Stable agrochemical composition

Abstract

The present disclosure relates to gel emulsion compositions, methods of making and uses thereof.

Description

[0001] This invention relates to stable liquid chemical compositions, the preparation of such compositions, and methods of using such compositions, for example, to combat pests or as plant growth regulators. Background Technology

[0002] Gel emulsions and gel emulsion formulations are disclosed, for example, in WO 2019217770A1, WO 2019217775A1, WO 2011 / 162944, and WO 2011 / 137170. Gel emulsion formulations are designed to contain soft, gel-like, ductile polymer matrix microparticles. While many advantages of such formulations have been disclosed, there is a general lack of published research on the possible use of a wide variety of components and combinations thereof. Using different components and combinations thereof can alter the properties of a formulation. However, when components are changed, it is not always clear how a particular property will change (improve or deteriorate). Therefore, there remains a need for gel emulsion formulations with improved properties.

[0003] Furthermore, challenges have been observed during the preparation of gel emulsions and their scaling up in production. Large-volume production tends to flocculate and form larger particle sizes. This flocculation can result in overly viscous compositions that cannot be processed effectively. Therefore, new methods are needed to facilitate the large-scale production of gel emulsions. Summary of the Invention

[0004] Embodiments of this disclosure include a method comprising: incorporating a first composition into a second composition to form a third composition, wherein the first composition is substantially immiscible with the second composition, the first composition comprising an agrochemically active ingredient, and the first composition comprising a liquid curable, coagulating, or polymerizable resin; emulsifying the third composition such that the first composition is a dispersed phase and the second composition is a continuous phase of the third composition, optionally wherein the median diameter of the dispersed phase is less than 200 μm; adding a dispersant to the third composition after said emulsification to form a fourth composition; and achieving curing, coagulation, or polymerization of the liquid curable, coagulating, or polymerizable resin in the fourth composition to form polymer matrix microparticles having said agrochemically active ingredient distributed therein.

[0005] Additional embodiments include a manufacturing system comprising: a first container having a mixer configured to agitate and / or mix a liquid within the first container, and a heater configured to heat a liquid composition within the first container; a second container in fluid communication with the first container having a shearing system configured to apply shear to a liquid within the second container; a third container having a mixer configured to agitate and / or mix a liquid within the third container; and a pump system configured to transfer liquid between the first container and the second container.

[0006] This manufacturing system can be used in methods involving: loading a first container with a first composition comprising an agrochemically active ingredient and a liquid curable, coagulating, or polymerizable resin, optionally mixing or agitating the first composition; loading a second container with a second composition substantially immiscible with the first composition, optionally mixing or agitating the second composition; pumping the first composition from the first container into the second container containing the second composition to form a third composition; shearing the third composition with a shearing system to emulsify the third composition such that the first composition is a dispersed phase; preparing a dispersant composition in the third container; transferring the dispersant composition from the third container to the first container; transferring the third composition to the first container after shearing; and, after transferring the dispersant composition and the third composition, achieving the curing, coagulation, or polymerization of the liquid curable, coagulating, or polymerizable resin to form polymer matrix microparticles having the agrochemically active ingredient distributed therein.

[0007] The method described in this article can be used to prepare agricultural chemical compositions.

[0008] The compositions disclosed herein may include liquid dispersion compositions comprising: (a) a continuous phase; (b) at least one dispersed phase comprising polymer matrix particles, wherein the polymer matrix particles have: (1) a hardness of less than 6 MPa, (2) a colloidal solid material present at the interface with the continuous phase, and (3) an agrochemically active ingredient therein; and (c) a dispersant system comprising: (c1) a sulfonate dispersant and a polyacrylate copolymer, and / or (c2) an alkylated vinylpyrrolidone nonionic polyacrylate polymer.

[0009] The compositions disclosed herein can be applied to plants, plant propagation material, or sites where pests are present in an effective amount for killing pests. Attached Figure Description

[0010] Figure 1A The first step in the manufacturing system according to this disclosure is shown.

[0011] Figure 1B The second step in the manufacturing system according to this disclosure is shown.

[0012] Figure 1C The third step in the manufacturing system according to this disclosure is shown.

[0013] Figure 1D The fourth step in the manufacturing system according to this disclosure is shown.

[0014] Figure 2A The diagram shows the formation of the serum of the composition over time at various temperatures.

[0015] Figure 2BThe results of the composition on the helipath at various temperatures and storage times are shown.

[0016] Figure 2C The viscosity of various dispersants in the composition is shown.

[0017] Figure 2D The pH values ​​of the various dispersants in the composition are shown.

[0018] Figure 2E A binary diagram showing the clear liquid formation of various dispersants after storage at various temperatures is presented.

[0019] Figure 2F The results of lifting racks for various dispersants after storage at various temperatures are shown.

[0020] Figure 2G The lifting support and binary sedimentation results for various combinations of dispersants in the composition are shown.

[0021] Figure 2H The lifting support and sedimentation results for various combinations of dispersants in the composition are shown. Detailed Implementation

[0022] This disclosure relates to “gel” or “gel-like” polymer matrix particles containing captured agrochemicals, said agrochemicals being uniformly or non-uniformly distributed within such particles or existing in the form of domains within such particles, wherein the outer surface regions of these particles contain colloidal solid material. As used herein, the terms “gel” and “gel-like” are intended as non-limiting common descriptors and are not intended to define or limit the application of “gel” or “gel-like” to polymer particles.

[0023] Therefore, in one embodiment, the liquid dispersion composition of the present invention comprises: (a) Continuous phase; (b) at least one dispersed phase comprising polymer matrix particles, wherein the polymer matrix particles have: (1) a hardness of less than 6 MPa, (2) a colloidal solid material present at the interface with the continuous phase, and (3) an agrochemically active ingredient therein; and (c) A dispersant system comprising: (c1) sulfonate dispersants and polyacrylate copolymers, and / or (c2) Alkylated vinylpyrrolidone nonionic polyacrylate polymer.

[0024] In some embodiments, the polymer matrix particles may also be defined by the polymer content of the polymer matrix particles themselves. The polymer content of the polymer matrix particles can be calculated by taking the amount of polymer in the polymer matrix particles and dividing it by the total content of the polymer matrix particles (or dispersed phase / oil phase). As used herein, the calculation is based on weight. The polymer content of the polymer matrix particles may be, for example, less than 50% w / w, less than 45% w / w, less than 40% w / w, less than 35% w / w, less than 30% w / w, less than 25% w / w, less than 20% w / w, less than 15% w / w, or less than 10% w / w, or even less than 5% w / w. In specific embodiments, there is at least 1% polymer content.

[0025] As used herein, the term "particle" refers to a tiny part of a substance. Particles can include portions of substances such as solids, liquids, or gels.

[0026] In one embodiment, these chemical reagents are agricultural chemical active ingredients.

[0027] In one embodiment, the colloidal solid material is a Pickering colloidal emulsion stabilizer.

[0028] In one embodiment, GE includes captured agrochemicals that are uniformly or non-uniformly distributed within such particles or exist within such particles in the form of domains.

[0029] In the context of this invention, the average particle or droplet size represents a volume-weighted average, typically specified as Dv50, as determined by dynamic light scattering.

[0030] In the context of this invention, particle hardness is measured using nanoindentation technology. Nanoindentation technology has been widely used to characterize the mechanical properties at material surfaces. It is based on the instrument standards ASTM E2546 and ISO 14577. Nanoindentation uses an established method in which an indenter tip with a known geometry (typically tapered for relatively soft samples) is pressed into a specific site in the material by applying an increasingly larger normal load. Once a pre-set maximum value is reached, the normal load is reduced until complete relaxation occurs. During the experiment, the position of the indenter relative to the sample surface is precisely monitored using a high-precision capacitive sensor. The resulting load / displacement curves provide data on material-specific mechanical properties. The hardness, elastic modulus, and other mechanical properties of the material are calculated using established physical models. The high spatial resolution of nanoindentation allows for the testing of localized mechanical properties.

[0031] In one embodiment, the agrochemical active ingredient is either a solid and distributed within a dispersed phase, or a liquid and distributed within a dispersed phase.

[0032] In another embodiment, the dispersion concentrate of the liquid agrochemical composition used in this invention is formed using a curing agent, monomer, oligomer, prepolymer, or blend thereof (which exhibit slow curing or polymerization when combined with these curing agents under ambient conditions). Particularly suitable are those curing agents, monomers, oligomers, prepolymers, or blends thereof that, after being mixed with a curing agent, do not exhibit a significant increase in viscosity under ambient conditions for at least 15 minutes, more particularly 30 minutes, and most particularly 1 hour.

[0033] According to one embodiment of the invention, polymerizable thermosetting resins are understood to include all molecules that can be irreversibly polymerized or cured to form a polymer matrix that does not melt or deform at elevated temperatures below its thermal decomposition point. The polymerization reaction can be thermally initiated by the addition of a chemical curing agent or by appropriate irradiation to generate free radicals or ions, such as by visible, UV, microwave, or other electromagnetic irradiation or electron beam irradiation. Examples include phenolic plastics, urea, melamine, epoxides, polyesters, silicones, rubbers, polyisocyanates, polyamines, and polyurethanes. Furthermore, bioplastics or biodegradable thermosetting resins can be used, including epoxy or polyester resins derived from natural materials such as vegetable oils, soybeans, or wood.

[0034] According to another embodiment of the invention, polymerizable thermoplastic resins are understood to include all molecules that can be polymerized or cured to form a polymer matrix that can melt or deform at elevated temperatures below its thermal decomposition point. The polymerization reaction can be thermally initiated by the addition of a chemical curing agent or by suitable irradiation to generate free radicals or ions, such as by visible, UV, or other electromagnetic irradiation or electron beam irradiation. Examples of suitable olefinically unsaturated monomers include styrene, vinyl acetate, α-methylstyrene, methyl methacrylate, and those described in US2008 / 0171658. Examples of thermoplastic polymers for use in polymer particles that can be prepared by in-situ microemulsion polymerization include polymethyl methacrylate, polystyrene, polystyrene-co-butadiene, polystyrene-co-acrylonitrile, polyacrylate, alkyl polyacrylate, alkyl polyacetate, polyacrylonitrile, or copolymers thereof.

[0035] According to yet another embodiment of the invention, a solidifiable thermoplastic resin is understood to include all such molecules that can be dissolved in a volatile solvent such that the solvent can be evaporated by heating to produce a polymer matrix that can melt or deform at elevated temperatures below the thermal decomposition point. The volatile solvent is selected to be immiscible with the continuous aqueous phase and sufficiently volatile such that it can be readily removed from the composition by heating to temperatures below where any significant decomposition occurs. Examples include polymers of the olefinically unsaturated monomers described above, as well as polymers such as cellulose acetate, polyacrylates, polycaprolactone, and polylactic acid. Reference may also be made to polymethyl methacrylate, polystyrene, polyethyl vinyl acetate, cellulose acetate, polyacrylates, polyacrylonitrile, polyamides, polyalkylene terephthalate, polycarbonate, polyesters, polyphenylene ether, polysulfone, polyimide, polyetherimide, polyurethane, polyvinylidene chloride, polyvinyl chloride, polypropylene, and waxes, etc. In addition, bioplastics or biodegradable polymers such as thermoplastic starch, polylactic acid, polyhydroxyalkanoates, polycaprolactone, and polyamide esters are also suitable for preparing polymer particles. Examples of volatile solvents include alkanes such as hexane and heptane, aromatic solvents such as benzene and toluene, and halogenated solvents such as dichloromethane and trichloromethane. Other examples of suitable polymers and solvents are described in WO 2011 / 040956 A1.

[0036] As used herein, the terms “polymer matrix particles” or “polymer matrix microparticles” refer to polymer particles in which the density and polymer composition are substantially uniform throughout the particle itself.

[0037] The term "microparticle" is a term commonly used to describe particles of very small size. The polymer matrix particles of the present invention differ from microcapsules, which are composed of different shell walls and hollow cores. According to the present invention, the polymer matrix microparticles of the dispersed phase have Dv50 particle sizes ranging from 1 to 200 micrometers, more particularly from 1 to 100 micrometers, and most particularly from 1 to 80 micrometers and 1-30 micrometers.

[0038] In one embodiment, the suitable polymerizable resin and polymer solution are those that are substantially immiscible with the liquid used in the continuous phase.

[0039] In the context of this invention, colloidal solid materials are those whose properties are determined by their surface interactions with other materials. Colloidal solids therefore necessarily have properties typically exceeding 10 μm. 2Those with high specific surface area per g. For example, colloidal solids can stabilize emulsions of immiscible liquids, as described in, for example, WO 2008 / 030749. When used for this purpose, such colloidal solids may be referred to as Pickering colloids, colloidal emulsion stabilizers, or other equivalent terms. Functional tests to determine whether a colloidal solid can stabilize an emulsion as used herein are known. Not all colloidal solids can stabilize any given pair of immiscible liquids in an emulsion, and those skilled in the art can use such functional tests to identify suitable colloids.

[0040] In another embodiment, where the continuous phase is aqueous, the affinity of the aqueous liquid suitable for use in the continuous phase a) for the agrochemically active ingredient distributed in the dispersed phase b) is such that substantially all of the agrochemically active ingredient remains in the dispersed solid phase and substantially none migrates into the continuous phase. Those skilled in the art will be able to readily determine whether a particular aqueous liquid meets this criterion for a specific agrochemically active ingredient under consideration by following any standard test procedure for determining the partition coefficient of a compound (in this case, the agrochemically active ingredient in the dispersed phase) between the continuous and dispersed solid phases. Therefore, the dispersed phase b) is immiscible with the continuous phase a).

[0041] In another embodiment, the aqueous liquid suitable for use in the continuous phase a) is a solution of a water-soluble solute in water.

[0042] Suitable water-soluble solutes for use in the continuous phase include salts such as ammonium, and halides, nitrates, sulfates, carbonates, phosphates, nitrites, sulfites, nitrides, and sulfides of metals (such as those in Groups 1 to 12 of the periodic table). Other suitable solutes include sugars and osmotic substances such as polysaccharides, proteins, betaines, and amino acids.

[0043] In one embodiment, the aqueous liquid suitable for use in continuous phase a) is a mixture of water and a substantially water-miscible non-aqueous liquid. In the context of this invention, the term "substantially water-miscible" means a non-aqueous liquid that forms a single phase when it is present in water at a concentration of up to at least 50 wt%.

[0044] Suitable water-miscible non-aqueous liquids for use in continuous phase a) include, for example, propylene carbonate; water-miscible diols selected from ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, hexanediol, and polyethylene glycol having a molecular weight up to about 800; acetylated diols, such as di(propylene glycol) methyl ether acetate or propylene glycol diacetate; triethyl phosphate; ethyl lactate; γ-butyrolactone; water-miscible alcohols, such as propanol or tetrahydrofurfuryl alcohol; N-methylpyrrolidone; dimethyl lactamide; and mixtures thereof. In one embodiment, the water-miscible, essentially water-miscible liquid used in continuous phase a) is a solvent for at least one optional agrochemically active ingredient.

[0045] In another embodiment, the aqueous, substantially water-miscible liquid used in continuous phase a) is fully miscible with water in all proportions. Alternatively, the aqueous, substantially water-miscible liquid used in continuous phase a) is a waxy solid, such as polyethylene glycol having a molecular weight greater than about 1000, and the mixture of this waxy solid and water maintains a liquid state by forming the composition at elevated temperatures.

[0046] In another embodiment, the continuous liquid phase is a non-aqueous liquid. In yet another embodiment, the continuous liquid phase is a non-aqueous liquid that is substantially immiscible with water. The non-aqueous liquid that is immiscible with water may be selected from petroleum distillates, vegetable oils, silicone oils, methylated vegetable oils, refined paraffinic hydrocarbons, alkyl lactates, mineral oils, alkylamides, alkyl acetates, and mixtures thereof.

[0047] In another embodiment, the continuous phase comprises a substantially water-miscible non-aqueous liquid. The water-miscible non-aqueous liquid may be selected from the group consisting of: propylene carbonate, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, hexanediol, polyethylene glycol having a molecular weight of up to about 800, bis(propylene glycol) methyl ether acetate, propylene glycol diacetate, triethyl phosphate, ethyl lactate, γ-butyrolactone, propanol, tetrahydrofurfuryl alcohol, N-methylpyrrolidone, dimethyl lactamide, and mixtures thereof.

[0048] Those skilled in the art will appreciate that the amount of water, as well as the nature and amount of the non-aqueous, water-miscible liquid or water-soluble solute, can be varied to provide a mixed aqueous liquid suitable for use in the continuous phase a), and these amounts can be determined without experimental testing. In one embodiment, the aqueous continuous phase comprises 5 to 95 wt%, more preferably 30 to 90 wt%, of ethylene glycol, with the remainder being water. In another embodiment, the aqueous continuous phase comprises 5 to 95 wt%, more preferably 30 to 90 wt%, of glycerol, with the remainder being water.

[0049] In one embodiment, the liquid dispersion concentrate composition of the present invention comprises a mixture of GEs, each of which contains one or more chemical reagents (such as agricultural chemical active ingredients). Each of the chemical reagents is contained within the same or different dispersed phases GM, and each corresponding dispersed phase particle optionally contains a different polymer matrix as described above. Optionally, each corresponding dispersed phase may have a different particle size.

[0050] In one embodiment, the liquid dispersion concentrate composition of the present invention comprises a dispersed phase in the form of finely divided, suspended polymer particles, which contain colloidal solid material at their outer surfaces and contain at least one agrochemically active ingredient.

[0051] The advantages of the liquid dispersion concentrate compositions (e.g., gel emulsions) of the present invention include: extended storage stability; convenient incorporation of a variety of agrochemicals in different physical states into a dispersion of mutually compatible particles; improved surface adhesion, allowing deposits on said surface to dry; reduced likelihood of crop damage due to the presence of solvents or other phytotoxic agents; improved acute toxicity; and simplified handling for the user, as dilution with water or other liquid carriers is possible for preparing application mixtures; the compositions can be easily resuspended or redispersed with only minimal stirring, and are less prone to aggregation when diluted with fertilizer solutions for preparing application mixtures. As used herein, the term "storage stable" means that a given composition has a Dv50 that has changed by less than about 20% over a period of 6 months at 70°F. Agricultural chemical active ingredients

[0052] The term "agrochemically active ingredient" refers to a chemical or biological composition, such as those described herein, that is effective in killing, preventing, or controlling the growth of unwanted pests (e.g., plants, insects, mice, microorganisms, algae, fungi, bacteria, etc.) (e.g., a pest-killing active ingredient). The term can also be applied to compounds that act as adjuvants to promote the absorption and delivery of other active compounds. The term can also be applied to compounds that control plant growth in a desired manner (e.g., plant growth regulators), compounds that mimic the tolerance responses activated by natural systems found in plant species (e.g., plant activators), or compounds that reduce phytotoxic responses to herbicides (e.g., safeners). If more than one of these agrochemically active ingredients is present, the amount is biologically effective when the composition is diluted in a suitable volume of liquid carrier (e.g., water) and applied to the intended target (e.g., the leaves of a plant or its site), if necessary.

[0053] Examples of agricultural chemically active ingredients suitable for use in the continuous phase a) or dispersed phase b) according to the present invention include, but are not limited to: fungicides such as azoxystrobin, benzalkonium chloride, chlorothalonil, cyclohexane, azoxystrobin, difenoconazole, benzyloxydim, fludioxonil, dimethomorph, metalaxyl, paclobutrazol, azoxystrobin, propiconazole, azoxystrobin, fluazinam, tebuconazole, thiabendazole, and oxadiazon; herbicides such as acetochlor, metolachlor, atrazine, sphagnum molybdate, atrazine, pyrimethanil, fluazinam, furazolidone, dimethomorph, pyrimethanil, pyrimethanil, fluazinam, bromobutyrazosulfuron, bromosulfuron, bromosulfuron, butachlor, flupropyrazosulfuron, chlorpyrifos, styrax, butachlor, chlorpyrifos ... Amine, glyphosate, chlorpromazine, diquat, cyprodinil, indole-methyl, cyclohexane, isoxaflutole, barnyardgrass, chlorpyrifos, cypermethrin, cyclohexane, betaine, diquat, diquatyl, pyrimethanil, piperazine, metolachlor, isoamyl methyl methacrylate, dimethyl phenoxychloride, succinate, dichlorvos, terbuprofen, fenpyroxene, flusulfanilamide, EPTC, pendimethalin, ethylbutyrate, ethoxysulfuron-methyl, ethoxybenzamide, oxadiazon, succinate, tetrazolium-methyl methacrylate, methyl methacrylate, isopropyl methacrylate, chlorpyrifos, fluthiamethoxam, flufenoxuron, propyzoxystrobin, fluroxypyr, flumetsulam, fluorenyl butyl ester, flupyridine, furazolidone, fluthiamethoxam, indicarb, Isoxachlor, isoxaflutole, cycloxadiazon, linuron, bensulfuron-methyl, mesotrione, pyrazosulfuron, methylbenzylthiazoline, methyl sulfadiazon, pyranolol, metolachlor, sulfadiazon, methoxyfenozide, cyhalofop-p-ethyl, haloxyfop-methyl, haloxyfop-p-ethyl, haloxyfop-p-ethyl, cyhalofop-p-ethyl, acesulfame K, chlorpyrifos, cyhalofop-p-ethyl, cyhalofop-p-ethyl, betaine, clodinafop-propargyl, chlorpyrifos, acetochlor, cyhalofop-p-ethyl, fluazinam, pyrazosulfuron ... The following herbicides are listed: pyrazolynate, pyrazoxyfen, barnyardgrass, pyrazosulfuron, pyrazosulfuron, cycloriburoxime, simazine, cyprodinil, metolachlor, sulfadiazine, mesotrione, sulfadiazine, sulfadiazine, methoxyfenozide, terbufos, methoxyfenozide, thiamethoxam, thiamethoxam, thiamethoxam, styraxazol, styraxazol, fenbufos, fenbufos, trifluralin, and metribuzin; herbicide safeners, such as pyrazosulfuron, dichloropropene, pyrazosulfuron, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl, pyrazosulfuron-methyl; alkali metal, alkaline earth metal, thionium, or ammonium cations of pyrazosulfuron-methyl; pyrazosulfuron-methyl and pyrazosulfuron-methyl.Insecticides, such as abamectin, thiamethoxam, cyantraniliprole, emamectin benzoate, γ-cyhalothrin, imidacloprid, lambda-cyhalothrin and its enantiomers such as lambda-cyhalothrin, heptafluthrin, pymetrozine, benzalkonium chloride, and thiamethoxam; nematicides, such as thiazophos, bensulfuron-methyl, and aldicarb.

[0054] The total amount of agrochemical active ingredients in polymer matrix granules can be calculated by taking the amount of agrochemical active ingredients in the polymer matrix granules and dividing it by the total content of the polymer matrix granules. As used herein, the calculation is based on weight. The total content of agrochemical active ingredients can be, for example, less than 95% w / w, less than 90% w / w, less than 85% w / w, less than 80% w / w, less than 75% w / w, less than 70% w / w, less than 65% w / w, less than 60% w / w, less than 55% w / w, less than 50% w / w, less than 45% w / w, less than 40% w / w, less than 35% w / w, less than 30% w / w, less than 25% w / w, even less than 20% w / w, even less than 15% w / w, even less than 10% w / w, or about 5% w / w, depending on the specific agrochemical active ingredient and the solvent used to dissolve at least one agrochemical active ingredient in the granules. Typically, the amount of agricultural chemical active ingredients is at least 5% w / w of the granules.

[0055] In one embodiment, the active ingredient in the continuous phase may be in the form of a solution, emulsion, microemulsion, microcapsule, or particles or fine particles. In the context of this invention, fine particles are particles significantly smaller than the GE size of the dispersed phase, such that multiple (at least 10) active ingredient particles are present within each particle of the dispersed phase, while non-fine particles are particles only slightly smaller than the GE size of the dispersed phase, such that each polymer particle contains only a few active ingredient particles.

[0056] Another aspect of the invention includes a method for preventing or combating pest infestation of plant species and regulating plant growth by diluting a quantity of a concentrated composition with a suitable liquid carrier, such as water or liquid fertilizer, and applying it to plants, trees, animals, or sites (as desired). The formulation of the invention can also be combined with water in a continuous flow device in a spray application apparatus, eliminating the need for storage tanks for diluting the product.

[0057] Liquid dispersion concentrate compositions can be conveniently stored in containers, and poured out or pumped out of the containers or added with a liquid carrier before application.

[0058] If solid agrochemically active materials are available, the solid active ingredients can be milled to the desired particle size before being dispersed in a polymerizable resin (monomer, oligomer, and / or prepolymer, etc.) that will form GE. If necessary, these solids can be milled in a dry state using an air mill or other suitable equipment to achieve the desired particle size. The particle size can be a Dv50 particle size of about 0.2 to about 20 micrometers, suitably about 0.2 to about 15 micrometers, and more suitably about 0.2 to about 10 micrometers.

[0059] As used herein, the term "effective amount of an agrochemical" means the amount of an agrochemically active compound that adversely controls or alters a target pest or regulates plant growth (PGR). For example, in the case of herbicides, "effective amount of a herbicide" is the dosage of herbicide sufficient to control or alter plant growth. Controlling or altering effects include all deviations from natural development, such as killing, inhibiting, leaf burn, albinism, dwarfing, etc. The term "plant" means all tangible parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, culms, leaves, and fruits. In the case of fungicides, the term "fungicide" should mean material that kills or significantly inhibits the growth, proliferation, division, reproduction, or spread of fungi. As used herein, the terms "effective amount of a fungicide" or "effective amount of fungal control or reduction" associated with fungicides refer to the amount that will kill or significantly inhibit a significant number of fungi from growing, multiplying, dividing, reproducing, or spreading. As used herein, the terms “insecticide,” “nematicide,” or “acaricide” shall mean material that kills or significantly inhibits the growth, proliferation, reproduction, or spread of insects, nematodes, or mites, respectively. An “effective amount” of an insecticide, nematicide, or acaricide is the amount that will kill or significantly inhibit a significant number of insects, nematodes, or mites from growing, multiplying, reproducing, or spreading.

[0060] In one respect, as used herein, “regulating (plant) growth,” “plant growth regulator,” PGR, “regulating,” or “regulation” includes the following plant responses: inhibition of cell elongation, such as a reduction in stem height and internode distance, strengthening of stem walls, thereby increasing lodging resistance; compact growth in ornamental plants for economic production to improve the quality of the plant; promotion of better fruiting; increase in the number of ovaries to increase yield; senescence that promotes tissue formation, enabling fruit to fall off; defoliation of nurseries and ornamental shrubs and trees used for fall mail-order businesses; defoliation of trees to interrupt the chain of parasitic infection; ripening to plan harvesting by reducing the harvest to one or two pickings and interrupting the food chain of harmful insects.

[0061] On the other hand, "regulating (plant) growth," "plant growth regulator," "PGR," "regulating," or "regulation" also includes the use of compositions as defined according to the invention for increasing yield and / or improving the vigor of agricultural plants. According to one embodiment of the invention, the compositions of the invention are used to improve the tolerance of agricultural plants to stressors such as fungi, bacteria, viruses, and / or insects, as well as stressors such as heat stress, nutrient stress, cold stress, drought stress, UV stress, and / or salt stress.

[0062] For those skilled in the art, it is customary to select the application rate of the composition of the present invention relative to providing the desired level of pest-killing activity. The application rate will depend on factors such as the level of pest stress, plant conditions, weather, and growing conditions, along with the activity of the agrochemical active ingredient and any applicable labeling ratio limitations. Example

[0063] The present invention also relates to gel emulsion agricultural chemical compositions, said compositions comprising a) a continuous aqueous liquid phase, optionally comprising at least one agrochemically active ingredient; and b) At least one dispersed phase comprising polymer particles prepared from a curable or polymerizable resin or a coagulating thermoplastic polymer and comprising a colloidal solid material on their outer surface, wherein the particles have a hardness greater than 0.001 MPa and less than 6 MPa, and wherein the particles have at least one agrochemically active ingredient distributed therein.

[0064] Another aspect of the invention relates to a diluted aqueous spray composition for use in combating pests or regulating plant growth in a field, the composition comprising... a) A continuous aqueous phase comprising a suitable liquid carrier, such as water or liquid fertilizer, sufficient to obtain the desired final concentration of each of the active ingredients in the spray composition; b) At least one dispersed phase comprising polymer particles prepared from a curable or polymerizable resin or a coagulated thermoplastic polymer and comprising a colloidal solid material on their outer surface, wherein the particles have a hardness greater than 0.001 MPa and less than 6 MPa, and wherein the particles have at least one agrochemically active ingredient distributed therein; and c) Optionally, at least one agrochemically active ingredient is dispersed, dissolved, suspended, microemulsified, and / or emulsified in the liquid carrier.

[0065] In another embodiment, the present invention relates to a diluted biocide and / or PGR composition for ultra-low volume (ULV) application, the composition comprising: a) A continuous phase comprising a carrier solvent having a flash point above 55°C in an amount sufficient to obtain the desired final concentration of each of the active ingredients in the ULV composition. b) At least one dispersed phase comprising polymer particles prepared from a curable or polymerizable resin or a coagulating thermoplastic polymer and comprising a colloidal solid material on their outer surface, wherein the particles have a hardness greater than 0.001 MPa and less than 6 MPa, and wherein the particles have at least one agrochemically active ingredient distributed therein.

[0066] The present invention also relates to a method for combating or preventing pests or regulating the growth of such crops in crops containing useful plants, the method comprising: 1) Treating a desired area, such as a plant, plant part, or its location, with a concentrated composition, said composition comprising: a) A continuous aqueous liquid phase, optionally containing at least one agrochemically active ingredient, and also optionally containing at least one acidic or basic component; b) At least one dispersed phase comprising polymer particles prepared from a curable or polymerizable resin or a coagulated thermoplastic polymer and comprising a colloidal solid material on their outer surface, wherein the particles have a hardness greater than 0.001 MPa and less than 6 MPa, and wherein the particles have at least one agrochemically active ingredient distributed therein; or 2) If necessary, the concentrated composition is diluted in a suitable carrier (such as water, liquid fertilizer) or a carrier solvent having a flash point above 55°C, the amount of which is sufficient to obtain the desired final concentration of each of the agrochemical active ingredients; and then the desired area, such as a plant, plant part or its location, is treated with a diluted spray or ULV composition. crop

[0067] The term "plant" refers to all the tangible parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, flowers, culms, leaves, and fruits. The term "site" refers to the place where a plant is growing or is expected to grow.

[0068] The compositions according to the invention are suitable for all application methods conventionally used in agriculture, such as pre-emergence application, post-emergence application, post-harvest application, and seed dressing. The compositions according to the invention are suitable for application to crop areas pre-emergence or post-emergence.

[0069] The compositions according to the invention are also suitable for combating and / or preventing pests in crops with beneficial plants or for regulating the growth of such crops. In some embodiments, the compositions can be applied by any conventionally used method, including spraying, drenching, and wicking. One advantage of the GE of the formulations of the invention is that their small size allows for uniform coverage of the plant stems and leaves in areas with small distances between the particles of the formulation. Therefore, the formulations more effectively contact pests that damage plants.

[0070] Preferred useful plant crops include canola, cereals such as maize, barley, oats, rye, and wheat, cotton, soybeans, sugar beets, fruits, berries, nuts, vegetables, flowers, trees, shrubs, and turf. The components used in the compositions of this invention can be applied at different concentrations using various methods known to those skilled in the art. The application rate of these compositions will depend on the specific type of pest to be controlled, the required level of control, and the timing and method of application.

[0071] Crops should be understood to include those crops that have been conferred tolerance to herbicides or multiple classes of herbicides (e.g., ALS-inhibitors, GS-inhibitors, EPSPS-inhibitors, PPO-inhibitors, ACC enzyme-inhibitors, and HPPD-inhibitors) through conventional breeding methods or through genetic engineering. Examples of crops that have been conferred tolerance to imidazolinones (e.g., methoxyfenozide) through conventional breeding methods are... Summer rapeseed (canola). Examples of crops that have been genetically engineered to tolerate herbicides include, for example, glyphosate and glufosinate-resistant maize varieties. and The trademark is available for purchase.

[0072] Crops should also be understood as those that have been genetically engineered to resist harmful insects, such as Bt corn (resistant to the European corn borer), Bt cotton (resistant to the cotton boll weevil), and Bt potato (resistant to the Colorado beetle). An example of Bt corn is... The Bt 176 maize hybrid (Syngenta Seeds). Bt toxin is a protein naturally formed by the soil bacteria Bacillus thuringiensis. Examples of the toxin or transgenic plants capable of synthesizing such toxins are described in EP-A-451 878, EP-A-374 753, WO 93 / 07278, WO 95 / 34656, WO 03 / 052073, and EP-A-427 529. Examples of transgenic plants containing one or more genes encoding insecticidal resistance and expressing one or more toxins are... (Corn), Yield (corn), (cotton), (cotton), (potato), as well as Plant crops or their seed material can be both herbicide-resistant and insect-resistant (“cumulative” transgenic results). For example, seeds can express the insecticidal Cry3 protein while simultaneously being resistant to glyphosate.

[0073] Crops should also be understood to include those obtained through conventional breeding methods or genetic engineering and that contain so-called exported traits (such as improved storage stability, higher nutritional value, and improved aroma).

[0074] Other useful plants include turfgrass, which is planted for lawns, such as on golf courses, lawns, parks, and roadsides, or commercially, as well as ornamental plants such as flowers or shrubs.

[0075] A crop area is a land area on which cultivated plants have already grown or on which the seeds of those cultivated plants have been sown, as well as land areas on which those cultivated plants are expected to grow. Additives

[0076] Other active ingredients, such as herbicides, plant growth regulators, algaecides, fungicides, bactericides, viricides, insecticides, acaricides, nematicides, or molluscicides, may be present in the formulations of the present invention or may be added as barrel blends of these formulations.

[0077] The compositions of the present invention may further comprise other inert additives. Such additives include thickeners, flow enhancers, dispersants, emulsifiers, wetting agents, defoamers, biocides, lubricants, fillers, drift control agents, sedimentation enhancers, adjuvants, evaporation inhibitors, cryoprotectants, insect attractant odorants, UV protectants, fragrances, and similar additives. The thickener may be a soluble or water-swellable compound, such as xanthan gum polysaccharide (e.g., anionic heteropolysaccharides, such as...). 23 (Xanthan Gum (Rhodia, Cranbury, NJ)), alginate, guar gum, or cellulose; synthetic polymers, such as cellulose-based polymers, polycarboxylate esters, bentonite, montmorillonite, lithium montmorillonite, or attapulgite. The cryoprotectant may be, for example, ethylene glycol, propylene glycol, glycerol, diethylene glycol, sucrose, water-soluble salts such as sodium chloride, sorbitol, triethylene glycol, tetraethylene glycol, urea, or mixtures thereof. Representative defoamers are silicone oils, polydialkylsiloxanes, especially polydimethylsiloxane, fluoroaliphatic esters, or perfluoroalkylphosphonic acids or their salts and mixtures thereof. Suitable defoamers are polydimethylsiloxanes, such as Dow Defoamer A, defoamer B, or defoamer MSA. Representative biocides include 1,2-benzisothiazolin-3-one, as... GXL (Arch Chemicals) is available. Conventional surfactants may only be present at low concentrations because they are capable of forming micelles in the aqueous phase, as these micelles extract solvents, plasticizers, and / or active ingredients from GE. Therefore, while conventional surfactants can be used to control the viscosity of GE dispersions, at higher concentrations they may extract components from the particles and negate their advantages. Therefore, the compositions of the present invention may not contain conventional surfactants at concentrations higher than those at which they form micelles, referred to as the critical micelle concentration (CMC). For this reason, non-micelle polymeric dispersants are preferred for controlling the viscosity of GE dispersions. Examples of conventional surfactants that form micelles are: linear and branched alcohol ethoxylates and their acid esters, tristyryl-phenol ethoxylates and their acid esters, alkyl-phenol ethoxylates and their acid esters, linear or branched alkyl-aryl sulfonates such as dodecyl-benzenesulfonates, fatty acid ethoxylates, alkylamine ethoxylates, and block copolymers of ethylene oxide with higher alkyl oxides (propylene oxide, butane oxide). Examples of non-micelle polymeric dispersants include polyvinylpyrrolidone homopolymers with molecular weights between 15 and 120 kDa, polyvinylpyrrolidone-vinyl acetate random copolymers, lignin sulfonates, sulfonated urea-formaldehyde condensates, styrene-acrylic copolymers, comb polymers with alkyl backbones and polyacrylic acid side chains, alkylated polyvinylpyrrolidone, and other general non-emulsifying dispersants.

[0078] The compositions of the present invention can be mixed with fertilizers while still maintaining their stability. Dispersant (DPA)

[0079] Dispersants are well known in the art, and this selection will involve various factors depending on the given formulation. Preferred dispersants include, but are not limited to, polyvinylpyrrolidone homopolymers having a molecular weight between 15 and 120 kDa, random copolymers of polyvinylpyrrolidone and vinyl acetate, alkylated polyvinylpyrrolidone, lignin sulfonates, sulfonated urea-formaldehyde condensates, styrene-acrylic copolymers, comb polymers having an alkyl backbone and polyacrylic acid side chains, alkylated polyvinylpyrrolidone, and other general non-emulsifying dispersants.

[0080] Typically, the total amount of the dispersant system in the composition can be from 0.1% w / w to 25% w / w, preferably from 0.5% w / w to 10% w / w, and most preferably from 0.5% w / w to 5% w / w. For example, the dispersant system can comprise a mixture of dispersants: a first dispersant, a second dispersant, and a third dispersant. Although the total amount (w / w) of each dispersant can vary depending on the specific dispersant selected, the typical amount of each dispersant (e.g., the first dispersant, the second dispersant, or the third dispersant) is 0.1 to 25% w / w, preferably from 0.5 to 10% w / w, and most preferably from 0.5 to 5% w / w.

[0081] Therefore, the compositions disclosed herein comprise a dispersant system having at least one dispersant, at least two dispersants, at least three dispersants, or even at least four dispersants.

[0082] The ratio (w / w) of any two dispersants may include 5:1 to 1:5, 4:1 to 1:4, 3:1 to 1:3, 2:1 to 1:2, or about 1:1, or a mixture of such ratios. The ratio of any three dispersants may include 5-0.2:5-0.2:5-0.2; including 4-0.25:4-0.25:4-0.25; including 3-0.3:3-0.3:3-0.3; including 2-0.5:2-0.5:2-0.5; or a mixture of about 1:1:1, or a mixture of such ratios. The ratio of any four dispersants may include 5-0.2:5-0.2:5-0.2:5-0.2; 4-0.25:4-0.25:4-0.25:4-0.25; 3-0.3:3-0.3:3-0.3:3-0.3; 2-0.5:2-0.5:2-0.5; or a mixture of about 1:1:1:1 or such ratios.

[0083] In embodiments containing at least two dispersants, the w / w% of each dispersant may be from 0.1% w / w to 25% w / w, preferably from 0.5% w / w to 10% w / w, and most preferably from 0.5% w / w to 5% w / w.

[0084] However, it has now been found that, in some embodiments, nonionic alkylated vinylpyrrolidone and polyacrylate polymers are unexpectedly preferred.

[0085] Alkylated vinylpyrrolidone and polyacrylate polymers are typically produced by randomly grafting α-olefins onto the vinylpyrrolidone polymer backbone and lactam ring. These products can have a "comb-like" structure. The alkylating group can be derived from C4-C. 20 For example, the alkylating group can be C4 (butane), C5 (butane), C6 (butane), C7 (butane), C8 (butane), C9 ... 16 (hexadiene) or C 20(Eicosene). In some embodiments, the vinylpyrrolidone / alkylation ratio is 90 / 10, 20 / 80, 50 / 50, or 30 / 70, or combinations thereof. The average molecular weight of such polymers can be from 12,000-22,000, 11,000-17,000, or 14,000-20,000. Their alkylated components induce lipophilicity, while the vinylpyrrolidone moiety in such polymers contributes to hydrophilicity; the presence of both lipophilic and hydrophilic elements in a single molecule makes them surface-active. This surface activity of these polymers promotes a reduction in the particle size of GE droplets.

[0086] Furthermore, nonionic alkylated vinylpyrrolidone and polyacrylate polymers appear to be surprisingly effective in GE's manufacturing process.

[0087] Examples of commercially available alkylated vinylpyrrolidone and polyacrylate polymers include: Agrimer TM AL, Agrimer TM AL 10LC, Agrimer TM AL 22, Agrimer TM AL 25, Agrimer TM AL 30, Agrimer TM AL 22D.

[0088] Furthermore, mixing nonionic alkylated vinylpyrrolidone and polyacrylate polymers with highly charged lignin sulfonated lignin sulfonate and nonionic comb-shaped polyacrylate polymers can improve the re-suspensibility of GE droplets in very hard water.

[0089] Sulfonate dispersants are dispersants containing sulfonate groups. In preferred embodiments, the sulfonate dispersant is a sodium or calcium salt. Examples of sulfonate dispersants include naphthalene sulfonate, lignin sulfonate, kraft lignin sulfonate, dodecyl sulfonate (SDS), and dodecylbenzene sulfonate (SDBS). In preferred embodiments, the sulfonate dispersant contains kraft lignin to increase water solubility. Furthermore, preferred sulfonate dispersants induce reinforcement and increase the glass transition temperature. An increased glass transition temperature is preferred for the manufacture of GE.

[0090] Examples of commercially available sulfonate dispersants include: Polyfon, Kraftsperse, Indulin, Borresperse, products NN 9104.

[0091] Polyacrylate copolymers are known in the art. These polymers are prepared using acrylic acid monomers and second monomers. In preferred embodiments, the copolymer is a graft polymer, wherein a first monomer forms the polymer backbone and a second monomer forms branches thereon. The desired comb-shaped polymer stabilizer structure consists of randomly introduced side chains with affinity for the dispersion medium, which are chemically attached to the anchoring polymer. These comb-shaped polymers induce dispersion properties based on steric stabilization mechanisms.

[0092] Examples of commercially available polyacrylate copolymers include: Dispersed PSL 100, Atlox 4913, Atlox 4917, and Agrilan 755. Application method

[0093] The compositions of this invention can be used in conventional agricultural methods. For example, the compositions of this invention can be mixed with water and / or fertilizer and applied to the desired location before and / or after emergence by any means, such as aircraft spray cans, irrigation equipment, direct injection sprayers, backpack spray cans, livestock dipping tanks, farm equipment used for ground spraying (e.g., nozzle sprayers, manual sprayers), etc. The desired location can be soil, plants, etc.

[0094] The present invention further includes a method for treating seeds or plant propagules, the method comprising contacting the seeds or plant propagules with the composition of the present invention. The present invention can be applied to seeds or plant propagules in any physiological state at any time: between seed harvest and seed sowing; during or after sowing; and / or after germination. Preferably, the seeds or plant propagules are in a sufficiently robust state that causes little or no damage, including physical or biological damage, during the treatment process. The formulation can be applied to the seeds or plant propagules using conventional coating or granulation techniques and machines, such as fluidized bed technology, drum milling, rotostatic seed treatment machines, and rotary drum coating machines. The seeds or plant propagules can be pre-sizinged before coating. After coating, the seeds or plant propagules are typically dried and then transferred to a screening machine for sieving. Such procedures are known in the art. In some embodiments, the composition of the present invention is applied as a component of a seed or plant propagule coating. The treated seeds can also be coated with a film to protect the coating. Such coatings are known in the art and can be applied using, for example, conventional fluidized bed and rotary drum coating techniques. manufacture

[0095] Different methods for producing dispersed phases of GE containing chemical reagents are within the scope of this invention, and are described in such a way that these chemical reagents are agricultural active ingredients.

[0096] A method for producing dispersed phase GE may include the following steps: incorporating a first composition into a second composition to form a third composition, wherein the first composition is substantially immiscible with the second composition, the first composition contains an agrochemically active ingredient, and the first composition contains a liquid curable, coagulating, or polymerizable resin; emulsifying the third composition such that the first composition is a dispersed phase and the second composition is a continuous phase of the third composition, optionally wherein the median diameter of the dispersed phase is less than 200 μm; adding a dispersant to the third composition after the emulsification to form a fourth composition; and achieving curing, coagulation, or polymerization of the liquid curable, coagulating, or polymerizable resin in the fourth composition to form polymer matrix microparticles having the agrochemically active ingredient distributed therein.

[0097] Such methods may also include preparing a dispersion concentrate (e.g., composition 1) by dissolving or suspending at least one agrochemically active ingredient in a non-aqueous curable liquid mixture, said non-aqueous curable liquid mixture comprising at least one suitable crosslinkable resin (comprising monomers, oligomers, prepolymers, or blends thereof), optionally a suitable hardener, catalyst, plasticizer, or initiator, optionally said resin containing hydrophilic groups. The dispersion concentrate can then be emulsified in an aqueous liquid to an average droplet size of 1-200 micrometers, said liquid containing colloidal solids as an emulsion stabilizer, optionally containing a plasticizer, and optionally, a suitable hardener, catalyst, or initiator capable of diffusing into the dispersed, uncured resin droplets.

[0098] Embodiments of the above methods may include variations, wherein the dispersion concentrate comprises a polymerizable resin instead of a crosslinkable resin as a non-aqueous liquid. Instead of a curing reaction, dispersed phase particles are formed by polymerization, such that the resulting dispersed phase comprises thermoplastic polymer particles instead of thermosetting polymer particles.

[0099] Additional steps applicable to the above method include 1. Dissolving or suspending at least one agrochemically active ingredient in a non-aqueous liquid mixture, said non-aqueous liquid mixture comprising at least one suitable solidifiable polymer dissolved in a volatile solvent, and one or more optional plasticizers; 2. Emulsifying the solution in an aqueous liquid to an average droplet size of 1-200 micrometers, wherein the liquid contains colloidal solids as an emulsion stabilizer and optionally contains a plasticizer; and 3. The volatile solvent is evaporated by heating the emulsion to a temperature of about 30°C-120°C for about 0.1-10 hours, and optionally thereafter absorbing a plasticizer to produce thermoplastic polymer particles and colloidal solid material on the surface of the particles, the particles having a hardness of less than 6 MPa, wherein at least one agricultural active ingredient is distributed therein.

[0100] The method of utilizing the above-mentioned disclosure in a solidified manner may include the following steps: 1. A dispersion concentrate is prepared by dissolving or suspending at least one agrochemically active ingredient in a non-aqueous curable liquid mixture, said non-aqueous curable liquid mixture comprising a melt of at least one suitable solidifiable thermoplastic polymer and optionally a plasticizer; 2. Emulsifying the dispersion concentrate in a heated aqueous liquid to an average droplet size of 1-200 micrometers, the liquid comprising colloidal solids as an emulsion stabilizer and optionally comprising a plasticizer; and 3. Cooling the emulsion, and optionally subsequently absorbing a plasticizer, to produce thermoplastic polymer particles and colloidal solid material on the surface of the particles, the particles having a hardness of less than 6 MPa, wherein at least one agricultural active ingredient is distributed therein.

[0101] In cases where the active ingredient is soluble or miscible with the plasticizer, the above method can be modified so that the active ingredient is added after the steps of curing, solidification, or extraction of solvent from liquid emulsion droplets, so that the active ingredient is absorbed or dissolved in GE after formation, rather than being initially present in the dispersion concentrate.

[0102] Accordingly, the method disclosed herein may include the following steps: a. Dissolving or suspending at least one agrochemically active ingredient in a non-aqueous liquid mixture (premix), said non-aqueous liquid mixture (premix) comprising at least one suitable curable or polymerizable resin (comprising monomers, oligomers, prepolymers or blends thereof), optionally a suitable hardener, plasticizer, catalyst or initiator; b. Emulsifying the solution or suspension in an aqueous liquid to an average droplet size of 1-200 micrometers, the liquid further comprising colloidal solids as an emulsion stabilizer and optionally comprising a plasticizer, a suitable hardener, catalyst, or initiator capable of diffusing into dispersed, uncured or unpolymerized resin droplets; and c. To achieve crosslinking, curing, or polymerization of a resin mixture, and optionally subsequently absorb a plasticizer to produce cured thermosetting or polymerized thermoplastic resin polymer particles and colloidal solid material on the surface of the particles, the particles having a hardness of less than 6 MPa, wherein at least one agricultural active ingredient is distributed therein, and dispersed in the aqueous liquid after curing.

[0103] The method may include adding a hardener via the continuous phase after the formation of the Pickering emulsion, preventing the dispersed phase premix from curing. Alternatively, a first very slow-reacting hardener may be used in the dispersion concentrate, and then a second fast-curing hardener, accelerator, or catalyst may be added throughout the continuous phase. Since these second agents are added to the continuous phase after the dispersed phase is emulsified, they must be selected to be miscible in the continuous phase. Suitable fast-curing, water-miscible hardeners include diethylenetriamine, triethylenetetramine, xylenediamine, polyethylene glycol diamine, isophorone diamine, and polyoxypropylene diamine. For additional flexibility, mixtures of hardeners may also be used.

[0104] The premix in the above method can be prepared as follows: 1) A premix of the dispersed phase is prepared by blending the following in a high-shear mixer: at least one agricultural active ingredient, at least one suitable curable or polymerizable resin monomer, oligomer, prepolymer or blend thereof, and a suitable curing agent, catalyst or initiator (as needed); 2) Premixes of continuous phases are prepared by blending the following using a low-shear mixer: aqueous liquids and colloidal solids as emulsion stabilizers.

[0105] As needed, to polymerize the dispersed phase, the resulting premix of the dispersed phase and the premix of the continuous phase are stirred under high shear conditions for an appropriate time to form a Pickering emulsion and then heated or exposed to light or other electromagnetic radiation conditions (UV, microwave). Those skilled in the art can readily determine the shear rate and the duration of emulsification based on the following observations: if the shear rate is too low, the emulsion and the resulting polymer matrix particles are relatively coarse and may be larger than desired; conversely, if the shear rate is too high or the duration is too long, the emulsion containing the stable colloid eventually becomes consumed from the continuous phase, leaving any new interfacial surface between the dispersed and continuous phases virtually unprotected, at which point rapid aggregation or flocculation of the dispersed phase occurs and the Pickering emulsion becomes non-uniform.

[0106] In one embodiment, the mixture of the dispersed premix and the continuous premix is ​​stirred under high shear conditions for 5-10 min and heated to a temperature of about 30°C-120°C for about 0.1-10 h to carry out a curing reaction.

[0107] In one embodiment, the dispersion concentrate is prepared by: a. Dissolving or suspending at least one agrochemically active ingredient in a non-aqueous liquid mixture, said non-aqueous liquid mixture comprising at least one suitable polymer dissolved in a volatile solvent; b. Emulsifying the solution in an aqueous liquid to an average droplet size of 1-200 micrometers, the liquid further comprising a colloidal solid as a (Picklerin) emulsion stabilizer; and c. The volatile solvent is evaporated by heating the emulsion to approximately 30°C-120°C for approximately 0.1-10 hours to produce thermoplastic particles and colloidal solid material on the surface of the particles, the particles having a hardness of less than 6 MPa, wherein at least one agricultural active ingredient is distributed therein, and these particles are dispersed in an aqueous liquid. If necessary, more liquid may be added to the continuous phase to replace any liquid loss during the evaporation process.

[0108] A system for implementing the above method is shown. Figure 2A-2D .

[0109] according to Figure 2A-2D The first step in the system preparation of GE is shown in Figure 2A The first step in preparing GE may include the preparation of various premixes.

[0110] A first premix can be prepared in a first container 101. Typically, the first premix will be a dispersed phase of an agricultural chemical composition as described above. The first container 101 may have a mixer 109 configured to agitate and / or mix the liquid within the first container 101 and a heater 107 configured to heat the liquid composition within the first container 101. In some embodiments, the heater 109 may additionally act as a cooler to remove heat from the first container 101. In a preferred embodiment, the heater 107 is located outside the first container 101 and surrounds its periphery. In alternative embodiments, the heater is located inside the first container 101 and in contact with the liquid in the first container. The mixer or agitation system includes a belt system, a tumble system, a planetary mixer, a centrifugal mixer, or... mix( Mixing (RAM) (RAM uses low-frequency energy to generate unique material movement and sound-induced (acoustic) interactions within the container without the need for internal mechanical drive components (such as impellers)).

[0111] There is no particular limitation on the size of the first container 101. The first container may have a volume greater than 10 gallons, for example, 10 to 1,000,000, or 100 to 500,000.

[0112] A second premix can be prepared in the second container 103. Typically, the second premix will be a continuous phase of the agrochemical composition described above. The second container 103 has a shearing system configured to apply shear to the liquid within the second container 103. In a preferred embodiment, the shearing system includes a first mixer 111 and a second mixer 113. The mixers may be the same as or different from the mixer in the first container 101. Typically, the shearing system can generate a force higher than 500 rpm, for example, 1000 rpm to 25,000 rpm, 1500 rpm to 10000 rpm, or 2000 rpm to 5000 rpm.

[0113] There are no particular restrictions on the size of the second container 103. The second container may have a volume greater than 10 gallons, for example, 10 to 1,000,000, or 100 to 500,000.

[0114] A third premix can be prepared in a third container 105. Typically, the third premix will be a dispersant added after emulsification but before solidification, coagulation, or polymerization. The third container 105 may have a mixer 115 configured to agitate and / or mix the liquids within the third container. Alternatively, the third container 105 can be agitated or mixed by hand. There are no particular limitations on the size of the third container 105. The third container 105 may have a volume greater than 1 gallon, for example, 1 to 1,000 or 1 to 500 gallons.

[0115] according to Figure 2A-2D The second step in the system preparation of GE is shown in Figure 2B The second step in preparing GE may include emulsifying the contents from the first container 101 and the second container 103. The system may include a pump 117 configured to transfer liquid between the first container 101 and the second container 103, and vice versa. The first container 101 and the second container 103 may be in fluid communication, such that the bottom of the first container 101 is in fluid communication with the top of the second container 103. This fluid communication may be achieved via a pipe or conduit through which the pump 117 is located.

[0116] Once the first premix from the first container 101 is transferred to the second premix in the second container 103, the shearing system of the second container 103 can be used to emulsify the contents therein.

[0117] according to Figure 2A-2D The third step in the systematic preparation of GE is shown in Figure 2C The third step in preparing GE may include adding a dispersant, followed by solidification, coagulation, or polymerization of the dispersed phase of the composition emulsified in the second container 103.

[0118] The system may use pump 117, which may be the same as or different from pump 117 used to move the first premix in the first container 101 to the second container 103. The fluid connection used to facilitate the transfer of liquid from the second container 103 to the first container 101 may be the same as or different from the pipe or conduit used to move the first premix in the first container 101 to the second container 103. For example, different fluid communication systems may connect the base of the second container 103 to the base of the first container 101.

[0119] A third premix from the third container 115 may be added to the first container 101 before the emulsion is transferred from the second container 103 to the first container 101. Alternatively, the third premix may be added after the emulsion has been transferred from the second container 103 to the first container 101. In some embodiments, the third premix is ​​added to the second container 103 before being transferred to the first container 101. In a preferred embodiment, the third premix is ​​mixed into the emulsion using the mixer 109 of the first container 101.

[0120] Once the third premix is ​​incorporated into the emulsion, polymerization, solidification, or coagulation of the emulsion can occur. In a preferred embodiment, polymerization is promoted by a heater 107 in the first container, and the contents of the first container are circulated by a mixer 109.

[0121] according to Figure 2A-2D The fourth step in the systematic preparation of GE is shown in Figure 2F The fourth step in preparing GE may include adding a diluent (e.g., water) and co-formulating and packaging the product for distribution.

[0122] Once the final GE is formed, the added diluent (e.g., water) and co-formulation are added to the first container 101 by conventional means, such as pouring through an opening in the first container 101. A mixer 109 can be used to ensure the homogeneity of the composition in the first container 101.

[0123] A liquid transfer system (including pipes or conduits, which may be the same as or different from a system for transferring liquid from a first container 101 to a second container 103) may be used to transfer a formulated composition in the first container 101 to a package 127 for distribution.

[0124] The liquid transfer system can use pump 119 to deliver the prepared product through grid 121. Once the prepared product has been transferred through grid 121, it can be temporarily stored in tote 123, 125 before being transferred to packaging 127 for distribution. polymer

[0125] Preferred polymerizable resins for preparing polymer particles of the dispersed phase include thermosetting resins such as epoxy resins, phenolic resins, amino plastic resins, polyester resins, polyacrylates, biodegradable polymers, polyurethanes, and polyureas. Epoxy resins are particularly preferred. Combinations of these resins can also be used to achieve miscibility with other components of the dispersed phase and to control polymerization kinetics.

[0126] Other suitable polymerizable resins for preparing polymer particles of the dispersed phase include thermoplastic resins such as styrene, methyl methacrylate, and acrylic resins. Combinations of these resins can also be used to achieve miscibility with other components of the dispersed phase.

[0127] Preferred thermoplastic polymers include polymers of the thermoplastic resins described above, as well as polymers such as cellulose acetate, polyacrylate, polycaprolactone, and polylactic acid.

[0128] The polymerization reaction can be thermally initiated by the addition of chemical curing agents and / or catalysts or by appropriate irradiation (such as by visible, UV, microwave or other electromagnetic irradiation, electron beam irradiation or ultrasound) to generate reactive species such as free radicals or ions.

[0129] Suitable monomers used in this invention include vinyl aromatic monomers such as styrene, α-methylstyrene, divinylbenzene, etc.; α,β-mono-olefinically unsaturated mono- and dicarboxylic acid esters, particularly acrylates such as ethyl acrylate, n-butyl acrylate, trimethylolpropionic acid, pentaerythritol triacrylate; and methacrylates such as ethyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, etc. Furthermore, suitable monomers are vinyl esters and allyl esters of aliphatic carboxylic acids, such as vinyl acetate and vinyl propionate; vinyl halides such as vinyl chloride and vinylidene chloride; and conjugated dienes such as butadiene and isoprene. Examples of suitable unsaturated monomers also include acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, N-vinylformamide and N-vinylpyrrolidone; and also acrylic acid, methacrylic acid, styrene sulfonic acid and vinylphosphonic acid.

[0130] Additional examples of polymers suitable for preparing the GE of the present invention include phenolic resins, urea, melamine, epoxy resins, silicones, polyisocyanates, polyamines and polyurethanes, polycarbonates, polyalkylene terephthalates, polyphenylene ethers, polysulfones, polyimides, polyetherimides, polyhydroxyalkanoates, polycaprolactones, polyamide esters, and polylactic acid. Furthermore, biopolymers or biodegradable resins derived from natural materials such as plants, algae, microorganisms, or animals can be used, including plant or algal oils, lignin, humic acids, glycoproteins, proteins, polypeptides, polysaccharides, cellulose, or hemicellulose, etc.

[0131] Regarding epoxy resins, all conventional mono-, di-, and polyepoxide monomers, prepolymers, or blends thereof are suitable epoxy resins for the practice of this invention. In one embodiment, suitable epoxy resins are those that are liquid at ambient temperature. These di- and polyepoxides can be aliphatic, alicyclic, or aromatic compounds. Typical examples of such compounds are diglycidyl ethers of bisphenol A, glycerol, or resorcinol; glycidyl ethers of aliphatic or alicyclic diols or polyols; and β-methylglycidyl ethers, including hydrogenated bisphenol A, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, diethylene glycol, polyethylene glycol, polypropylene glycol, glycerol, trimethylolpropane, or 1,4-dimethylolcyclohexane or 2,2-bis(4-hydroxycyclohexyl)propane; and glycidyl ethers of diphenols and polyphenols, typically resorcinol. Glycidyl ethers of 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl-2,2-propane, phenolic varnishes, and 1,1,2,2-tetra(4-hydroxyphenyl)ethane, and other examples are N-glycidyl compounds, including diglycidyl compounds of ethylidene urea, 1,3-propylidene urea, or 5-dimethylhydantoin or 4,4'-methylene-5,5'-tetramethyldihydantoin, or those such as triglycidyl isocyanurate or biodegradable / bio-derived epoxy resins (based on vegetable oils).

[0132] Other technically important glycidyl compounds are carboxylic acids, especially glycidyl esters of di- and polycarboxylic acids. Typical examples are glycidyl esters of succinic acid, adipic acid, azelaic acid, sebacic acid, phthalic acid, terephthalic acid, tetra- and hexahydrophthalic acid, isophthalic acid, or trimellitic acid, or glycidyl esters of partially polymerized (e.g., dimerized) fatty acids.

[0133] Examples of polyepoxides that differ from glycidyl compounds are vinylcyclohexene and dicyclopentadiene, diepoxides of 3-(3',4'-epoxycyclohexyl)-8,9-epoxy-2,4-dioxaspiro[5.5]undecane, 3',4'-epoxycyclohexylmethyl esters of 3,4-epoxycyclohexane carboxylic acid, butadiene diepoxides or isoprene diepoxides, epoxidized linoleic acid derivatives or epoxidized polybutadiene.

[0134] Other suitable epoxy resins are diglycidyl ethers or higher diglycidyl ethers of hydroxyphenol or dihydroxy fatty alcohols with 2 to 4 carbon atoms, preferably diglycidyl ethers or higher diglycidyl ethers of 2,2-bis(4-hydroxyphenyl)propane and bis(4-hydroxyphenyl)methane, or mixtures of these epoxy resins.

[0135] Suitable epoxy resin curing agents for the practice of this invention can be any suitable epoxy resin curing agent, typically selected from primary and secondary amines and their adducts, ammonia nitrile, dicyandiamide, polycarboxylic acids, anhydrides of polycarboxylic acids, polyamines, polyaminoamides, polyadducts of amines and polyepoxides, and polyols.

[0136] Many amine compounds (mono-, di-, or polyamines) can be used as curing agents, such as aliphatic amines (diethylenetriamine, polyoxypropylenetriamine, etc.), alicyclic amines (isophorone diamine, aminoethylpiperazine, or diaminocyclohexane, etc.), or aromatic amines (diaminodiphenylmethane, xylenediamine, phenylenediamine, etc.). Primary and secondary amines are widely used as curing agents, while tertiary amines typically act as catalysts.

[0137] Although epoxy curing agents are typically amines, other options exist, and they offer additional flexibility to adjust for chemical agents that may be unstable or soluble in the presence of amines, or allow for a wider range of curing rates.

[0138] For example, other suitable curing agents are anhydrides of polycarboxylic acids, typically phthalic anhydride, nadic anhydride, methyl nadic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, and also tetrahydrophthalic anhydride and hexahydrophthalic anhydride.

[0139] For the purposes of this invention, certain epoxy polymers are preferred. Preferred epoxy polymers are polymers derived from one or more preferred epoxy monomers and one or more preferred amine curing agents. Preferred epoxy monomers include: cyclohexanediethanol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, bisphenol A diglycidyl ether, resorcinol diglycidyl ether, glycerol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, diglycidyl 1,2-cyclohexane dicarboxylate, isosorbide diglycidyl ether, and 1,6-hexanediol diglycidyl ether. Preferred amine curing agents include: polyoxypropylene diamine, polyoxypropylene triamine, polyoxyethylene diamine, N-aminoethyl-piperazine, trimethyl-1,6-hexanediamine, isophorone diamine, N,N-dimethyl-1,3-diaminopropane, diethylenetriamine, N,N′-dimethylethylenediamine, and hexanediamine.

[0140] Appropriate catalysts can be optionally used to accelerate the epoxy curing reaction, such as tertiary amines, boron trifluoride, monoethylamine, imidazole, triethanolamine, aminoethylpyrazine, tris(dimethylaminomethyl)phenol, bis(dimethylaminomethyl)phenol, and dicyandiamide. colloidal solids

[0141] According to the present invention, prior to the step of solidifying the dispersed phase into the polymer matrix, any type of Pickering colloidal emulsion stabilizer can be used to stabilize the emulsion, regardless of the type of polymer matrix, wherein the dispersed phase contains chemical reagents, such as agrochemical active ingredients.

[0142] More specifically, solids, such as silica and clay, have been described in the literature as viscosity modifiers in agrochemical formulations to suppress gravity-driven sedimentation or emulsion separation by forming a network or gel throughout the continuous phase, thereby increasing low-shear viscosity and slowing the movement of small particles, surfactant micelles, or emulsion droplets. The colloidal solids of this invention, on the contrary, are used to stabilize droplets containing these resin monomers during curing by adsorbing to the transient liquid-liquid interface, thereby forming a barrier around the cured droplets to prevent contacting or adjacent cured droplets from coalescing (regardless of whether these cured droplets have already coalesced in sediment or emulsion layers). Colloidal solids also serve to prevent GE from coagulating under stress conditions (as observed) when plasticizers are incorporated into conventional latex dispersions. The two different functional-rheological modifications or emulsion and dispersion stabilizations can be distinguished by functional tests as described below. The effectiveness of the colloidal solids in stabilizing emulsions of cured polymer droplets depends on particle size, particle shape, particle concentration, particle wettability, and interparticle interactions. The colloidal solids must be small enough to coat the surface of dispersed, curing liquid polymer droplets, and the curing liquid droplets must be small enough for use in conventional application equipment. These final polymer particles (and therefore the colloidal solids) will also need to be small enough to provide an acceptablely uniform product distribution at the target sites. The colloidal solids must also have sufficient affinity for both liquids forming the dispersed and continuous phases, allowing them to adsorb at the transient liquid-liquid interface and thereby stabilize the emulsion during curing. This wettability characteristic, particle shape, and suitability for stabilizing Pickering-type emulsions can be readily evaluated by preparing control formulations lacking colloidal solids used as emulsion stabilizers. In this case, the curing liquid polymer droplets coalesce and form aggregated clumps instead of a dispersion of polymer particles.

[0143] In one embodiment, the colloidal solid has a number-weighted median particle size diameter of 0.001-2.0 micrometers, particularly 0.5 micrometers or less, and more particularly 0.1 micrometers or less, as measured by scanning electron microscopy.

[0144] A wide variety of solid materials can be used as colloidal stabilizers for preparing the dispersions of the present invention, including carbon black, metal oxides, metal hydroxides, metal carbonates, metal sulfates, polymers, silica, mica, and clay. Suitable colloidal stabilizers are insoluble in any liquid phase present in the preparation of the concentrate formulation. An agrochemically active ingredient may also be used as a colloidal stabilizer if it has a suitably low solubility (below about 100 ppm at room temperature) in any liquid used to dilute the final composition, and in both the continuous phase and the (transient) dispersed liquid phase, and can be prepared at a suitable particle size, and has wettability suitable for the transient liquid-liquid interface as described above. Examples of inorganic particulate materials are oxygen-containing compounds (or derivatives of such materials) of at least one of calcium, magnesium, aluminum, and silicon, such as silica, silicates, marble, clay, and talc. Inorganic particulate materials can be naturally occurring or synthesized in a reactor. These inorganic particulate materials can be minerals selected from, but not limited to, kaolin, bentonite, alumina, limestone, bauxite, gypsum, magnesium carbonate, calcium carbonate (ground or precipitated), perlite, dolomite, diatomite, calcium-magnesium carbonate, magnesite, boehmite, sepiolite, palygorskite, mica, vermiculite, illite, hydrotalcite, lithium montmorillonite, hydrous kaolinite, and gibbsite. Other suitable clays (e.g., aluminosilicates) include those from the illite group containing kaolin, montmorillonite, or clay minerals. Other specific examples are attapulgite, lithium saponite, and sepiolite. Polymers of flocculants (such as xanthan gum in the case of colloidal kaolin) can also improve the stability of Pickering emulsions. Other polymers suitable as colloidal solids include cross-linked star polymers, such as those exemplified in Saigal et al. [Trishna Saigal, Alex Yoshikawa, Dennis Kloss, Masanari Kato, Patricia Lynn Golas, Krzysztof Matyjaszewski, Robert D. Tilton, “Stable emulsions with thermally responsive microstructure and rheology using poly(ethylene oxide) star polymers as emulsifiers”, Journal of Colloid and Interface Science, 394(2013), 284-292].

[0145] The type and amount of colloidal solids are selected to provide acceptable physical stability of the composition during curing, polymerization, solvent evaporation, or other polymer coagulation processes. The colloidal solids should also be present in an amount that provides a stable dispersion of the composition. As used herein, the term "stable dispersion" means that, under optical microscopy, the particles are substantially spherical (in suspension) and readily distinguishable from each other after dilution. This can be readily determined by those skilled in the art through routine evaluation of a series of compositions with varying amounts of this component. For example, the ability of these colloidal solids to stabilize the composition can be verified by preparing samples containing them, and it can be confirmed that the emulsion of droplets is stable and does not exhibit agglomeration. Agglomeration is evident through the formation of large, visually visible droplets, and ultimately through the formation of liquid monomer layers, polymer melts, or polymer solutions within the formulation. If there is no significant agglomeration, the physical stability of the composition during and after curing, polymerization, solvent evaporation, or other polymer coagulation is acceptable, and these GEs are present as a dispersion. For example, in one embodiment, these colloidal solids are used in amounts ranging from 1% to 80%, particularly from 4% to 50%, by weight of the dispersed phase. Mixtures of colloidal solids may be used. plasticizer

[0146] The mechanical properties required by this invention can be achieved by one or a combination of means. In some embodiments, a plasticizer is used. A plasticizer is a relatively small, non-reactive molecule (below 1000 Da) that partially dissolves polymer molecules to allow segment movement, thereby imparting flexibility and reducing the rigidity of the entire polymer matrix. Plasticizers are chemically distinct and vary depending on the polymer matrix in question; they must be miscible with any monomer and the final polymer matrix. Plasticizers can be added to the monomer or polymer before GM formation, or they can be added to the continuous phase after the polymer matrix particles have formed. In other embodiments, the type of polymer used in the formulation can impart the desired mechanical properties. The selection of polymers with relatively long segments (more than about 5 bond lengths) between possible intermolecular crosslinking sites results in these segments having short persistence lengths (less than the segment length) and a low tendency to form organized crystalline domains, thereby imparting flexibility to the entire polymer matrix. In other embodiments, some or all of the monomers or copolymers used may instead be multifunctional to allow branching or crosslinking of the polymer matrix. The lower functionality of these monomers reduces the overall crosslinking density during the curing reaction, resulting in polymer matrix particles with a hardness between 0.001 MPa and 6 MPa. In the case of crosslinked thermosetting epoxy polymer matrices, preferred means of reducing the crosslinking density include mixing monoglycidyl ethers with conventional polyglycidyl ethers, and / or mixing one or more monoprimary amines, mono- or di-secondary amines with conventional bis-, tri-, or higher-functionality primary amine curing agents. Specifically preferred monoepoxides are butyl glycidyl ether, 2-ethylhexyl glycidyl ether, tert-butyl glycidyl ether, phenyl glycidyl ether, o-tolyl glycidyl ether, C12-C14 alkyl glycidyl ether, epoxy octane, allyl glycidyl ether, styrene oxide, pentadecylphenol glycidyl ether, and epoxidized soybean oil.

[0147] In some embodiments of the present invention, it will not be necessary to include a specific plasticizer to achieve the desired particle hardness. For example, and without limitation, the agrochemical active ingredient itself may possess chemical and physical properties that would make it unnecessary to include a plasticizer, or allow the active ingredient itself to act as a plasticizer. Other components of the polymer particles may also produce this same effect / function. Example

[0148] Example 1. A method comprising: The first composition is incorporated into the second composition to form a third composition, wherein the first composition is substantially immiscible with the second composition, the first composition contains an agrochemically active ingredient, and the second composition contains a liquid-curable, coagulating, or polymerizable resin. The third composition is emulsified such that the first composition is the dispersed phase and the second composition is the continuous phase of the third composition, wherein the median diameter of the dispersed phase is less than 200 μm; A dispersant is added to the third composition after emulsification to form a fourth composition; The liquid solidifiable, coagulating, or polymerizable resin in the fourth composition is solidified, coagulated, or polymerized to form polymer matrix particles having the agrochemically active ingredients distributed therein.

[0149] Example 2. The method as described in Example 1, wherein the dispersant is selected from sulfonated dispersants, substituted or unsubstituted polyvinylpyrrolidone, and / or nonionic comb-shaped polyacrylate polymers.

[0150] Example 3. The method as described in Example 2, wherein the dispersant is the sulfonated dispersant selected from lignin sulfonates and / or naphthalene sulfonates, and optionally wherein the dispersant is present at 0.01 to 10% w / w, preferably 0.1 to 5% w / w, or most preferably 0.1 to 2% w / w.

[0151] Example 4. The method as described in Example 2, wherein the dispersant is the substituted or unsubstituted polyvinylpyrrolidone, optionally wherein the dispersant is present at 0.01 to 10% w / w, preferably 0.1 to 5% w / w, or most preferably 0.2 to 2% w / w.

[0152] Example 5. The method as described in Example 2, wherein the dispersant is polyvinylpyrrolidone, and optionally the dispersant is present at 0.01 to 10% w / w, preferably 0.1 to 5% w / w, or most preferably 0.1 to 2% w / w.

[0153] Example 6. The method as described in Example 5, wherein the polyvinylpyrrolidone is alkylated.

[0154] Example 7. The method as described in Example 5, wherein the dispersant is unsubstituted.

[0155] Example 8. The method as described in Example 7, wherein the dispersant is a mixture of lignin sulfonate, polyvinylpyrrolidone, and nonionic comb-shaped polyacrylate polymer, and is optionally present at 0.1 to 20% w / w, preferably 0.2 to 15% w / w, or most preferably 0.5 to 10% w / w.

[0156] Example 9. The method of any one of Examples 1-8, wherein the second composition comprises a colloidal solids emulsion stabilizer, optionally wherein the colloidal solids emulsion stabilizer is present at 0.1 to 25% w / w, preferably 0.5 to 15% w / w, or most preferably 1 to 12% w / w.

[0157] Example 10. The method of any one of Examples 1-9, wherein the first composition or at least one of the second composition contains a plasticizer, optionally wherein the plasticizer is present in an amount of 0.1 to 20% w / w, preferably 0.5 to 10% w / w, or most preferably 1 to 8% w / w.

[0158] Example 11. The method of any one of Examples 1-10, wherein the first composition contains a chemical curing agent, optionally wherein the chemical curing agent is present at 0.1 to 20% w / w, preferably 0.5 to 10% w / w, or most preferably 1 to 5% w / w.

[0159] Example 12. The method of any one of Examples 1-11, wherein the liquid curable, coagulating or polymerizable resin is selected from epoxy resins, polyisocyanates, polyamines, amino plastics, phenolic resins and polyesters.

[0160] Example 13. The method as described in Example 11, wherein the resin is a thermosetting epoxy resin.

[0161] Example 14. The method of any one of Examples 1-13, wherein the second composition is greater than 50 wt% water or a mixture of water and a non-aqueous liquid substantially miscible with water, wherein the non-aqueous liquid forms a single phase when present in water at a concentration of up to at least 50 wt%.

[0162] Example 15. The method of any one of Examples 1-14, wherein the first composition further comprises a solvent to dissolve the agrochemically active ingredient, wherein the solvent is present at 5 to 75% w / w, preferably 10 to 50% w / w, or most preferably 15 to 30% w / w.

[0163] Example 16. The method as described in any one of Examples 1-15, wherein the hardness of the polymer matrix microparticles is less than 6 MPa, for example less than 5 MPa, less than 1 MPa, less than 0.1 MPa, less than 0.001 MPa, or alternatively, 6 MPa, 0.001 MPa and less than 1 MPa, 0.001 MPa and less than 0.1 MPa, or 0.001 MPa and less than 0.01 MPa.

[0164] Example 17. The method of any one of Examples 1-16, wherein the polymer matrix microparticles have a median diameter of less than 200 μm, for example 1-200 μm, 1-100 μm, 1-50 μm, 1-20 μm or 8-18 μm.

[0165] Example 18. The method as described in any one of Examples 1-17, wherein during the curing, solidification, or polymerization of the liquid curable, coagulating, or polymerizable resin, the viscosity of the fourth composition remains below 2000 cP, for example, 100 cP-1000 cP or 300 cP-600 cP.

[0166] Example 19. The method of any one of Examples 1-18, further comprising shear mixing the fourth composition during the curing, solidification or polymerization of the first composition, optionally wherein the shear mixing is above 500 rpm, for example 1000 rpm to 25,000 rpm, 1500 rpm to 10000 rpm, or 2000 rpm to 5000 rpm.

[0167] Example 20. The method of any one of Examples 1-19, wherein the third composition is greater than 90% w / w of the fourth composition, for example, 90% w / w to 99.9% w / w, 95% to 99.9% w / w.

[0168] Example 21. A manufacturing system comprising: The first container includes: A mixer configured to agitate and / or mix the liquid in the first container. A heater configured to heat the liquid composition within the first container; A second container in fluid communication with the first container, the second container comprising: A shearing system configured to apply shear to the liquid within the second container; The third container includes: A mixer configured to agitate and / or mix the liquids within the third container; A pump system configured to transfer liquid between the first container and the second container.

[0169] Example 22. The system as described in Example 21, wherein: The first container has a volume greater than 10 gallons, for example, 10 to 1,000,000, or 100 to 500,000. The second container has a volume greater than 10 gallons, for example, 10 to 1,000,000, or 100 to 500,000; and / or The third container has a volume greater than 1 gallon, for example, 1 to 1,000 or 1 to 500 gallons.

[0170] Example 23. The system as described in Example 21 or 22, further comprising at least one bulk storage and shipping container in fluid communication with the first container, optionally wherein the at least one bulk storage and shipping container has a volume greater than 100 gallons, for example 275 to 330 gallons.

[0171] Example 24. The system as described in Example 23 further includes a mesh filter between the at least one bulk storage and shipping container and the first container, optionally wherein the mesh filter is 100 mesh.

[0172] Example 25. The system as described in Example 23 or 24, further comprising a plurality of end-use product containers, optionally wherein the plurality of end-use product containers have a volume of less than 5 gallons, such as 2 gallons, 1 gallon, 1 liter, or 0.5 liters.

[0173] Example 26. A method for preparing an agricultural chemical composition, the method comprising the system as described in any one of Examples 22-25, including: The first container is loaded with a first composition containing agricultural chemically active ingredients and a liquid curable, coagulating or polymerizable resin, and the first composition is optionally mixed or stirred. The second container is loaded with a second composition that is substantially immiscible with the first composition, and the first composition is optionally mixed or agitated. The first composition is pumped from the first container into the second container containing the second composition to form the third composition; The third composition is sheared using the shearing system to emulsify the third composition, such that the first composition is a dispersed phase; The dispersant composition is prepared in the third container: The dispersant composition in the third container is transferred to the first container; After shearing, the third composition is transferred to the first container; After transferring the dispersant composition and the third composition, the liquid solidifiable, coagulating or polymerizable resin is cured, coagulated or polymerized to form polymer matrix microparticles having the agrochemically active ingredients distributed therein.

[0174] Example 27. An agricultural chemical composition prepared by any one of Examples 1-21 and 26.

[0175] Example 28. A liquid dispersion composition comprising: (a) Continuous phase; (b) at least one dispersed phase comprising polymer matrix particles, wherein the polymer matrix particles have: (1) a hardness of less than 6 MPa, (2) a colloidal solid material present at the interface with the continuous phase, and (3) an agrochemically active ingredient therein; and (c) A dispersant system comprising: (c1) sulfonate dispersants and polyacrylate copolymers, and / or (c2) Alkylated vinylpyrrolidone nonionic polyacrylate polymer.

[0176] Example 29. The composition as described in Example 28, wherein the polyacrylate copolymer is present in an amount of 0.01 to 10% w / w, preferably 0.1 to 5% w / w, or most preferably 0.2 to 2% w / w.

[0177] Example 30. The composition of claim 28 or 29, wherein the sulfonate dispersant is present at 0.01 to 10% w / w, preferably 0.1 to 5% w / w, or most preferably 0.1 to 2% w / w.

[0178] Example 31. The composition of any one of Examples 28-30, wherein the alkylated vinylpyrrolidone nonionic polyacrylate polymer is present in 0.01 to 10% w / w, preferably 0.1 to 5% w / w, or most preferably 0.1 to 2% w / w.

[0179] Example 32. The composition as described in any one of Examples 28-31, wherein the sulfonate dispersant is a sodium salt.

[0180] Example 33. The composition of any one of Examples 28-32, wherein the sulfonate dispersant is naphthalene sulfonate.

[0181] Example 34. The composition as described in any one of Examples 28-33, wherein the sulfonate dispersant is a lignin sulfonate.

[0182] Example 35. The composition as described in any one of Examples 29-34, wherein the agrochemically active ingredient is selected from azoxystrobin, benzovindiflupyr, fludioxonil, propiconazole, fluopyram, and cypermethrin.

[0183] Example 36. The composition as described in Example 35, wherein the agrochemically active ingredient is heptafluthrin.

[0184] Example 37. The composition as described in Example 35 further comprises a second agrochemically active ingredient distributed in the polymer matrix particles, wherein the agrochemically active ingredient is benzo[a]flufenicol and the second agrochemically active ingredient is fludioxonil.

[0185] Example 38. A liquid dispersion composition comprising: (a) Continuous phase; (b) at least one dispersed phase comprising polymer matrix particles, wherein the polymer matrix particles have: (1) a hardness of less than 6 MPa, (2) a colloidal solid material present at the interface with the continuous phase, and (3) an agrochemically active ingredient therein; and (c) at least one dispersant; After two months of storage at 23°C or 54°C, the clear liquid formation remains below 10%, and / or after two months of storage at 23°C or 54°C, the maximum value of the lifting support remains below 120.

[0186] Example 39. The composition as described in Example 38, wherein each dispersant may be 0.1 to 25% w / w, preferably 0.5 to 10% w / w, and most preferably 0.5 to 5% w / w, and optionally wherein the total amount of dispersant is 0.1 to 25% w / w, preferably 0.5 to 10% w / w, and most preferably 0.5 to 5% w / w.

[0187] Example 40. A composition as described in Example 38 or 39, wherein the composition comprises at least two dispersants.

[0188] Example 41. A composition as described in Example 38 or 39, wherein the composition comprises at least three dispersants.

[0189] Example 42. A composition as described in Example 38 or 39, wherein the composition comprises at least four dispersants.

[0190] Example 43. A composition as described in any one of Examples 38-42, wherein the at least one dispersant is selected from polyvinylpyrrolidone homopolymers, sulfonate dispersants, polyvinylpyrrolidone-vinyl acetate random copolymers, alkylated polyvinylpyrrolidone, lignin sulfonates, sulfonated urea-formaldehyde condensates, styrene-acrylic copolymers, comb polymers having alkyl backbones and polyacrylic acid side chains, and alkylated polyvinylpyrrolidone.

[0191] Example 44. A method for controlling pests, the method comprising: applying a pest-killing effective amount of a composition as described in any one of Examples 28-43 to a plant, plant propagation material, or the site of the pest.

[0192] Example 45. The method as described in Example 44, further comprising identifying plants vulnerable to pests, plant propagation material, or sites of pests.

[0193] Example 46. The method as described in Example 44 or 45, further comprising diluting the composition prior to application. Example

[0194] The following examples further illustrate some aspects of the invention, but are not intended to limit its scope. Unless otherwise specified throughout this specification and the claims, all percentages are by weight.

[0195] The table below describes the product and trade names used in the following examples. manufacture Example 1

[0196] The first composition is prepared by producing a mixture of water (about 80% w / w) and glycerol (about 20% w / w).

[0197] By combining fludioxonil (approximately 19% w / w) and benzovindiflubenzuron (approximately 2% w / w) in... To prepare the second composition, mix M-8-10 (approximately 64% w / w) until fludioxonil and benzoyl permethrin dissolve. Then, triisophosphate and resorcinol diglycidyl ether are mixed into the second composition.

[0198] The first composition, the second composition and D230 was combined to form a third composition and mixed under high shear for 15 minutes. Water (approximately 40% w / w) and a premix of aluminum silicate (approximately 40% w / w) were added to the third composition and sheared until the desired particle size was achieved.

[0199] The composition was then heated at 70°C for 4 hours. The resulting formulation was highly viscous, making it difficult to process further.

[0200] By adding AL 10LC and then add The batch was further treated with ACP-1500, Acticide CT, Proxel GXL, and water to obtain the following composition. Example 2

[0201] The third composition was prepared using the procedure of Example 1, but without triisophosphate. After shearing the third composition to the desired particle size, water (approximately 80% w / w) and The premix of AL 10LC (approximately 20% w / w) was mixed for 15 minutes with gentle agitation.

[0202] The third composition was then heated at 70°C for 4 hours. The resulting formulation remained flowable.

[0203] By adding PSL100, sulfonated sodium lignin sulfonate The batch was further treated with ACP-1500, a biocidal system, water, and 75% phosphoric acid. Dispersant test

[0204] The following table describes the blank design of the preparation materials: The value has been rounded to the nearest tenth.

[0205] The dispersant V1 used in this variation is 0.56% w / v. Preparation of a 100M formulation (Example 1). Testing the stability of the formulation for up to six months of storage at various temperatures. Recording the formation of a clear liquid. Figure 2A ) and viscosity measured via the lifting support ( Figure 2B ).

[0206] Using the above formulation blank, the post-cured product varied with the following dispersants.

[0207] Various The differences between the products are summarized in the table below.

[0208] The effects of dispersants on viscosity and pH are shown in the figures below. Figure 2C and Figure 2D .

[0209] After two weeks of storage, the settlement of the above-mentioned preparations was also examined at -18°C, 23°C, and 54°C, and on a lifting support. Settlement testing was performed as a binary review, where 0 indicates no settlement (less than 10%) and 1 indicates settlement (greater than 10%). The results are shown below. Figure 2E and Figure 2F .

[0210] Change the blank item to include ingredients. 50 (0.5% w / w), and reviewed the 2-way and 3-way combinations of dispersants, resulting in the following formulation blanks.

[0211] The following combinations were tested.

[0212] As discussed above, the maximum values ​​of settlement and lifting support for these components were tested. Surprisingly, only... 2020 and 788 (1:1); 4913 and 788 (1:1); and PSL100 and 788 (1:1) showed settlement at 23°C and 54°C. Other combinations showed no settlement after 2 weeks. The results and settlement summary for the lifting support are shown below. Figure 2G The experiment on the above-mentioned preparations was extended to two months, and the results of the lifting support and settlement are shown in... Figure 2H . Resusceptibility in hard water

[0213] The following two formulations were prepared according to the method described in this article.

[0214] The two formulations were diluted in 1000 ppm hard water and allowed to stand for 24 hours. The composition was then run through 50 and 100 mesh sieves. Results for Example 1 are provided in... Figure 2A The results for Example 2 are provided in... Figure 2B As shown, significant residues were produced in Example 1, while no residues were observed in Example 2.

[0215] While only a few exemplary embodiments of the invention have been described in detail above, those skilled in the art will readily understand that many modifications to the exemplary embodiments are possible without substantially departing from the novel teachings and advantages of the invention. Therefore, all such modifications are intended to be included within the scope of the invention as defined in the following claims.

Claims

1. A method comprising: The first composition is incorporated into the second composition to form a third composition, wherein the first composition is substantially immiscible with the second composition, the first composition contains an agrochemically active ingredient, and the first composition contains a liquid-curable, coagulating, or polymerizable resin. The third composition is emulsified such that the first composition is the dispersed phase and the second composition is the continuous phase of the third composition, wherein the median diameter of the dispersed phase is less than 200 μm; A dispersant is added to the third composition after emulsification to form a fourth composition; as well as The liquid solidifiable, coagulating, or polymerizable resin in the fourth composition is solidified, coagulated, or polymerized to form polymer matrix particles having the agrochemically active ingredients distributed therein.

2. The method as described in claim 1, wherein, The dispersant is selected from sulfonated dispersants, substituted or unsubstituted polyvinylpyrrolidone, and / or nonionic comb-shaped polyacrylate polymers.

3. The method as described in claim 2, wherein, The dispersant is the sulfonated dispersant selected from lignin sulfonates and / or naphthalene sulfonates, optionally wherein the dispersant is present at 0.01 to 10% w / w, preferably 0.1 to 5% w / w, or most preferably 0.1 to 2% w / w.

4. The method of claim 2, wherein, The dispersant is the substituted or unsubstituted polyvinylpyrrolidone, optionally wherein the dispersant is present at 0.01 to 10% w / w, preferably 0.1 to 5% w / w, or most preferably 0.1 to 2% w / w.

5. The method according to any one of claims 1-4, wherein, The second composition comprises a colloidal solid emulsion stabilizer, optionally wherein the colloidal solid emulsion stabilizer is present at 0.1 to 25% w / w, preferably 0.5 to 15% w / w, or most preferably 1 to 12% w / w.

6. The method according to any one of claims 1-5, wherein, During the curing, solidification, or polymerization of the liquid curable, solidifiable, or polymerizable resin, the viscosity of the fourth composition remains below 2000 cP, for example, 100 cP-1000 cP or 300 cP-600 cP.

7. The method of any one of claims 1-6, further comprising shear mixing the fourth composition during the curing, solidification, or polymerization of the first composition, optionally wherein, The shear mixing is above 500 rpm, for example, 1000 rpm to 25,000 rpm, 1500 rpm to 10000 rpm, or 2000 rpm to 5000 rpm.

8. The method according to any one of claims 1-7, wherein, The third composition is greater than 90% w / w of the fourth composition, for example, 90% w / w to 99.9% w / w, 95% to 99.9% w / w.

9. A manufacturing system suitable for performing the method as described in any one of claims 1 to 8, the manufacturing system comprising: The first container includes: A mixer configured to agitate and / or mix the liquid in the first container. A heater configured to heat the liquid composition within the first container; A second container in fluid communication with the first container, the second container comprising: A shearing system configured to apply shear to the liquid within the second container; The third container includes: A mixer configured to agitate and / or mix the liquids within the third container; A pump system configured to transfer liquid between the first container and the second container.

10. A method for preparing an agricultural chemical composition, the method comprising the system of claim 9, comprising: The first container is loaded with a first composition containing agricultural chemically active ingredients and a liquid curable, coagulating or polymerizable resin, and the first composition is optionally mixed or stirred. The second container is loaded with a second composition that is substantially immiscible with the first composition, and the second composition is optionally mixed or agitated. The first composition is pumped from the first container into the second container containing the second composition to form the third composition; The third composition is sheared using the shearing system to emulsify the third composition, such that the first composition is a dispersed phase; The dispersant composition is prepared in the third container: The dispersant composition in the third container is transferred to the first container; After shearing, the third composition is transferred to the first container; After transferring the dispersant composition and the third composition, the liquid solidifiable, coagulating or polymerizable resin is cured, coagulated or polymerized to form polymer matrix microparticles having the agrochemically active ingredients distributed therein.

11. An agricultural chemical composition prepared by the method according to any one of claims 1-8 and 10.

12. A liquid dispersion composition comprising: (a) Continuous phase; (b) at least one dispersed phase comprising polymer matrix particles, wherein the polymer matrix particles have: (1) a hardness of less than 6 MPa, (2) a colloidal solid material present at the interface with the continuous phase, and (3) an agrochemically active ingredient therein; and (c) A dispersant system comprising: (c1) sulfonate dispersants and polyacrylate copolymers, and / or (c2) Alkylated vinylpyrrolidone nonionic polyacrylate polymer.

13. The composition of claim 12, wherein, The polyacrylate copolymer is present in the form of 0.01% w / w to 10% w / w, preferably 0.1% w / w to 5% w / w, or most preferably 0.2% w / w to 2% w / w; and / or The sulfonate dispersant is selected from naphthalene sulfonate and / or lignin sulfonate, optionally present at 0.01 to 10% w / w, preferably 0.1 to 5% w / w, or most preferably 0.1 to 2% w / w; and / or The alkylated vinylpyrrolidone nonionic polyacrylate polymer is present in 0.01 to 10% w / w, preferably 0.1 to 5% w / w, or most preferably 0.1 to 2% w / w.

14. A method for controlling pests, the method comprising: Apply an effective amount of the composition as described in any one of claims 12-13 to plants, plant propagation material, or the site of said pests.

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