Chlorothalonil suspension agent containing plant source functional components and preparation method thereof

Abstract

The application provides a chlorothalonil suspension agent containing a plant source functional component and a preparation method thereof, and belongs to the technical field of plant source functional additives, and comprises the following components: chlorothalonil 20%-60%; a functional film-forming synergistic component 1%-15%; a dispersing agent 2%-10%; a wetting agent 1%-6%; a rheological modifier 0.1%-3%; an antifreezing agent 2%-10%; an antifoaming agent 0.05%-1%; a preservative 0.05%-0.5%; a pH regulator 0.05%-1%; and water as the balance. The functional film-forming synergistic component is a product obtained by esterification reaction of alpha-eleostearic acid and eugenol, and the functional film-forming synergistic component comprises eugenol alpha-eleostearate. The plant source functional component obtained by esterification reaction of alpha-eleostearic acid and eugenol is introduced into the chlorothalonil suspension agent, which is beneficial to improving the adhesion and retention of chlorothalonil on the plant leaf surface, thereby improving the rainwater washing resistance of the preparation.

Description

Technical Field

[0001] This invention belongs to the field of plant-derived functional adjuvants technology, specifically relating to a chlorothalonil suspension containing plant-derived functional components and its preparation method. Background Technology

[0002] Chlorothalonil is a commonly used protective fungicide that primarily exerts its disease prevention effect by forming a covering layer on the plant surface and maintaining a certain residual amount. Therefore, the actual effectiveness of chlorothalonil formulations depends not only on the active ingredient itself, but also on its adhesion, retention, and resistance to rain washout on the leaf surface.

[0003] In existing technologies, to improve the leaf surface adhesion and post-rain retention of chlorothalonil and other protective fungicides, dispersants, wetting agents, thickeners, adhesives, organosilicon adjuvants, polymer adjuvants, or vegetable oil adjuvants are typically added to the formulation. While this approach can improve the wetting, spreading, and physical adhesion of the formulation to some extent, it often relies primarily on physical effects and struggles to simultaneously ensure both the formulation's storage stability and its ability to adhere to the interface after application.

[0004] On the other hand, plant-derived components have the potential to be used as functional adjuvants in pesticides due to their wide availability and diverse structures. However, when some plant-derived components are directly introduced into water-based suspension systems, problems such as volatility, migration, insufficient compatibility, or poor storage stability may arise. At the same time, some unsaturated plant-derived fatty acids have high reactivity, which, if not properly controlled, is also detrimental to formulation applications.

[0005] Therefore, it is necessary to provide a new chlorothalonil suspension containing plant-derived functional components and its preparation method to improve the adhesion and rain erosion resistance of chlorothalonil on plant leaves, while taking into account the processability and storage stability of the formulation. Summary of the Invention

[0006] In view of the above situation and to overcome the defects of the prior art, the purpose of the present invention is to provide a chlorothalonil suspension containing plant-derived functional components and its preparation method, so as to at least partially solve the problems mentioned in the background art.

[0007] The technical solution adopted in this invention is as follows: The first aspect of this invention provides a chlorothalonil suspension containing plant-derived functional components, comprising the following components by total weight percentage: Chlorothalonil 20%-60%; Functional film-forming synergistic components: 1%-15%; Dispersant 2%-10%; Wetting agent 1%-6%; Rheology modifier 0.1%-3%; Antifreeze 2%-10%; Defoamer 0.05%-1%; Preservative 0.05%-0.5%; pH adjuster 0.05%-1%; Water is the remainder; The functional film-forming enhancing component is a product obtained by esterification of α-tung acid and eugenol, and the functional film-forming enhancing component includes α-tung acid eugenol ester.

[0008] In some embodiments of the present invention, the mass content of α-eugenol ester in the functional film-forming synergist is more than 40%, and the acid value of the functional film-forming synergist is 5-30 mg KOH / g.

[0009] In some embodiments of the present invention, the dispersant is selected from one or more of lignin sulfonate, naphthalene sulfonate formaldehyde condensate, polycarboxylate dispersant, polyacrylate, maleic anhydride copolymer and its salts.

[0010] In some embodiments of the present invention, the wetting agent is selected from one or more of fatty alcohol polyoxyethylene ether, castor oil polyoxyethylene ether, sorbitol esters, alkyl glycosides, dioctyl sulfosuccinate, and EO / PO block copolymers.

[0011] In some embodiments of the present invention, the rheology modifier is selected from one or more of xanthan gum, magnesium aluminum silicate, attapulgite, bentonite, and hydroxyethyl cellulose; the antifreeze is selected from one or more of propylene glycol, glycerin, ethylene glycol, and sorbitol.

[0012] In some embodiments of the present invention, the pH of the suspension is 5.5-8.0, and the D90 particle size of the chlorothalonil particles in the suspension is not greater than 10 μm.

[0013] A second aspect of this invention provides a method for preparing a chlorothalonil suspension containing plant-derived functional components, comprising the following steps: S1. Add α-tung acid, eugenol, catalyst, polymerization inhibitor and dehydrating agent to the reactor, mix under an inert atmosphere, and heat to carry out esterification reaction to obtain a reaction system containing α-tung acid eugenol ester. S2. After cooling the reaction system obtained in step S1, perform post-processing to obtain the functional film-forming enhancement component; S3. Mix water, dispersant, wetting agent, antifreeze, defoamer, preservative, thickener and pH adjuster to obtain aqueous base material; S4. The functional film-forming and enhancing components obtained in step S2 are mixed with a portion of the aqueous phase base material and subjected to high-speed shearing to prepare a pre-emulsified dispersion. Then, the pre-emulsified dispersion is added to the remaining aqueous phase base material, and chlorothalonil is added for high-speed shearing to obtain a coarse dispersion slurry. S5. The coarse dispersion slurry obtained in step S4 is subjected to wet grinding, and the pH and viscosity are adjusted to obtain the chlorothalonil suspension.

[0014] In some embodiments of the present invention, in step S1, the molar ratio of α-tung acid to eugenol is 1:(0.9-1.3), the amount of catalyst is 0.1%-1.0% of the total feed mass, the amount of polymerization inhibitor is 0.05%-0.5% of the total feed mass, and the amount of dehydrating agent is 20%-100% of the mass of α-tung acid.

[0015] In some embodiments of the present invention, the esterification reaction temperature in step S1 is 110°C-160°C.

[0016] In some embodiments of the present invention, in step S1, the catalyst is selected from one or more of p-toluenesulfonic acid, methanesulfonic acid, acidic ion exchange resin, and organotitanium catalyst; the polymerization inhibitor is selected from one or more of hydroquinone, 2,6-di-tert-butyl-p-cresol, tert-butylcatechol, and phenylthiazide; and the dehydrating agent is selected from toluene, xylene, and mixtures thereof.

[0017] The beneficial effects achieved by this invention are as follows: This invention introduces a plant-derived functional component, obtained through the esterification reaction of α-tung oil acid and eugenol, into chlorothalonil suspension. This enhances the adhesion and retention of chlorothalonil on plant leaves, thereby improving the formulation's resistance to rain washout. The introduction of this plant-derived functional component allows chlorothalonil to form a more stable deposition on the leaf surface, helping to reduce the loss of active ingredients due to rain washout and surface migration after application, thus maintaining the efficacy of the pesticide.

[0018] Meanwhile, the plant-derived functional components are prepared through a pre-esterification reaction before being introduced into the chlorothalonil suspension system. Compared to directly physical blending the relevant plant-derived substances, this method is more conducive to improving their compatibility and application stability in the formulation system. By first forming relatively stable functional components and then performing formulation processing, it is beneficial to the dispersion and use of the plant-derived components in the water-based suspension system, while also taking into account the processing adaptability and storage stability of the formulation. Detailed Implementation

[0019] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0020] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those familiar to those skilled in the art. Furthermore, any methods and materials similar to or equivalent to those described herein may be applied to this invention. The preferred embodiments and materials described herein are for illustrative purposes only and do not limit the scope of this invention.

[0021] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0022] To address the problems raised in the background art, the first aspect of this invention provides a chlorothalonil suspension containing plant-derived functional components, comprising the following components by total weight percentage: chlorothalonil 20%-60%; functional film-forming synergist 1%-15%; dispersant 2%-10%; wetting agent 1%-6%; rheology modifier 0.1%-3%; antifreeze 2%-10%; defoamer 0.05%-1%; preservative 0.05%-0.5%; pH adjuster 0.05%-1%; and water as the balance. The "functional film-forming synergistic component" refers to the reaction product obtained by esterification of α-tungstic acid and eugenol, wherein the reaction product contains α-tungstic acid eugenol ester. In this invention, the functional film-forming synergistic component is not limited to a single pure compound, but can be a reaction product system with the esterification product as the main component. In other words, in addition to containing α-tungstic acid eugenol ester, the functional film-forming synergistic component may also contain a small amount of unreacted raw materials remaining after the esterification reaction and a small amount of byproducts formed during the reaction, as long as it as a whole belongs to the functional components obtained by esterification of α-tungstic acid and eugenol and can be used in the chlorothalonil suspension of this invention.

[0023] In this invention, chlorothalonil is the main fungicidal active ingredient in the suspension. Functional film-forming synergists are used to introduce plant-derived functional units and improve the adhesion and retention properties of chlorothalonil on plant surfaces. Dispersants are used to promote the dispersion of chlorothalonil technical in the aqueous phase and improve the stability of the suspension system. Wetting agents are used to improve the wetting and distribution properties of chlorothalonil technical and the aforementioned functional film-forming synergists in the aqueous phase. Rheology modifiers are used to adjust the viscosity and rheological properties of the suspension to improve its anti-settling ability and storage stability. Antifreeze agents are used to improve the stability of the formulation under low-temperature conditions. Defoamers are used to suppress foam generated during the preparation process. Preservatives are used to improve the resistance to microbial contamination during the storage of the aqueous system. pH adjusters are used to adjust the pH of the system. Water is used as the continuous phase medium to construct the aqueous dispersion system of the chlorothalonil suspension.

[0024] In some embodiments, the mass content of α-eugenol ester in the functional film-forming synergist is 40% or more, and the acid value of the functional film-forming synergist is 5-30 mg KOH / g.

[0025] Limiting the mass content of α-eugenol ester in the functional film-forming synergistic component to 40% or more helps ensure a high proportion of esterified products in the functional component, thereby enabling it to exert a more stable functional effect in chlorothalonil suspension. Preferably, the mass content of α-eugenol ester is 45% or more, more preferably 50% or more. It should be noted that the mass content can be determined using conventional quantitative analysis methods in the art, such as gas chromatography, liquid chromatography, or nuclear magnetic resonance combined with internal standard method.

[0026] Limiting the acid value of the functional film-forming synergist to 5-30 mg KOH / g is beneficial for balancing the degree of esterification reaction, formulation compatibility, and storage stability. A high acid value indicates a large amount of residual free acid in the system, which may adversely affect compatibility and storage stability in subsequent formulation processes. Conversely, a low acid value may imply stringent post-treatment or reaction control conditions, which are detrimental to the stability and economy of industrial implementation. Preferably, the acid value is 5-25 mg KOH / g, more preferably 5-20 mg KOH / g.

[0027] In some embodiments, the functional film-forming synergist may be a light yellow to brownish-yellow liquid, a semi-fluid liquid, or a low-viscosity resin that can meet the processing requirements of subsequent pre-emulsification, dispersion, or addition to an aqueous system at room temperature.

[0028] In some embodiments, the dispersant is selected from one or more of lignin sulfonate, naphthalene sulfonate formaldehyde condensate, polycarboxylate dispersant, polyacrylate, maleic anhydride copolymer and its salts.

[0029] The lignin sulfonate can be one or more of sodium lignin sulfonate, calcium lignin sulfonate, or ammonium lignin sulfonate. The naphthalene sulfonate formaldehyde condensate can be a sodium salt of naphthalene sulfonate formaldehyde condensate. The polycarboxylate dispersant can be a polyacrylic acid, polymaleic acid, or a carboxyl-containing copolymer dispersant. The polyacrylate can be sodium polyacrylate or its derivative salts. The maleic anhydride copolymer and its salts can be copolymer salts formed by maleic anhydride and olefin monomers.

[0030] In some preferred embodiments, the dispersant is a combination of two or more types. Combining different types of dispersants helps to balance the initial wetting and dispersing effect of chlorothalonil technical material with the long-term storage stability of the suspension. Preferably, the total amount of the dispersant is 3%-8%.

[0031] In some embodiments, the wetting agent is selected from one or more of fatty alcohol polyoxyethylene ether, castor oil polyoxyethylene ether, sorbitol esters, alkyl glycosides, dioctyl sulfosuccinate, and EO / PO block copolymers.

[0032] The fatty alcohol polyoxyethylene ether may be one or more of C8-C18 fatty alcohol polyoxyethylene ethers. The castor oil polyoxyethylene ether may be hydrogenated or non-hydrogenated castor oil polyoxyethylene ether. The sorbitol ester may be a Span or Tween wetting agent. The alkyl glycoside may be a C8-C16 alkyl glycoside. The dioctyl sulfosuccinate may be its sodium salt. The EO / PO block copolymer may be a nonionic surfactant commonly used in the art.

[0033] The wetting agent is used to improve the wetting properties and interfacial distribution of chlorothalonil technical and functional film-forming synergistic components in the aqueous phase. Preferably, the total amount of the wetting agent is 1.5%-4%. In some embodiments, the wetting agent may be a combination of an anionic wetting agent and a nonionic wetting agent to obtain better wetting effect and system adaptability.

[0034] In some embodiments, the rheology modifier is selected from one or more of xanthan gum, magnesium aluminum silicate, attapulgite, bentonite, and hydroxyethyl cellulose; the antifreeze is selected from one or more of propylene glycol, glycerin, ethylene glycol, and sorbitol.

[0035] The rheology modifier is used to adjust the viscosity, thixotropy, and anti-sedimentation ability of the suspending agent. Xanthan gum and hydroxyethyl cellulose can be used to increase the viscosity of the system and improve its rheological behavior; magnesium aluminosilicate, attapulgite, and bentonite can be used to enhance the suspension stability and anti-stratification properties of the system. Preferably, the amount of the rheology modifier is 0.2%-1.5%.

[0036] The antifreeze agent is used to improve the stability of the formulation under low-temperature storage conditions, preventing phenomena such as freezing, water separation, crystallization, or irreversible thickening from occurring in the system. Preferably, the amount of the antifreeze agent is 3%-8%. In some embodiments, the antifreeze agent is one or both of propylene glycol and glycerol.

[0037] In some embodiments, the pH of the suspension is 5.5-8.0, and the D90 particle size of the chlorothalonil particles in the suspension is not greater than 10 μm.

[0038] Controlling the pH of the suspension in the range of 5.5-8.0 is beneficial for balancing the stability of the chlorothalonil technical in the system, the suitability of the dispersant and wetting agent, and the compatibility of the functional film-forming synergist in the formulation. Preferably, the pH of the suspension is 6.0-7.5.

[0039] Controlling the D90 of the chlorothalonil granules in the suspension to no greater than 10 μm is beneficial for improving the dispersion uniformity, suspension stability, and sprayability of the suspension. Preferably, the D90 is no greater than 8 μm. The D90 can be measured using conventional methods in the art, such as a laser particle size analyzer.

[0040] In some embodiments, the chlorothalonil granules are wet-milled to form a narrower particle size distribution, which is beneficial for the functional film-forming synergistic component to be more uniformly distributed on the surface of the drug particles and in the surrounding interface area, thereby facilitating the acquisition of better formulation performance.

[0041] A second aspect of this invention provides a method for preparing a chlorothalonil suspension containing plant-derived functional components, comprising the following steps: S1. Add α-tung acid, eugenol, catalyst, polymerization inhibitor and dehydrating agent to the reactor, mix under an inert atmosphere, and heat to carry out esterification reaction to obtain a reaction system containing α-tung acid eugenol ester. S2. After cooling the reaction system obtained in step S1, perform post-processing to obtain the functional film-forming enhancement component; S3. Mix water, dispersant, wetting agent, antifreeze, defoamer, preservative, thickener and pH adjuster to obtain aqueous base material; S4. The functional film-forming and enhancing components obtained in step S2 are mixed with a portion of the aqueous phase base material and subjected to high-speed shearing to prepare a pre-emulsified dispersion. Then, the pre-emulsified dispersion is added to the remaining aqueous phase base material, and chlorothalonil is added for high-speed shearing to obtain a coarse dispersion slurry. S5. The coarse dispersion slurry obtained in step S4 is subjected to wet grinding, and the pH and viscosity are adjusted to obtain the chlorothalonil suspension.

[0042] In this invention, steps S1 and S2 are used to prepare the plant-derived functional components, and steps S3 to S5 are used to introduce the plant-derived functional components into the chlorothalonil water-based suspension system. By first preparing the functional film-forming synergistic component and then performing pre-emulsification, dispersion, and grinding, it is beneficial to improve the uniformity of distribution and application stability of the functional component in the suspension system.

[0043] In some embodiments, the inert atmosphere in step S1 is nitrogen, argon, or other protective atmospheres that can reduce the oxygen content, preferably nitrogen. Using an inert atmosphere helps reduce the risk of premature and adverse oxidation of α-tung acid during the reaction, thereby facilitating the controlled conduct of the esterification reaction.

[0044] In some embodiments, the "post-treatment" in step S2 includes one or more of neutralization, adsorption, filtration, and solvent removal. Post-treatment helps to reduce the adverse effects of residual catalyst, incompletely removed water-carrying agent, and small amounts of impurities on subsequent formulation processes, thereby improving the application stability of functional film-forming synergistic components.

[0045] In some embodiments, the order of addition of each adjuvant in step S3 can be adjusted according to the formulation system, as long as a uniform and stable aqueous phase base can be formed. Preferably, the dispersant, wetting agent and antifreeze are first added to water and mixed, and then the defoamer, preservative, rheology modifier and pH adjuster are added to facilitate the formation of an aqueous phase system suitable for the subsequent addition of functional film-forming synergistic components and chlorothalonil technical.

[0046] In some embodiments, in step S4, the functional film-forming synergist is first mixed with a portion of the aqueous phase matrix and subjected to high-speed shearing. The purpose is to allow the functional component to first form a relatively stable pre-emulsified dispersion state before being introduced into the main aqueous phase. This pretreatment method helps to reduce the occurrence of local agglomeration, uneven distribution, or insufficient compatibility when the functional film-forming synergist is directly added to the main system.

[0047] In some embodiments, the high-speed shearing in step S4 can be performed using high-speed dispersion equipment commonly used in the art, and the shearing speed and time can be adjusted according to the material system and batch size. Preferably, the shearing speed is 1500 rpm-5000 rpm, and the shearing time is 5 min-40 min.

[0048] In some embodiments, the wet grinding in step S5 can be carried out using a sand mill, bead mill, or other wet pulverizing equipment suitable for preparing pesticide suspensions. After grinding, water can be added as needed to adjust the pH and viscosity of the system to obtain a chlorothalonil suspension product that meets the requirements for storage and application.

[0049] In some embodiments, in step S1, the molar ratio of α-tung acid to eugenol is 1:(0.9-1.3), the amount of catalyst is 0.1%-1.0% of the total feed mass, the amount of polymerization inhibitor is 0.05%-0.5% of the total feed mass, and the amount of dehydrating agent is 20%-100% of the mass of α-tung acid.

[0050] By limiting the molar ratio of α-tung acid to eugenol within the aforementioned range, it is beneficial to balance the esterification reaction efficiency, the composition of the reaction product, and the adaptability to subsequent formulation. When the amount of eugenol is too low, it may lead to insufficient esterification; when its amount is too high, it may increase unreacted residues and affect the post-processing and application stability of the functional components. Preferably, the molar ratio of α-tung acid to eugenol is 1:(0.95-1.15).

[0051] In this invention, the catalyst dosage is 0.1%-1.0% of the total feed mass. When the catalyst dosage is too low, the esterification reaction rate may be slow, which is detrimental to industrial preparation efficiency; when the catalyst dosage is too high, it may increase the risk of side reactions and increase the burden of post-processing. Preferably, the catalyst dosage is 0.2%-0.8% of the total feed mass.

[0052] In this invention, the amount of polymerization inhibitor is 0.05%-0.5% of the total feed mass. Adding the polymerization inhibitor helps to suppress the excessively rapid oxidative polymerization of α-tung acid under conditions of increased temperature and low oxygen content. Preferably, the amount of polymerization inhibitor is 0.08%-0.3% of the total feed mass.

[0053] In this invention, the amount of dehydrating agent used is 20%-100% of the mass of α-tungstic acid. The dehydrating agent can be used to form an azeotropic system with the generated water, thereby promoting the esterification reaction towards the product. Preferably, the amount of dehydrating agent used is 30%-80% of the mass of α-tungstic acid.

[0054] In some embodiments, the esterification reaction temperature in step S1 is 110°C-160°C.

[0055] In this invention, controlling the esterification reaction temperature within the range of 110℃-160℃ is beneficial for balancing the esterification reaction rate and system stability. When the reaction temperature is too low, the esterification reaction rate is slow, which is not conducive to improving the reaction efficiency; when the reaction temperature is too high, it may lead to adverse side reactions in the α-tung acid system, and affect the composition and subsequent application performance of the obtained functional film-forming synergistic component.

[0056] Preferably, the esterification reaction temperature is 120℃-145℃. Within this temperature range, the esterification reaction proceeds more smoothly while also ensuring the controllability of the reaction process.

[0057] In some embodiments, the reaction endpoint can be determined in step S1 by changes in acid value, water separation, changes in infrared absorption, or changes in the system state. Preferably, the reaction ends when the acid value drops to a predetermined range and tends to stabilize.

[0058] In some embodiments, in step S1, the catalyst is selected from one or more of p-toluenesulfonic acid, methanesulfonic acid, acidic ion exchange resin, and organotitanium catalyst; the polymerization inhibitor is selected from one or more of hydroquinone, 2,6-di-tert-butyl-p-cresol, tert-butylcatechol, and phenylthiazide; and the dehydrating agent is selected from toluene, xylene, and mixtures thereof.

[0059] The catalyst is used to promote the esterification reaction between α-tungstic acid and eugenol. Among them, p-toluenesulfonic acid and methanesulfonic acid are acidic catalysts, which can effectively promote the esterification reaction; acidic ion exchange resins are beneficial for subsequent separation; and organotitanium catalysts can be used as another optional catalytic system.

[0060] The polymerization inhibitor is used to suppress unwanted polymerization or oxidation side reactions of α-tung acid under heating conditions. Hydroquinone, 2,6-di-tert-butyl-p-cresol, tert-butylcatechol, and phenylthiazide can all be used as polymerization inhibitors in this invention.

[0061] The dehydrating agent is used to assist in removing the generated water during the reaction, promoting a shift in the esterification equilibrium towards ester formation. Toluene, xylene, and mixtures thereof can all be used in this invention. Preferably, xylene is used as the dehydrating agent.

[0062] In some preferred embodiments, the catalyst is p-toluenesulfonic acid, the polymerization inhibitor is 2,6-di-tert-butyl-p-cresol, and the dehydrating agent is xylene.

[0063] The present invention will be described below through specific embodiments. It should be noted that these embodiments are for illustrative purposes only and should not be considered as limiting the scope of the invention. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0064] Example 1: Preparation of functional film-forming synergistic components: Add 100g of α-tung acid, 105g of eugenol, 1.2g of p-toluenesulfonic acid, 0.4g of 2,6-di-tert-butyl-p-cresol, and 60g of xylene to a reactor equipped with a stirrer, water separator, and reflux device. Stir and mix under nitrogen protection, and heat to 130-135℃ for esterification reaction. Water is continuously separated during the reaction.

[0065] Once the acid value drops to 15-20 mg KOH / g and tends to stabilize, the reaction is stopped, the system is cooled to 60-70℃, an appropriate amount of triethylamine is added for neutralization, xylene is removed under reduced pressure, and filtration is performed if necessary to obtain functional film-forming enhancing component A.

[0066] Preparation of chlorothalonil suspension: Weigh the following raw materials per 1000g: 400g chlorothalonil technical grade, 60g functional film-forming synergist A, 35g sodium lignosulfonate, 20g polycarboxylate dispersant, 15g castor oil polyoxyethylene ether, 8g sodium dioctyl sulfosuccinate, 3g xanthan gum, 6g magnesium aluminum silicate, 50g propylene glycol, 2g silicone defoamer, 1g isothiazolinone preservative, appropriate amount of pH adjuster, and deionized water to 1000g.

[0067] First, add a portion of deionized water to a dispersion tank, then add sodium lignosulfonate, polycarboxylate dispersant, castor oil polyoxyethylene ether, sodium dioctyl sulfosuccinate, propylene glycol, silicone defoamer, isothiazolinone preservative, xanthan gum, and magnesium aluminum silicate in sequence, and stir until homogeneous to obtain an aqueous phase base.

[0068] A portion of the aqueous phase base material is mixed with functional film-forming synergist A and subjected to high-speed shearing to prepare a pre-emulsified dispersion. Then, the pre-emulsified dispersion is added to the remaining aqueous phase base material, and chlorothalonil technical material is added and subjected to high-speed shearing to obtain a coarse dispersion slurry.

[0069] The coarsely dispersed slurry was wet-milled to control the D90 of chlorothalonil particles to be no greater than 10μm. After milling, the remaining water was added and the pH of the system was adjusted to 6.0-7.0. After maturation, chlorothalonil suspension containing plant-derived functional components was obtained.

[0070] Example 2: Preparation of functional film-forming synergistic components: Add 100g of α-tung acid, 110g of eugenol, 1.0g of methanesulfonic acid, 0.3g of hydroquinone, and 50g of xylene to a reactor equipped with a stirring, water separation, and reflux device. Stir and mix under nitrogen protection, and heat to 125-130℃ for esterification reaction, with continuous water separation during the reaction.

[0071] Once the acid value drops to 10-18 mg KOH / g and tends to stabilize, the reaction is stopped, the system is cooled to 60-70℃, an appropriate amount of organic base is added for neutralization, xylene is removed under reduced pressure, and filtration is performed if necessary to obtain functional film-forming enhancing component B.

[0072] Preparation of chlorothalonil suspension: Weigh the following raw materials per 1000g: 380g of chlorothalonil technical grade, 80g of functional film-forming synergist B, 30g of sodium lignosulfonate, 25g of polycarboxylate dispersant, 12g of castor oil polyoxyethylene ether, 10g of sodium dioctyl sulfosuccinate, 2g of xanthan gum, 8g of magnesium aluminum silicate, 45g of glycerin, 2g of organosilicon defoamer, 1g of isothiazolinone preservative, appropriate amount of pH adjuster, and deionized water to 1000g.

[0073] First, add a portion of deionized water to a dispersion tank, then add sodium lignosulfonate, polycarboxylate dispersant, castor oil polyoxyethylene ether, sodium dioctyl sulfosuccinate, glycerin, silicone defoamer, isothiazolinone preservative, xanthan gum, and magnesium aluminum silicate in sequence, and stir until homogeneous to obtain the aqueous phase base material.

[0074] A portion of the aqueous phase base material is mixed with functional film-forming synergist B and subjected to high-speed shearing to prepare a pre-emulsified dispersion. Then, the pre-emulsified dispersion is added to the remaining aqueous phase base material, and chlorothalonil technical material is added and subjected to high-speed shearing to obtain a coarse dispersion slurry.

[0075] The coarsely dispersed slurry was wet-milled to control the D90 of chlorothalonil particles to be no greater than 10μm. After milling, the remaining water was added and the pH of the system was adjusted to 6.0-7.0. After maturation, chlorothalonil suspension containing plant-derived functional components was obtained.

[0076] Example 3: Preparation of functional film-forming synergistic components: Add 100g of α-tungstic acid, 100g of eugenol, 0.8g of p-toluenesulfonic acid, 0.3g of 2,6-di-tert-butyl-p-cresol, and 70g of toluene to a reactor equipped with a stirring, water separation, and reflux device. Stir and mix under nitrogen protection, and heat to 135-140℃ for esterification reaction, with continuous water separation during the reaction.

[0077] When the acid value drops to 12-20 mg KOH / g and tends to stabilize, the reaction is stopped, the system is cooled to 60-70℃, an appropriate amount of organic base is added for neutralization, toluene is removed under reduced pressure, and filtration is performed if necessary to obtain functional film-forming enhancing component C.

[0078] Preparation of chlorothalonil suspension: Weigh the following raw materials per 1000g: 450g of chlorothalonil technical grade, 40g of functional film-forming synergist C, 28g of sodium lignosulfonate, 22g of polycarboxylate dispersant, 10g of fatty alcohol polyoxyethylene ether, 6g of alkyl glycoside, 2g of xanthan gum, 6g of bentonite, 55g of propylene glycol, 2g of polyether defoamer, 1g of preservative, appropriate amount of pH adjuster, and deionized water to 1000g.

[0079] First, add a portion of deionized water to a dispersion tank, then add sodium lignosulfonate, polycarboxylate dispersant, fatty alcohol polyoxyethylene ether, alkyl glycoside, propylene glycol, polyether defoamer, preservative, xanthan gum, and bentonite in sequence, and stir until homogeneous to obtain an aqueous phase base.

[0080] A portion of the aqueous phase base material is mixed with the functional film-forming synergist C and subjected to high-speed shearing to prepare a pre-emulsified dispersion. Then, the pre-emulsified dispersion is added to the remaining aqueous phase base material, and chlorothalonil technical material is added and subjected to high-speed shearing to obtain a coarse dispersion slurry.

[0081] The coarsely dispersed slurry was wet-milled to control the D90 of chlorothalonil particles to be no greater than 10μm. After milling, the remaining water was added and the pH of the system was adjusted to 6.5-7.5. After maturation, chlorothalonil suspension containing plant-derived functional components was obtained.

[0082] Comparative Example 1 This comparative example provides a chlorothalonil suspension that does not contain plant-derived functional components.

[0083] Compared with Example 1, the only difference is that: no functional film-forming synergist A is added in this comparative example, the missing mass is made up with deionized water, and the composition of other raw materials and preparation methods are the same as in Example 1, so as to obtain a chlorothalonil suspension without plant-derived functional components.

[0084] Comparative Example 2 This comparative example provides a chlorothalonil suspension containing a physical mixture of α-tung oil and eugenol.

[0085] Compared with Example 1, the only difference is that in this comparative example, a physical mixture of 30g of α-tung acid and 30g of eugenol is used to replace the functional film-forming synergist A in Example 1. The composition of the remaining raw materials and the preparation method are the same as in Example 1, resulting in a chlorothalonil suspension containing a physical mixture of plant-derived substances.

[0086] Comparative Example 3 This comparative example provides a chlorothalonil suspension containing only α-tung oil.

[0087] Compared with Example 1, the only difference is that 60g of α-tung acid was used to replace the functional film-forming synergist A in Example 1 in this comparative example. The composition of the remaining raw materials and the preparation method are the same as in Example 1, so as to obtain a chlorothalonil suspension containing only α-tung acid.

[0088] Comparative Example 4 This comparative example provides a chlorothalonil suspension containing only eugenol.

[0089] Compared with Example 1, the only difference is that 60g of eugenol was used to replace the functional film-forming synergist A in Example 1 in this comparative example, while the composition of the remaining raw materials and the preparation method were the same as in Example 1, resulting in a chlorothalonil suspension containing only eugenol.

[0090] To verify the beneficial effects of the present invention, performance tests were conducted on the products obtained in Examples 1-3 and Comparative Examples 1-4.

[0091] Test method: 1. Acid value determination The acid value of the functional film-forming synergistic component was determined by acid-base titration, expressed as mgKOH / g. An appropriate amount of sample was dissolved in an ethanol-ether mixture and titrated to the endpoint with a potassium hydroxide standard solution. The acid value was then calculated.

[0092] 2. Particle size test The particle size distribution of chlorothalonil granules in the sample was determined using a laser particle size analyzer, and the D90 value was recorded. The test method was performed according to GB / T19077-2024 "Particle size analysis by laser diffraction".

[0093] 3. Suspension rate test The dispersion stability of the sample was evaluated by measuring the suspension rate of pesticides according to GB / T14825-2023 "Determination of Pesticide Suspension Rate".

[0094] 4. Initial deposition test on leaf surface Each sample was diluted to the same concentration of active ingredient and sprayed onto the leaf surface of the same crop. After natural drying, the leaves were harvested. The initial deposition of chlorothalonil on the leaf surface was determined using high-performance liquid chromatography (HPLC).

[0095] 5. Simulated rainfall residue test After spraying and drying, the leaves were placed under a simulated rainfall device and treated under the same rainfall intensity and duration. After the rainfall, the residual amount of chlorothalonil on the leaf surface was determined using high-performance liquid chromatography (HPLC), and the residue retention rate was calculated using the following formula: Residual retention rate (%) = Chlorothalonil residue on leaves after rainfall / Initial chlorothalonil deposition on leaves before rainfall × 100% The simulated rainfall conditions can be set as follows: rainfall intensity 20-40 mm / h, rainfall duration 30-60 min.

[0096] Test results: Table 1. Acid value test results of functional film-forming synergists

[0097] As shown in Table 1, the acid values ​​of the functional film-forming synergistic components obtained in Examples 1-3 are all within the range specified in this invention, indicating that the esterification reaction of α-tung acid and eugenol can proceed smoothly and yield plant-derived functional components suitable for subsequent formulation.

[0098] Table 2. Results of formulation performance tests for each sample

[0099] As shown in Table 2, the samples obtained in Examples 1-3 all exhibited good formulation performance, with the D90 of chlorothalonil granules not exceeding 10 μm and a high suspension rate, indicating that the technical solution of this invention can meet the basic formulation requirements of chlorothalonil suspension. Meanwhile, in Comparative Examples 3 and 4, the suspension rate decreased when only a single plant-derived component was added, indicating that replacing the plant-derived functional component of this invention with a single component has limited improvement on system stability.

[0100] Table 3. Results of leaf surface deposition and rain erosion resistance tests for each sample.

[0101] As shown in Table 3, the initial leaf deposition and residual retention rates after simulated rainfall in Examples 1-3 were higher than those in Comparative Examples 1-4. This indicates that the introduction of plant-derived functional components obtained by the esterification reaction of α-tung acid and eugenol in this invention is beneficial to improving the adhesion of chlorothalonil to the leaf surface and its retention capacity after rain. Among them, Example 2 showed the highest residual retention rate, indicating that under the conditions of this example, the plant-derived functional components had a more significant effect on improving the leaf surface fixation and rain erosion resistance of chlorothalonil.

[0102] Further comparison of Example 1 and Comparative Example 2 shows that although the physical mixture of α-tunglic acid and eugenol was added in Comparative Example 2, its residue retention rate was higher than that of Comparative Example 1, but still significantly lower than that of Example 1. This indicates that pre-esterifying α-tunglic acid and eugenol to form a plant-derived functional component before introducing it into the chlorothalonil suspension system is more beneficial for improving the application effect of this component in the formulation. Combined with Comparative Examples 3 and 4, it can be seen that adding only α-tunglic acid or only eugenol can improve leaf retention performance to some extent, but its effect is still lower than that of the embodiments of the present invention. This indicates that the plant-derived functional component of the present invention is not a simple substitution or simple combination of related plant-derived substances.

[0103] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0104] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the protection scope of the present invention.

Claims

1. A chlorothalonil suspension containing plant-derived functional components, characterized in that, By weight percentage, it includes the following components: Chlorothalonil 20%-60%; Functional film-forming synergistic components: 1%-15%; Dispersant 2%-10%; Wetting agent 1%-6%; Rheology modifier 0.1%-3%; Antifreeze 2%-10%; Defoamer 0.05%-1%; Preservative 0.05%-0.5%; pH adjuster 0.05%-1%; Water is the remainder; The functional film-forming enhancing component is a product obtained by esterification of α-tung acid and eugenol, and the functional film-forming enhancing component includes α-tung acid eugenol ester.

2. The chlorothalonil suspension according to claim 1, characterized in that, The functional film-forming synergist contains 40% or more of α-tungoic acid eugenol ester, and the acid value of the functional film-forming synergist is 5-30 mg KOH / g.

3. The chlorothalonil suspension according to claim 1, characterized in that, The dispersant is selected from one or more of lignin sulfonate, naphthalene sulfonate formaldehyde condensate, polycarboxylate dispersant, polyacrylate, maleic anhydride copolymer and its salts.

4. The chlorothalonil suspension according to claim 1, characterized in that, The wetting agent is selected from one or more of fatty alcohol polyoxyethylene ether, castor oil polyoxyethylene ether, sorbitol esters, alkyl glycosides, dioctyl sulfosuccinate, and EO / PO block copolymers.

5. The chlorothalonil suspension according to claim 1, characterized in that, The rheology modifier is selected from one or more of xanthan gum, magnesium aluminum silicate, attapulgite, bentonite, and hydroxyethyl cellulose; the antifreeze is selected from one or more of propylene glycol, glycerin, ethylene glycol, and sorbitol.

6. The chlorothalonil suspension according to claim 1, characterized in that, The pH of the suspension is 5.5-8.0, and the D90 particle size of the chlorothalonil granules in the suspension is not greater than 10 μm.

7. A method for preparing a chlorothalonil suspension containing plant-derived functional components according to any one of claims 1-6, characterized in that, Includes the following steps: S1. Add α-tung acid, eugenol, catalyst, polymerization inhibitor and dehydrating agent to the reactor, mix under an inert atmosphere, and heat to carry out esterification reaction to obtain a reaction system containing α-tung acid eugenol ester. S2. After cooling the reaction system obtained in step S1, perform post-processing to obtain the functional film-forming enhancement component; S3. Mix water, dispersant, wetting agent, antifreeze, defoamer, preservative, thickener and pH adjuster to obtain aqueous base material; S4. The functional film-forming and enhancing components obtained in step S2 are mixed with a portion of the aqueous phase base material and subjected to high-speed shearing to prepare a pre-emulsified dispersion. Then, the pre-emulsified dispersion is added to the remaining aqueous phase base material, and chlorothalonil is added for high-speed shearing to obtain a coarse dispersion slurry. S5. The coarse dispersion slurry obtained in step S4 is subjected to wet grinding, and the pH and viscosity are adjusted to obtain the chlorothalonil suspension.

8. The preparation method according to claim 7, characterized in that, In step S1, the molar ratio of α-tung acid to eugenol is 1:(0.9-1.3), the amount of catalyst is 0.1%-1.0% of the total feed mass, the amount of polymerization inhibitor is 0.05%-0.5% of the total feed mass, and the amount of dehydrating agent is 20%-100% of the mass of α-tung acid.

9. The preparation method according to claim 6, characterized in that, The esterification reaction temperature in step S1 is 110℃-160℃.

10. The preparation method according to claim 6, characterized in that, In step S1, the catalyst is selected from one or more of p-toluenesulfonic acid, methanesulfonic acid, acidic ion exchange resin, and organotitanium catalyst; the polymerization inhibitor is selected from one or more of hydroquinone, 2,6-di-tert-butyl-p-cresol, tert-butylcatechol, and phenylthiazide; and the dehydrating agent is selected from toluene, xylene, and mixtures thereof.

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