Chemical compositions stabilized by cellulose nanocrystals

Abstract

Disclosed are: liquid compositions having a first phase, a second phase immiscible and dispersed in the first phase, a matrix of crosslinked cellulose nanocrystals at the interface between the first and second phases, and at least one agrochemically active ingredient in the second phase; and methods of use and manufacture thereof.

Description

[0001] Cross-reference to related applications

[0002] This application claims the benefit of U.S. Provisional Application Serial No. 63 / 262,525, filed on October 14, 2021, the entire contents of which are incorporated herein by reference. Technical Field

[0003] 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

[0004] Currently, encapsulation technologies used for agrochemicals typically rely on the formation of polyurea walls through the condensation reaction of isocyanate monomer structural units. These formulations result in the release of microplastics, which are not particularly biodegradable and can persist in the environment for many years. Therefore, biodegradable alternatives are needed. Summary of the Invention

[0005] The use of cellulose nanocrystals (“CNC”) in chemical agrochemical formulations has solved these and other problems.

[0006] The present invention includes a liquid composition having a first phase, a second phase that is immiscible and dispersed in the first phase, a matrix of cross-linked cellulose nanocrystals at the interface between the first phase and the second phase, and at least one agrochemically active ingredient in the second phase.

[0007] The present invention includes a method relating to preparing a first phase, preparing a second phase, dissolving or suspending an agrochemically active ingredient in the second phase, incorporating cellulose nanocrystals into one or both of the first and second phases, combining the first and second phases to form a composition, stirring the composition to form an emulsion; and crosslinking the cellulose nanocrystals to form a matrix shell surrounding droplets of the second phase.

[0008] The present invention includes a manufactured article having a plant seed coated with a first phase, a second phase immiscible and dispersed in the first phase, a matrix of cross-linked cellulose nanocrystals at the interface between the first phase and the second phase, and at least one agrochemically active ingredient in the second phase. Attached Figure Description

[0009] Figure 1 These are images of cross-linked and non-cross-linked CNC formulations after two weeks of temperature cycling.

[0010] Figure 2 These are microscopic images of cross-linked and non-cross-linked CNC formulations after drying.

[0011] Figure 3 This is a graph showing the release rate of dimethyl phthalate from cross-linked and non-cross-linked CNC formulations.

[0012] Figure 4 This is a graph showing the release rate of λ-cyhalothrin.

[0013] Figure 5 This is a further graph showing the release rate of λ-cyhalothrin.

[0014] Figure 6 This is a graph showing the release rate of λ-cyhalothrin after two weeks of storage at 25℃ or 54℃. Detailed Implementation

[0015] Embodiments of the present invention use CNC (carbon nanoparticles) to stabilize and / or encapsulate agrochemicals in formulations. CNC is used as colloidal particles in Pickering emulsions to stabilize the oil-water interface. See U.S. Patent 9,260,551, which is incorporated herein by reference.

[0016] CNCs are particularly unique in the field of emulsion stabilization due to their amphiphilic nature resulting from their long-range crystal structure. This structure allows hydrophilic hydroxyl groups to be on one facet and hydrophobic alkyl groups to be on the juxtaposed faces. This feature allows CNCs to wet the interfacial region between aqueous and non-aqueous media, thus producing Pickering-stabilized emulsion systems.

[0017] Furthermore, the relatively high aspect ratio of CNC (exhibiting needle-like or rod-like structures) also contributes to emulsion stability. Cellulose materials are used as benchmarks in microbial biodegradation studies; therefore, their application as Pickering stabilizers offers numerous benefits in terms of physical stability and encapsulation of agriculturally active ingredients, while providing an environmentally friendly interfacial matrix that should be readily biodegradable in soil.

[0018] In this invention, the source and / or polymorphism of CNC are not limited. Embodiments of this invention can use any CNC, whether artificial or naturally occurring. Furthermore, CNC can be derived from naturally occurring biomaterials such as hardwood and softwood pulp, non-wood residues, tunicates and bacteria, and other sources. Using established combinations of mechanical and chemical treatments, the raw material can be broken down from its macrostructure into individual fibrils and ultimately into crystalline cellulose regions.

[0019] Typically, CNC machining will have a needle-like or elongated shape. These elongated or needle-like shapes can be understood as having both length and width in dimensions. For a needle-like shape, the width is the maximum width of the pointer. In some embodiments, the CNC has a width of 1-50 nm. In a preferred embodiment, the width is 4-25 nm. Therefore, it follows that the width can be any of about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50 nm, or any range using these widths. In other embodiments, the CNC can have a length of 50-1000 nm. In a preferred embodiment, the length is 100-400 nm. Therefore, the length can be approximately 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550 nm. Any of 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880, 890, 900, 910, 920, 930, 940, 950, 960, 970, 980, 990, or 1000 nm, or any range of these lengths, or between such lengths.

[0020] In some embodiments, the CNC can be defined based on its dimensions, specifically its aspect ratio. The aspect ratio is defined as the ratio between the width and length. A CNC can have an aspect ratio of 1:2 to 1:200. In a preferred embodiment, the aspect ratio is 1:20 to 1:80. Therefore, the width can be any of approximately 1:15, 1:16, 1:17, 1:18, 1:19, 1:20, 1:21, 1:22, 1:23, 1:24, 1:25, 1:26, 1:27, 1:28, 1:29, 1:30, 1:31, 1:32, 1:33, 1:34, 1:35, 1:36, 1:37, 1:38, 1:39, 1:40, 1:41, 1:42, 1:43, 1:44, 1:45, 1:46, 1:47, 1:48, 1:49, and 1:50, or any range using these aspect ratios.

[0021] The CNC dimensions used in the preparation can exhibit a Gaussian distribution. In specific embodiments, the CNC may have a multimodal distribution. Multimodal distributions include bimodal, trimodal, or more peaks. The standard deviation can vary depending on the specific parameter; for example, the standard deviation of the width can be 0.1, 1, 2, 3, 5, or 10 nm, or a range between these values. Alternatively, the standard deviation of the length can be 1, 5, 10, 25, 50, 100, 250, or 500 nm, or a range between these values. In some embodiments, the standard deviation of the aspect ratio length can be ±1, ±2, ±3, ±5, ±10, or ±20, or a range between these values.

[0022] According to embodiments, CNC is about 0.1-3% w / w of the total composition. In preferred embodiments, CNC is 0.5-1.5% w / w. Therefore, the total amount of CNC in the composition can be any one of about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, or 3.0, or a range between both. In some embodiments, CNC may be included in excess. In these embodiments, the total amount of CNC can be at least about 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10% w / w.

[0023] In a specific embodiment, the formulation provides a liquid composition comprising a first phase, a second phase that is immiscible and dispersed in the first phase, a matrix of cross-linked cellulose nanocrystals at the interface between the first and second phases, and at least one agrochemically active ingredient in the second phase.

[0024] In some embodiments, the first phase may be selected such that the agrochemically active ingredient is distributed only or substantially only in the second phase. In such embodiments, no or substantially no agrochemically active ingredient migrates into the first phase. By following any standard test procedure for determining the partition coefficient of a compound between the first and second phases, those skilled in the art will be able to readily determine whether a particular aqueous liquid meets this criterion for a particular agrochemically active ingredient under consideration.

[0025] In another embodiment, the first phase is an aqueous liquid or a solution of a water-soluble solute in water.

[0026] Suitable water-soluble solutes for the first 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.

[0027] In one embodiment, the aqueous liquid suitable for use in the first phase is a mixture of water and a non-aqueous liquid that is substantially miscible with water. In the context of this invention, the term "substantially miscible with water" 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%.

[0028] Suitable water-miscible non-aqueous liquids for use in the first phase 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 of 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 non-aqueous, water-miscible liquid used in the first phase is a solvent for at least one optional agrochemically active ingredient.

[0029] In another embodiment, the aqueous, substantially water-miscible liquid used in the first phase is sufficiently miscible with water in all proportions. Alternatively, the aqueous, substantially water-miscible liquid used in the first phase 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 a composition at elevated temperatures.

[0030] In another embodiment, the second phase is a non-aqueous liquid. In another embodiment, the first 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.

[0031] In another embodiment, the first phase comprises a non-aqueous liquid that is substantially miscible with water. The non-aqueous liquid miscible with water 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.

[0032] Those skilled in the art will understand that the amount of water, as well as the properties and amounts of non-aqueous water-miscible liquids or water-soluble solutes, can be varied to provide a mixed aqueous liquid suitable for use in the first phase, and these amounts can be determined without experimental testing.

[0033] A second phase that is immiscible with the first phase can be selected. The second phase can be selected based on the first phase, or vice versa. Furthermore, both the first and second phases can be selected based on the physical properties of the chosen agrochemical active ingredient, thereby achieving appropriate suspension or solvation.

[0034] In a preferred embodiment, the second phase is a non-aqueous solvent or oil, such as, but not limited to, alkylated aromatic carboxylic acids (acetophenone, benzyl benzoate, butyl benzoate); tris(2-ethylhexyl) phosphate; fatty acid oils (stearic acid, linoleic acid, oleic acid, rapeseed oil, soybean oil); alkylated fatty acid oils (e.g., methylated rapeseed oil, methyl oleate, methylated soybean oil); aromatic hydrocarbons; diisononyl cyclohexane-1,2-dicarboxylic acid; petroleum distillates (including mineral oil); alkylated pyrrolidones; simple alkanes (e.g., heptane, dodecane, hexadecane and their isomers); and fatty alcohols (octanol, stearyl alcohol, oleyl alcohol).

[0035] According to embodiments, the first phase may comprise 50-90% w / w of the composition, while the second phase may comprise 10-50% w / w of the composition. In some embodiments, the second phase is any one of about 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, and 50%, or an amount and range between both.

[0036] Typically, the matrix of crosslinked CNC at the interface between the first phase and the second phase is formed by dispersing CNC in one of the first phase or the second phase, merging the first phase and the second phase, mixing and / or stirring the first phase and the second phase to disperse the second phase in the first phase, and then crosslinking the CNC.

[0037] In some embodiments, salts may be used, if necessary, to adjust the surface charge density on the CNC surface to ensure maximum coverage of the CNC on the droplet surface. Specific salts include, but are not limited to, monovalent and polyvalent metal halides such as NaCl or CaCl2, or organic salt derivatives such as (NH4)2SO4. The salt concentration can be from 0.001 to 0.1 M. These salts may be present before crosslinking or in the final composition. In some embodiments, the amount of salt is 0.001, 0.005, 0.01, 0.05, or 0.1, or amounts and ranges between these values.

[0038] A surfactant may be further included to contribute to particle size uniformity and stability. The surfactant may be selected based on the specific first and second phases or the active substances contained therein. Typically, the surfactant may be from about 0.01 to 5% w / w. In a specific embodiment, the surfactant is sodium dodecyl sulfate. Specific embodiments relate to solvent-free formulations.

[0039] Some embodiments of the present invention relate to compositions in which the interface between a first phase and a second phase is CNC-machined to 30%-100%. 100% coverage corresponds to a solid matrix. In specific embodiments, the interface is CNC-machined to at least 60%. In other embodiments, the interface is CNC-machined to 50%-80%. CNC-machined coverage can be about 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 100%, or amounts and ranges between these values.

[0040] CNC can be crosslinked using any technique known in the art. Preferred crosslinking methods include chemical and physical crosslinking with polyaldehydes, polyphenols, polyamines, or polycarboxylic acids. Specific crosslinking agents include glutaraldehyde, citric acid, tannic acid, and boric acid. Preferred crosslinking agents include glutaraldehyde and citric acid.

[0041] Other crosslinking methods can be achieved by using various multivalent metals and their corresponding salts (general examples include, but are not limited to, salts of Mg(II), Ca(II), Fe(III), Cu(II), Zn(II), or Al(III)) and utilizing the ionic interactions between CNC particles.

[0042] The amount of crosslinking agent used can depend on the specific crosslinking agent. Typically, the amount of crosslinking agent can be greater than 0.01% w / w, and in some embodiments, the crosslinking agent is present at 0.01 to 10% w / w. In preferred embodiments, the crosslinking agent is present at 0.01 to 5% w / w. In some embodiments, the amount of crosslinking agent is 0.01%, 0.02%, 0.05%, 0.1%, 0.2%, 0.5%, 0.7%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, or 10% w / w, or amounts and ranges between these values.

[0043] In specific embodiments, the second phase comprises droplets having a diameter between 1 and 100 micrometers. In preferred embodiments, the droplet size is 1 to 30 micrometers. The diameter can be defined by the average diameter. Thus, the diameter can be 1, 1.5, 2, 2.5, or 3 micrometers, or a quantity and range between both. In specific embodiments, the diameter is less than 10 micrometers, less than 5 micrometers, less than 3 micrometers, less than 2 micrometers, less than 1 micrometer, or less than 0.5 micrometers.

[0044] In some embodiments, formulations and droplets can be defined by their properties, such as the release rate or storage stability of agrochemicals.

[0045] In some embodiments, the release rate is defined as the rate at which the agricultural active ingredient diffuses across the interfacial matrix into the surrounding medium, such as into soil, leaves, or solvent reservoirs. For quantitative purposes, release rate tests can be performed to compare the rate at which the active ingredient diffuses across the interfacial matrix with other formulations. Without being bound by theory, modifications (such as crosslinking) can modulate the release rate based on the percentage of release as a function of time, resulting in delayed or rapid-release capsules. Both rapid-release and slow-release capsules are advantageous for agricultural pest control products and are the goal of using this technology. In some embodiments, the maximum release of the agricultural active ingredient load is achieved within 1, 2, 3, 4, 5, 6, 12, or 24 hours after application. In other embodiments, the maximum release of the agricultural active ingredient load is achieved within 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 days after application.

[0046] In some embodiments, storage stability is defined as the ability of a formulated product to remain physically and chemically stable over a storage period of at least 2 years. This can be achieved through long-term storage at low temperatures, ambient temperatures, or high temperatures, as well as temperature cycling procedures that simulate aging processes. Physical stability refers to the ability of a formulation to resist emulsion failure through coalescence, Oswald ripening, flocculation, emulsification, phase separation, or other physical changes such as thickening or sedimentation. Additionally, chemical stability is defined as the ability of a formulated product to withstand chemical degradation of the agricultural active ingredient contained in the formulation. Typically, acceptable tolerances for active ingredient decomposition during these simulated storage conditions are ±10% for 0-1 wt% loadings, ±5% for 1-20 wt% loadings, and ±3% for loadings greater than 20 wt%.

[0047] The term "agrochemically active ingredient" refers to chemical and biological compositions, such as those described herein, that are effective in killing, preventing, or controlling the growth of unwanted pests (e.g., plants, insects, mice, microorganisms, algae, fungi, bacteria, etc.) (e.g., pest-killing active ingredients). This 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.

[0048] In addition to their enantiomers, the following are examples of suitable agricultural chemical active ingredients, but 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, bromobutyroxyfen, bromosulfuron, butachlor, flupropyrazosulfuron, chlorpyrifos, styrax, butachlor, chlorpyrifos ... Ammonium chloride, chlorpromazine, diquat, cyprodinil, indole-methyl, cyclohexane, isoxaflutole, barnyardgrass, chlorpyrifos, cypermethrin, cyclohexane, betaine, diquat, diquat acetonitrile, pyrifluquinazon, piperazine, metolachlor, isoamyl ethoxysulfuron, dimethyl phenoxysulfuron, succinyl phenoxysulfuron, dichlorvos, terbuprofen, fenpyroxene, flusulfuron, EPTC, pendimethalin, ethylbutyrate, ethoxysulfuron, ethoxybenzamide, quizalofop-p-ethyl, succinyl ethoxysulfuron, tetrazolium, methyl methacrylate, methyl methacrylate, isopropyl methacrylate, chlorpyrifos, fluthiamethoxam, flumethrin, propyzoxystrobin, fluroxypyr, flumetsulam, fluorenyl ester, flupyridine, furazolidone, fluthiamethoxam, indica, isoxaflutole Amine, isoxaflutole, cycloxadiazon, linuron, bensulfuron-methyl, mesotrione, pyrazosulfuron, methylbenzylthiazoline, methyl sulfadiazon, pyranolol, metolachlor, sulfadiazon, methoxyfenozide, cyhalothrin, clethodim, fenproxil, fenproxil, pyrazosulfuron, fenproxil, fenproxil, fenproxil, fenproxil, fenproxil, fenproxil, fenproxil, fenproxil, fenproxil, fenproxil, fenproxil, fenproxil, fenproxil, fenproxil, fenproxil, fenproxil, fenproxil, fenproxil, fenproxil, fenproxil, fenproxil, fenproxil, fenproxil, fenproxil, fenproxil, fenproxil, fenproxil, fenproxil, fenproxil, fenproxil, fenproxil, fenproxil, pyrazosulfuron, fenproxil Pyrazolynate, pyrazoxyfen, barnyardgrass, pyrazosulfuron, pyrazosulfuron, cyhalothrin, simazine, cyhalothrin, metolachlor, sulfadiazine, mesotrione, sulfadiazine, sulfadiazine, sulfadiazine, methoxyfenozide, terbufos, methoxythiamethoxam, thiamethoxam, thiamethoxam, thiamethoxam, styraxazol, styraxazol, fenbendazim, fenbendazim, 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; 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, cyhalothrin and its enantiomers such as lambda-cyhalothrin, heptafluthrin, pymetrozine, benzalkonium chloride, and thiamethoxam; nematicides, such as thiazophos, bensulfuron-methyl, and aldicarb.

[0049] In one embodiment, any active ingredient in the second phase may be in the form of a solution or a suspension of particles. Furthermore, any active ingredient contained in the first phase may be in the form of a solution or suspended particles.

[0050] 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.

[0051] The compositions of the present invention can be conveniently stored in a container, and poured out or pumped out of the container or added to it with a liquid carrier before application.

[0052] 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.

[0053] On the one hand, as used herein, “regulating”, “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 spacing, and strengthening of stem walls, thus increasing lodging resistance; compact growth of ornamental plants for economic production of plants to improve quality; promotion of better fruit setting; increase in the number of ovaries (with an eye toward increased yield); aging that promotes the formation of tissues that allow fruit to detach; defoliation in autumn for nurseries and ornamental shrubs and trees used in mail-order businesses; defoliation of trees that interrupts the chain of parasitic infection; and accelerated ripening by reducing harvesting to one or two picks and interrupting the food chain of harmful insects in order to plan the harvest.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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 conferred tolerance to imidazolinones (e.g., methoxyfenozide) through conventional breeding methods are... Summer rapeseed (Carnora). Examples of crops that have been conferred herbicide tolerance through genetic engineering include, for example, maize varieties resistant to glyphosate and glufosinate. and The trademark is available for purchase.

[0061] Crops should also be understood as those crops that have been genetically engineered to be resistant to harmful insects, such as Bt corn (resistant to the European corn borer), Bt cotton (resistant to the 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 produced by the soil bacterium Bacillus thuringiensis. Examples of toxins 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 events). For example, seeds can express the insecticidal Cry3 protein while simultaneously being resistant to glyphosate.

[0062] 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).

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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 can 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.

[0067] Examples of surfactants that can be used include 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 dodecylbenzenesulfonates, 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, random copolymers of polyvinylpyrrolidone and vinyl acetate, lignin sulfonates, sulfonated urea-formaldehyde condensates, styrene-acrylic acid copolymers, comb polymers with alkyl backbones and polyacrylic acid side chains, alkylated polyvinylpyrrolidone, and other general non-emulsifying dispersants.

[0068] Dispersants are well known in the art, and such selection will involve various factors depending on the given formulation. Preferred dispersants, as noted above, include, but are not limited to, polyvinylpyrrolidone homopolymers having a molecular weight between 15 and 120 kDa, random copolymers of polyvinylpyrrolidone and vinyl acetate, lignin sulfonates, sulfonated urea-formaldehyde condensates, styrene-acrylic acid copolymers, comb polymers having an alkyl backbone and polyacrylic acid side chains, alkylated polyvinylpyrrolidone, and other general non-emulsifying dispersants.

[0069] The compositions of the present invention can be mixed with fertilizers while still maintaining their stability.

[0070] 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.

[0071] 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.

[0072] Some embodiments of the present invention relate to methods for preparing compositions. Examples of preparation methods include preparing a first phase, preparing a second phase, dissolving or suspending an agrochemically active ingredient in the second phase, incorporating cellulose nanocrystals into one or both of the first and second phases, combining the first and second phases to form a composition, stirring the composition to form an emulsion; and crosslinking the cellulose nanocrystals to form a matrix shell surrounding droplets of the second phase.

[0073] Various embodiments

[0074] Example 1. A liquid composition comprising:

[0075] First phase;

[0076] The second phase is immiscible and dispersed in the first phase;

[0077] The matrix of cross-linked cellulose nanocrystals at the interface between the first phase and the second phase; and

[0078] At least one agrochemically active ingredient in the second phase.

[0079] Example 2. The composition as described in Example 1, further comprising a dispersant.

[0080] Example 3. The composition as described in Example 1, wherein the composition does not contain emulsifying surfactants.

[0081] Example 4. The composition as described in Example 1, wherein these cross-linked cellulose nanocrystals are cross-linked with glutaraldehyde.

[0082] Example 5. The composition as described in Example 1, wherein these cross-linked cellulose nanocrystals cover 40%-80% of the interface between the first phase and the second phase.

[0083] Example 6. The composition as described in Example 1, wherein the first phase contains cellulose nanocrystals, which, compared to a composition in which the first phase does not contain the cellulose nanocrystals, are sufficient to cause a viscosity change of more than 10% in the composition.

[0084] Example 7. The composition as described in Example 1, wherein these cross-linked cellulose nanocrystals are cross-linked with citric acid.

[0085] Example 8. The composition as described in Example 1, wherein these cross-linked cellulose nanocrystals are cross-linked with tannic acid.

[0086] Example 9. The composition as described in Example 1, wherein the first phase comprises water, one or more non-aqueous liquids substantially miscible with water, or a mixture of water and one or more water-miscible liquids.

[0087] Example 10. The composition as described in Example 9, wherein the substantially water-miscible non-aqueous liquid is selected from 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, di(propylene glycol), glycerol diacetate, glycerol triacetate, dimethyl ether acetate, propylene glycol diacetate, triethyl phosphate, ethyl lactate, γ-butyrolactone, propanol, tetrahydrofurfuryl alcohol, N-methylpyrrolidone, dimethyl lactamide, and mixtures thereof.

[0088] Example 11. The composition as described in Example 1, wherein the first phase comprises water and a water-soluble solute.

[0089] Example 12. The composition as described in Example 11, wherein the water-soluble solute is selected from acids, bases, salts, sugars, polysaccharides, proteins, amino acids, betaine, and mixtures thereof.

[0090] Example 13. The composition as described in Example 1, wherein the first phase further comprises at least one agrochemically active ingredient and the active ingredient is in a suspension selected from solutions or particles.

[0091] Example 14. The composition as described in Example 1, wherein these cross-linked cellulose nanocrystals are cross-linked with boric acid.

[0092] Example 15. A composition as described in Example 1, wherein the cross-linked cellulose nanocrystals are 0.1-5% w / w of the composition.

[0093] Example 16. The composition as described in Example 1, wherein the cross-linked cellulose nanocrystals are about 1-2% w / w of the composition.

[0094] Example 17. The composition as described in Example 1, wherein the cross-linked cellulose nanocrystals are about 3-5% w / w of the composition.

[0095] Example 18. A composition as described in Example 1, wherein these cross-linked cellulose nanocrystals have an aspect ratio of 1:1 to 1:100.

[0096] Example 19. The composition as described in Example 1, wherein these cross-linked cellulose nanocrystals have an aspect ratio of about 1:50.

[0097] Example 20. The composition as described in Example 1, wherein these cross-linked cellulose nanocrystals have a width of about 1-100 nm and a length of about 100-1000 nm.

[0098] Example 21. The composition as described in Example 1, wherein these cross-linked cellulose nanocrystals have a multi-peak distribution.

[0099] Example 22. The composition as described in Example 1, wherein these cross-linked cellulose nanocrystals are obtained from microorganisms.

[0100] Example 23. The composition as described in Example 1, wherein these cross-linked cellulose nanocrystals are obtained from plant material.

[0101] Example 24. The composition as described in Example 1, wherein the second phase comprises droplets with a median diameter between 1 and 100 micrometers.

[0102] Example 25. The composition as described in Example 24, wherein the second phase comprises droplets with a median diameter between 1 and 50 micrometers.

[0103] Example 26. The composition as described in Example 25, wherein the second phase comprises droplets with a median diameter between 1 and 10 micrometers.

[0104] Example 27. A method for combating plant species from pest infestation or regulating plant growth by diluting an effective amount of the concentrated composition as described in Example 1 with an aqueous liquid carrier selected from water and liquid fertilizers or combinations thereof, and applying the diluted composition to the plant species or their sites.

[0105] Example 28. A method comprising:

[0106] Preparation of the first phase;

[0107] Preparation of a second phase;

[0108] The agricultural chemical active ingredients are dissolved or suspended in the second phase;

[0109] Cellulose nanocrystals are incorporated into one or both of the first phase and the second phase;

[0110] The first phase and the second phase are combined to form a composition;

[0111] Stir the composition to form an emulsion; and

[0112] These cellulose nanocrystals are cross-linked to form a matrix shell surrounding the second-phase droplet.

[0113] Example 29. The method as described in Example 28, wherein the crosslinking is performed using glutaraldehyde.

[0114] Example 30. The method as described in Example 29, wherein the crosslinking is performed using citric acid.

[0115] Example 31. The method as described in Example 28, wherein the crosslinking is performed using tannic acid.

[0116] Example 32. The method as described in Example 28, wherein the crosslinking is performed using boric acid.

[0117] Example 33. The method as described in Example 28, further comprising stirring the first phase and / or the second phase after incorporation but before merging.

[0118] Example 34. The method as described in Example 28, further comprising incorporating salt into the first phase and / or the second phase.

[0119] Example 35. The method as described in Example 28, wherein the second phase comprises droplets with a median diameter between 1 and 100 micrometers.

[0120] Example 36. An article comprising:

[0121] Plant seeds coated with the composition as described in Example 1.

[0122] Example 37. The article of claim 36, wherein the composition is dried.

[0123] Example 38. The composition as described in Example 1, wherein the at least one agrochemically active ingredient is released slowly at maximum effective load through the matrix of the cross-linked cellulose nanocrystals.

[0124] Example 39. The composition as described in Example 1, wherein the at least one agrochemically active ingredient is rapidly released at maximum effective load through the matrix of the cross-linked cellulose nanocrystals.

[0125] Example

[0126] 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.

[0127] Example 1: Preparation of CNC-controlled preparations

[0128]

[0129]

[0130] The compositions corresponding to those in the table above were prepared as follows: NaCl was dissolved in water, and then the desired amount of CNC solids was added and homogenized using high-shear mixing until any CNC particles or aggregates were discrete and less than 20 μm. λ-cyhalothrin was dissolved in an oil phase solvent and then added to the water and CNC composition. The resulting composition was homogenized using high-shear mixing (Turrax 15 k RPM, 2 × 3 min) to obtain emulsion droplet sizes of 1–10 μm.

[0131] Example 2: Preparation of cross-linked formulations

[0132]

[0133] The formulation was prepared in the same manner as described in Example 1. Once the target droplet size was reached, the crosslinking agent was slowly added under gentle stirring: citric acid (2 wt%), tannic acid (0.5 wt%), or glutaraldehyde (4 wt% of a 25% aqueous solution). After the addition was complete, the formulation was heated to 60°C for 4 hours and then allowed to cool to room temperature.

[0134] Example 3: Storage

[0135] Accelerated storage studies were conducted on CNC formulations containing and without glutaraldehyde crosslinking agents. Tests showed significant improvement after storage at high temperatures and temperature cycling. Crosslinked samples did not separate, while non-crosslinked samples failed under the temperature cycling protocol. Furthermore, the pH and viscosity profiles of the crosslinked samples showed much smaller changes compared to the initial measurements, while in the absence of the crosslinking agent, a 2-unit decrease in pH and significant thickening were observed. Figure 1The table below shows a comparison of formulations after two weeks of cycling at temperatures between -10°C and 50°C for 20 hours each: (A) containing 2% glutaraldehyde and (B) without glutaraldehyde. The results are presented in the table below:

[0136]

[0137] Example 4: Drying

[0138] Crosslinked and non-crosslinked samples were allowed to dry on a microscope slide, enabling the observation of the fine structure of the emulsion after the aqueous carrier evaporated. Without a crosslinking agent, no fine structure was observed, and the emulsion clearly collapsed. When glutaraldehyde or citric acid was included as a crosslinking agent, the fine structure was clearly visible under a microscope, showing an increase in the mechanical strength of the CNC matrix at the interface. Figure 2 Microscopic images are provided.

[0139] Example 5: Release rate experiment

[0140]

[0141] The formulation was prepared in the same manner as described in Example 1, using the amounts indicated in the table above. Dimethyl phthalate (DMP) was loaded into the second phase. The composition was divided into three equal portions, wherein one batch was retained without crosslinking agent (water was added to a total of 100% to replace the crosslinking agent in the other samples to maintain a consistent loading), citric acid crosslinking agent was added to the second batch, and glutaraldehyde crosslinking agent was added to the third batch. All batches were cured at 50°C for 18 hours. Each sample was subjected to the following protocol, respectively, to evaluate the diffusion of UV-active DMP through the interfacial matrix layer.

[0142] 1) Prepare 30cm long dialysis tubes by soaking them in deionized water for 18 hours.

[0143] 2) Seal the bottom of the dialysis tube by tying a knot.

[0144] 3) Inject 1 ml of the preparation into the center of the dialysis tube, and then tie a knot at the top.

[0145] 4) Place the tube into 100ml of deionized water in a 150ml glass bottle, shake, and take 3ml as the initial sample.

[0146] 5) Place the glass bottle containing the dialysis tube on the roller.

[0147] 6) The UV spectrum of a 3 ml sample on a UV spectrophotometer is collected in the range of 250-300 nm because DMP absorbs at 275 nm.

[0148] 7) Record the absorbance at 275nm.

[0149] 8) Place the sample back into the glass vial containing the dialysis tube.

[0150] 9) Repeat the process at 30 minutes, 1 hour, 2 hours, or until a plateau is reached.

[0151] The results of these studies are shown in Figure 3 The release rate study showed that, compared with the absence of a crosslinking agent, the use of a crosslinking agent suppressed the release rate of DMP across the interfacial matrix. In other words, in the absence of a crosslinking agent, a larger amount of DMP was released at a faster rate.

[0152] Example 6: Release Rate Experiment

[0153]

[0154] Prepare the formulation in the same manner as described in Example 1, using the amounts indicated in the table above. Divide the composition into six equal portions, with batch A remaining uncrosslinked. Add citric acid crosslinking agent to batches B and C at loadings of 4 w / w% and 2 w / w%, respectively. Add tannic acid to batches D and E at loadings of 2 w / w% and 0.14 w / w%, respectively. Add glutaraldehyde as a 25% aqueous solution (1 w / w glutaraldehyde content, 4% aqueous solution content) to batch F. Cure all batches at 50°C for 18 hours. Each sample was subjected, individually, to the following protocol, a slightly modified version of the CIPAC method 'Determination of Release Characteristics of MT 190-λ-Cyfluthrin CS Formulation', to evaluate the diffusion of the agricultural active ingredient across the interfacial matrix layer. The modification to this method omits the use of ethanol in the internal standard solution.

[0155] 1. Prepare an internal standard (IS) solution containing dicyclohexyl phthalate (350 mg) dissolved in hexane (1 L).

[0156] 2. Dilute approximately 500 mg of the preparation in deionized water to 6 mL and record the accurate mass of the preparation used.

[0157] 3. Add 100 mL of IS solution to the diluted preparation prepared in step 2.

[0158] 4. Gently rotate and remove 1 mL of the hexane layer aliquot into a GC vial containing 1 drop of trifluoroacetic acid. Then cap and seal the vial.

[0159] 5. Then place the sample on a horizontal roller, not end to end, and set it to roll at 70 rpm.

[0160] 6. Remove another 1 mL aliquot from the hexane fraction and place it in a GC vial at the desired time points, such as 5, 10, 15, 30, 60, 90, 180, 360, and 1440 minutes. Add 1 drop of trifluoroacetic acid before sealing. After each aliquot removal, place the sample back onto the roller.

[0161] 7. The λ-cyhalothrin content was then measured by GC using the procedure outlined in CIPAC Method MT190.

[0162] The results of these studies are shown in Figure 4 Release rate studies showed that the use of a cross-linking agent inhibited the release rate of λ-cyhalothrin across the interfacial matrix compared to the absence of a cross-linking agent, depending on the type and amount of cross-linking agent used. When no cross-linking agent was used, a pseudo-reverse exponential release was observed, exhibiting an initial burst release curve that gradually decreased over time. The use of citric acid resulted in a relatively rapid linear release of λ-cyhalothrin in a stable state, while glutaraldehyde and tannic acid significantly moderated the release rate, with higher amounts of tannic acid leading to a slower release rate.

[0163] Example 7: Release Rate Experiment

[0164]

[0165] Prepare formulations using the amounts indicated in the table above, in the same manner as described in Example 1. Test the release rates of these compositions using the method of Example 6. Results are provided in Figure 5 In this study, the trend followed similar to that seen in Example 6, where different cross-linking agents reduced the release of λ-cyhalothrin across the interfacial matrix. Tannic acid provided the highest release barrier, followed by glutaraldehyde, then citric acid, which provided the weakest release barrier to the cross-linking agent. As a control, no cross-linking agent showed the fastest release rate, illustrating the effect of cross-linking agents on the diffusion of λ-cyhalothrin.

[0166] Following the initial testing, the formulation was stored at 25°C or 54°C for two weeks. The release rate was then tested again. Results are provided. Figure 6 In general, these cross-linked systems show little or no change in their release rate profiles and diffusion kinetics after storage, indicating their long-term physical stability as slow- or fast-release systems.

[0167] 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 liquid composition comprising: First phase; A second phase that is immiscible and dispersed in the first phase; The matrix of cross-linked cellulose nanocrystals at the interface between the first phase and the second phase; and At least one agrochemically active ingredient in the second phase.

2. The composition of claim 1, wherein, The cross-linked cellulose nanocrystals are cross-linked with glutaraldehyde.

3. The composition of claim 1, wherein, The cross-linked cellulose nanocrystals cover 40%-80% of the interface between the first phase and the second phase.

4. The composition of claim 1, wherein, The first phase contains cellulose nanocrystals, which, compared to a composition in which the first phase does not contain the cellulose nanocrystals, are sufficient to cause a change in the viscosity of the composition of more than 10%.

5. The composition of claim 1, wherein, The cross-linked cellulose nanocrystals are cross-linked with citric acid.

6. The composition of claim 1, wherein, The cross-linked cellulose nanocrystals are cross-linked with tannic acid.

7. The composition of claim 1, wherein, The cross-linked cellulose nanocrystals are cross-linked with boric acid.

8. The composition of claim 1, wherein, The cross-linked cellulose nanocrystals are 0.1-5% w / w of the composition.

9. The composition of claim 1, wherein, The cross-linked cellulose nanocrystals have a multi-peak distribution.

10. The composition of claim 1, wherein, The second phase comprises droplets with a median diameter between 1 and 10 micrometers.

11. The composition of claim 1, wherein, The at least one agrochemically active ingredient is released slowly at its maximum effective load through the matrix of the cross-linked cellulose nanocrystals.

12. The composition of claim 1, wherein, The at least one agrochemically active ingredient is rapidly released at maximum effective load through the matrix of the cross-linked cellulose nanocrystals.

13. A method for combating plant species from pest infestation or regulating plant growth by diluting an effective amount of the concentrated composition of claim 1 with an aqueous liquid carrier selected from water and liquid fertilizers or combinations thereof, and applying the diluted composition to the plant species or its location.

14. A method comprising: The agricultural chemical active ingredients are dissolved or suspended in the first phase; Cellulose nanocrystals are incorporated into one or both of the first phase and the second phase; The first phase and the second phase are combined to form a composition; The composition is stirred to form an emulsion; as well as The cellulose nanocrystals are cross-linked to form a matrix shell surrounding the second phase droplet.

15. The method of claim 14, further comprising incorporating salt into the first phase and / or the second phase.

16. An article comprising: Plant seeds coated with the composition as described in claim 1.

17. The article of claim 16, wherein, The composition is dried.

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