1, the temperature of the stirring reaction is 40-45°C, and the time is 1-2 hours. This mild condition ensures that the cation exchange reaction proceeds completely, while avoiding the structural damage of sodium-based bentonite or the decomposition of organic ammonium that may be caused by high-temperature and long-term reactions. If the temperature is too low or the time is too short, the exchange reaction will be incomplete; if the temperature is too high or the time is too long, the interlayer structure of sodium-based bentonite may be damaged or organic ammonium may be degraded.

[0034] In some embodiments, in step S2, the ratio of styrene ethyltrimethoxysilane, anhydrous toluene, organically modified sodium bentonite, and azobisisobutyronitrile is 1.5-2 g: 100 mL: 20 g: 0.1-0.14 g. This ratio ensures sufficient grafting of active double bonds and appropriate introduction of initiator in the crosslinking copolymerization reaction, forming a stable and moderately crosslinked network. If the amount of silane is too small, the degree of crosslinking is insufficient, and the modified layer is prone to detachment at high temperatures. If the amount of silane is too large, over-crosslinking or the formation of free polymers may occur. If the amount of initiator is inappropriate, the reaction will be incomplete or side reactions will increase.

[0035] In some embodiments, the ultrasonic dispersion time in step S2 is 30-40 minutes. This treatment time allows the organically modified sodium bentonite to be uniformly dispersed in anhydrous toluene, providing good interfacial contact for the subsequent copolymerization reaction. If the ultrasonic time is too short, the dispersion will be uneven, resulting in uneven grafting reaction. If the ultrasonic time is too long, it may damage the lamellar structure of sodium bentonite or cause the grafted molecular chains to break.

[0036] In some embodiments, in step S2, the heating reaction temperature is 70-80°C and the time is 3-6 hours. These reaction conditions ensure that the free radical copolymerization reaction proceeds fully and forms a stable cross-linked polymer network. If the temperature is too low or the time is too short, the polymerization reaction will be incomplete and the degree of cross-linking will be insufficient. If the temperature is too high or the time is too long, side reactions may occur or polymer degradation may result.

[0037] In some embodiments, in step S3, the ratio of the highly hydrophobic composite modified sodium-based bentonite, the ethanol aqueous solution, and the nano zinc oxide is 10g:80-100mL:2-4g; the volume ratio of anhydrous ethanol to deionized water in the ethanol aqueous solution is 7:3. This ratio ensures sufficient hydrolysis of silane in the ethanol aqueous solution and uniform dispersion and chemical bonding of the nano zinc oxide; if there is too little nano zinc oxide, the thermal stability will not be sufficiently improved; if there is too much nano zinc oxide, it may agglomerate and increase costs; if the solvent volume is inappropriate, insufficient hydrolysis or an overly dilute system will affect the reaction efficiency.

[0038] In some embodiments, in step S3, the heating and stirring temperature is 70-80°C for 1-2 hours; the continued heating temperature is 70-80°C for 1-2 hours. These two heating conditions ensure that the hydrolysis and condensation of silane and the covalent bonding reaction with nano-zinc oxide proceed fully. If the temperature is too low or the time is too short, the hydrolysis and condensation reactions will be incomplete, and the bonding between silane and sodium bentonite and zinc oxide will not be strong. If the temperature is too high or the time is too long, the already bonded structure may be destroyed or the nano-zinc oxide may agglomerate excessively.

[0039] In some embodiments, the antifreeze agent is any one or more of ethylene glycol, polyethylene glycol, glycerol, and benzoic acid. It can effectively lower the freezing point of the formulation, prevent freezing and demulsification at low temperatures, and simultaneously exhibit good compatibility with the suspension system without affecting the stability of the active ingredient.

[0040] In some embodiments, the wetting agent is any one or more of fatty alcohol polyoxyethylene ether, lauryl alcohol polyoxyethylene ether, and isooctyl alcohol polyoxyethylene ether. It can significantly reduce the surface tension of the pesticide solution, promote rapid wetting and uniform dispersion of pesticide particles in water, and improve the spreading and penetration ability of the pesticide solution on the target surface.

[0041] In some embodiments, the thickener is either xanthan gum or hydroxypropyl cellulose ether. This can appropriately increase the viscosity of the continuous phase, slow down particle settling, prevent stratification and water separation, and enhance the storage physical stability of the suspending agent.

[0042] In some embodiments, the defoamer is an organosilicone defoamer. It possesses highly efficient defoaming and long-lasting foam-suppressing capabilities, rapidly eliminating foam generated during production and use, and preventing inaccurate metering, waste of the solution, and packaging defects caused by foam.

[0043] Secondly, the present invention provides a method for preparing flutriafol-carbendazim suspension, comprising the following steps: Mix flutriafol, carbendazim, antifreeze, wetting agent, thickener, defoamer and water. After mixing for 3-5 minutes, add modified sodium bentonite and continue mixing for 10-16 minutes. Grind the mixture until the solid particle size is 3-5 μm, then stop grinding and cool to room temperature to obtain flutriafol-carbendazim suspension.

[0044] The preparation method involves first premixing flutriafol, carbendazim, and all excipients except modified sodium bentonite with water for 3-5 minutes. After the system is homogeneous, modified sodium bentonite is added and mixing continues for 10-16 minutes. Finally, the mixture is ground to a solid particle size of 3-5 μm. This stepwise mixing method avoids the damage to the lamellar structure or the shedding of surface graft chains caused by prolonged high shear during the premixing stage of modified sodium bentonite, thus protecting the integrity of its hydrophobic network and chemical anchoring structure. At the same time, the particle size is precisely controlled at 3-5 μm, which ensures good dispersibility and high suspension rate of pesticide particles in the suspension, while avoiding the increased energy consumption and agglomeration risk caused by excessively fine grinding. This ensures the thermal stability of the formulation, the efficacy release efficiency, and the economic efficiency of production.

[0045] The specific embodiments of the present invention will be described in detail below, but it should be understood that the scope of protection of the present invention is not limited to the specific embodiments.

[0046] In this invention, the particle size of the nano zinc oxide is 10 nm.

[0047] Preparation Example 1 The preparation method of the modified sodium-based bentonite in this preparation example is as follows: S1. Add 10g of dried sodium bentonite powder that has passed through an 80-mesh sieve to 50mL of octadecyl dimethyl allyl ammonium chloride solution. The concentration of the octadecyl dimethyl allyl ammonium chloride solution is 50mmol / L. Stir and react at 40℃ for 1h. Wash and dry to obtain organic modified sodium bentonite. S2. Add 1.5g of styrene-ethyltrimethoxysilane to 100mL of anhydrous toluene, then add 20g of organically modified sodium bentonite, sonicate for 30min, add 0.1g of azobisisobutyronitrile under nitrogen protection, heat to 70℃ for 3h, centrifuge, wash, and dry to obtain highly hydrophobic composite modified sodium bentonite. S3. Add 10g of highly hydrophobic composite modified sodium-based bentonite to 80mL of ethanol aqueous solution. The volume ratio of anhydrous ethanol to deionized water in the ethanol aqueous solution is 7:3. Heat and stir at 70℃ for 1h. Then add 2g of nano zinc oxide and continue heating at 70℃ for 1h. Dry, pulverize and pass through a 200-mesh sieve to obtain modified sodium-based bentonite.

[0048] Preparation Example 2 The preparation method of the modified sodium-based bentonite in this preparation example is as follows: S1. Add 10g of dried sodium bentonite powder that has passed through a 100-mesh sieve to 50mL of octadecyl dimethyl allyl ammonium chloride solution with a concentration of 65mmol / L. Stir and react at 43℃ for 1.5h, wash and dry to obtain organic modified sodium bentonite. S2. Add 1.7g of styrene-ethyltrimethoxysilane to 100mL of anhydrous toluene, then add 20g of organically modified sodium bentonite, sonicate for 35min, add 0.12g of azobisisobutyronitrile under nitrogen protection, heat to 75℃ for 4h, centrifuge, wash, and dry to obtain highly hydrophobic composite modified sodium bentonite. S3. Add 10g of highly hydrophobic composite modified sodium-based bentonite to 90mL of ethanol aqueous solution. The volume ratio of anhydrous ethanol to deionized water in the ethanol aqueous solution is 7:3. Heat and stir at 75℃ for 1.5h. Then add 3g of nano zinc oxide and continue heating at 75℃ for 1.5h. Dry, pulverize and pass through a 200-mesh sieve to obtain modified sodium-based bentonite.

[0049] Preparation Example 3 The preparation method of the modified sodium-based bentonite in this preparation example is as follows: S1. Add 10g of dried sodium bentonite powder that has passed through a 100-mesh sieve to 50mL of octadecyl dimethyl allyl ammonium chloride solution with a concentration of 80mmol / L. Stir and react at 45℃ for 2h, wash and dry to obtain organic modified sodium bentonite. S2. Add 2g of styrene ethyltrimethoxysilane to 100mL of anhydrous toluene, then add 20g of organically modified sodium bentonite, sonicate for 40min, add 0.14g of azobisisobutyronitrile under nitrogen protection, heat to 80℃ for 6h, centrifuge, wash, and dry to obtain highly hydrophobic composite modified sodium bentonite. S3. Add 10g of highly hydrophobic composite modified sodium-based bentonite to 100mL of ethanol aqueous solution. The volume ratio of anhydrous ethanol to deionized water in the ethanol aqueous solution is 7:3. Heat and stir at 80℃ for 2h. Then add 4g of nano zinc oxide and continue heating at 80℃ for 2h. Dry, pulverize and pass through a 200-mesh sieve to obtain modified sodium-based bentonite.

[0050] Compare with Example 1 The only difference between this comparative example and preparation example 1 is that, in step S2, "styrene ethyltrimethoxysilane" is replaced with an equal amount of "styrene".

[0051] Compare with Example 2 The only difference between this comparative example and preparation example 1 is that step S2 is omitted. Specifically: S1. Add 10g of dried sodium bentonite powder that has passed through an 80-mesh sieve to 50mL of octadecyl dimethyl allyl ammonium chloride solution. The concentration of the octadecyl dimethyl allyl ammonium chloride solution is 50mmol / L. Stir and react at 40℃ for 1h. Wash and dry to obtain organic modified sodium bentonite. S3. Add 10g of organically modified sodium-based bentonite to 80mL of ethanol aqueous solution. The volume ratio of anhydrous ethanol to deionized water in the ethanol aqueous solution is 7:3. Heat and stir at 70℃ for 1h. Then add 2g of nano zinc oxide and continue heating at 70℃ for 1h. Dry, pulverize and pass through a 200-mesh sieve to obtain modified sodium-based bentonite.

[0052] Compare with Example 3 The only difference between this comparative example and preparation example 1 is that step S2 is omitted, and octadecyldimethylallylammonium chloride in step S1 is also omitted. Specifically: 10g of dried sodium-based bentonite powder that has passed through an 80-mesh sieve was added to 80mL of an ethanol-water solution with a volume ratio of anhydrous ethanol to deionized water of 7:3. The mixture was heated and stirred at 70℃ for 1h, then 2g of nano zinc oxide was added, and the mixture was heated at 70℃ for another 1h. After drying, the mixture was pulverized and passed through a 200-mesh sieve to obtain modified sodium-based bentonite.

[0053] Example 1 This embodiment provides a flutriafol-carbendazim suspension, which, by weight percentage, comprises: 12% flutriafol, 10% carbendazim, 0.5% modified sodium bentonite obtained in Preparation Example 1, 0.8% antifreeze ethylene glycol, 5% wetting agent fatty alcohol polyoxyethylene ether, 0.1% thickener xanthan gum, 0.2% organosilicon defoamer, and the balance being water.

[0054] Its preparation method is as follows: Fluticasone, carbendazim, antifreeze, wetting agent, thickener, defoamer and water are mixed and mixed for 3 minutes. Modified sodium bentonite is then added and mixed for another 10 minutes. The mixture is then ground until the solid particle size is 3-5 μm. Grinding is then stopped and the mixture is cooled to room temperature to obtain fluticasone and carbendazim suspension.

[0055] Example 2 This embodiment provides a flutriafol-carbendazim suspension, which, by weight percentage, comprises: 12% flutriafol, 10% carbendazim, 0.7% modified sodium bentonite obtained in Preparation Example 1, 1.1% antifreeze ethylene glycol, 7% wetting agent fatty alcohol polyoxyethylene ether, 0.3% thickener xanthan gum, 0.4% organosilicon defoamer, and the balance being water.

[0056] Its preparation method is as follows: Fluticasone, carbendazim, antifreeze, wetting agent, thickener, defoamer and water are mixed and mixed for 4 minutes. Modified sodium bentonite is then added and mixed for another 13 minutes. The mixture is then ground until the solid particle size is 3-5 μm. Grinding is then stopped and the mixture is cooled to room temperature to obtain fluticasone and carbendazim suspension.

[0057] Example 3 This embodiment provides a flutriafol-carbendazim suspension, which, by weight percentage, comprises: 12% flutriafol, 10% carbendazim, 0.9% modified sodium bentonite obtained in Preparation Example 1, 1.4% antifreeze ethylene glycol, 10% wetting agent fatty alcohol polyoxyethylene ether, 0.5% thickener xanthan gum, 0.6% organosilicon defoamer, and the balance being water.

[0058] Its preparation method is as follows: Fluticasone, carbendazim, antifreeze, wetting agent, thickener, defoamer and water are mixed and mixed for 5 minutes. Modified sodium bentonite is then added and mixed for another 16 minutes. The mixture is then ground until the solid particle size is 3-5 μm. Grinding is then stopped and the mixture is cooled to room temperature to obtain fluticasone and carbendazim suspension.

[0059] Example 4 The only difference between this embodiment and Example 3 is that the modified sodium-based bentonite obtained in Example 1 is replaced with an equal amount of the modified sodium-based bentonite obtained in Example 2.

[0060] Example 5 The only difference between this embodiment and Example 3 is that the modified sodium-based bentonite obtained in Example 1 is replaced with an equal amount of the modified sodium-based bentonite obtained in Example 3.

[0061] Example 6 The only difference between this embodiment and Example 3 is that "fluticasone 12% and carbendazim 10%" is changed to "fluticasone 13% and carbendazim 12%".

[0062] Example 7 The only difference between this embodiment and Example 3 is that "fluticasone 12% and carbendazim 10%" is changed to "fluticasone 15% and carbendazim 14%".

[0063] Comparative Example 1 The only difference between this comparative example and Example 1 is that the modified sodium-based bentonite obtained in Preparation Example 1 was replaced with an equal amount of the modified sodium-based bentonite obtained in Control Example 1.

[0064] Comparative Example 2 The only difference between this comparative example and Example 1 is that the modified sodium-based bentonite obtained in Preparation Example 1 was replaced with an equal amount of modified sodium-based bentonite obtained in Control Example 2.

[0065] Comparative Example 3 The only difference between this comparative example and Example 1 is that the modified sodium-based bentonite obtained in Preparation Example 1 was replaced with an equal amount of modified sodium-based bentonite obtained in Control Example 3.

[0066] Comparative Example 4 The only difference between this comparative example and Example 1 is that an equal amount of sodium-based bentonite was used to replace the modified sodium-based bentonite obtained in Preparation Example 1.

[0067] The performance of the suspensions prepared in Examples 1-7 and Comparative Examples 1-4 was tested. The dispersibility of the suspensions was tested according to the FAO standard CIPAC method; the suspension rate was tested according to GB / T14825-2023; and the thermal stability of the suspensions at 14 days and 28 days was tested according to GB / T19136-2021 (Grade A: uniform appearance, no stratification, no water separation, no sedimentation, no paste formation. Grade B: slight stratification or a small amount of water separation occurs, which can be restored to uniformity after shaking, with no hard sedimentation or paste formation. Grade C: obvious stratification, a large amount of water separation, hard sedimentation or paste formation occurs, and cannot be completely restored to uniformity after shaking). The test results are shown in Table 1. Table 1

[0068] As shown in Table 1, Examples 1-5 all used the modified sodium-based bentonite prepared in Examples 1-3, exhibiting excellent dispersibility, a suspension rate of 93-99%, and thermal stability reaching A / A grade, indicating that the modified sodium-based bentonite of this invention significantly improves the performance of the suspension concentrate. Examples 6-7, due to the increase in the total pesticide content (25%, 29%), showed a decrease in dispersibility to good, suspension rate, and thermal stability, but were still superior to the comparative examples. Comparative Example 1, by replacing silane with styrene, experienced a decrease in its binding ability with nano-zinc oxide, resulting in reduced performance; Comparative Example 2 omitted the S2 crosslinking step, leading to easy detachment of the modified layer; Comparative Example 3 lacked organic modification and crosslinking, resulting in poor hydrophobicity; Comparative Example 4 directly used unmodified sodium-based bentonite, exhibiting the worst performance. The results indicate that the synergistic modification of long-chain alkyl groups, benzene rings, silane crosslinking, and nano-zinc oxide is crucial for the suspension rate and thermal stability of the suspension concentrate.

[0069] The above-disclosed embodiments are merely a few specific examples of the present invention. However, the embodiments of the present invention are not limited thereto, and any variations that can be conceived by those skilled in the art should fall within the protection scope of the present invention.

Claims

1. A flutriafol-carbendazim suspension concentrate, characterized in that, The ingredients, by weight percentage, include: flutriafol 12-15%, carbendazim 10-14%, modified sodium bentonite 0.5-0.9%, antifreeze 0.8-1.4%, wetting agent 5-10%, thickener 0.1-0.5%, defoamer 0.2-0.6%, with the balance being water.

2. The flutriafol-carbendazim suspension concentrate as described in claim 1, characterized in that, The preparation method of the modified sodium-based bentonite is as follows: S1. Add dry sodium-based bentonite powder to octadecyldimethylallylammonium chloride solution, stir to react, wash, and dry to obtain organically modified sodium-based bentonite. S2. Styrene ethyltrimethoxysilane was added to anhydrous toluene, followed by the addition of organically modified sodium bentonite. The mixture was ultrasonically dispersed, and azobisisobutyronitrile was added under nitrogen protection. The mixture was heated and reacted, then centrifuged, washed, and dried to obtain highly hydrophobic composite modified sodium bentonite. S3. Add the highly hydrophobic composite modified sodium-based bentonite to an ethanol aqueous solution, heat and stir, then add nano zinc oxide, continue heating, dry, and pulverize through a 200-mesh sieve to obtain modified sodium-based bentonite.

3. The flutriafol-carbendazim suspension concentrate as described in claim 2, characterized in that, In step S1, the dried sodium-based bentonite powder is sodium-based bentonite that has passed through an 80-100 mesh sieve.

4. The flutriafol-carbendazim suspension concentrate as described in claim 2, characterized in that, In step S1, the ratio of the dried sodium bentonite powder to the octadecyl dimethyl allyl ammonium chloride solution is 10 g: 50 mL; the concentration of the octadecyl dimethyl allyl ammonium chloride solution is 50-80 mmol / L. In step S1, the temperature of the stirring reaction is 40-45℃ and the time is 1-2h.

5. The flutriafol-carbendazim suspension concentrate as described in claim 2, characterized in that, In step S2, the ratio of styrene ethyltrimethoxysilane, anhydrous toluene, organically modified sodium bentonite, and azobisisobutyronitrile is 1.5-2g:100mL:20g:0.1-0.14g.

6. The flutriafol-carbendazim suspension concentrate as described in claim 2, characterized in that, In step S2, the ultrasonic dispersion time is 30-40 minutes; In step S2, the temperature of the heating reaction is 70-80℃, and the time is 3-6 hours.

7. The flutriafol-carbendazim suspension concentrate as described in claim 2, characterized in that, In step S3, the ratio of the amount of the highly hydrophobic composite modified sodium-based bentonite, the ethanol aqueous solution, and the nano zinc oxide is 10g:80-100mL:2-4g; the volume ratio of anhydrous ethanol to deionized water in the ethanol aqueous solution is 7:

3.

8. The flutriafol-carbendazim suspension concentrate as described in claim 2, characterized in that, In step S3, the heating and stirring temperature is 70-80℃ and the time is 1-2 hours; the continued heating temperature is 70-80℃ and the time is 1-2 hours.

9. The flutriafol-carbendazim suspension concentrate as described in claim 1, characterized in that, The antifreeze agent is any one or more of ethylene glycol, polyethylene glycol, glycerol, and benzoic acid; The wetting agent is any one or more of fatty alcohol polyoxyethylene ether, lauryl alcohol polyoxyethylene ether, and isooctyl alcohol polyoxyethylene ether. The thickener is either xanthan gum or hydroxypropyl cellulose ether. The defoamer is an organosilicone defoamer.

10. A method for preparing a flutriafol-carbendazim suspension concentrate, used to prepare the flutriafol-carbendazim suspension concentrate according to any one of claims 1-9, characterized in that, Includes the following steps: Mix flutriafol, carbendazim, antifreeze, wetting agent, thickener, defoamer and water. After mixing for 3-5 minutes, add modified sodium bentonite and continue mixing for 10-16 minutes. Grind the mixture until the solid particle size is 3-5 μm, then stop grinding and cool to room temperature to obtain flutriafol-carbendazim suspension.

Images