Application of polymer aid G-101 in delaying crystallization of pyraclostrobin in suspending agent

By adding the polymer adjuvant G-101 and segmented temperature-controlled sand milling technology to pyraclostrobin suspension, a stable interface structure is formed, which solves the problem of crystal precipitation in the suspension at high temperatures, and achieves long-term stability and sustained efficacy of the suspension, making it suitable for high-temperature environments.

CN121753787APending Publication Date: 2026-03-31SHANTOU SHENTAI NEW MATERIAL TECH DEV CO LTD
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Patent Information

Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Filing Date
2026-01-14
Publication Date
2026-03-31

AI Technical Summary

Technical Problem

Pyraclostrobin suspension concentrate is prone to crystal precipitation under high temperature conditions, which leads to a decrease in suspension rate, uneven spraying and unstable efficacy, affecting product quality and application effect.

Method used

Adding polymeric additive G-101 to the suspending agent and using segmented temperature-controlled sand milling technology to form a stable interface structure hinders crystal nucleation and growth. Combined with the synergistic effect of dispersant G-725, the physical and chemical stability of the suspending agent is optimized.

Benefits of technology

It significantly delays the crystal precipitation time of pyraclostrobin suspension, improves thermal stability and efficacy persistence, meets the requirements for high-temperature storage and transportation, and reduces production costs and environmental risks.

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Abstract

The invention relates to an application of a polymer additive G-101 in delaying crystallization of pyraclostrobin in a suspending agent, which is characterized in that the polymer additive G-101 is added into the suspending agent containing pyraclostrobin to delay crystallization of pyraclostrobin contained in the suspending agent. Meanwhile, the invention further relates to a suspending agent containing the polymer additive G-101 and a preparation method of the suspending agent. According to the invention, a heat-storage anti-bleeding mechanism that the polymer additive G-101 is used as a main stabilizer of the pyraclostrobin-containing suspending agent is initiated, the industrial problem that the traditional pyraclostrobin-containing suspending agent is easy to layer at high temperature is broken through, and a synergistic anti-crystallization mechanism of the polymer additive G-101 and the dispersing agent G-725 is also disclosed; and the storage period is doubled after heat storage is converted into normal temperature.
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Description

Technical Field

[0001] This invention belongs to the field of pesticide adjuvants and pesticide formulations, and in particular relates to the use of polymeric adjuvant G-101 for delaying the crystallization of pyraclostrobin in suspensions containing pyraclostrobin and inhibiting the growth of particle size. Background Technology

[0002] Pyraclostrobin, a highly effective broad-spectrum fungicide, exists in various crystalline forms in the solid state, with melting temperatures ranging from 40℃ to 67℃. Due to the lower melting points of some crystalline forms, pyraclostrobin-containing suspensions can melt during storage, transportation, or use, especially under heat conditions (such as high summer temperatures or tropical environments). During cooling, the melted pyraclostrobin recrystallizes. This melt-recrystallization behavior often leads to decreased stability of the suspension system, manifesting as suspended crystallization, crystal formation at the bottom, or crystal precipitation on the container walls, severely affecting the physical appearance and uniformity of the formulation. Crystallization not only causes localized enrichment of the active ingredient and reduces the suspension rate but can also lead to inaccurate dosage during spraying, nozzle clogging, and consequently affect the stability and repeatability of field efficacy. For end-users, crystallization (also known as crystal precipitation) reduces product acceptability and brand reputation, increasing the risk of after-sales complaints. For manufacturers, quality fluctuations can lead to rework or batch scrapping, increasing costs and limiting the product's application in hot regions.

[0003] To address the crystallization problem caused by the low-melting-point crystal form of pyraclostrobin, researchers have explored various strategies to improve the heat stability of suspension concentrates. Common approaches include: optimizing crystal form control by using solvent regulation, heat treatment, or additive induction during synthesis or processing to ensure pyraclostrobin exists in a stable crystal form with a higher melting point; adjusting the formulation system by increasing the amount of thickeners and suspending agents or using high-viscosity, sterically hindered protective colloids to increase system viscosity and inhibit crystal migration and aggregation; introducing co-grinding or surface coating technologies to simultaneously act the active ingredient and specific adjuvants during sand milling, forming an adsorption layer or slight coating on the particle surface to reduce the driving force for crystal growth; and using composite solvents or antifreeze agents to adjust the melting point, thus delaying the melting-crystallization process to some extent. In addition, some studies have explored the synergistic formulation of multiple active components, utilizing other high-melting-point or high-thermal-stability active ingredients to dilute or "lock" the heat-sensitive crystal form of pyraclostrobin, thereby mitigating the crystallization tendency of a single component. However, while these methods improve heat resistance, they may compromise suspension rate, dispersibility, or efficacy, and they have high requirements for process window and equipment conditions.

[0004] In existing inventions, some patents have proposed improved products or processes to address the crystallization problem of pyraclostrobin. For example, invention patent CN116210689A discloses a pyraclostrobin and captan compound suspension, which uses a stabilizer containing ascorbic acid fatty acid esters or their derivatives to reduce the decomposition rate of captan in the suspension and avoid problems such as the suspension forming a paste at the bottom, the growth of micro-particle crystals, and water separation. Furthermore, CN119563643A discloses a pyraclostrobin and boscalid compound suspension and its preparation method. The wetting and dispersing agent in the suspension is selected from two, three, or four of the following: comb-type polymer EMULSON AG TRN 14105, sulfonate dispersant FR-S10, alkyl naphthalene sulfonate formaldehyde condensate D-425, phosphate ester dispersant 1015, polycarboxylate dispersant RD-95, EOPO block 10500, methacrylate copolymer 4913, sulfate ester dispersant 3016, anionic modified styrene-acrylic polymer ATLOX 4917, and EOPO block PE / F127. The particle size D98 of pyraclostrobin and boscalid in the suspension is 3.025–3.325 μm. This patent improves the stability of suspensions through composite dispersants. The suspensions prepared in Examples 1-8 of this patent all showed no crystallization after being heated to room temperature, but the duration of this non-crystallization period was not specified. Comparative Examples 1-11, after being heated to room temperature, crystallized for a maximum of 9 days. Compared to the comparative examples, Examples 1-8 effectively solved the crystallization problem, meaning the crystallization time should be extended by more than 9 days, but the specific extension period is not specified.

[0005] In recent years, with advancements in adjuvant science and formulation processes, the use of specialized functional adjuvants and customized preparation methods has shown promising promise in addressing the low-melting-point crystallization problem of pyraclostrobin. For example, the use of polymeric dispersants and block copolymer adjuvants can form a more robust 3D barrier on the particle surface, significantly reducing the migration and rearrangement rates of crystals during thermal storage. Introducing thermally stable nanocarriers or inorganic layered silicates can inhibit the aggregation and recrystallization of molten liquids through physical barriers and interfacial energy regulation. Some reactive or in-situ polymerizing adjuvants can also interact controllably with the surface of the active ingredient microcrystals during milling or curing, forming a stable molecular anchoring layer that maintains the original particle size and distribution after thermal shock. Simultaneously, specialized preparation methods such as segmented temperature-controlled milling, gradient homogenization, and multi-stage curing can optimize the particle dispersion and adjuvant distribution uniformity at the microstructural level, reducing nucleation sites for heat-sensitive crystal forms. By combining precise crystal form screening and formulation simulation, the synergy between these adjuvants and processes is expected to significantly improve the heat stability of pyraclostrobin suspension concentrate while ensuring high suspension rate, good flowability and excellent efficacy, thus expanding its reliable application in different climate zones around the world and providing a feasible path for developing multifunctional, high-thermal-stability compound fungicide suspension systems.

[0006] The inventors of this invention used various products of the company to study the extension of the crystallization time of suspensions containing pyraclostrobin, and found that the polymer adjuvant G-101 can extend the crystallization time of single-agent and compound formulations of pyraclostrobin, and can also improve the stability of the suspension. Summary of the Invention

[0007] Specifically, the present invention provides a use of polymeric adjuvant G-101, wherein the use is to add polymeric adjuvant G-101 to a suspension containing pyraclostrobin to delay the crystal precipitation of pyraclostrobin contained therein.

[0008] Preferably, in the above-mentioned uses, the mass content of pyraclostrobin in the suspension is 10% to 30%, and the mass content of polymeric adjuvant G-101 in the suspension is 3% to 6%.

[0009] "Polymer Additive G-101" is a trade name, also known as suspending agent functional additive G-101. In the following text, "Polymer Additive G-101" will be used to refer to this additive. Polymer Additive G-101 is developed, produced, and sold by Shantou Shengtai New Material Technology Development Co., Ltd. Polymer Additive G-101 is a polymer emulsion dispersant with wetting, dispersing, and emulsifying properties. It appears as an emulsion (at 25°C), has a slight raw material odor, a solid content greater than or equal to 25.0%, and a pH value (2.0% aqueous solution, 25°C) of 4.0–6.0.

[0010] Preferably, the above-mentioned uses further include adding the polymeric adjuvant G-101 to the suspension containing pyraclostrobin to reduce water separation during hot storage and inhibit particle size growth during room temperature storage. Addressing the two major stability defects of pyraclostrobin-containing suspensions during storage—water separation during hot storage and particle size growth at room temperature—the addition of the polymeric adjuvant G-101 to the formulation optimizes and improves these issues, comprehensively enhancing the physical and chemical stability of the suspension and ensuring stable performance throughout its shelf life.

[0011] Preferably, in the above-mentioned uses, the mass content of polymeric additive G-101 in the suspending agent is 3% to 4%, and more preferably, the mass content of polymeric additive G-101 in the suspending agent is 3%.

[0012] Preferably, in the above-mentioned uses, the suspending agent further comprises dispersant G-725, and the mass content of dispersant G-725 in the suspending agent is 1% to 3%, and more preferably, the mass content of dispersant G-725 in the suspending agent is 2%.

[0013] Dispersant G-725 is developed, produced and sold by Shantou Shentai New Material Technology Development Co., Ltd. It is a light yellow liquid (at 25°C) with a faint raw material odor. Its solid content is greater than or equal to 15.0%, and its pH value (2.0% aqueous solution, 25°C) is 7.0 to 10.0.

[0014] Preferably, in the above-mentioned uses, the suspending agent further comprises a wetting and dispersing agent G-625, wherein the mass content of the wetting and dispersing agent G-625 in the suspending agent is 0.5% to 2%, and more preferably, the mass content of the wetting and dispersing agent G-625 in the suspending agent is 1%.

[0015] Wetting and dispersing agent G-625 is developed, produced and sold by Shantou Shentai New Material Technology Development Co., Ltd. It is a light yellow liquid (at 25°C) with a faint raw material odor. The solid content is greater than or equal to 93.0%, and the pH value (2.0% aqueous solution, 25°C) is 7.0 to 9.0.

[0016] Preferably, in the above-mentioned uses, the suspending agent further includes a thickener, which is selected from one or two of xanthan gum, magnesium aluminum silicate, and silica. The mass content of the thickener in the suspending agent is 0.1% to 1.5%, preferably, the mass content of the thickener in the suspending agent is 0.4% to 1.3%.

[0017] Preferably, in the above-mentioned uses, the suspending agent further comprises one or more of antifreeze, defoamer, and preservative.

[0018] Preferably, in the above-mentioned uses, the antifreeze is selected from one or two of propylene glycol, ethylene glycol, glycerol, and polyethylene glycol, and the mass content of the antifreeze in the suspension is 3% to 8%.

[0019] Preferably, in the above-mentioned uses, the defoamer is selected from one or more of modified siloxanes, polyoxypropylene glycerol ethers, polyglycerol, and fatty acid defoamers, and the mass content of the defoamer in the suspension is 0.1% to 0.5%.

[0020] Preferably, in the above-mentioned uses, the preservative is selected from one or more of sodium benzoate, sorbic acid, potassium sorbate, p-hydroxybenzoate, benzisothiazolinone, and citric acid, and the mass content of the preservative in the suspension is 0.05% to 0.3%.

[0021] Preferably, in the above-mentioned uses, the suspension further comprises a second active ingredient, which is selected from one or more of the following: thiophanate-methyl, ethirimol, difenoconazole, propiconazole, cyazofamid, quinoline copper, cyazofamid, fluopyram, chlorfluazuron, azoxystrobin, pyraclostrobin, tebuconazole, pyraclostrobin, pyraclostrobin, pyraclostrobin, fluopyram, fluopyram, fenoxystrobin, imidacloprid, flutriafol, tebuconazole, hexaconazole, prothioconazole, flusilazole, cyproconazole, triadimefon, triadimefon, paclobutrazol, tebuconazole, and thifluzamide.

[0022] Preferably, in the above-mentioned uses, the second active ingredient is selected from one of fluopyram and flutriafol.

[0023] Preferably, in the above-mentioned uses, the second active ingredient accounts for 1% to 30% of the mass of the suspension, and the sum of the mass of pyraclostrobin and the second active ingredient accounts for 15% to 50% of the mass of the suspension.

[0024] The present invention also provides a suspension containing pyraclostrobin, wherein the suspension contains the active ingredient pyraclostrobin and the polymeric adjuvant G-101, wherein the polymeric adjuvant G-101 accounts for 3% to 6% of the mass of the suspension.

[0025] Preferably, the above-mentioned suspending agent further includes dispersant G-725, wherein the dispersant G-725 accounts for 1% to 3% of the mass content of the suspending agent, and more preferably, the mass content of dispersant G-725 in the suspending agent is 2%.

[0026] Preferably, the suspending agent further comprises a wetting and dispersing agent G-625, wherein the mass content of the wetting and dispersing agent G-625 in the suspending agent is 0.5% to 2%, and more preferably, the mass content of the wetting and dispersing agent G-625 in the suspending agent is 1%.

[0027] Preferably, the suspending agent further comprises a thickener selected from one or two of xanthan gum, magnesium aluminum silicate, and silica. The mass content of the thickener in the suspending agent is 0.1% to 1.5%, preferably 0.4% to 1.3%.

[0028] Preferably, the suspending agent further comprises one or more of antifreeze, defoamer, and preservative.

[0029] Preferably, in the above-mentioned suspending agent, the antifreeze agent refers to one or two of propylene glycol, ethylene glycol, glycerol, and polyethylene glycol, and the mass content of the antifreeze agent in the suspending agent is 3% to 8%.

[0030] Preferably, in the above-mentioned suspending agent, the defoamer is selected from one or more of modified siloxanes, polyoxypropylene glycerol ethers, polyglycerol, and fatty acid defoamers, and the mass content of the defoamer in the suspending agent is 0.1% to 0.5%.

[0031] Preferably, in the above-mentioned suspending agent, the preservative is selected from one or more of sodium benzoate, sorbic acid, potassium sorbate, p-hydroxybenzoate, benzisothiazolinone, and citric acid, and the mass content of the preservative in the suspending agent is 0.05% to 0.3%.

[0032] Preferably, the above-mentioned suspending agent further comprises a second active ingredient, which is selected from one or more of the following: thiophanate-methyl, ethirimol, difenoconazole, propiconazole, cymoxanil, copper quinoline, cyazofamid, fluopyram, chlorfluazuron, azoxystrobin, pyraclostrobin, tebuconazole, pyraclostrobin, pyraclostrobin, pyraclostrobin, fluopyram, fluopyram, fenoxystrobin, imidacloprid, flutriafol, tebuconazole, hexaconazole, prothioconazole, flusilazole, cyproconazole, triadimefon, triadimefon, paclobutrazol, tebuconazole, and thifluzamide.

[0033] Preferably, in the above-mentioned suspending agent, the second active ingredient is selected from one of fluopyram and flutriafol.

[0034] Preferably, in the above-mentioned suspension, the second active ingredient accounts for 1% to 30% of the mass of the suspension, and the sum of the mass of pyraclostrobin and the second active ingredient accounts for 15% to 50% of the mass of the suspension.

[0035] The present invention also provides a method for preparing the above-mentioned suspension containing pyraclostrobin, the method comprising the following steps: Step 1: According to the mass content, mix polymeric additive G-101, dispersant G-725, wetting and dispersing agent G-625, magnesium aluminum silicate, antifreeze, defoamer, preservative and water thoroughly until completely dispersed. Then add pyraclostrobin technical and / or the second active ingredient and mix evenly. Homogenize at high speed for 5 min to 10 min until the mixture is uniform and obtain the material. Step 2: Transfer all the material prepared in Step 1 to a sand mill. Add zirconia beads with a particle size of 1-1.6 mm at a ratio of material volume to zirconia bead volume of 1:(0.7-4.0). Seal the sand mill and start the stirring and cooling system. Sand mill at a speed of 1500-3000 r / min. During the sand milling process, heat the material to 60℃-70℃ using a hot water jacket and maintain this temperature for 20-40 minutes. Then, gradually cool the material to 30℃-40℃ using a cold water jacket and maintain this temperature for 20-40 minutes before stopping the sand milling. Step 3: After sand milling, filter the zirconia beads, add xanthan gum curing solution, stir evenly, and then homogenize at a speed of 500-10000 r / min for 5-10 minutes. Finally, discharge the material to obtain a suspension containing pyraclostrobin.

[0036] Preferably, in the above method, the xanthan gum curing solution is a 1.5% xanthan gum aqueous solution.

[0037] Preferably, in the above method, the volume ratio of the material to the zirconium oxide beads is 1:(2.5-4.0).

[0038] Preferably, in the above method, the volume ratio of the material to the zirconium oxide beads is 1:(0.7-1.5).

[0039] The above-mentioned preparation process of the present invention solves the problems of crystal precipitation, poor stability and insufficient efficacy of traditional suspensions under high temperature conditions. Its advantage is that it significantly slows down the crystallization rate of active ingredients during high temperature storage or use, improves the thermal stability and physicochemical stability of the suspension, and thus extends the shelf life of the preparation and the duration of efficacy during use.

[0040] The above method departs from the traditional practice of low-temperature sand milling throughout the entire process, innovatively introducing a segmented temperature-controlled sand milling strategy of first heating and then cooling. First, the material is heated to 60℃~70℃ under the action of a hot water jacket, and sand milling is maintained at this temperature for 20~40 minutes. Because pyraclostrobin technical material can partially melt or soften within this temperature range, the originally solid technical material particles transform into a liquid-like or highly fluid micro-region, allowing dispersants, wetting agents, and other adjuvant molecules to more fully penetrate, adsorb, and coat the surface of the molten pyraclostrobin, forming a more stable and uniform interfacial structure. This "pre-dispersion and coating" effect at the microscopic level enhances the compatibility and binding force between the technical material particles and the liquid phase system. Subsequently, the temperature is gradually lowered to 30℃~40℃ using a cold water jacket, and sand milling continues at this temperature for another 20~40 minutes, allowing the molten pyraclostrobin, which has fully reacted with the adjuvants, to re-solidify into fine particles. This "melting-mixing-re-solidification" process is equivalent to pre-constructing a stable protective layer of additives inside and on the surface of the particles, hindering the migration and rearrangement of molecules under subsequent high-temperature conditions, thereby delaying the crystal nucleation and growth process. Therefore, when the suspension is subjected to a high-temperature environment again, the solidified particles are not easy to melt and recrystallize rapidly, resulting in a longer crystal formation time, a more stable system, and ultimately improved thermal storage stability and efficacy persistence of the formulation.

[0041] The beneficial effects of this invention are: This invention pioneers a heat-storage and anti-water separation mechanism using the polymeric adjuvant G-101 as the main stabilizer in pyraclostrobin-containing suspensions, overcoming the industry-wide problem of easy high-temperature stratification in traditional pyraclostrobin-containing suspensions. This invention clarifies the core role of the polymeric adjuvant G-101 in suspensions: by constructing a high-temperature stable three-dimensional network structure and utilizing steric hindrance, it solves the liquid-liquid separation problem caused by intensified Brownian motion of particles at high temperatures in traditional suspensions. Traditional suspensions cannot meet the stringent requirements of tropical regions or summer transportation; the suspension of this invention can achieve 14 days of heat storage without water separation, proving that it inhibits the exudation of the dispersion medium at high temperatures by improving the viscoelasticity of the continuous phase and the repulsive force between particles. This innovation expands the product's applicable climatic range, avoids the chain reaction problems such as uneven concentration of active ingredients and decreased suspension rate caused by heat storage water separation, and ensures the efficacy stability of pyraclostrobin-containing suspensions after high-temperature processing or storage. The introduction of polymeric additive G-101 provides a new approach to the thermal stability design of pyraclostrobin suspensions, breaking the limitation that relying on thickeners makes it difficult to cope with high-temperature challenges, and has significant industry-leading value.

[0042] This invention reveals the synergistic anti-crystallization mechanism of polymeric adjuvant G-101 and dispersant G-725, doubling the storage period after conversion from heat storage to room temperature. This invention innovatively discovers the synergistic effect of polymeric adjuvant G-101 and dispersant G-725, overcoming the technical bottleneck of easy crystallization in suspensions stored at room temperature through a dual-mechanism combination of "main stable network construction + crystal facet selective inhibition." The crystal-free period of pyraclostrobin suspension using only polymeric adjuvant G-101 after conversion from heat storage to room temperature is extended by more than 35 days. With the combined application of dispersant G-725, the crystal-free period is extended to more than 70 days, doubling the storage period. This allows suspension products containing pyraclostrobin to meet the time requirements for commercial storage and distribution, significantly reducing the risk of efficacy loss due to crystallization, and ensuring uniform dispersion and target deposition efficiency during spraying.

[0043] The present invention achieves synergistic optimization of the lifecycle stability of suspension concentrates, with overall performance surpassing existing technologies. The pyraclostrobin-containing suspension concentrate of the present invention optimizes the lifecycle performance of the suspension concentrate in terms of "initial dispersibility – thermal storage stability – room temperature storage stability – long-term particle size control," ensuring excellent dispersibility and efficacy throughout its entire lifecycle. This innovative effect of lifecycle optimization upgrades the suspension concentrate from "short-term usability" to "long-term reliability," significantly reducing quality control costs in production, transportation, and use, and providing a high-performance solution for the industrial-scale promotion of pyraclostrobin-containing suspension concentrates.

[0044] This invention reduces production costs and environmental risks, promoting the development of green and efficient pesticide formulations. The compound system of this invention improves performance while simultaneously controlling production costs and environmental risks by reducing adjuvant dosage and optimizing the formulation structure. Traditional suspension concentrates often require large amounts of thickeners or other adjuvants to improve stability, resulting in complex formulations, high costs, and potential increased environmental residues. In contrast, this invention requires only 3%–6% by mass of the polymeric adjuvant G-101 to achieve full-cycle stability. From an industry perspective, the improved stability of this formulation reduces returns and waste due to storage failure. From a user perspective, the long shelf life and stable efficacy reduce the frequency of repeated applications, indirectly reducing pesticide usage and ecological risks. This innovative effect of "high performance – low cost – low environmental impact" aligns with the development trend of green pesticide formulations and has significant economic and social benefits. Detailed Implementation

[0045] The materials used in the following embodiments are as follows: Polymer additive G-101 is produced by Shantou Shentai New Material Technology Development Co., Ltd. Dispersant G-725 is produced by Shantou Shentai New Material Technology Development Co., Ltd. Wetting and dispersing agent G-625 is produced by Shantou Shengtai New Material Technology Development Co., Ltd. Xanthan gum curing solution is an aqueous solution with a xanthan gum content of 1.5%, also known as "1.5% xanthan gum".

[0046] Example 1: Preparation and crystallization investigation of 25% pyraclostrobin suspension.

[0047] First, a single-agent suspension of pyraclostrobin was prepared. The raw material components and contents of the suspension were set as shown in Table 1 below. The mass, particle size and crystallization of the suspension were studied when the content of polymeric adjuvant G-101 was 3%, 6% and 9%.

[0048] Table 1. Ingredients of 25% Pyraclostrobin Suspension Concentrate

[0049] The preparation methods for the five suspension samples in Table 1 above are as follows: Step 1: Pre-dispersion First, add the calculated amount of deionized water to the mixing tank. Then, while stirring, sequentially add the polymeric additive G-101, dispersant G-725, magnesium aluminum silicate, ethylene glycol, polyoxypropylene glycerol ether, and benzisothiazolinone. Stir thoroughly for 15 minutes until all powdered additives are completely and evenly dispersed, forming a transparent or semi-transparent pre-dispersion liquid. Next, add 98% pyraclostrobin technical grade and continue stirring until the technical grade particles are fully wetted. Finally, turn on the high-speed homogenizer and homogenize at 8000 rpm for 5 minutes to obtain a uniform and fine initial material.

[0050] The specific feeding amount and process for each sample in step one are as follows: BZ-00: Add 48.6 parts of water, 2 parts of dispersant G-725, 0.4 parts of magnesium aluminum silicate, 4 parts of ethylene glycol, 0.4 parts of polyoxypropylene glycerol ether, and 0.1 parts of benzisothiazolinone. After stirring and dispersing, add 25.5 parts of pyraclostrobin technical grade.

[0051] BZ-01: Add 47.6 parts of water, 3 parts of polymeric additive G-101, 0.4 parts of magnesium aluminum silicate, 4 parts of ethylene glycol, 0.4 parts of polyoxypropylene glycerol ether, and 0.1 parts of benzisothiazolinone. After stirring and dispersing, add 25.5 parts of pyraclostrobin technical grade.

[0052] BZ-02: Add 45.6 parts of water, 3 parts of polymeric additive G-101, 2 parts of dispersant G-725, 0.4 parts of magnesium aluminum silicate, 4 parts of ethylene glycol, 0.4 parts of polyoxypropylene glycerol ether, and 0.1 parts of benzisothiazolinone. After stirring and dispersing, add 25.5 parts of pyraclostrobin technical grade.

[0053] BZ-03: Add 42.6 parts of water, 6 parts of polymeric additive G-101, 2 parts of dispersant G-725, 0.4 parts of magnesium aluminum silicate, 4 parts of ethylene glycol, 0.4 parts of polyoxypropylene glycerol ether, and 0.1 parts of benzisothiazolinone. After stirring and dispersing, add 25.5 parts of pyraclostrobin technical grade.

[0054] BZ-04: Add 39.6 parts of water, 9 parts of polymeric additive G-101, 2 parts of dispersant G-725, 0.4 parts of magnesium aluminum silicate, 4 parts of ethylene glycol, 0.4 parts of polyoxypropylene glycerol ether, and 0.1 parts of benzisothiazolinone. After stirring and dispersing, add 25.5 parts of pyraclostrobin technical grade.

[0055] Step 2: Sanding Transfer all the material prepared in step one to a sand mill. Add zirconia beads with a particle size of 1-1.6 mm at a material volume to zirconia bead volume ratio of 1:1.3. Seal the sand mill, start the stirring and cooling system, and perform sand milling at a speed of 1500 r / min. During the sand milling process, heat the material to 70°C using a hot water jacket and maintain this temperature for 30 minutes. Then, gradually cool the material to 35°C using a cold water jacket and maintain this temperature for 30 minutes before stopping the sand milling.

[0056] Step 3: Maturation and Discharging After sand milling, the material in the sand mill is pumped out and filtered through a sieve to remove zirconia beads, and the filtrate is collected. The filtrate is transferred to a clean discharge tank, and 19 parts of pre-prepared xanthan gum curing solution are added while stirring. The mixture is stirred for 20 minutes to ensure homogeneity. Subsequently, a high-speed homogenizer is turned on again and homogenized at 5000 r / min for 5 minutes to eliminate any possible agglomerates and stabilize the system. Finally, the resulting finished material is discharged, metered, and packaged to obtain the corresponding 25% pyraclostrobin suspension products BZ-00, BZ-01, BZ-02, BZ-03, and BZ-04.

[0057] For the suspending agents prepared by the above method, the particle size, suspension rate and 200-mesh wet sieve were measured directly after discharge. The results for each sample are shown in Table 2 below.

[0058] Table 2. Test results of pyraclostrobin suspension concentrate output quality.

[0059] In Table 2 above, "√" indicates that the product is qualified. The suspension rate and 200-mesh wet sieve of BZ-00, BZ-01, BZ-02, BZ-03 and BZ-04 are all qualified.

[0060] The above-mentioned suspension samples BZ-00, BZ-01, BZ-02, BZ-03, and BZ-04 were subjected to heat storage at 54°C for 14 days. The quality of the suspensions was checked on day 1, day 7, and day 14. The specific results are shown in Table 3 below.

[0061] Table 3. Thermal storage stability of pyraclostrobin suspension concentrate

[0062] In Table 3 above, "√" indicates qualified. BZ-02 and BZ-03 are qualified after being stored at 54℃ for 14 days, meeting the quality requirements of suspending agents.

[0063] The above-mentioned heat-stored products were transferred to a room temperature of 15℃~35℃. The crystallization of the suspension samples was observed every 7 days. Then, after 91 days, the D90 of the suspension was measured. The crystallization and particle size are shown in Table 4 below.

[0064] Table 4. Crystallization and particle size of pyraclostrobin suspension concentrate during heat storage and transition to ambient temperature.

[0065] In Table 4 above, "×" indicates that crystallization has occurred in the product, and "√" indicates that crystallization has not occurred. The method for judging crystallization is as follows: Under room temperature conditions, visually inspect the sample to see if there are needle-like or flaky crystals at the bottom of the bottle or on the wall, or if there is any precipitate. If crystals or precipitate are present, scrape off a small amount of crystals or precipitate and crush it by hand. If it feels gritty, it is determined that crystallization has occurred. In Table 4, 7, 14, 21... represent the number of days from thermal storage to room temperature storage. In the tables below regarding crystallization and particle size during the transition from thermal storage to room temperature, these numbers also represent the number of days from thermal storage to room temperature storage.

[0066] As can be seen from the results in Tables 2 to 4 above, the polymeric adjuvant G-101 exhibits a significant stabilizing effect in 25% pyraclostrobin suspension: BZ-00 without the addition of polymeric adjuvant G-101 showed 16% water precipitation after 7 days of heat storage at 54℃, and the water precipitation increased to 20% after 14 days. Crystallization began on the 21st day after the heat storage was turned to room temperature (it may actually be earlier than the 21st day, because the observation was done every 7 days, so the observation day is used to describe the time of crystallization, and this will be understood in the following analysis without further explanation). After 91 days, the particle size D90 increased to 12.3 μm, indicating that the system is prone to phase separation and crystal precipitation. BZ-02 showed no water precipitation during 14 days of heat storage at 54℃, and crystallization was not observed until 77 days after the heat storage was turned to room temperature. After 91 days, the particle size only increased to 3.2 μm. This shows that under appropriate ratios, polymeric adjuvant G-101 can inhibit phase separation and crystal growth to the greatest extent. The likely reason is that the hydrophobic benzene ring of the polymeric adjuvant G-101 can undergo π-π interactions with pyraclostrobin molecules, achieving strong adsorption. Meanwhile, the hydrophilic carboxyl / ester groups form a stable steric hindrance layer facing outwards, preventing particle aggregation and sedimentation during thermal storage and inhibiting water separation by increasing system viscosity and imparting thixotropy. Simultaneously, the dense polymer film formed by G-101 on the particle surface hinders the diffusion and migration of solute molecules and constructs a solvation layer with water molecules to increase the supersaturation threshold, thereby delaying crystal nucleation and growth, and maintaining a low increase in particle size during long-term storage. Therefore, it is evident that the polymeric adjuvant G-101, through multiple mechanisms of adsorption localization, interfacial film protection, and rheological regulation, not only significantly improves the thermal and storage stability of the suspension, but also, under optimal dosage and combination conditions, minimizes water separation, crystallization, and particle size growth.

[0067] The experiment showed that when the dosage of polymeric additive G-101 increased from 3% to 6% and then to 9% (corresponding to samples BZ-02, BZ-03, and BZ-04), although the water separation and particle size control in the initial stage of heat storage were still better than the blank sample BZ-00, the crystallization time and particle size growth control after the heat storage was transferred to room temperature showed an inverse trend: crystallization of BZ-03 (6% polymeric additive G-101) occurred at 70 days and the particle size increased to 4.2 μm at 91 days; crystallization of BZ-04 (9% polymeric additive G-101) occurred even earlier at 49 days and the particle size further increased to 6.3 μm, both of which were inferior to BZ-02 (3%). The performance of polymeric adjuvant G-101, which crystallized after 77 days and had a particle size of only 3.2 μm, indicates that there is an optimal dosage range for G-101 in the current system, approximately 3% to 6%. Exceeding this range weakens its effect in delaying crystallization. The principle behind this may be related to changes in the structure and distribution of the adsorption layer caused by excessively high concentrations of the polymeric adjuvant: at low to medium dosages (3% to 6%), G-101 molecules can uniformly and completely cover the surface of pyraclostrobin particles, forming a moderately thick and continuous interfacial film that effectively blocks the diffusion and recrystallization of solute molecules. However, when the dosage is further increased to 9%, the number of free polymer chains in the system increases, which may lead to multilayer adsorption or local accumulation on the particle surface, resulting in uneven thickness or even defects in the interfacial film. In some areas, the reduced steric hindrance leads to exposed crystal faces, providing nucleation sites for solute molecules and accelerating the crystallization process. In addition, high concentrations of the polymeric additive G-101 can significantly increase the viscosity of the aqueous phase and change the rheological properties of the system, which may inhibit the Brownian motion and uniform distribution of particles, leading to an increase in local concentration gradients and promoting crystal growth. At the same time, excessive polymer may cause chain entanglement or partial precipitation during storage, interfering with the continuity of the original stable network and weakening the steric barrier effect on particles. Therefore, it shows a decrease in effectiveness during the crystallization-sensitive stage of transitioning from thermal storage to room temperature.

[0068] Introducing dispersant G-725 into the polymeric additive G-101 further enhances their synergistic effect. This is most evident in BZ-02 (3% polymeric additive G-101 + 2% dispersant G-725). This formulation not only showed no water separation during 14 days of heat storage at 54℃, but also exhibited the latest crystallization after transitioning from heat storage to room temperature, with a particle size increase of only 3.2μm after 91 days. Its overall performance is superior to BZ-00 and BZ-01, which use polymeric additive G-101 or dispersant G-725 alone. Polymeric additive G-101 and dispersant G-725 complement each other in terms of interfacial adsorption, rheological regulation, and crystallization inhibition, significantly improving the overall stability and long-term dispersing performance of pyraclostrobin suspension. Under the optimal ratio of BZ-02, it achieved excellent performance with zero water separation during heat storage, the longest crystallization delay, and the smallest particle size increase.

[0069] As can be seen from Example 1 above, the polymeric adjuvant G-101 can delay the crystallization time of pyraclostrobin suspension, extending it to a maximum of 77 days. This is under the condition of 14 days of heat storage at 54°C, indicating that the polymeric adjuvant can significantly delay the crystallization of pyraclostrobin suspension. Under normal temperature storage conditions, the crystallization time of pyraclostrobin suspension will be longer, which is beneficial to the transportation, storage and application of the product.

[0070] This study investigates the compound formulation of pyraclostrobin and explores whether the polymer adjuvant G-101 can still delay the precipitation of pyraclostrobin crystals in compound formulations.

[0071] Example 2: Preparation and crystallization investigation of a compound suspension of flutriafol and pyraclostrobin.

[0072] The raw material components and their contents were prepared as shown in Table 5 below for the preparation of a 4.7% flutriafol·12.3% pyraclostrobin compound suspension.

[0073] Table 5. Ingredients of 4.7% Flutriafol·12.3% Pyraclostrobin Suspension Concentrate

[0074] Refer to the preparation method of the suspending agent in Example 1. Specifically, the three suspending agent samples in Table 5 above were prepared according to the following method.

[0075] Step 1: Pre-dispersion First, add the calculated amount of deionized water to the mixing tank. Then, while stirring, sequentially add the polymeric additive G-101, dispersant G-725, magnesium aluminum silicate, propylene glycol, polyoxypropylene glycerol ether, and benzisothiazolinone. Stir thoroughly for 15 minutes until all powdered additives are completely and evenly dispersed, forming a transparent or semi-transparent pre-dispersion. Next, add 97% flutriafol technical and 98% pyraclostrobin technical, and continue stirring until the technical particles are fully wetted. Finally, turn on the high-speed homogenizer and homogenize at 8000 r / min for 5 minutes to obtain a homogeneous initial mixture.

[0076] The specific feeding amount and process for each sample in step one are as follows: FHBZ-00: Add 58.2 parts water, 2 parts dispersant G-725, 1 part magnesium aluminum silicate, 4 parts propylene glycol, 0.4 parts polyoxypropylene glycerol ether, and 0.1 parts benzisothiazolinone. After stirring and dispersing, add 4.8 parts flutriafol technical and 12.5 parts pyraclostrobin technical.

[0077] FHBZ-01: Add 57.2 parts of water, 3 parts of polymeric additive G-101, 1 part of magnesium aluminum silicate, 4 parts of propylene glycol, 0.4 parts of polyoxypropylene glycerol ether, and 0.1 parts of benzisothiazolinone. After stirring and dispersing, add 4.8 parts of flutriafol technical and 12.5 parts of pyraclostrobin technical.

[0078] FHBZ-02: Add 55.2 parts of water, 3 parts of polymeric additive G-101, 2 parts of dispersant G-725, 1 part of magnesium aluminum silicate, 4 parts of propylene glycol, 0.4 parts of polyoxypropylene glycerol ether, and 0.1 parts of benzisothiazolinone. After stirring and dispersing, add 4.8 parts of flutriafol technical and 12.5 parts of pyraclostrobin technical.

[0079] Step 2: Sanding Transfer all the material prepared in step one to a sand mill. Add zirconia beads with a particle size of 1-1.6 mm at a material volume to zirconia bead volume ratio of 1:1.4. Seal the sand mill, start the stirring and cooling system, and perform sand milling at a speed of 1800 r / min. During the sand milling process, heat the material to 60°C using a hot water jacket and maintain this temperature for 20 minutes. Then, gradually cool the material to 40°C using a cold water jacket and maintain this temperature for 40 minutes before stopping the sand milling.

[0080] Step 3: Maturation and Discharging After sand milling, the material in the sand mill is pumped out and filtered through a sieve to remove zirconia beads, and the filtrate is collected. The filtrate is transferred to a clean discharge tank, and 17 parts of pre-prepared xanthan gum curing solution are added while stirring. The mixture is stirred for 20 minutes to ensure homogeneity. Subsequently, a high-speed homogenizer is turned on again and homogenized at 5000 r / min for 5 minutes to eliminate any possible agglomerates and stabilize the system. Finally, the resulting finished material is discharged, metered, and packaged to obtain the corresponding 4.7% flutriafol·12.3% pyraclostrobin suspension products FHBZ-00, FHBZ-01, and FHBZ-02.

[0081] For the suspending agents prepared by the above method, the particle size, suspension rate and 200-mesh wet sieve were measured directly after discharge. The results for each sample are shown in Table 6 below.

[0082] Table 6. Quality test results of flutriafol·pyraclostrobin suspension concentrate.

[0083] In Table 6 above, "√" indicates that the product is qualified. The suspension rate and 200-mesh wet sieve of FHBZ-00, FHBZ-01 and FHBZ-02 are all qualified.

[0084] The above-mentioned suspension samples FHBZ-00, FHBZ-01, and FHBZ-02 were subjected to heat storage at 54°C for 14 days. The quality of the suspensions was checked on day 1, day 7, and day 14. The specific results are shown in Table 3 below.

[0085] Table 7. Thermal storage stability of flutriafol·pyraclostrobin suspension concentrate

[0086] In Table 7 above, "√" indicates that it is qualified. FHBZ-01 and FHBZ-02 are qualified after being stored at 54℃ for 14 days, which meets the quality requirements of the suspending agent.

[0087] The above-mentioned heat-stored products were transferred to a normal temperature of 15℃~35℃, and the crystallization of the suspension samples was observed every 7 days. Then, after 91 days, the D90 of the suspension was measured. The crystallization and particle size are shown in Table 8 below.

[0088] Table 8. Crystallization and particle size of flutriafol·pyraclostrobin suspension concentrate during heat storage and conversion to ambient temperature.

[0089] In Table 8 above, "×" indicates that crystallization has occurred in the product, and "√" indicates that crystallization has not occurred in the product. The method for determining crystallization is the same as in Example 1.

[0090] Based on the experimental data above, FHBZ-00, which does not contain polymeric additive G-101, showed 7% water separation after 7 days of heat storage at 54℃, and the water separation reached 12% after 14 days, indicating that the system structure had been damaged. In contrast, FHBZ-01 and FHBZ-02, which contain 3% polymeric additive G-101, showed no water separation throughout the entire heat storage process under the same heat storage conditions. This indicates that polymeric additive G-101 can effectively maintain continuous phase change stability and inhibit water separation and phase change in a high-temperature environment. During the transition from heat storage to ambient temperature storage, FHBZ-00 crystallized on day 14, with the particle size increasing from an initial 2.6 μm to 9.4 μm at day 91. This indicates that in the absence of the polymeric adjuvant G-101, crystals easily precipitate and are accompanied by severe agglomeration. In contrast, the crystallization initiation time of FHBZ-01 was delayed until day 35, with the particle size only increasing to 4.8 μm. This demonstrates that the polymeric adjuvant G-101 not only plays a role during the heat storage stage but also slows down the crystallization kinetics of pyraclostrobin and reduces the particle growth rate under ambient temperature conditions. Furthermore, the initial particle size of FHBZ-01 (2.2 μm) is slightly smaller than that of FHBZ-00, suggesting that the polymeric adjuvant G-101 may also have a certain dispersing promoting effect.

[0091] By comparing FHBZ-01, which contains only polymeric additive G-101, and FHBZ-02, which contains both polymeric additive G-101 and dispersant G-725, it can be found that both exhibit consistent thermal storage stability, but show a significant synergistic effect in room temperature storage stability. FHBZ-02 and FHBZ-01 both passed the thermal storage tests at 1, 7, and 14 days, indicating that dispersant G-725's contribution to resisting high-temperature water separation is limited or can be masked by polymeric additive G-101. However, significant differences exist under room temperature conditions: FHBZ-01 showed crystallization on day 35 after transitioning to room temperature following thermal storage, while the crystallization initiation time for FHBZ-02 was delayed to day 63, nearly doubling the crystallization delay period. This suggests that dispersant G-725 has an additional inhibitory effect on crystal precipitation and particle agglomeration in a room temperature environment. From the particle size evolution perspective, FHBZ-01 had a D90 of 4.8 μm at 91 days, while FHBZ-02 only had 3.7 μm, indicating that the dual-agent system is better able to maintain the particle dispersion state. Regarding the initial particle size, FHBZ-02 had a D90 of 1.5 μm, which is not only superior to FHBZ-01's 2.2 μm, but also superior to FHBZ-00's 2.6 μm without any such agent. Dispersant G-725 may have worked with polymeric additive G-101 during the dispersion stage to optimize wetting and distribution, thereby achieving a finer initial particle size.

[0092] FHBZ-02, a formulation incorporating both polymeric additive G-101 and dispersant G-725, exhibits the best overall stability among the three, which can be rigorously described from three dimensions: initial state, thermal storage stability, and long-term stability at room temperature. Upon completion of the suspension product preparation, the particle size D90 was 1.5 μm, and the suspension rate and 200-mesh wet sieve performance were both qualified, indicating that the system has achieved a high level of dispersion and rheological properties. The synergistic effect of polymeric additive G-101 and dispersant G-725 results in a more uniform particle size distribution and good redispersibility. In the 54℃ thermal storage test, FHBZ-02 did not show any water separation after 1 day, 7 days, and 14 days, demonstrating thermal storage stability equal to or even better than FHBZ-01 using polymeric additive G-101 alone. This confirms that the dual-agent system possesses reliable high-temperature resistance and can maintain the integrity of the dosage form under hot climates or transportation conditions. In a more stringent long-term storage evaluation at room temperature, under conditions of heat storage followed by a return to room temperature, FHBZ-02 did not show crystallization until day 63, which is 28 days longer than FHBZ-01 using polymeric additive G-101 alone, and 49 days longer than FHBZ-00 without polymeric additive G-101, demonstrating a significant advantage in resisting crystallization. By day 91, its particle size had only increased to 3.7 μm, far smaller than FHBZ-01's 4.8 μm and FHBZ-00's 9.4 μm, indicating that the dual-additive system can effectively inhibit crystal growth and aggregation during storage. This full-cycle stability stems from the synergistic mechanism of polymeric additive G-101 maintaining system homogeneity at high temperatures and dispersant G-725 inhibiting crystal migration and aggregation at room temperature, allowing the active ingredient to maintain good dispersion and bioavailable form even after long-term storage. Therefore, this suspending agent has achieved comprehensive optimization in its formulation design, including initial performance, thermal storage durability, and shelf life after transitioning from thermal storage to ambient temperature, thus possessing high industrial application value and market competitiveness.

[0093] Example 3: Preparation and crystallization investigation of a compound suspension of fluopyram and pyraclostrobin.

[0094] The raw material components and their contents for preparing the compound suspension of 21.2% fluopyram·21.2% pyraclostrobin are shown in Table 9 below.

[0095] Table 9. Ingredients of 21.2% Fluopyram·21.2% Pyraclostrobin Suspension Concentrate

[0096] Refer to the preparation method of the suspending agent in Example 1. Specifically, the three suspending agent samples in Table 9 above were prepared according to the following method.

[0097] Step 1: Pre-dispersion First, add the calculated amount of deionized water to the mixing tank. Then, while stirring, sequentially add polymeric additive G-101, dispersant G-725, wetting and dispersing agent G-625, magnesium aluminum silicate, ethylene glycol, polyoxypropylene glycerol ether, and benzisothiazolinone. Stir thoroughly for 15 minutes until all powdered additives are completely and evenly dispersed, forming a transparent or semi-transparent pre-dispersion. Next, add 97% fluopyram technical and 98% pyraclostrobin technical, and continue stirring until the technical particles are fully wetted. Finally, turn on the high-speed homogenizer and homogenize at 8000 r / min for 5 minutes to obtain a uniform and fine initial material.

[0098] The specific feeding amount and process for each sample in step one are as follows: FBBZ-00: Add 41.8 parts of water, 2 parts of dispersant G-725, 1 part of wetting and dispersing agent G-625, 0.3 parts of magnesium aluminum silicate, 4 parts of ethylene glycol, 0.4 parts of polyoxypropylene glycerol ether, and 0.1 parts of benzisothiazolinone. After stirring and dispersing, add 21.8 parts of fluopyram technical and 21.6 parts of pyraclostrobin technical.

[0099] FBBZ-01: Add 40.8 parts of water, 3 parts of polymeric additive G-101, 1 part of wetting and dispersing agent G-625, 0.3 parts of magnesium aluminum silicate, 4 parts of ethylene glycol, 0.4 parts of polyoxypropylene glycerol ether, and 0.1 parts of benzisothiazolinone. After stirring and dispersing, add 21.8 parts of fluopyram technical and 21.6 parts of pyraclostrobin technical.

[0100] FBBZ-02: Add 38.8 parts of water, 3 parts of polymeric additive G-101, 2 parts of dispersant G-725, 1 part of wetting and dispersing agent G-625, 0.3 parts of magnesium aluminum silicate, 4 parts of ethylene glycol, 0.4 parts of polyoxypropylene glycerol ether, and 0.1 parts of benzisothiazolinone. After stirring and dispersing, add 21.8 parts of fluopyram technical and 21.6 parts of pyraclostrobin technical.

[0101] Step 2: Sanding Transfer all the material prepared in step one to a sand mill. Add zirconia beads with a particle size of 1-1.6 mm at a material volume to zirconia bead volume ratio of 1:1.5. Seal the sand mill, start the stirring and cooling system, and perform sand milling at a speed of 2500 r / min. During the sand milling process, heat the material to 70°C using a hot water jacket and maintain this temperature for 30 minutes. Then, gradually cool the material to 30°C using a cold water jacket and maintain this temperature for 30 minutes before stopping the sand milling.

[0102] Step 3: Maturation and Discharging After sand milling, the material in the sand mill is pumped out and filtered through a sieve to remove zirconia beads, and the filtrate is collected. The filtrate is transferred to a clean discharge tank, and 7 parts of pre-prepared xanthan gum curing solution are added while stirring. The mixture is stirred for 20 minutes to ensure homogeneity. Subsequently, a high-speed homogenizer is turned on again and homogenized at 5000 r / min for 5 minutes to eliminate any possible agglomerates and stabilize the system. Finally, the resulting finished material is discharged, metered, and packaged to obtain the corresponding 43.6% fluopyram·21.6% pyraclostrobin suspension products FBBZ-00, FBBZ-01, and FBBZ-02.

[0103] For the suspending agents prepared by the above method, the particle size, suspension rate and 200-mesh wet sieve were measured directly after discharge. The results for each sample are shown in Table 10 below.

[0104] Table 10. Test results of the discharge quality of fluopyram·pyraclostrobin suspension concentrate.

[0105] In Table 10 above, "√" indicates that the product is qualified. The suspension rate and 200-mesh wet sieve of FBBZ-00, FBBZ-01 and FBBZ-02 are all qualified.

[0106] The above-mentioned suspension samples FBBZ-00, FBBZ-01, and FBBZ-02 were subjected to heat storage at 54°C for 14 days. The quality of the suspensions was checked on days 1, 7, and 14. The specific results are shown in Table 11 below.

[0107] Table 11. Thermal storage stability of 43.6% fluopyram·21.6% pyraclostrobin suspension concentrate

[0108] In Table 11 above, "√" indicates that it is qualified. FBBZ-01 and FBBZ-02 are qualified after being stored at 54℃ for 14 days, which meets the quality requirements of the suspending agent.

[0109] The above-mentioned heat-stored products were transferred to a room temperature of 15℃~35℃. The crystallization of the suspension samples was observed every 7 days. Then, after 91 days, the D90 of the suspension was measured. The crystallization and particle size are shown in Table 12 below.

[0110] Table 12 Crystallization and Particle Size of Fluopyram·Pyraclostrobin Suspension Concentrate During Heat Storage and Transition to Room Temperature

[0111] In Table 12 above, “×” indicates that crystallization has occurred in the product, and “√” indicates that crystallization has not occurred in the product. The method for judging crystallization is the same as in Example 1.

[0112] Based on the performance test results of the above-mentioned suspending agents, the FBBZ-00 sample showed 6% water separation after 14 days of heat storage at 54℃, indicating that the system lacked an effective spatial stabilization or thickening mechanism, leading to liquid phase separation at high temperatures. In contrast, the FBBZ-01 sample with 3% polymeric additive G-101 remained qualified under the same heat storage conditions. At room temperature, FBBZ-00 crystallized after only 7 days, and the particle size increased to 17.1 μm after 91 days (significant crystal agglomeration and growth). The crystallization-free period of FBBZ-01 was extended to 35 days, with the particle size increasing to only 4.6 μm, demonstrating that polymeric additive G-101 can adsorb onto the surface of active ingredient particles or regulate interparticle forces. By inhibiting water separation during heat storage and crystallization after transitioning from heat storage to room temperature, polymeric additive G-101 extends the effective storage period of the suspending agent from less than two weeks to more than two months, significantly reducing the risk of product failure due to improper storage.

[0113] The synergistic effect of polymeric additive G-101 and dispersant G-725 is manifested in their complementary mechanism, which further enhances the storage stability of the suspension, especially showing a significant synergistic effect in the anti-crystallization performance during the transition from thermal storage to room temperature. Comparing the data of FBBZ-01 (containing only polymeric additive G-101) and FBBZ-02 (containing polymeric additive G-101 + dispersant G-725), we can see that: the anti-crystallization period of FBBZ-01 during the transition from thermal storage to room temperature is 42 days, while that of FBBZ-02 is extended to 70 days, nearly doubling the anti-crystallization period; after 91 days, the particle size of FBBZ-02 is 3.1 μm, smaller than that of FBBZ-01 (4.6 μm), indicating that the synergistic effect not only prolongs the stabilization period but also strengthens the inhibition of particle growth.

[0114] The FBBZ-02 sample, with the addition of polymeric additive G-101 and dispersant G-725, exhibited excellent stability in multiple dimensions. In terms of initial performance, FBBZ-02 had a particle size D90 of 1.9 μm (the finest of the three), and its suspension rate and 200-mesh wet sieve performance were both satisfactory, indicating that the combination of polymeric additive G-101 and dispersant G-725 did not affect dispersibility during processing; on the contrary, it may have improved initial fineness by synergistically optimizing particle surface characteristics. Regarding thermal stability, FBBZ-02 showed no water separation or stratification after 14 days of thermal storage at 54℃, comparable to FBBZ-01, indicating that the main stabilizing effect of polymeric additive G-101 sufficiently ensured liquid-phase stability at high temperatures, and the addition of dispersant G-725 did not weaken this performance. Its core advantage lies in its stability during room temperature storage. FBBZ-02 has a crystal-free period of up to 70 days, far exceeding the 42 days of FBBZ-01 and the 14 days of FBBZ-00. This means that the product can remain crystal-free for more than 3 months under normal storage conditions, meeting the time requirements for commercial distribution. In terms of long-term particle size control, the particle size of FBBZ-02 only increased to 3.1μm after 91 days (an increase of 63%), which is much lower than the 92% (2.4→4.6μm) of FBBZ-01 and the 490% (2.9→17.1μm) of FBBZ-00. This indicates that the two work together to effectively inhibit particle agglomeration and crystal growth, ensuring the uniformity of dispersion and consistency of efficacy during spraying. In summary, FBBZ-02 exhibits comprehensive advantages in stability, including excellent initial dispersion, resistance to water separation during thermal storage, resistance to crystallization over a long period at room temperature, and stable particle size over a long period. This verifies the crucial role of the combination of polymeric additive G-101 and dispersant G-725 in ensuring the overall stability of the suspension throughout its lifecycle.

[0115] The present invention has been described in detail above with reference to specific embodiments. However, the above description is only a preferred embodiment of the present invention and should not be construed as a limitation on the scope of protection of the present invention. Any equivalent substitutions or simple modifications made based on the technical solutions of the present invention, as long as their technical essence is the same as or similar to that of the present invention, should fall within the scope of protection of the present invention.

Claims

1. One use of polymeric adjuvant G-101, wherein the use is to add polymeric adjuvant G-101 to a suspension containing pyraclostrobin to delay the crystal precipitation of pyraclostrobin contained therein.

2. The use according to claim 1, characterized in that... The suspension contains 10% to 30% by mass of pyraclostrobin and 3% to 6% by mass of polymeric adjuvant G-101.

3. The use according to claim 2, characterized in that... The mass content of polymeric additive G-101 in the suspension is 3% to 4%.

4. The use according to claim 2, characterized in that... The suspending agent also contains dispersant G-725, and the mass content of dispersant G-725 in the suspending agent is 1% to 3%.

5. The use according to claim 4, characterized in that... The suspension also contains a wetting and dispersing agent G-625, and the mass content of the wetting and dispersing agent G-625 in the suspension is 0.5% to 2%.

6. The use according to any one of claims 1 to 5, characterized in that... The suspending agent also contains a second active ingredient, which is selected from fluopyram and flutriafol.

7. A suspension containing pyraclostrobin, wherein the suspension contains the active ingredient pyraclostrobin and the polymeric adjuvant G-101, wherein the polymeric adjuvant G-101 accounts for 3% to 6% of the mass of the suspension.

8. The suspending agent according to claim 7, characterized in that... The suspending agent also contains dispersant G-725, wherein the dispersant G-725 accounts for 1% to 3% of the mass of the suspending agent, and more preferably, the mass content of dispersant G-725 in the suspending agent is 2%.

9. The suspending agent according to claim 7, characterized in that... The suspension also contains a second active ingredient, which is selected from one of the following: thiophanate-methyl, ethirimol, difenoconazole, propiconazole, cymoxanil, quinoline copper, cyazofamid, fluopyram, chlorfluazuron, azoxystrobin, pyraclostrobin, acetamiprid, fenfluramid, fluopyram, fenfluramid, fenfluramid, imidacloprid, flutriafol, tebuconazole, hexaconazole, prothioconazole, flusilazole, cyproconazole, triadimefon, triadimefon, paclobutrazol, tebuconazole, and thifluzamide.

10. The suspending agent according to claim 9, characterized in that... The second active ingredient is selected from fluopyram and flutriafol.

Citation Information

Patent Citations

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