Microencapsulated pheromone formulations

Abstract

Described herein are compositions comprising a microencapsulated pheromone. Also described herein are methods of making compositions comprising microencapsulated pheromones. Also described herein are methods of controlling pests with the compositions.

Description

RELATED APPLICATIONS Cross reference

[0001] This application claims priority to U.S. Provisional Patent Application No. 63 / 471,198, filed June 5, 2023, the contents of which are incorporated herein by reference. Technical Field

[0002] This document describes compositions comprising microencapsulated pheromones. It also describes methods for preparing compositions comprising microencapsulated pheromones. Furthermore, it describes methods for controlling pests using said compositions. Background Technology

[0003] Pheromonial compositions are difficult to formulate for a number of reasons, including reactions with other components in the formulation matrix, degradation of the pheromone over time, and unfavorable release rates of the pheromone from the formulation. This is especially true when the pheromone is an active agrochemical ingredient and must be delivered over time at certain release rates. Therefore, there is a need in the art for compositions containing pheromones with improved release rates and degradation properties.

[0004] Microencapsulation provides a means of formulating pheromones for large-scale application in controlling insect populations by disrupting pheromone-mediated communication. Microencapsulation also helps control the volatility of pheromones. However, despite previous demonstrations of pheromone microencapsulation, there remains a need for improved formulations containing microencapsulated pheromones.

[0005] This disclosure provides formulations containing microencapsulated pheromones. These formulations have improved properties compared to conventional formulations containing microencapsulated pheromones. This disclosure realizes a pheromone formulation that can be used in sprayable agricultural formulations. Such sprayable formulations are essential for application to row crops.

[0006] The formulations containing microencapsulated pheromones according to this disclosure can be prepared by known interfacial polymerization methods, and they can be applied over large areas using conventional spraying equipment. They have numerous variables that can be manipulated to control release properties (capsule wall composition, capsule wall thickness, capsule size, and internal composition). Summary of the Invention

[0007] In one embodiment, this disclosure relates to a composition comprising: an antifreeze agent; and microcapsules comprising: a core containing: a pheromone; and a solvent; and a shell encapsulating the core; wherein the shell comprises a polymer generated by the autopolymerization of monomers; and wherein the microcapsules have a d90 value of less than about 40 μm.

[0008] In another embodiment, this disclosure relates to a method of preparing a composition, the method comprising: forming a mixture comprising an antifreeze agent; and microcapsules comprising a core containing a pheromone; and a solvent; and a shell encapsulating the core; wherein the shell comprises a polymer produced by the autopolymerization of monomers; and wherein the microcapsules have a d90 value of less than about 40 μm.

[0009] In another embodiment, this disclosure relates to a method for controlling pests, the method comprising contacting the pest or its environment with a bioactive amount of a composition comprising: an antifreeze agent; and microcapsules comprising: a core comprising: a pheromone; and a solvent; and a shell encapsulating the core; wherein the shell comprises a polymer produced by the autopolymerization of monomers; and wherein the microcapsules have a d90 value of less than about 40 μm. Detailed Implementation

[0010] This written description uses examples to illustrate this disclosure, including the best practices, and also enables any person skilled in the art to practice this disclosure, including preparing and using any composition or system and performing any of the covered methods. The patentable scope of this disclosure is defined by the claims, but may include other examples that would occur to a person skilled in the art. Such other examples are intended to fall within the scope of the claims if they have elements that do not differ from the literal language of the claims, or if they include equivalent elements that do not substantially differ from the literal language of the claims.

[0011] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” “contains,” “containing,” “characterized in,” or any other variation thereof are intended to cover non-exclusive inclusion, which is subject to any expressly indicated limitations. For example, a composition, mixture, process, or method that comprises a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such compositions, mixtures, processes, or methods.

[0012] The transitional phrase "composed of..." excludes any unspecified elements, steps, or ingredients. If in a claim, this closes the claim to exclude any material other than that listed in the claim, except for impurities that usually accompany it. When the phrase "composed of..." appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the elements set forth in that clause; other elements are not excluded from the entire claim.

[0013] The transitional phrase "consistently of..." is used to define a composition or method that further includes materials, steps, features, components, or elements beyond those explicitly disclosed, provided that such additional materials, steps, features, components, or elements do not materially affect the essential and novel features of the claimed invention. The term "consistently of..." falls between "comprising" and "consisting of...". The use of "consistently of..." herein allows the applicant, as a lexicographer, to define the claimed invention by excluding any materials, steps, features, etc., that the applicant considers non-critical to the claimed invention, but which may be known in the prior art and may otherwise be included in the claimed invention, regardless of whether such inclusion or exclusion is specifically described in the specification. The applicant may exclude any materials, steps, features, etc., solely to exclude prior art elements that affect the novelty of the claimed invention and thus its patentability. Therefore, the use of "consistently of..." herein does not require explicit support from the specification to exclude any prior art elements from the claimed invention if including such elements would be detrimental to the patentability of the claimed invention.

[0014] In the case of the use of open-ended terms such as “comprising” to define the invention or a portion thereof, it should be readily understood that (unless otherwise stated) the description should be interpreted as also using the terms “substantially consisting of” or “consisting of” to describe such inventions.

[0015] Furthermore, unless explicitly stated otherwise, "or" refers to an inclusive "or" rather than an exclusive "or". For example, conditions A or B satisfy any of the following: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and both A and B are true (or exist).

[0016] Furthermore, the indefinite articles “a” and “an” preceding the elements or components of the invention are intended to be non-limiting in terms of the number of instances (i.e., occurrences) of the elements or components. Therefore, “a” and “an” should be understood to include one or at least one, and the singular form of the elements or components also includes the plural, unless the quantity clearly indicates a singularity.

[0017] As used herein, depending on the context in which it is used, the term "about" provides an estimate of a value associated with the claimed invention, wherein the estimated value is reasonable when considered in the context of the description of the invention and taking into account what is known in publicly available information, as such information would be understood or interpreted by one of ordinary skill in the art. Generally, as used herein, the term "about" means that the estimated value falls within plus or minus 10% of the associated value. The term "about" may be further defined by the context, and the applicant, as a lexicographer, has the right to define how "about" should be interpreted in the specific context in which the term is used in describing the invention.

[0018] As used herein, “weight%” means the weight percentage of the component relative to the total weight of the composition.

[0019] As used herein, “substantially free” generally means no more than 2% by weight. In some embodiments, “substantially free” means no more than 1.5% by weight, no more than 1.0% by weight, no more than 0.5% by weight, or no more than 0.1% by weight.

[0020] As used in this article, "d10 value" means that 10% of the particles have a diameter smaller than this value.

[0021] As used in this article, the "d50 value" means that 50% of the particles have a diameter smaller than this value.

[0022] As used in this article, the "d90 value" means that 90% of the particles have a diameter smaller than this value.

[0023] Particle size can be determined using a variety of different methods, techniques, and devices. As described in this disclosure, particle size is not limited to any particular method, technique, or device. In some embodiments, particle size is determined using a technique selected from light scattering, static light scattering, dynamic light scattering, and combinations thereof. In some embodiments, particle size is determined using a particle size analyzer. In some embodiments, particle size is determined using a particle size analyzer configured to calculate particle size using the Fraunhofer approximation method of light scattering. In some embodiments, particle size is determined using a particle size analyzer selected from Malvern Mastersizer 2000, Malvern Mastersizer 3000, HELOS / BR Sucell, and combinations thereof.

[0024] As used herein, "antifreeze" means a substance that can be added to water or an aqueous mixture to lower the freezing point of said water or aqueous mixture.

[0025] In the context of this disclosure, "invertebrate pest control" means inhibiting the development of invertebrate pests (including death, reduced feeding, and / or interference with mating), and similar expressions are defined.

[0026] As mentioned in this disclosure, the term "invertebrate pests" includes arthropods, gastropods, nematodes, and worms that are economically important pests. The term "arthropods" includes insects, mites, spiders, scorpions, centipedes, millipedes, pill bugs, and symphylans. The term "gastropods" includes snails, slugs, and other stylomatophores. The term "nematodes" includes members of the phylum Nematoda, such as herbivorous nematodes and parasitic helminth nematodes. The term "worm" includes all parasitic worms, such as roundworms (Nematoda), heartworms (Nematoda, Secernentea), flukes (Platyhelminthes, Tematoda), acanthocephala, and tapeworms (Platyhelminthes, Cestoda).

[0027] The term "agronomic" refers to the production of field crops such as those used for food and fiber, including the cultivation of corn or maize, soybeans and other legumes, rice, cereals (e.g., wheat, oats, barley, rye, and rice), leafy vegetables (e.g., lettuce, cabbage, and other cole crops), fruit vegetables (e.g., tomatoes, peppers, eggplants, cruciferous and cucurbitaceous plants), potatoes, sweet potatoes, grapes, cotton, tree fruits (e.g., pome fruits, stone fruits, and citrus fruits), small fruits (e.g., berries and cherries), and other specialty crops (e.g., canola, sunflower, and olives).

[0028] The term “non-agricultural” refers to crops other than field crops, such as horticultural crops (e.g., ornamental plants grown in greenhouses, nurseries, or not in the field), residential, agricultural, commercial, and industrial structures, turf (e.g., turf farms, ranches, golf courses, lawns, sports fields, etc.), wood products, stored products, agroforestry and vegetation management, public health (i.e., human) and animal health (e.g., domesticated animals such as pets, livestock, and poultry, and undomesticated animals such as wildlife).

[0029] The term "crop vigor" refers to the growth rate or biomass accumulation of a crop plant. "Increased vigor" refers to an increase in growth or biomass accumulation in a crop plant relative to an untreated control crop plant. The term "crop yield" refers to the quantitative and qualitative return of crop material obtained after harvesting the crop plant. "Increased crop yield" refers to an increase in crop yield relative to an untreated control crop plant.

[0030] The term “biologically effective amount” refers to the amount of a bioactive compound that, when applied (i.e., exposed to) the invertebrate pest to be controlled or its environment, or when applied to a plant, the seeds of the plant, or the location of the plant (e.g., the growing medium), is sufficient to produce the desired biological effect to protect the plant from invertebrate pests or for other desired effects (e.g., to increase plant vigor).

[0031] Non-agricultural applications include protecting animals from invertebrate parasitic pests by administering to animals a parasitically effective (i.e., biologically effective) amount of the bioactive compounds of this disclosure (typically in the form of compositions formulated for veterinary use). As mentioned in this disclosure and the claims, the terms "parasitoid" and "parasitoid" refer to an observable effect on invertebrate parasitic pests to protect animals from their effects. Parasitoid effects typically involve reducing the presence or activity of the target invertebrate parasitic pest. Such effects on pests include necrosis, death, stunted growth, reduced mobility or ability to remain on or within the host animal, reduced feeding, and reproductive inhibition. These effects on invertebrate parasitic pests provide control (including prevention, reduction, or elimination) of parasitic infestation or infection in animals.

[0032] Surprisingly, this paper reveals that substantial improvements in the volatility control of pheromone compositions can be achieved using compositions comprising an antifreeze and microcapsules, wherein the microcapsules are small and contain co-encapsulated pheromones and solvents. The most significant improvements were observed for microcapsules having shells containing polymers generated through the autopolymerization of monomers, and for microcapsules with d90 values ​​less than about 40 μm.

[0033] In some embodiments, compositions are described herein comprising: an antifreeze agent; and microcapsules comprising: a core containing: a pheromone; and a solvent; and a shell encapsulating the core. The shell comprises a polymer produced by the autopolymerization of monomers, and the microcapsules have a d90 value of less than about 40 μm.

[0034] Typically, compositions according to this disclosure may comprise microcapsules of any suitable size known in the art that contribute to the compositions described herein. The size of the microcapsules affects various properties of the encapsulating agent because its size indicates the amount of carrier material constituting the encapsulating agent. Reactivity and stability are directly related to the size of the microcapsules. Another important characteristic affected by the size of the resulting microcapsules is sedimentation in the dispersion and during product application. Formulations according to this disclosure surprisingly exhibit good pheromone release rate characteristics, and the capsules did not sediment during accelerated storage stability studies.

[0035] In some embodiments, the microcapsules have a d90 value of about 10 μm to about 40 μm. In some embodiments, the microcapsules have a d90 value of about 10 μm to about 25 μm.

[0036] In some embodiments, the microcapsules have a d90 value of at least 10 μm, at least 11 μm, at least 12 μm, at least 13 μm, at least 14 μm, at least 15 μm, at least 16 μm, at least 17 μm, at least 18 μm, at least 19 μm, at least 20 μm, at least 21 μm, at least 22 μm, at least 23 μm, at least 24 μm, at least 25 μm, at least 26 μm, at least 27 μm, at least 28 μm, at least 29 μm, at least 30 μm, at least 31 μm, at least 32 μm, at least 33 μm, at least 34 μm, at least 35 μm, at least 36 μm, at least 37 μm, at least 38 μm, or at least 39 μm. In some embodiments, the microcapsules have d90 values ​​of up to 11 μm, up to 12 μm, up to 13 μm, up to 14 μm, up to 15 μm, up to 16 μm, up to 17 μm, up to 18 μm, up to 19 μm, up to 20 μm, up to 21 μm, up to 22 μm, up to 23 μm, up to 24 μm, up to 25 μm, up to 26 μm, up to 27 μm, up to 28 μm, up to 29 μm, up to 30 μm, up to 31 μm, up to 32 μm, up to 33 μm, up to 34 μm, up to 35 μm, up to 36 μm, up to 37 μm, up to 38 μm, up to 39 μm, or up to 40 μm.

[0037] In some embodiments, the microcapsules have a d50 value of about 5 μm to about 25 μm. In some embodiments, the microcapsules have a d50 value of about 5 μm to about 24 μm.

[0038] In some embodiments, the microcapsules have a d10 value of about 1 μm to about 10 μm.

[0039] Typically, compositions according to this disclosure may contain any suitable excipients known in the art that contribute to the compositions described herein. The compositions may contain encapsulated excipients and / or unencapsulated excipients. In some embodiments, the composition contains at least one excipient. In some embodiments, the composition contains at least two excipients. In some embodiments, the composition contains at least three excipients. In some embodiments, the composition contains at least four excipients.

[0040] In some embodiments, the excipients are selected from dispersants, surfactants, emulsifiers, wetting agents, biocides, defoamers, antifreeze agents, rheology modifiers, solvents, stabilizers, UV stabilizers, UV absorbers, salts, excipients, antioxidants, and combinations thereof.

[0041] In some embodiments, the excipient comprises a rheology modifier selected from the following: xanthan gum (e.g., Rhodopol 23, Kelzan S), clay, montmorillonite clay, bentonite clay, lithium montmorillonite clay, magnesium aluminum silicate clay (e.g., Acti-Gel 208, Veegum R), organically modified lithium montmorillonite clay (e.g., Bentone LF), silica (e.g., Aerosil 200), hydrophobically modified ethoxylated ethyl carbamate (HEUR), hydrophobically modified anionic polyacrylate copolymer (HASE), anionic polyacrylate copolymer (ASE), rheology modifiers for aqueous systems (e.g., Rheovis rheology modifiers), and combinations thereof.

[0042] Typically, compositions according to this disclosure may contain any suitable pheromones known in the art that contribute to the compositions described herein. In some embodiments, the pheromones are selected from aldehyde pheromones, acetate pheromones, alcohol pheromones, ketone pheromones, epoxide pheromones, hydrocarbon pheromones, ester pheromones, and combinations thereof. In some embodiments, the pheromones do not contain aldehyde pheromones. Examples of pheromones include: formaldehyde; 2,2-dibromoacetaldehyde; acetaldehyde; 2-methyl-2-propenal; 2-methylpropanal; 2-propenal; 3,3-dibromo-2-propenal; propanal; 2-butenal; 2-methyl-2-butenal; 2-methylbutanal; 2-ethylpropenal (2-Methylenebutanal); 3-methyl-2-butenal; 3-methyl-3-butenal; 3-methylbutanal; butanal; (E)-2-pentenal; 2-propylpropenal (2-Methylenepentanal); 2-pentenal; 3-methyl-1-(ethoxy)-butane; 4- Methylpentanal; 4-pentenal; 5-methylfurfural; furan-2-carbaldehyde; pentanal; (E)-2-hexenal; (E)-2-methyl-2-hexenal; (E)-3-hexenal; (E)-4-oxo-2-hexenal; (E,E)-2,4-dimethyl-2,4-hexadienal; (E,E)-2,4-hexadienal; (Z)-2-hexenal; (Z)-3-hexenal; (Z)-4-oxo-2-hexenal; 1-hexenal; 2,3-dihydroxybenzaldehyde; 2-hexenal; 3-((E)-2-hexenooxy)-hexanal; 3,5-dimethylhexanal; 3-ethoxyhexanal; 3 - Hydroxybenzaldehyde; 3-Hydroxyhexanal; 4-Hydroxy-3,5-Dimethoxybenzaldehyde; 4-Hydroxybenzaldehyde; 5-Methylhexanal; Hexanal; (1R,2S,5R)-2-Methyl-5-((R)-1-oxopropyl-2-yl)-cyclopentanecarbaldehyde; (1R,2S,5S)-2-Methyl-5-((R)-1-oxopropyl-2-yl)-cyclopentanecarbaldehyde; (1R,5S)-6,6-Dimethylbicyclo[3.1.1]hept-2-en-2-carbaldehyde; (1S,2S,5R)-2-Methyl-5-((R)-1-oxopropyl-2-yl)-cyclopentanecarbaldehyde; (3S,8R)- 2-Methyl-5-(1-formylethyl)-1-cyclopenten-1-carboxaldehyde; (3S,8S)-2-methyl-5-(1-formylethyl)-1-cyclopenten-1-carboxaldehyde; (5S,8S)-2-methyl-5-(1-formylethyl)-1-cyclopenten-1-carboxaldehyde; (E)-2-(2-hydroxyethyl)-6-methyl-2,5-heptadienal; (E)-2-(2-hydroxyethylidene)-6-methyl-5-heptenal; (E)-2-heptenal; (E)-2-isopropyl-5-methyl-2-hexenal; (E)-2-methyl-2-heptenal; (E,Z)-2,4-heptadienal;(R)-2,6-dimethyl-5-heptenal; (S)-4-(prop-1-en-2-yl)-cyclohex-1-encarbaldehyde; (Z)-2-isopropyl-5-methyl-2-hexenal; (Z,Z)-2,4-heptadienal; 2-(3-methylcyclopentyl)-propanal; 2-(3-methylcyclopentyl)-propanal; 2,3,6-tribromo-4,5-dihydroxybenzaldehyde; 2,3-dibromo-4,5-dihydroxybenzaldehyde; 2,6-dimethyl-5-heptenal; 2-methoxybenzaldehyde; 2-methyl-1-cyclopentenal; 2-methyl-2-heptenal; 2-methyl-5-(1-oxoprop-2-yl)-cyclopentanal; 2-methylcyclopent-1-encarbaldehyde; 3,3-dimethyl-5- Oxo-7-oxabicyclo[4.1.0]heptane-1-carboxaldehyde; 3,4-dimethylbenzaldehyde; 3,5-dibromo-4,5-dihydroxybenzaldehyde; 3,5-dibromo-4-hydroxybenzaldehyde; 3-bromo-4,5-dihydroxybenzaldehyde; 3-bromo-4-hydroxybenzaldehyde; 3-bromo-5-hydroxy-4-methoxybenzaldehyde; 3-hydroxybenzaldehyde-1,2-dicarboxaldehyde; 3-methylbenzaldehyde; 4-(heptoxy)-butanal; 4-methoxybenzaldehyde; 5-(1-formylethyl)-2-methyl-2-cyclopenten-1-carboxaldehyde; 6-methyl-5-heptenal; 6-methylheptanal; benzaldehyde; cartilagineal; cyclohexanedialdehyde; heptanal; Taxifolial D; (1R,2S)-cis-2-isopropenyl-1-methylcyclobutaneacetaldehyde; (1S,2R,3S)-2-(1-formylvinyl)-5-methylcyclopentaneacetaldehyde; (1S,2S,3S)-2-(1-formylvinyl)-5-methylcyclopentaneacetaldehyde; (2Z,6E)-8-chloro-6-chloromethyl-2-methyl-2,6-octadienal; (4S)-(3-oxopropen-1-en-2-yl)-cyclohex-1-enal; (E)-(3,3-dimethyl)-cyclohexyleneacetaldehyde; (E)-2-(3,3-dimethylcyclohexylene)acetaldehyde; (E)-2-(4-methyl-3-pentenyl)butenedialdehyde; (E)-2-(4-methyl-3-pentenyl)butadialdehyde (E)-2,7-Octadenal; (E)-2-Methyl-2-octenal; (E)-2-Methyl-5-(3-furanyl)-2-pentenal; (E)-2-octenal; (E)-3,7-Dimethyl-2,6-octadenal; (E)-3,7-Dimethyl-2,6-octadenal; (E)-3-octenal; (E)-4-oxo-2-octenal; (E)-7-Methyl-2-octenal; (E,E)-2,4-octadenal; (E,E)-2,6-Dimethyl-8-hydroxy-2,6-octadenal; (E,E)-2,6-octadenal; (E,E)-2,6-octadenal; (E,E)-2,6-octadenial; (E,Z)-2,4-octadenal; (E,Z)-2,6-octadenal;(R)-1,2-Dimethyl-3-methylenecyclopentylacetaldehyde; (R)-3,7-Dimethyl-6-octenal; (Z)-(3,3-dimethyl)cyclohexylacetaldehyde; (Z)-2-(3,3-dimethylcyclohexyl)acetaldehyde; (Z)-3,7-dimethyl-2,6-octadienal; (Z,E)-3,7-dimethyl-2,6-octadienal; 1-octenal; 2-(1-formylvinyl)-5-methylcyclopentanal; 2-(3,4-dihydroxyphenyl)-2-oxoacetaldehyde; 2,6,6-trimethyl-1-cyclohexen-1-carboxaldehyde; 2-ethyloctanal; 2-hydroxy-6-methylbenzaldehyde; 2-methylbenzaldehyde; 2-methyl-5-(1-formylethyl)-1-cyclopentanal 1-Carbaldehyde; 2-Octenal; 2-Phenylacetaldehyde; 2-Phenylacetaldehyde; 3,4-Dihydroxyphenylglyoxal; 3,7-Dimethyl-6-octenal; 3-Ethoxy-4-hydroxybenzaldehyde; 3-Ethylbenzaldehyde; 3-Isopropyl-6-methylbenzaldehyde; 3-Octenal; 3-Oxo-4-isopropylidene-1-cyclohexene-1-carbaldehyde; 4-Ethylbenzaldehyde; 4-Hydroxy-2-methylbenzaldehyde; 4-Hydroxy-3-methoxybenzaldehyde; 4-Isopropenyl-1-cyclohexene-1-carbaldehyde; 4-Isopropenyl-3-oxo-1-cyclohexene-1-carbaldehyde; 4S-4-Isopropenyl-3-oxo-1-cyclohexene-1-carbaldehyde; 5-Ethylcyclopentanyl-1-en-carbaldehyde; 6,6-Dimethylbicyclo[3.1]. 1] Hept-2-en-2-carboxaldehyde; 6-methyloctanal; 7-methyloctanal; Anisomorphal; cis-2-isopropenyl-1-methylcyclobutaneacetaldehyde; octanal; Peruphasmal; (1R,2S,6R)-2,6-dimethyl-3-oxabicyclo[4.2.0]octan-2-carboxaldehyde; (E)-2-methyl-2-nonenal; (E)-2-nonenal; (E)-3-phenyl-2-propenal; (E)-4,8-nonadienal; (E)-8-methyl-2-nonenal; (E,E)-2,4-nonadienal; (E,E,E)-2,4,6-nonatrienal; (E,E,Z)-2,4,6-nonatrienal; (E,Z)-2,6-nonadienal Enal; (E,Z,Z)-2,4,6-nonatrienal; (Z)-2-methyl-2-nonenal; (Z)-3-nonenal; (Z)-4,8-nonadienal; (Z)-4-nonenal; (Z)-8-methyl-2-nonenal; 2,6-nonadienal; 2-formyl-3-methylcyclopentenal; 2-nonenal; 2-phenyl-2-butenal; 3-(4-methoxyphenyl)-2-propenal; 3,5-di-tert-butyl-4-hydroxybenzaldehyde; 3-phenyl-2-propenal; 3-phenylpropanal; 6-ethylbenzaldehyde; 7,7-dimethylbicyclo[4.1.0]hept-3-en-3-carboxaldehyde; 7-methylnonanal; 8-methylnonanal; 9-acetoxynonanal; Gibepyrone C; nonanal;(4R,8R)-4,8-dimethyldecanoal; (4R,8S)-4,8-dimethyldecanoal; (E)-17,18,19,20-Tetranorloba-8,10,13(15)-trien-16-al; (E)-2,9-decadienal; (E)-2-decenal; (E)-2-methyl-2-decenal; (E)-2-methyl-3-(2,3-dibromo-4,5-dihydroxyphenyl)-propenal; (E)-4-oxo-2-decenal; (E)-8-hydroxy-4,8-dimethyl-4,9-decadienal; (E)-9-methyl-2-decenal; (E,E)-2,4-decadienal; (E,Z)-2,4-decadienal; (Z)-4-decenal; (Z)-5-decenal; (Z)-9-methyl-2-decenal; (Z,Z)-2,4-decadienal; 1-decenal; 2-decenal; 2-ethyldecenal; 3-(2,3- Dibromo-4,5-dihydroxyphenyl)-2-methylpropanal; 4,5-dimethyldecanal; 4,8-dimethyldecanal; Caraibical; Decanal; Rogiolal; (2E,4E)-2,6,10-trimethylundec-2,4,9-trienal; (2E,4E,7Z)-2,6,10-trimethylundec-2,4,7,9-tetraenal; (5E)-2,6,10-trimethylundec-5,9-dienal; (E)-2-Undecenal; (E)-6-Ethyl-2,10-dimethyl-5,9-undecadienal; (Z)-4-Undecenal; 10-Undecenal; 2-Butyl-2-octenal; 2-Undecenal; 3-Isopropyl-6-methyl-10-oxoundec-2,6-dienal; 5-Methyl-2-phenyl-2-hexenal; 8-Isopropyl-5-methyl-3,4,4a,5,6,7,8,8a-octahydronaphthalene-2-carboxaldehyde; Austrodoral; Oxytoxin 1; cis-4,6-dimethylundecenal; Taxifolial A; Taxifolial B; Taxifolial C; undecanoaldehyde; (1R,6R,7S,10R)-1-hydroxy-4-cadinen-15-al ((1R,6R,7S,10R)-1-Hydroxy-4-cadinen-15-al); (2R,7S,11R)-7-acetoxy-2-hydroxynardosin-1(10)-en-12-al ((2R,7S,11R)-7-Acetoxy-2-hydroxynardosin-1(10)-en-12-al); (3R,5R,9R)-3,5,9-trimethyldodecanoaldehyde; (3S,6E)-7-ethyl-3,11-dimethyldodecano-6,10-dienal; (9R)-3,5,9-trimethyldodecanoaldehyde; (E)-10-dodecenoal;(E)-2-dodecenoal; (E)-3,7,11-trimethyl-6,10-dodecadienal; (E)-5-dodecenoal; (E)-6-dodecenoal; (E)-7-dodecenoal; (E)-8-dodecenoal; (E)-9,11-dodecadienal; (E)-9-dodecenoal; (E,E)-3,7,11-trimethyl-2,6,10-dodectrienal; (E,E)-7-ethyl-3,11-dimethyl-2,6,10-dodectrienal; (E,E)-8,10-dodecadienal; (E,E,E)-3,7-dimethyl-8,11-dioxo-2,6,9-dodectrienal ;(E,E,Z)-3,7-dimethyl-8,11-dioxo-2,6,9-dodecadienal; (E,Z)-2,6-dodecadienal; (E,Z)-5,7-dodecadienal; (E,Z)-7,9-dodecadienal; (E,Z)-8,10-dodecadienal; (R)-10-oxo-isodauc-3-en-15-al ((R)-10-Oxo-isodauc-3-en-15-al); (S,E)-3,7,11-trimethyl-6,10-dodecadienal; (Z)-2-methyl-5-((1R,5R,6S)-2,6-dimethylbicyclo[3.1.1]hept-2- (Z)-6-yl)-pent-2-enal; (Z)-5-dodecenal; (Z)-7-dodecenal; (Z)-9,11-dodecadienal; (Z)-9-dodecenal; (Z,E)-3,7,11-trimethyl-2,6,10-dodectrienal; (Z,E)-5,7-dodecadienal; (Z,E)-7-ethyl-3,11-dimethyl-2,6,10-dodectrienal; (Z,E)-8,10-dodecadienal; (Z,Z)-5,7-dodecadienal; 10-methyldodecanoal; 2,10-dibromo-3-chloro-7-c hamigrene); 2-dodecenoal; 2-ethyldodecenoal; 2-formylguaiazoline; 3,7,11-trimethyl-(E)-6,10-dodecadienal; 5-hydroxy-8-methoxycalamanen-15-al; 5-hydroxy-8-methoxydehydrocalamenene-15-al; Aplysinal; Debromoaplysinal; dodecenoal; Parahigginol D; Polygodial; Sclerosporal; Sinuketal; cis-4,6-dimethyldodecenoal;trans-Calamenen-13-al; (3R,5S,9R,7E,11E)-3,5,9,11-tetramethyl-7,11-tetracenedienal; (3S,4R,6E,10Z)-3,4,7,11-tetramethyl-6,10-tetracenedienal; (E,E)-3,5,9,11-tetramethyltetracene-7,11-dienal; (Z)-4-tetracenedienal; 13,14,15,16-Tetranorclerod-3-en-12-al; 13-acetoxytetracene; 4,6-bis(4-methylpent-3-en-1-yl)-6-methylcyclo-1,3-hexadienal; Acanthodoral; Ancistrodial; Cespitulin F; Isoacanthodoral; Tridecylaldehyde; (E)-11,13-tetradecadienal; (E)-11-tetradecenal; (E,E)-8,10-tetradecadienal; (E,Z)-4,9-tetradecadienal; (E,Z)-8,10-tetradecadienal; (Z)-11,13-tetradecadienal; (Z)-11-tetradecenal; (Z)-5-tetradecenal; (Z)-7-tetradecenal; (Z)-8-tetradecenal; (Z)-9,13-tetradecadien-11-ynedialdehyde; (Z)-9-tetradecenal Carbocarbazone; (Z,E)-9,11,13-tetradecadienal; (Z,E)-9,11-tetradecadienal; (Z,E)-9,12-tetradecadienal; (Z,Z)-5,8-tetradecadienal; (Z,Z)-8,10-tetradecadienal; (Z,Z)-9,11-tetradecadienal; 10,12-tetradecadienal; 2,4-tetradecadienal; 2-ethyltetradecaneal; 3-oxo-13-tetradeceneal; 3-oxo-tetradecaneal; 5,8-tetradecadienal; 5-tetradeceneal; Norasperenal A; Norasperenal B; Norasperenal C; Norasperenal D; Sargasal I; Sargasal II; Tetradecanoal; (6R)-6-Acetoxidichotoma-3,14-diene-1,17-dial; (6R)-6-Hydroxydichotoma-3,14-diene-1,17-dial; (E,E)-3,7,11,15-Tetramethyl-6,10,14-hexadecadienal; (E,Z)-6,8-pentadecanadienal; (E,Z)-9,11-pentadecanadienal; (E,Z,Z)-2,6,9-pentadecantrienal; (Z)-10-pentadecanenal; (Z)-2-chloropentadecan-2-enal; (Z)-6,14-pentadecanadienal;(Z,Z)-6,9-pentadecanedialdehyde; (Z,Z)-9,11-pentadecanedialdehyde; 2-hexyl-2-decenal; Azamial A; Azamial B; Isopachydictyolal; pentadecadecanal; Sinularial A; Umbellacin A; Xeniafaraunol A; (1R)-Pimaral; (E)-10-hexadecenal; (E)-11-hexadecenal; (E)-14-hexadecenal; (E)-14-methyl-8-hexadecenal; (E)-3,7,11,15-tetramethyl-2-hexadecenal; (E,E)-10,12-hexadecadienal; (E,E)-10,14-hexadecadienal; (E,E)-11,13-hexadecadienal; (E,E)-9,11-hexadecadienal; (E,E,E)-10,12,14-hexadectrienal; (E,E,E)-3 7,11,15-Tetramethyl-2,6,10,14-Hexadecatheragenal; (E,E,Z)-10,12,14-Hexadecathrienal; (E,E,Z)-4,6,11-Hexadecathrienal; (E,E,Z,Z)-4,6,11,13-Hexadecatheragenal; (E,Z)-10,12-Hexadecadienal; (E,Z)-11,13-Hexadecadienal; (E,Z)-4,6-Hexadecadienal; (E,Z)-6,11-Hexadecadienal; (E,Z)-8,11-Hexadecadienal; (E,Z)-9,11-Hexadecadienal; (R)- (E)-14-methyl-8-hexadecenal; (R)-(Z)-14-methyl-8-hexadecenal; (S)-(E)-14-methyl-8-hexadecenal; (S)-(Z)-14-methyl-8-hexadecenal; (Z)-10-hexadecenal; (Z)-11-hexadecenal; (Z)-12-hexadecenal; (Z)-13-hexadecen-11-ynedialdehyde; (Z)-14-methyl-8-hexadecenal; (Z)-3,7,11,15-tetramethyl-2-hexadecenal; (Z)-3-oxo-9-hexadecenal; (Z)-7-hexadecenal; (Z (Z,E)-9-hexadecadienal; (Z,E)-10,12-hexadecadienal; (Z,E)-11,13-hexadecadienal; (Z,E)-7,11-hexadecadienal; (Z,E)-9,11-hexadecadienal; (Z,Z)-10,12-hexadecadienal; (Z,Z)-11,13-hexadecadienal; (Z,Z)-7,10-hexadecadienal; (Z,Z)-7,11-hexadecadienal; (Z,Z)-9,11-hexadecadienal; (Z,Z,E)-7,11,13-hexadectrienal; 11-hexadecadienal; 11-hexadecyneal;13(16),14-Spongiadien-19-al; 2-Methylhexadecaldehyde; 7-Hexadecenal; 9-Hexadecenal; Deacetyl-dihydro-nor-thuridillonal; Dictyodial A; Dihydro-nor-thuridillonal; Hexadecaldehyde; Keikipukalide A; Keikipukalide B; Keikipukalide C; Keikipukalide D; Keikipukalide E; Nor-thuridillonal; Pseudoplexaural; Pukalide aldehyde; Sanadaol; (E)-2-Trigeclidin-2-Heptadecanenal; (Z)-9-Heptadecanenal; 1-Heptadecanenal; 2-Heptadecanenal; Globostelletin C; Globostelletin D; Heptadecanal; (E)-11-octadecenal; (E)-13-octadecenal; (E)-14-octadecenal; (E)-2-octadecenal; (E)-6-octadecenal; (E,E)-11,14-octadecadienal; (E,Z)-2,13-octadecadienal; (E,Z)-3,13-octadecadienal; (E,Z)-6,11-octadecadienal; (Z)-11-octadecenal; (Z)-13-octadecenal; (Z)-9-octadecenal; (Z,E)-13,15-octadecadienal; (Z,Z)- 11,13-Octadecadienal; (Z,Z)-13,15-Octadecadienal; (Z,Z)-3,13-Octadecadienal; (Z,Z)-9,12-Octadecadienal; (Z,Z,Z)-9,12,15-Octadecatrienal; 11-Octadecaenal; 13,15-Octadecadienal; 13-Octadecaenal; 16-Methyloctadecaldehyde; 1-Octadecaenal; 3,6-Dihydroxy-24-nor-9-oxo-9,11-cholestano-7,22-dien-11-al; 9-Octadecaenal; Methyloctadecaldehyde; Octadecaldehyde; Panicein B2; Panicein B3; Panicein C; (Z)-10-Ninedecenal; (Z)-9-Ninedecenal; 9(11)-Pargueren-16-al; Hyrtiosal; Nonadecanal; (2E,6Z,9Z)-2-Methyl-2,6,9-Eicoscartrienal; (Z)-11-Eicoscarenal; 11-Eicoscarenal; 12,18-di-Episcalaradial;12b-(3'b-Hydroxybutanoyloxy)-20,24-dimethyl-24-oxo-scalara-16-en-25-al; 12b-(3'b-Hydroxypentanoyloxy)-20,24-dimethyl-24-oxo-scalara-16-en-25-al; 12-Deacetoxy-12-oxo-scalaradial; 12-Episcalaradial; 15-eicosylenal; 1-eicosylenal; 3-Deacetyl-22,23-dihydro-24,28-dehydroluffasterol B; 3-Deacetylluffasterol B; 9-eicosylenal; Anthogorgiene B; Deacetylscalaradial; eicosyldienal; eicosylaldehyde; Mooloolabene A; Mooloolabene B; Scalaradial; and combinations thereof.

[0043] Notable pheromones include: (Z)-5-decenyl acetate, dodecyl acetate, (Z)-7-dodecenyl acetate, (E)-7-dodecenyl acetate, (Z)-8-dodecenyl acetate, (E)-8-dodecenyl acetate, (Z)-9-dodecenyl acetate, (E)-9-dodecenyl acetate, (E)-10-dodecenyl acetate, 11-dodecenyl acetate, (Z)-9,11-dodecadienyl acetate, (E)-9,11-dodecadienyl acetate, (Z)-11-tetracenyl acetate, (E)-11-tetracenyl acetate, tetradecyl acetate, (E)-7-tetradecenyl acetate, and (E)-5-decenyl acetate. Z)-8-Tetradecenyl ester, E)-8-Tetradecenyl ester, Z)-9-Tetradecenyl ester, E)-9-Tetradecenyl ester, Z)-10-Tetradecenyl ester, E)-10-Tetradecenyl ester, Z)-11-Tetradecenyl ester, E)-11-Tetradecenyl ester, Z)-12-Pentadecanenyl ester, E)-12-Pentadecanenyl ester, Hexadecyl acetate, Z)-7-Hexadecenyl ester, Z)-11-Hexadecenyl ester, E)-11-Hexadecenyl ester, Octadecanyl acetate, E,Z)-7,9-Dodecadienyl ester, E,Z-7,9 - Dodecadienyl ester, Acetic acid (E,E)-7,9-dodecadienyl ester, Acetic acid (Z,Z)-7,9-dodecadienyl ester, Acetic acid (E,E)-8,10-dodecadienyl ester, Acetic acid (E,Z)-9,12-dodecadienyl ester, Acetic acid (E,Z)-4,7-tetracenedienyl ester, Acetic acid (E,E)-9,11-tetradecadienyl ester, Acetic acid (Z,Z)-9,12-tetradecadienyl ester, Acetic acid (Z,Z)-7,11-hexadecadienyl ester, Acetic acid (E,Z)-7,11-hexadecadienyl ester, Acetic acid (Z,E)-7,11-hexadecadienyl ester, Acetic acid (Z,E)-3 ,13-Octadecadienyl ester, (E,Z)-3,13-Octadecadienyl ester, (E,E)-3,13-Octadecadienyl ester, Decanol, (Z)-6-Nonenol, (E)-6-Nonenol, Dodecanol, (Z)-5-Decanol, 11-Dodecenol, (Z)-7-Dodecenol, (E)-7-Dodecenol, (Z)-8-Dodecenol, (E)-8-Dodecenol, (E)-9-Dodecenol, (Z)-9-9-Dodecenol, (E)-9,11-Dodecenol, (Z)-9,11-Dodecenol, (Z,E)-5,7-Dodecenol, (E,E)-5,7-Dodecenol, (E,E)-8,10-Dodecadien-1-ol, (E,Z)-8,10-dodecadienol, (Z,Z)-8,10-dodecadienol, (Z,E)-8,10-dodecadienol, (E,Z)-7,9-dodecadienol, (Z,Z)-7,9-dodecadienol, (E)-5-tetradecenol, (Z)-8-tetradecenol, (Z)-9-tetradecenol, (E)-9-tetradecenol, (Z)-10-tetradecenol, (Z)-11-tetradecenol, (E)-11-tetradecenol, (Z)-11-hexadecenol, (Z,E)-9,11-tetradecadienol, (Z (E)-9,12-tetradecadienol, (Z,Z)-9,12-tetradecadienol, (Z,Z)-10,12-tetradecadienol, (Z,Z)-7,11-hexadecadienol, (Z,E)-7,11-hexadecadienol, (E)-14-methyl-8-hexadecen-1-ol, (Z)-14-methyl-8-hexadecen-1-ol, (E,E)-10,12-hexadecadienol, (E,Z)-10,12-hexadecadienol, dodecanol, (Z)-9-dodecanol, tetradecanol, (Z)-7-tetradecenol, (Z)-9-tetradecenol, (Z)-11-decadecanol Tetracarnealdehyde, (E)-11-tetracarnealdehyde, (E)-11,13-tetracarnedienaldehyde, (E,E)-8,10-tetracarnedienaldehyde, (Z,E)-9,11-tetracarnedienaldehyde, (Z,E)-9,12-tetracarnedienaldehyde, hexadecanealdehyde, (Z)-8-hexadecanealdehyde, (Z)-9-hexadecanealdehyde, (Z)-10-hexadecanealdehyde, (E)-10-hexadecanealdehyde, (Z)-11-hexadecanealdehyde, (E)-hexadecanealdehyde, (Z)-12-hexadecanealdehyde, (Z)-13-hexadecanealdehyde, (Z)-14-methyl-8-hexadecanealdehyde, (E)-14-methyl- 8-Hexadecenal, (Z,Z)-7,11-Hexadecenal, (Z,E)-7,11-Hexadecenal, (Z,E)-9,11-Hexadecenal, (E,E)-10,12-Hexadecenal, (E,Z)-10,12-Hexadecenal, (Z,E)-10,12-Hexadecenal, (Z,Z)-10,12-Hexadecenal, (Z,Z)-10,12-Hexadecenal, (Z,Z)-11,13-Hexadecenal, Octadecenal, (Z)-11-Octadecenal, (E)-13-Octadecenal, (Z)-13-Octadecenal, 3-Methylbutyric acid (Z)-5-decenyl ester, (+) cis-7,8-epoxy-2-methyloctadecane.

[0044] Other noteworthy pheromones include: citral; geraniol; neraldehyde; tetradecane-1-aldehyde; pentadecane-1-aldehyde; pentadecene-1-aldehyde; hexadecane-1-aldehyde; (Z)-9-hexadecene-1-aldehyde; (Z)-11-hexadecene-1-aldehyde; (7E,9E)-undecene-7,9-diene-1-aldehyde; (11Z,13Z)-hexadecene-1-aldehyde; (9Z,12E)-tetradecene-1-aldehyde; (8E,10E)-dodecene-1-aldehyde; (1 (1Z)-hexadecadien-1-aldehyde; (9Z)-tetradecene-1-aldehyde; 6,10-dimethyl-5,9-undecadien-2-ol; (6E)-7,11-dimethyl-3-methylene-1,6,10-dodecanetriene; [1S-(1a,2b,5a)]-4,6,6-trimethyl-bicyclo[3.1.1]hept-3-en-2-ol; 10-hexadeceneal; (Z)-10-hexadeceneal; (E)-10-hexadeceneal; and combinations thereof.

[0045] In some embodiments, the pheromone is selected from: (Z)-5-decenyl acetate, dodecyl acetate, (Z)-7-dodecenyl acetate, (E)-7-dodecenyl acetate, (Z)-8-dodecenyl acetate, (E)-8-dodecenyl acetate, (Z)-9-dodecenyl acetate, (E)-9-dodecenyl acetate, (E)-10-dodecenyl acetate, 11-dodecenyl acetate, (Z)-9,11-dodecadienyl acetate, (E)-9,11-dodecadienyl acetate, (Z)-11-decenyl acetate Tridecylenyl acetate, (E)-11-tetratenyl acetate, tetradecyl acetate, (E)-7-tetradecylenyl acetate, (Z)-8-tetradecylenyl acetate, (E)-8-tetradecylenyl acetate, (Z)-9-tetradecylenyl acetate, (E)-9-tetradecylenyl acetate, (Z)-10-tetradecylenyl acetate, (E)-10-tetradecylenyl acetate, (E)-10-tetradecylenyl acetate, (Z)-11-tetradecylenyl acetate, (E)-11-tetradecylenyl acetate, (Z)-12-pentadecanylenyl acetate, (E)-12-pentadecanylenyl acetate, hexadecyl acetate Alkyl esters, (Z)-7-hexadecenyl acetate, (Z)-11-hexadecenyl acetate, (E)-11-hexadecenyl acetate, octadecyl acetate, (E,Z)-7,9-dodecadienyl acetate, (Z,E)-7,9-dodecadienyl acetate, (E,E)-7,9-dodecadienyl acetate, (Z,Z)-7,9-dodecadienyl acetate, (E,E)-8,10-dodecadienyl acetate, (E,Z)-9,12-dodecadienyl acetate, (E,Z)-4,7-tetracenedienyl acetate, (E... (Z,Z)-9,11-tetradecadienyl ester, (Z,Z)-9,12-tetradecadienyl ester, (Z,Z)-7,11-hexadecadienyl ester, (Z,Z)-7,11-hexadecadienyl ester, (Z,Z)-7,11-hexadecadienyl ester, (Z,E)-7,11-hexadecadienyl ester, (Z,E)-3,13-octadecadienyl ester, (Z,Z)-3,13-octadecadienyl ester, (Z,E)-3,13-octadecadienyl ester, (Z,E)-3,13-octadecadienyl ester, (Z,E)-3,13-octadecadienyl ester, (Z)-5-decenyl ester of 3-methylbutyrate, (+) cis-7,8-epoxy-2-methyloctadecane, (Z)-2,4-decadienoic acid methyl ester, 2,6,10-trimethyltetrate methyl ester, and combinations thereof.

[0046] In some embodiments, the pheromone loading level relative to the entire formulation is from about 5% to about 30% by weight. In some embodiments, the pheromone loading level relative to the entire formulation is from about 5% to about 15% by weight. The loading level is achieved by in-situ autopolymerization of isocyanate monomers to form a polymer film.

[0047] In some embodiments, the pheromone load relative to the entire formulation is at least about 5% by weight, at least about 6% by weight, at least about 7% by weight, at least about 8% by weight, at least about 9% by weight, at least about 10% by weight, at least about 11% by weight, at least about 12% by weight, at least about 13% by weight, at least about 14% by weight, at least about 15% by weight, at least about 16% by weight, at least about 17% by weight, at least about 18% by weight, at least about 19% by weight, at least about 20% by weight, at least about 21% by weight, at least about 22% by weight, at least about 23% by weight, at least about 24% by weight, at least about 25% by weight, at least about 26% by weight, at least about 27% by weight, at least about 28% by weight, or at least about 29% by weight. In some embodiments, the pheromone load level relative to the whole formulation is up to about 6% by weight, up to about 7% by weight, up to about 8% by weight, up to about 9% by weight, up to about 10% by weight, up to about 11% by weight, up to about 12% by weight, up to about 13% by weight, up to about 14% by weight, up to about 15% by weight, up to about 16% by weight, up to about 17% by weight, up to about 18% by weight, up to about 19% by weight, up to about 20% by weight, up to about 21% by weight, up to about 22% by weight, up to about 23% by weight, up to about 24% by weight, up to about 25% by weight, up to about 26% by weight, up to about 27% by weight, up to about 28% by weight, up to about 29% by weight, or up to about 30% by weight.

[0048] In some embodiments, the pheromone is present in a percentage of about 10% by weight to about 100% by weight in the organic phase. In some embodiments, the pheromone is present in a percentage of about 50% by weight to about 100% by weight in the organic phase. In some embodiments, the pheromone is present in a percentage of about 70% by weight to about 100% by weight in the organic phase.

[0049] In some embodiments, the percentage of the pheromone in the organic phase is at least about 10% by weight, at least about 15% by weight, at least about 20% by weight, at least about 25% by weight, at least about 30% by weight, at least about 35% by weight, at least about 40% by weight, at least about 45% by weight, at least about 50% by weight, at least about 55% by weight, at least about 60% by weight, at least about 65% by weight, at least about 70% by weight, at least about 75% by weight, at least about 80% by weight, at least about 85% by weight, at least about 90% by weight, or at least about 95% by weight. In some embodiments, the percentage of the pheromone in the organic phase is up to about 10% by weight, up to about 15% by weight, up to about 20% by weight, up to about 25% by weight, up to about 30% by weight, up to about 35% by weight, up to about 40% by weight, up to about 45% by weight, up to about 50% by weight, up to about 55% by weight, up to about 60% by weight, up to about 65% by weight, up to about 70% by weight, up to about 75% by weight, up to about 80% by weight, up to about 85% by weight, up to about 90% by weight, up to about 95% by weight, or up to about 100% by weight.

[0050] In some embodiments, the wall material (e.g., isocyanate) is present in a percentage of about 5% to about 20% by weight relative to the organic phase. In some embodiments, the wall material (e.g., isocyanate) is present in a percentage of about 7% to about 15% by weight relative to the organic phase. In some embodiments, the wall material (e.g., isocyanate) is present in a percentage of about 10% to about 16% by weight relative to the organic phase. In some embodiments, the wall material (e.g., isocyanate) is present in a percentage of about 8% to about 12% by weight relative to the organic phase.

[0051] In some embodiments, the wall material (e.g., isocyanate) is present in a percentage of at least about 3% by weight, at least about 4% by weight, at least about 5% by weight, at least about 6% by weight, at least about 7% by weight, at least about 8% by weight, at least about 9% by weight, at least about 10% by weight, at least about 11% by weight, at least about 12% by weight, at least about 13% by weight, at least about 14% by weight, at least about 15% by weight, at least about 16% by weight, at least about 17% by weight, at least about 18% by weight, or at least about 19% by weight. In some embodiments, the wall material (e.g., isocyanate) is present in a percentage of up to about 4% by weight, up to about 5% by weight, up to about 6% by weight, up to about 7% by weight, up to about 8% by weight, up to about 9% by weight, up to about 10% by weight, up to about 11% by weight, up to about 12% by weight, up to about 13% by weight, up to about 14% by weight, up to about 15% by weight, up to about 16% by weight, up to about 17% by weight, up to about 18% by weight, up to about 19% by weight, or up to about 20% by weight.

[0052] Generally, compositions according to this disclosure may contain any suitable solvent known in the art that is helpful to the compositions described herein. The solvent may be a single solvent or a mixture of solvents. In some embodiments, the solvent is selected from hydrophobic solvents, including high flash point solvents, methylated seed oils, methyl oleate methyl ester oil, methyl linoleate methyl ester oil, mineral oils, paraffin oils, tall oil fatty acid-based solvents, aromatic solvents (e.g., Aromatic 200, Aromatic 200ND), aromatic ester solvents, polybutene, fatty acid methyl esters, tributyl 2-acetate citrate, alkylamides (e.g., Agnique AMD10), benzyl acetate, wax esters, and combinations thereof. In some embodiments, the solvent includes methyl oleate methyl ester oil and methyl linoleate methyl ester oil. In some embodiments, the solvent includes methyl oleate oil and methyl linoleate oil, as well as solvents selected from hydrophobic solvents, including high flash point solvents, methylated seed oils, mineral oils, paraffin oils, tall oil fatty acid-based solvents, aromatic solvents, aromatic ester solvents, polybutene, fatty acid methyl esters, 2-acetyl tributyl citrate, alkylamides, benzyl acetate, wax esters, and combinations thereof.

[0053] In some embodiments, the pheromone and the solvent are encapsulated separately. In some embodiments, the pheromone and the solvent are co-encapsulated. In some embodiments, the pheromone and the solvent are co-encapsulated with at least one excipient.

[0054] Typically, compositions according to this disclosure may contain any suitable antifreeze known in the art that contributes to the compositions described herein. In some embodiments, the antifreeze is selected from propylene glycol, glycerin, glycols, ethylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, methanol, ethanol, propanol, butanol, and combinations thereof. In some embodiments, the antifreeze is unencapsulated. In some embodiments, a portion of the antifreeze is encapsulated.

[0055] In many embodiments, the shell comprises polyurea, isocyanate, and / or polyisocyanate. Suitable isocyanates include polyisocyanates and polyisocyanate prepolymers, such as polymethylene polyphenyl isocyanate (e.g., PAPI 27), polymeric diphenylmethane diisocyanate (MDI) (e.g., Rubinate M or Suprasec 5025), isocyanates based on diphenylmethylene diisocyanate (XDI), including but not limited to Takenate™ 500 (XDI), Takenate™ 600 (hydrogenated XDI), Takenate™ D-110N (an adduct of XDI and trimethylolpropane), Takenate™ D-131N (an XDI trimer), and Takenate™ D-120 (an adduct of hydrogenated XDI and trimethylolpropane), polyisocyanate-polyol adducts, polyfunctional aliphatic isocyanates, etc. In these embodiments, the shell is formed without the addition of any additional amines. In some embodiments, the shell is formed by in-situ autopolymerization. When the shell comprises a polyurea, the polyurea is formed by in-situ autopolymerization of isocyanate monomers. Without being bound by any particular theory, it is believed that the isocyanate monomers can react with water in an aqueous phase to form carbamic acid, which is then converted into an amine and carbon dioxide. The amine then reacts with the isocyanate monomers to form the polyurea.

[0056] In some embodiments, the composition is an agricultural chemical composition. In some embodiments, the composition is in the form of a premix and a tank mix. In some embodiments, the composition is a sprayable composition.

[0057] The compositions according to this disclosure may be any suitable composition known in the art that contributes to the compositions described herein. Particularly preferred formulations of the compositions according to this disclosure are capsule suspension concentrates (CS), mixed formulations comprising a mixture of suspension concentrates (SC) and capsule suspension concentrates (CS) (ZC), mixed formulations comprising a mixture of oil-in-water emulsions (EW) and capsule suspension concentrates (CS) (ZW), and mixed formulations comprising a mixture of suspensions (SE) and capsule suspension concentrates (CS) (ZE).

[0058] In some embodiments, the composition is in the form of a CS formulation, a ZC formulation, a ZW formulation, or a ZE formulation.

[0059] Sprayable formulations are typically diluted in a suitable medium before spraying. These formulations are prepared to be easily diluted in the spraying medium, usually water, but occasionally other suitable media such as aromatics or alkanes or vegetable oils. Spraying volumes can range from about one liter to several thousand liters per hectare, but more typically from about ten liters to several hundred liters per hectare. Sprayable formulations can be mixed with water or other suitable media for foliar application via air or ground application, or applied to the plant's growing medium. Formulations can be metered directly into drip irrigation systems or metered into furrows during planting. Formulations can be applied as a seed treatment to the seeds of crops and other desired vegetation prior to planting to protect developing roots and other underground plant parts and / or leaves through systemic absorption.

[0060] The compositions according to this disclosure can be delivered by an autonomous vehicle. The autonomous vehicle can be a ground vehicle. The autonomous vehicle can operate during the day and / or at night.

[0061] The compositions according to this disclosure can be delivered by air. The compositions according to this disclosure can be delivered by unmanned vehicles or unmanned aerial vehicles (UAVs). The compositions according to this disclosure can be delivered by helicopters or fixed-wing aircraft.

[0062] Generally, the compositions according to this disclosure can be prepared according to any suitable method known in the art that is helpful to the compositions described herein.

[0063] In some embodiments, a method for preparing a composition is described herein, the method comprising: forming a mixture comprising an antifreeze agent; and microcapsules comprising a core containing a pheromone; and a solvent; and a shell encapsulating the core. The shell comprises a polymer produced by the autopolymerization of monomers, and the microcapsules have a d90 value of less than about 40 μm.

[0064] In some embodiments, the method further includes encapsulating the pheromone and the solvent in the microcapsules prior to forming the mixture. In these embodiments, the microcapsules are added to the mixture.

[0065] In some embodiments, the method includes encapsulating the pheromone and the solvent in the microcapsules within the mixture. In these embodiments, the microcapsules are formed in situ in the mixture using known interfacial polymerization methods. Microencapsulated formulations prepared by interfacial polymerization are advantageous for at least three reasons: i) they are readily prepared on a large scale using known techniques; ii) they are readily applied over large areas using conventional spraying equipment; and iii) they have numerous variables that can be manipulated to control release characteristics (e.g., capsule wall thickness, capsule wall composition, capsule size, and internal composition).

[0066] Generally, the compositions according to this disclosure can be used for any suitable purpose known in the art that is conducive to the composition described herein.

[0067] In some embodiments, this document describes a method for controlling pests, the method comprising contacting the pest or its environment with a bioactive amount of a composition comprising: an antifreeze agent; and microcapsules comprising: a core containing: a pheromone; and a solvent; and a shell encapsulating the core. The shell comprises a polymer produced by the autopolymerization of monomers, and the microcapsules have a d90 value of less than about 40 μm.

[0068] The compositions disclosed herein can be used to control a broad spectrum of invertebrate pests. These pests include invertebrates that inhabit a variety of environments, such as plant leaves, roots, soil, harvested crops or other food, building structures, or animal hides. These pests include, for example, invertebrates that feed on leaves (including leaves, stems, flowers, and fruits), seeds, wood, textile fibers, or animal blood or tissues, thereby causing harm or damage to, for example, growing or stored agronomic crops, forest crops, greenhouse crops, ornamental plants, nursery crops, stored food or fiber products, or houses or other structures or their contents, or are harmful to animal health or public health. Those skilled in the art will understand that not all compositions are equally effective against all growth stages of all pests.

[0069] Therefore, these compositions of the present invention can be used agronomically to protect field crops from phytophagous invertebrate pests, and non-agronomically to protect other horticultural crops and plants from phytophagous invertebrate pests. This use includes protecting crops and other plants containing genetic material introduced through genetic engineering (i.e., transgenics) or modified through mutagenesis to provide advantageous traits (i.e., agronomical and non-agronomical). Examples of such traits include herbicide tolerance, resistance to phytophagous pests (e.g., insects, mites, aphids, spiders, nematodes, snails, plant pathogenic fungi, bacteria, and viruses), improved plant growth, enhanced tolerance to adverse growth conditions (e.g., high or low temperatures, low or high soil moisture, and high salinity), increased flowering or fruiting, greater harvest yield, faster maturity, higher quality and / or nutritional value of the harvested product, or improved storage or processing characteristics of the harvested product. Transgenic plants can be modified to express a variety of traits. Examples of plants containing traits provided through genetic engineering or mutagenesis include those expressing the insecticidal Bacillus thuringiensis (Bt). Bacillus Thuringian Toxins in corn, cotton, soybean, and potato varieties, such as YIELD GARD ® KnockOut ® Starlink ® Bolgard ® NuCOTN® and NewLeaf ® INVICTA RR2 PROTM; and herbicide-tolerant corn, cotton, soybean, and rapeseed varieties, such as Roundup Ready. ® Liberty Link ® IMI ® STS ® and Clearfield ® ; and expression N - Acetyltransferase (GAT) to provide resistance to glyphosate herbicides; or crops containing the HRA gene, which provides resistance to herbicides that inhibit acetyllactate synthase (ALS). The compositions of the present invention can exhibit enhancing effects on traits introduced through genetic engineering or modified through mutagenesis, thus enhancing the phenotypic expression or effectiveness of said trait, or increasing the effectiveness of the compounds and compositions of the present invention in controlling invertebrate pests. In particular, the compositions of the present invention can exhibit enhancing effects on the phenotypic expression of proteins or other natural products toxic to invertebrate pests, providing greater-than-additive control over these pests.

[0070] The compositions disclosed herein may optionally contain phytonutrients, such as fertilizer compositions containing at least one phytonutrient selected from nitrogen, phosphorus, potassium, sulfur, calcium, magnesium, iron, copper, boron, manganese, zinc, and molybdenum. It is noteworthy that compositions containing at least one fertilizer composition contain at least one phytonutrient selected from nitrogen, phosphorus, potassium, sulfur, calcium, and magnesium. Further, compositions of this disclosure containing at least one phytonutrient may be in liquid or solid form. Solid formulations in granule, rod, or tablet form are noteworthy. Solid formulations containing fertilizer compositions can be prepared by mixing the compositions of this disclosure together with the formulation ingredients, and then preparing the formulation by methods such as granulation or extrusion. Alternatively, solid formulations can be prepared by spraying a solution or suspension of the compositions of this disclosure in a volatile solvent onto a previously prepared fertilizer composition in the form of a size-stable mixture (e.g., granules, rods, or tablets), and then evaporating the solvent.

[0071] Non-agricultural uses refer to the control of invertebrate pests in areas outside the field where crop plants are grown. Non-agricultural uses of the compositions of this invention include the control of invertebrate pests in stored grains, legumes, and other food products, as well as textiles such as clothing and carpets. Non-agricultural uses of the compositions of this invention also include the control of invertebrate pests in ornamental plants, forests, yards, roadsides and railway land, and turf (e.g., lawns, golf courses, and pastures). Non-agricultural uses of the compositions of this invention also include the control of invertebrate pests in houses and other buildings that may be occupied by humans and / or companion animals, farms, pastures, zoos, or other animals. Non-agricultural uses of the compositions of this invention also include the control of pests such as termites, which can damage timber or other structural materials used in buildings.

[0072] Non-agricultural uses of the compositions of this invention also include protecting human and animal health by controlling invertebrate pests that parasitize or transmit infectious diseases. Control of animal parasites includes controlling external parasites that parasitize the surface of the host animal (e.g., shoulders, armpits, abdomen, inner thighs) and internal parasites that parasitize the body of the host animal (e.g., stomach, intestines, lungs, veins, subcutaneous tissue, lymphatic tissue). External parasitic or disease-transmitting pests include, for example, chiggers, ticks, lice, mosquitoes, flies, mites, and fleas. Internal parasites include heartworms, hookworms, and worms. The compositions disclosed herein are suitable for systemic and / or non-systemic control of parasitic infestations or infections on animals. The compositions disclosed herein are suitable for combating external parasitic or disease-transmitting pests. The compositions disclosed herein are suitable for combating parasites infecting the following animals: agricultural working animals, such as cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, hens, turkeys, ducks, geese, and bees; pet animals and domesticated animals, such as dogs, cats, pet birds, and ornamental fish; and so-called laboratory animals, such as hamsters, guinea pigs, rats, and mice. By combating these parasites, mortality and performance degradation (in terms of meat, milk, fur, hides, eggs, honey, etc.) are reduced, making animal husbandry more economical and simpler with the application of the compositions disclosed herein.

[0073] Examples of agronomic and non-agronomic invertebrate pests include eggs, larvae, and adults of Lepidoptera, such as armyworms, cutworms, inchworms, and heliothines (e.g., the rice stem borer). Bringing sesame seeds Walker), corn stalk borer (corn stalk borer) Sesamia nonagrioides Lefebvre), Southern Armyworm (Southern Armyworm ( Spodoptera eridania Cramer), fall armyworm (fall armyworm) Spodoptera frugiperda JE Smith), beet armyworm (beet armyworm ( Spodoptera small Hübner), cotton leafworm (cotton leafworm) Spodoptera littoralis Boisduval), Yellow-striped Gray-winged Noctuid Moth (Yellow-striped Gray-winged Noctuid Moth) Spodoptera ornithogalum Guenée), small cutworm (small cutworm ( Agrotis ipsilon Hufnagel), soybean caterpillar (Velvetbean caterpillar) (Soybean caterpillar) Anticarsia gemmatalis Hübner), green fruitworm (green fruitworm Lithophane antennata Walker), cabbage looper (cabbage looper) Cabbage patch Linnaeus), soybean looper (soybean looper) (soybean looper) Pseudoplusia including Walker), cabbage looper (cabbage looper) Trichoplusia ni Hübner), Tobacco budworm (Tobacco budworm) Heliothis greening Fabricius; Pyralidae family: corn borers, sheath moths, webworms, coneworms, cabbage worms, and skeletonizers (such as the European corn borer). Clouded oyster Hübner), navel orange moth (navel orange moth ( Amyelois transitella Walker), corn root webworm (corn root webworm) Dark-skinned crab Clemens), sod webworm (family Pyralidae: subfamily Pyralinae) Crambin Such as the sod worm (rice leafhopper). Herpetogramma licarsisalis Walker), two-spotted stem borer (sugarcane stem borer) (two-spotted stem borer) Chilo infuscatelli Snellen), Tomato Small Boar (Tomato Small Boar) Neoleucinodes elegantalis Guenée), rice leaf roller (green leafroller) (rice leaf roller) Cnaphalocrocis medinalis Guenée), grape leaf worm (grape leaffolder) Desmia funeralHübner, pickleworm (cucumber pickleworm) Bright transparency Stoll), cabbage center grub ( Hydra's hydra Guenée, yellowstem borer (yellowstem borer) Scirpophaga incertulas Walker), white stem borer (white stem borer) (white stem borer) Scirpophaga innotata Walker), top shoot borer (top shoot borer) Scirpophaga nivella Fabricius), dark-headed rice borer (Fabius) Chilo polychrysus Meyrick), striped riceborer (striped riceborer) Kilo suppressed Walker), cabbage cluster caterpillar (cabbage cluster caterpillar) Crocidolomia binotalis Zeller); Leafrollers, budworms, seed worms, and fruit worms of the Tortricidae family (such as the codling moth and the small apple roller). Cydia pomonella Linnaeus), Grape Berry Moth (Grape Berry Moth ( Paralobesia viteana Clemens), pear fruit moth (pear fruit moth ( Grapholite pest Busck), the apple variegated leafroller (citrus false codling moth) (the apple variegated leafroller) Cryptophlebia leucotreta Meyrick), citrus heartworm (citrus heartworm) Gymnandrosoma aurantianum Lima), Red-banded Leaf Roller (Red-banded Leaf Roller) Argyrotaenia velutinana Walker), striped leafroller (striped leafroller ( Choristoneura rosaceana Harris), apple light brown leafroller (apple light brown leafroller) Epiphyas postvittana Walker), European grape berry moth (ringed needle single-striped leafroller) Eupoecilia ambiguous Hübner), apple bud moth (Apple bud moth) Pandemis pyrusana Kearfott), omnivorous leafroller (omnivorous leafroller) Platynota stultanaWalsingham), barred fruit-tree tortrix (Barred fruit-tree tortrix) Cherry blossom Hübner), apple brown roller (apple brown roller ( Heparin pandemic Denis & Schiffermüller); and many other important economic lepidopterans (such as the diamondback moth). Plutella xylostella Linnaeus), pink bollworm (Pinus linnaeus) Pectinophora gossypiella Saunders), gypsymoth (Gypsymoth) Lymantria dispar Linnaeus), peach fruit borer (Peach fruit borer ( Carp Japanese Walsingham), the peach-leaf moth (the peach-leaf moth) Anarsia lineatella Zeller), potato tuber moth (potato tuber moth) Phthorimaea operculella Zeller), the mottled leafminer (the mottled leafminer) Phyllonorycter blancardella Fabricius), Asiatic apple leafminer (Asiatic apple leafminer) (Asiatic apple leafminer) Lithocolletis ringoniella Matsumura), rice leaf folder (Matsumura) Lerodea euphala Edwards, apple leafminer (Edwards), apple leafminer (Edwards) White-winged small bowl Zeller); eggs, nymphs, and adults of the order Blattodea, including cockroaches of the families Blattellidae and Blattidae (such as the Oriental cockroach). Oriental cockroach Linnaeus), Asian cockroach (Asian cockroach) Blatella asahinai Mizukubo), German cockroach (German cockroach) German cockroach Linnaeus), brownbanded cockroach (long-bearded cockroach) Supella longipalpa Fabricius), American cockroach (American cockroach) American periplaneta Linnaeus), brown cockroach (Brown cockroach) Brown periplaneta Burmeister), Madeira cockroach (Madeira cockroach ( Leucophaea maderaeFabricius), Black-breasted cockroach (smoky brown cockroach) (Black-breasted cockroach) Sooty periplaneta Serville), Australian Cockroach (Australian Cockroach) Periplaneta Australasia Fabr.), lobster cockroach (lobster cockroach) Grey Nauphoeta Olivier), smooth cockroach (smooth cockroach) Symplocus pales. Stephens); Coleoptera eggs and larvae and adults that feed on leaves, fruits, roots, seeds, and vascular tissue, including weevils of the families Anthribidae, Bruchidae, and Curculionidae (such as the boll weevil). Anthonomus grandis Boheman), rice weevil (rice weevil ( Lissorhoptrus oryzophilus Kuschel), Valley Elephant (Valley Elephant ( Sitophilus granarius Linnaeus), rice elephant (rice elephant ( Sitophilus oryzae Linnaeus), annual bluegrassweevil (grass weevil) Listronotus maculicollis Dietz), Bluegrass weevil (Bluegrass weevil) Small sphenophorus Gyllenhal), the hunting billbug (a type of grass beetle) Sphenophorus dressed in hunting gear Chittenden), Rocky Mountain billbug (Los Angeles Elephant) Sphenophorus cicatriatus Fahraeus); Chrysomelidae family includes flea beetles, cucumber beetles, rootworms, leaf beetles, potato beetles, and leaf miners (e.g., Colorado potato beetle). Leptinotarsa ​​ten-lineata Say), western corn rootworm (corn rootworm) Diabrotica virgifera LeConte); scarab beetles and other beetles from the family Scarabaeidae (e.g., Japanese scarab beetle (Japanese scarab beetle ( Japanese popillia Newman), Oriental beetle (Newman) Oriental anomaly Waterhouse, Northern masked chafer (Northern masked chafer) Cyclocephalus borealis Arrow), Southern masked chafer (Southern masked chafer) Cyclocephala immaculata Olivier or C. lurida Bland), dung beetle, and white grub (genus *Olivier*). Aphodius s) species), Black Turfgrassataenius ( Ataenius spretulus Haldeman), Green June Beetle (Haldeman), Clean, clean, clean. Linnaeus, Asiatic garden beetle ( Misfortune chestnut Arrow), May / June beetle (Genus *Ceratophyllum*) Phyllophagus ) species) and European scarab beetle ( Rhizotrogus majalis Razoumowsky); the carpet beetle from the family Dermestidae; the wireworm from the family Elateridae; the bark beetle from the family Scolytidae; and the flour beetle from the family Tenebrionidae.

[0074] In addition, agricultural and non-agricultural pests include: eggs, adults, and larvae of Dermaptera, including earwigs from the family Forficulidae (e.g., the European earwig). Earwig Linnaeus), black earwig (black earwig) Chelisochus I dieFabricius; eggs, larvae, adults, and nymphs of the order Hemiptera, such as plant bugs from the family Miridae, cicadas from the family Cicadidae, and leafhoppers from the family Cicadellidae (e.g., the genus *Cicada*). Empoasca ) species), bed bugs from the family Cimicidae (e.g., temperate bed bugs ( Bed bug Linnaeus, planthoppers from Fulgoridae and Delphacidae, treehoppers from Membracidae, psyllids from Liviidae, Psyllidae, and Triozidae, whiteflies from Aleyrodidae, aphids from Aphididae, phylloxera from Phylloxeridae, mealybugs from Pseudococcidae, scale insects from Coccidae, Diaspididae, and Margarodidae, and lace bugs from Tingidae. bugs, including stink bugs from the Pentatomidae family and chinch bugs from the Lygaeidae family (e.g., the hairy chinch bug). Blissus leucopterus hirtus Montandon)) and Southern Long Bug (Southern Long Bug) Island bliss Barber) and other seed bugs from the family Cercopidae, spidger bugs from the family Coreidae, and red bugs and cotton stainers from the family Pyrrhocoridae.

[0075] Agricultural and non-agricultural pests also include: eggs, larvae, nymphs, and adults of mites (Acari), such as spider mites and red mites of the family Tetranychidae (e.g., the European red mite). Panonychus elm Koch), two-spotted spider mite (two-spotted spider mite) Spider mite Koch), Michael's spider mite (Michael's spider mite) Tetranychus mcdanieli McGregor); Flat mite of the family Tenuipalpidae (e.g., *Citrus flat mite*). Brevipalpus lewisi McGregor); rust mites and bud mites of the family Eriophyidae, as well as other leaf-feeding mites and mites important to human and animal health, namely dust mites of the family Epidermoptidae, follicle mites of the family Demodecidae, and grain mites of the family Glycyphagidae; ticks of the family Ixodidae, commonly known as hard ticks (e.g., *Ixodidae scapularis*). Ixodes scapularis Say, Australian paralysis tick (Symplocos rubrum) Ixodes holocyclus Neumann tick), American dog tick (American dog tick) Dermacentor variabilis Say), Lone Star Tick (Lone Star Tick) (Lone Star Tick) Amblyomma americanum Linnaeus and ticks of the family Argasidae, commonly known as soft ticks (e.g., the relapsing fever tick). Ornithodoros turicata Duges), common fowl ticks (fowl ticks) (radiater ticks) Radiated argas Raillet); scab mites and itch mites of the families Psoroptidae, Pyemotidae, and Sarcoptidae; eggs, adults, and larvae of Orthoptera, including grasshoppers, locusts, and crickets (e.g., migratory grasshoppers; e.g., blood locusts). Melanoplus sanguineus Fabricius, special locust species (M. differential Thomas, American grasshoppers (e.g., American sand locusts) Schistocerca americana Drury), desert locust (desert locust) Schistocerca gregarious Forsskål), locust (locust ( Migratory locust Linnaeus), bush locust (bush locust) (Gnaphal locust) Zonocerus ) species), house cricket (house cricket ( Domesticated Acheta Linnaeus), mole crickets (e.g., the yellowish-brown mole cricket) Scapteriscus vicinus Scudder and mole cricket ( Scapteriscus borellii Giglio-Tos); eggs, adults, and larvae of Diptera, including leaf miners (e.g., leaf miners of the genus Giglio-Tos); Liriomyza ) species, such as the American serpentine leafminer (Self-leaved leafminer) (Self-leaved leafminer) Liriomyza sativa Blanchard, midges, fruit flies (Tephritidae), straw flies (e.g., Swedish straw flies) Oscinella frit Linnaeus), soil maggots, houseflies (e.g., houseflies) Housefly Linnaeus), housefly (e.g., summer toilet fly (Linnaeus)), and small housefly (e.g., summer toilet fly (Linnaeus)). Fannia canicularis Linnaeus, small housefly ( Femoral F. Stein), stable fly (e.g., stable fly ( Stomachache kicking Linnaeus), face fly, horn fly, blow fly (e.g., golden fly genus) Chrysomya ) species, genus *Fly* ( Phormia ) species) and other fly pests, horseflies (e.g., horseflies) Horsefly ) species), bot flies (e.g., the genus *Gastropoda*). Gasterophilus ) species, genus *Ceratophyllum* ( Estrus ) species, cattle grubs (e.g., genus Cattle grubs) Hypodermis (Species), deer fly (e.g., the genus *Tetranychus*) Chrysops ) species), sheep ticks (keds) (e.g., sheep ticks ( Sheep's hawkLinnaeus and other suborders of Brachycera, mosquitoes (e.g., Aedes genus) House ) species, Anopheles genus ( Anopheles ) species, Culex genus ( Mosquito ) species), black fly (e.g., the genus Protoceratops) Proximum ) species, genus *Nematoda* ( Simulacrum ) species), biting midges, sandflies, sciarids and other Nematocera; eggs, adults and larvae of Thysanoptera, including onion thrips (onion thrips) Tobacco thrips Lindeman), flower thrips (the genus *Thrips*) Frankliniella ) species) and other leaf-eating thrips; insect pests of the order Hymenoptera, including ants of the family Formicidae, including the Florida carpenter ant (Florida carpenter ant). Camponotus floridanus Buckley), Redwood Ants Camponotus ferruginous Fabricius, blackwood ant (Pennsylvania carpenter ant) Camponotus pennsylvanicus De Geer), white-footed ant (white-footed ant) Technomyrmex albipes F. Smith), big-headed ants (genus *F. Smith*) Pheidole ) species), ghost ant (black-headed sour ant (black-headed sour ant ( Tapioca black-headed Fabricius); Pharaoh ants (Pharaoh ants ( Pharaoh's Monomorium Linnaeus), small fire ants (small fire ants ( Wasmannia auropunctata Roger), tropical fire ants (fire ants) (tropical fire ants) Solenopsis geminata Fabricius), red imported fire ant (red imported fire ant) Solenopsis invicta Buren), Argentine ant (Argentine ant ( Iridomyrmex humilis Mayr), Crazy ant (crazy ant) Paratrechina longhorn Latreille), pavement ant (pavement ant) Tetramorium turbinatum Linnaeus), corn ants (cornfield ants) Stranger's lasiusFörster) and odorous house ant (odorous house ant) Sessile tapinoma Say). Other Hymenoptera include bees (including carpenterbee), hornets, yellow jackets, wasps, and sawflies (Neopine sawfly genus). Neodiprion ) species; Stem bee genus ( Cephus ) species); insect pests of the order Isoptera, including termites (e.g., giant termites). Macrotermes ) species, fat-bodied subterranean termites ( Odontotermes obesus Rambur), Kalotermitidae (e.g., the genus *Kalotermitidae*) Cryptotermes ) species), and the family Rhinotermitidae (e.g., subterranean termites ( ) Reticulitermes ) species, genus *Dalbergia* ( Coptotermes ) species, slender termite ( Heterotermes tenuis Hagen termites, specifically the Eastern subterranean termite (Northern subterranean termite). Reticulitermes flavipes Kollar), western subterranean termite (Western subterranean termite) Reticulitermes hesperus Banks), Formosan subterranean termite (Formosan subterranean termite) Coptotermes handsome Shiraki), West Indian drywood termite (West Indian drywood termite) Incisitermes immigrans Snyder), powderer post-termite (powder post-termite) Cryptotermes brevis Walker termite), drywood termite (Snyder termite) Incisitermes snyderi Light), Virginia subterranean termite (Virginia subterranean termite) Reticulitermes virginicus Banks), western drywood termite (Chinese termite) Incisitermes minor Hagen), arboreal termites such as the genus *Hymenopterus* (Hymenopterus var. *hagen*), and arboreal termites such as the genus *Hymenopterus* (Hymenopterus var. *hagen*). Nasutitermes ) species, as well as other economically important termites; insect pests of the order Thysanura, such as silverfish (silverfish) Sugar silverfish Linnaeus and silverfish Thermobia domestica Packard; insect pests of the orders Mallophaga and Phthiraptera, including head lice (head lice... Human head louse De Geer)), body lice (body lice ( Human louse Linnaeus), chicken lice ( Menacanthus stramineus Nitzsch), dog lice (dog lice) Trichodectes canis De Geer), hairy lice ( Hen's goniocotes DeGeer), sheep louse (sheep body louse) Cow and sheep Schrank), short-nosed cattle lice ( Haematopinus eurysternus Nitzsch), long-nosed cattle lice ( Calf-footed tortoise Linnaeus and other piercing-sucking and chewing parasitic lice that attack humans and animals; insect pests of the order Siphonoptera, including the oriental rat flea (Linnaeus spp.) Xenopsylla cheopis Rothschild)), cat flea (cat flea (cat flea) Ctenocephalides felis Bouché), dog comb-head flea (dog comb-head flea ( Ctenocephalidae dog Curtis), hen flea (hen flea) (hen flea) Hen's hornwort Schrank), sticktight flea (Schrank), sticktight flea (Schrank) Echidnophaga gallinacea Westwood), fleas (fleas) Irritating flea Linnaeus and other fleas that plague mammals and birds. Other arthropod pests covered include spiders of the order Araneae, such as the brown recluse spider (Brown Recluse Spider). Loxosceles recluse Gertsch & Mulaik) and the black widow spider (black widow spider) Robber slaughterer Fabricius), and centipedes of the order Scutigeromorpha, such as centipedes (Scutigeromorpha (Scutigeromorpha) Scutigera beetle Linnaeus).

[0076] Examples of invertebrate pests that infest stored grains include the large grain borer (Granaria spp.). Prostephanus truncatus Horn), lesser grain borer (horn) Rhyzopertha dominica Fabricius), Rice Elephant Sitophilus oryzae Linnaeus, maize weevil (maize weevil ( Sitophilus zeamais Motschulsky), cowpea weevil (cowpea weevil) Callosobruchus maculatus Fabricius), Red flour beetle (Red flour beetle) Chestnut Tribolium Herbst), Valley Elephant Sitophilus granary Linnaeus, Indian meal moth (Indian meal moth) Plodia interpunct Hübner), Mediterranean mealy bug (Mediterranean mealy borer (Mediterranean mealy borer) Ephestia kuehniella Zeller)) and the longhorned flatbread beetle or the rusty flatbread beetle (rusty flatbread beetle ( Cryptolestes ferrugineus Stephens).

[0077] The compositions disclosed herein can be used to control members of the classes Nematoda, Cestoda, Trematoda, and Acanthocephala, including economically important members of the orders Strongylida, Ascaridida, Oxyurida, Rhabditida, Spirurida, and Enoplida, such as, but not limited to, economically important agricultural pests (i.e., root-knot nematodes). Meloidogyne Root-knot nematodes and short-bodied nematodes ( ) Pratylenchus Root-rot nematodes (lesionnematode) and hairy nematodes ( Trichodorus The list includes stubby root nematodes, as well as pests affecting animal and human health (i.e., all economically important flukes, tapeworms, and roundworms, such as the common roundworm in horses). Strongylus vulgaris Toxocara canis in dogs ( Toxocara canis ), Hemagglutinationis contortus in sheep ( Haemonchus contortus ), canine filarial worms ( Heartworm disease Leidy), the leaf-shaped naked-headed tapeworm in horses ( Anoplocephala perfoliata Liver flukes in ruminants ( Fasciola hepaticaLinnaeus et al.

[0078] The compositions disclosed herein can be used to control pests in the order Lepidoptera (e.g., kapok beetles). Alabama clayey Hübner (cotton leaf worm), fruit tree yellow roller ( Archips argyrospila Walker (fruit tree leaf roller), rose leaf roller ( A. rosana Linnaeus (European leaf roller) and other leaf rollers (Linnaeus) Archippus ) species, rice stem borer, rice leaf roller, corn root borer, early-maturing grass borer Red-footed crampon Zincken (bluegrass webworm), apple leafroller, Egyptian borer ( Island Earias Boisduval (Egyptian spiny bollworm), Emerald spiny bollworm ( Earias vetlana Fabricius (spotted bollworm), cotton bollworm ( Helicoverpa armigera Hübner) (Old Worldbollworm), Spodoptera exigua ( Helicoverpa zea Boddie (corn earworm), tobacco bud borer (tobacco bud borer), rice leaf cutter borer (sod webworm), grape flower leaf roller ( Lobesia botrana Denis & Schiffermüller (grape berry moth), cotton bollworm, citrus leafminer ( Phyllocnistis citrella Stainton (citrus leafminer), European white butterfly ( Cabbage Pieris Linnaeus (European White butterfly, large white butterfly), Cabbage White butterfly ( Pieris turnips Linnaeus (small white butterfly), diamondback moth (diamondback moth), beet armyworm (beet armyworm), beet armyworm (striped armyworm) Spodoptera lituraFabricius (Tobaccocutworm, Cluster Caterpillar), Fall Armyworm, Powdered Armyworm, and Tomato Leafminer ( Absolutely safe Meyrick (tomato leafminer).

[0079] The compositions disclosed herein can be used to control members of the order Hemiptera, including: pea aphids ( Acyrthosiphon pea Harris (pea aphid), bean aphid ( Aphis spicatus Koch (bean aphid), beet aphid ( Bean aphid Scopoli (beet aphid, black bean aphid), cotton aphid ( Aphis gossypii Glover (cotton aphid, melon aphid) and apple yellow aphid ( Aphid apples De Geer (apple aphid), Spirea aphid ( Aphis spiraecola Patch (Spiraea aphid), Eggplant aphid ( Nightshade Kaltenbach (Foxglove aphid), Strawberry trichotillo ( Chaetosiphon fragaefolii Cockerell (strawberry aphid), wheat double-tailed aphid ( Diuraphis noxious Kurdjumov / Mordvilko (Russian wheat aphid), Plantago asiatica ( Dysaphis plantain Passerini (Rosy apple aphid), Apple woolly aphid ( Eriosoma woolly Hausmann (woolly apple aphid), European plum aphid ( Hyalopterus plumi Geoffroy (Mealy plum aphid), Radish aphid ( Lipaphis pseudo-brassica Davis (turnip aphid), wheat webless long-tubed aphid ( Metopolophium dirhod Walker (rose-grain aphid), potato aphid ( Macrosiphum euphorbiaThomas (potato aphid), peach aphid ( Myzus persica Sulzer (peach-potato aphid, green peach aphid) and currant lettuce aphid ( Nasovia blackcurrant Mosley (lettuce aphid), genus *Mosley* ( Pemphigus Species (root aphid and ball aphid), corn aphid ( Rhopalosiphum maidis Fitch (corn leaf aphid), cereal constrictor aphid ( Rhopalosiphum padi Linnaeus (birdcherry-oat aphid), wheat aphid ( Schizaphis grass Rondani (greenbug), wheat long-tubed aphid ( Sitobion oat Fabricius (English grainaphid), Alfalfa spotted aphid ( Therioaphis maculata Buckton (spotted alfalfaaphid), Citrus bifurcate aphid ( Toxoptera aurantii Boyer de Fonscolombe (blackcitrus aphid) and orange aphid ( Toxoptera citricidus Kirkaldy (brown citrusaphid); genus *Kirkaldy* (*Kirkaldy*) Adelges Species (Adelgid); Hickory phylloxera ( Phylloxera devastating Pergande (pecan phylloxera); whitefly ( Bemisia tabaci Gennadius (tobacco whitefly, sweet potato whitefly), silver leaf whitefly ( Bemisia silverleaf Bellows & Perring (silver leaf whitefly), citrus whitefly ( Citrus citronella Ashmead (citrus whitefly) and greenhouse whitefly ( Trialeurodes vaporariorum Westwood); Bean leafhopper ( Bean sprouts Harris (potato leafhopper), gray planthopper ( Laodelphax striatellusFallén (smaller brown planthopper), Aster leafhopper ( Macrosteles quadrilineatus Forbes (aster leafhopper), black-tailed leafhopper Nephotettix cincticeps Uhler (green rice leafhopper), two green rice leafhoppers ( Black-spotted Nephotettix Stål) (two black-tailed leafhoppers (rice leafhopper)), brown planthopper ( Nilaparvata is mourning. Stål) (brown planthopper), corn flower-winged planthopper ( The pilgrim maid Ashmead (corn planthopper), white-backed planthopper ( Sogatella furcifera Horváth (white-backed planthopper), rice planthopper ( Tagosodes oryzicolus Muir (rice planthopper), apple leafhopper ( Typhlocyba pomaria McAtee (white apple leafhopper), species of the genus *Erythroneura* (grape leafhopper); periodic cicadas ( Seventeen magic spells Linnaeus (periodic cicada); cottony cushion scale ( Icerya purchasi Maskell (cottony cushion scale), pear-shaped scale ( Quadraspidiotus pernicious Comstock) (San Jose scale); Plumpy scale ( Planococcus citri Risso (Citrus mealybug); genus Citrus ( Pseudococci ) species (other mealybug groups); pear psyllid ( Cockroach firecracker Foerster) (pear psyllid), persimmon psyllid ( Trioza diospyri Ashmead) (Persimmon psyllid).

[0080] The compositions disclosed herein can be used to control members of the order Hemiptera, including: green bugs ( Acrosternum cheerful Say) (green stink bug), pumpkin-edged bug ( Sad duck DeGeer (squash bug), wheat bug ( Bliss butterfly butterflySay) (chinch bug), temperate bed bug (bed bug), lace bug ( Corythucha gossypii Fabricius (cotton lace bug), tomato bug ( Cyrtopeltis modesta Distant) (tomato bug), cotton red bug ( Dysdercus suturellus Herrich-Schäffer (cotton red bug), brown stink bug ( Euschistus, servant Say) (brown stink bug), single-spotted bug ( Euschistus variegated Palisot de Beauvois (one-spotted stink bug) Graptostethus Genus and species (seed-bearing bug group), tea-winged bug ( Halyomorpha halys Stål (brownmarmorated stink bug), pine root bug ( Leptoglossus corculus Say) (leaf-footed pine seed bug) and American pasture mirid bug ( Lygus lineolaris Palisot de Beauvois (American tarnished plant bug), rice green bug ( Green-leaved nezara Linnaeus (southern green stink bug), brown rice bug ( The fighting bull Fabricius (rice estink bug), milkweed bug ( Oncopeltus fasciatus Dallas (large milkweed bug), cotton boll bug ( Pseudomoscelis seriatus Reuter (cotton fleahopper). Other insect orders controlled by the compounds disclosed herein include Thysanoptera (e.g., western flower thrips). Frankliniella western Pergande (Western flower thrips), Citrus thrips ( Citrus Scirtothrips Moulton) (citrus thrips), soybean thrips ( Scirtothrips variabilis Beach thrips (soybean thrips) and smoke thrips (smoke thrips); as well as Coleoptera (e.g., potato leaf beetle, Mexican bean ladybug) Epilachn you are wearing a variety of clothes Mulsant) and the genus *Mulsant* ( Agriots ), Mountain beetle genus ( Athos) or genus *Tegus spp.* Limonius (wireworms).

[0081] In some embodiments, the pest is selected from invertebrate pests, insects, arthropods, and combinations thereof.

[0082] In some implementations, the environment is selected from farmland, orchards, forests, and combinations thereof.

[0083] The composition embodiments of this disclosure can be combined with the method embodiments of this disclosure in any way. Similarly, the method embodiments of this disclosure can be combined in any way. Therefore, the following embodiments should be interpreted as merely illustrative and not as limiting the disclosure in any way.

[0084] The various aspects of this disclosure are provided by the subject matter of the following provisions: 1. A composition comprising: Antifreeze; and Microcapsules, the microcapsules comprising: Core, the core comprising: Pheromones; and Solvent; and A shell encapsulating the core; The shell comprises a polymer produced by the autopolymerization of monomers; and The microcapsules have a d90 value of less than about 40 μm.

[0085] 2. The composition according to the foregoing clauses, wherein the microcapsules have a d90 value of about 5 μm to about 40 μm.

[0086] 3. The composition according to any one of the preceding clauses, wherein the microcapsules have a d90 value of about 5 μm to about 25 μm.

[0087] 4. The composition according to any one of the preceding clauses, wherein the microcapsules have a d50 value of about 5 μm to about 25 μm.

[0088] 5. The composition according to any one of the preceding clauses, wherein the microcapsules have a d10 value of about 1 μm to about 10 μm.

[0089] 6. The composition according to any one of the preceding clauses, wherein the composition further comprises excipients selected from: dispersants, surfactants, emulsifiers, wetting agents, biocides, defoamers, antifreeze agents, rheology modifiers, solvents, stabilizers, UV stabilizers, UV absorbers, salts, excipients, antioxidants, and combinations thereof.

[0090] 7. The composition according to any one of the preceding clauses, wherein the composition is an agricultural chemical composition.

[0091] 8. The composition according to any one of the preceding clauses, wherein the composition is selected from premixes and barrel mixtures.

[0092] 9. The composition according to any one of the preceding clauses, wherein the composition is in the form of a CS formulation or a ZC formulation.

[0093] 10. The composition according to any one of the preceding clauses, wherein the shell comprises polyurea, isocyanate and / or polyisocyanate.

[0094] 11. The composition according to any one of the preceding clauses, wherein the pheromone is selected from aldehyde pheromones, acetate pheromones, alcohol pheromones, ketone pheromones, epoxide pheromones, hydrocarbon pheromones, and combinations thereof.

[0095] 12. The composition according to any one of the preceding clauses, wherein the pheromone does not include aldehyde pheromones.

[0096] 13. The composition according to any of the preceding clauses, wherein the pheromone is selected from: (Z)-5-decenyl acetate, dodecyl acetate, (Z)-7-dodecenyl acetate, (E)-7-dodecenyl acetate, (Z)-8-dodecenyl acetate, (E)-8-dodecenyl acetate, (Z)-9-dodecenyl acetate, (E)-9-dodecenyl acetate, (E)-10-dodecenyl acetate, 11-dodecenyl acetate, (Z)-9,11-dodecadienyl acetate, (E)-9,11-dodecadienyl acetate, and (Z)-5-decenyl acetate. E-11-Tetracene-enyl acetate, E-11-Tetracene-enyl acetate, Tetradecyl acetate, E-7-Tetradecene-enyl acetate, E-8-Tetradecene-enyl acetate, E-8-Tetradecene-enyl acetate, E-9-Tetradecene-enyl acetate, E-9-Tetradecene-enyl acetate, E-10-Tetradecene-enyl acetate, E-10-Tetradecene-enyl acetate, E-10-Tetradecene-enyl acetate, E-11-Tetradecene-enyl acetate, E-11-Tetradecene-enyl acetate, E-12-Pentadeca-enyl acetate, E-12-Pentadeca-enyl acetate Hexadecyl acetate, (Z)-7-hexadecenyl acetate, (Z)-11-hexadecenyl acetate, (E)-11-hexadecenyl acetate, octadecyl acetate, (E,Z)-7,9-dodecadienyl acetate, (Z,E)-7,9-dodecadienyl acetate, (E,E)-7,9-dodecadienyl acetate, (Z,Z)-7,9-dodecadienyl acetate, (E,E)-8,10-dodecadienyl acetate, (E,Z)-9,12-dodecadienyl acetate, (E,Z)-4,7-tetracenedienyl acetate, acetic acid (E,E)-9,11-tetradecadienyl ester, (Z,Z)-9,12-tetradecadienyl ester, (Z,Z)-7,11-hexadecadienyl ester, (E,Z)-7,11-hexadecadienyl ester, (Z,E)-7,11-hexadecadienyl ester, (E,E)-7,11-hexadecadienyl ester, (Z,E)-3,13-octadecadienyl ester, (E,Z)-3,13-octadecadienyl ester, (E,E)-3,13-octadecadienyl ester, 3-methylbutyric acid (Z)-5-decenyl ester, (+) cis-7,8-epoxy-2-methyloctadecane, (E,Z)-2,4-decadienoic acid methyl ester, 2,6,10-trimethyltetrazoic acid methyl ester, citral, geranialdehyde, neraldehyde, tetradecane-1-aldehyde, pentadecane-1-aldehyde, pentadecene-1-aldehyde, hexadecane-1-aldehyde, (Z)-9-hexadecene-1-aldehyde, (Z)-11-hexadecene-1-aldehyde, (7E,9E)-undecane-7,9-diene-1-aldehyde, (11Z,(13Z)-hexadecadien-1-aldehyde, (9Z,12E)-tetradecadien-1-aldehyde, (8E,10E)-dodecadien-1-aldehyde, (11Z)-hexadecadien-1-aldehyde, (9Z)-tetradecen-1-aldehyde, 6,10-dimethyl-5,9-undecadien-2-ol, (6E)-7,11-dimethyl-3-methylene-1,6,10-dodecanetriene, [1S-(1a,2b,5a)]-4,6,6-trimethyl-bicyclo[3.1.1]hept-3-en-2-ol, 10-hexadecenal, (Z)-10-hexadecenal, (E)-10-hexadecenal, and combinations thereof.

[0097] 14. The composition according to any one of the preceding clauses, wherein the antifreeze is selected from propylene glycol, glycerin, glycol, ethylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, methanol, ethanol, propanol, butanol, and combinations thereof.

[0098] 15. The composition according to any one of the preceding clauses, wherein the solvent is selected from hydrophobic solvents, high flash point solvents, methylated seed oils, methyl oleate oils, methyl linoleate oils, mineral oils, paraffin oils, tall oils, fatty acid-based solvents, aromatic solvents, aromatic ester solvents, polybutene, fatty acid methyl esters, 2-acetyl tributyl citrate, alkylamides, benzyl acetate, wax esters, and combinations thereof.

[0099] 16. A method for preparing a composition, the method comprising: A mixture is formed, the mixture comprising: Antifreeze; and Microcapsules, the microcapsules comprising: Core, the core comprising: Pheromones; and Solvent; and A shell encapsulating the core; The shell comprises a polymer produced by the autopolymerization of monomers; and The microcapsules have a d90 value of less than about 40 μm.

[0100] 17. The method according to the foregoing clause, wherein the method further comprises encapsulating the pheromone and the solvent in the microcapsules prior to forming the mixture.

[0101] 18. A method for controlling pests, the method comprising contacting the pest or its environment with a bioactive amount of a composition, the composition comprising: Antifreeze; and Microcapsules, the microcapsules comprising: Core, the core comprising: Pheromones; and Solvent; and A shell encapsulating the core; The shell comprises a polymer produced by the autopolymerization of monomers; and The microcapsules have a d90 value of less than about 40 μm.

[0102] 19. The method according to any one of the preceding clauses, wherein the pest is selected from invertebrate pests, insects, arthropods, and combinations thereof.

[0103] 20. The method described under any of the foregoing clauses, wherein the environment is selected from farmland, orchard, forest, and combinations thereof.

[0104] Without further detailed description, it is believed that those skilled in the art will be able to make full use of the invention using the foregoing description. Therefore, the following embodiments should be interpreted as merely illustrative and not as limiting this disclosure in any way.

[0105] Example Example 1. Solvent screening.

[0106] Emulsions (EW) containing Z9-14 acetate pheromones were prepared using solvents with different chemical compositions. A control, a solvent-free EW formulation, was also prepared and evaluated. Table 1 summarizes the volatility and chemical stability of the EW formulations, and the results are ranked according to optimal volatility control, with the best-performing sample listed last. The EW formulation using Steposol ME (methyl oleate / methyl linoleate oil from Stepan) outperformed other EW formulations in the series. The solvent-free formulation exhibited the worst performance.

[0107] To determine chemical stability, the EW formulation was placed in tightly sealed scintillation vials, which were then placed in an oven heated to 60°C for 4 hours. The remaining Z9-14 acetate pheromone in each vial was quantified. Because the scintillation vials were tightly sealed, the loss of Z9-14 acetate pheromone was related to chemical degradation. Chemical stability was determined as the remaining weight percentage of Z9-14 acetate pheromone.

[0108] To determine volatility, the EW formulation was placed in uncapped vials, which were then placed in an oven and heated to 60°C for 4 hours. The remaining Z9-14 acetate pheromone in each vial was quantified. Because the scintillation vials were uncapped, the Z9-14 acetate pheromone was able to evaporate. Volatility was determined as the remaining weight percentage of Z9-14 acetate pheromone.

[0109] Table 1. Chemical stability and volatility of EW formulations containing Z9-14 acetate pheromone.

[0110] Example 2. Volatility control of unencapsulated water-in-oil (EW) pheromone formulations.

[0111] To prepare the water-in-oil (EW) formulation, pheromones (Z-11-16 aldehyde and Z-11-16 acetate), butylated hydroxytoluene (BHT), and 1,6-hexanediol were dissolved in a solvent (Steposol ME) and combined with an oil-soluble emulsifier (Atlox 4916). An aqueous phase was generated in separate containers by combining water with a water-soluble emulsifier (Toximul SEE 340 and Toximul 8320 or Atlas G5000). An organic phase was then slowly added to the aqueous phase, followed by a high-shear step to produce a concentrated emulsion. In the final step, a biocide, rheology modifier, and antifreeze were added.

[0112] The table below provides volatility control data for the prepared EW formulation. The volatility of the final formulation was investigated in a dark environment chamber with high airflow.

[0113] Dilute the sample to the appropriate concentration. Add an appropriate amount of HPLC-grade water to form a 1000 ppm spray solution. For the initial (0 h) sample, add 3.0 ml of acetone to a scintillation vial, followed by 30 μL of the 1000 ppm spray solution. For the remaining aged samples (24 h, 48 h), spot 30 μL at a 1000 ppm concentration onto German glass coverslips in 24-well Falcon plates. Place these in an ambient chamber at 25 °C and 50% humidity. Extract the sample by sonicating on ice with the glass slide in a scintillation vial containing 3 ml of acetone for two 30-minute cycles. Transfer the extract to an autosampler vial. Analyze by GC-FID using a DB5ms column with a splitless 2 μL injection.

[0114] For these unencapsulated pheromones, poor volatility control is achieved.

[0115] Table 2. Volatility control of unencapsulated water-in-oil (EW) pheromone formulations.

[0116] Example 3. Volatility control of microencapsulated Z9-14 acetate formulation.

[0117] The pheromone encapsulation was achieved by forming microcapsules using only isocyanate monomers without the addition of amines. The isocyanate monomers self-polymerized. Capsules with different particle sizes (d90 from 14 μm to 50 μm) were prepared.

[0118] The table below provides data on the volatility control of the prepared formulation. The volatility control of pheromones in the CS formulation was determined as follows. In the PEACH Drop Method, an aqueous spray solution of the formulation material was applied as droplets onto glass. After the desired time period under simulated solar light (0 to 99 hours), the glass was extracted in a solvent. The amount of pheromones remaining on the glass in the extract was analyzed by GC. T24hr, T44hr, T46hr, and T99hr represent 24 hours, 44 hours, 46 hours, and 99 hours, respectively, in a simulated solar light chamber with continuous illumination. Each 24 hours of simulated solar light is equivalent to 2.5 days of sunlight.

[0119] Encapsulation was found to improve volatility control of the (Z)-11-tetradecenyl acetate pheromone. Optimal volatility control was achieved with a formulation containing capsules of approximately 14.5 μm and a d90 value.

[0120] Table 3. Volatility control of microencapsulated Z9-14 acetate formulation.

[0121] Example 4. Volatility control of microencapsulated Z11-16 acetate formulation.

[0122] The pheromone encapsulation was achieved by forming microcapsules using only isocyanate monomers without the addition of amines. The isocyanate monomers self-polymerized. Capsules with different particle sizes (d90 from 19 μm to 38 μm) were prepared.

[0123] The table below provides volatility control data for the prepared formulations. The volatility control of pheromones in the CS formulations was determined as described above.

[0124] Encapsulation was found to improve volatility control of the (Z)-11-hexadecenyl acetate pheromone. Optimal volatility control was achieved with a formulation containing capsules of approximately 19.7 μm and a d90 value.

[0125] Table 4. Volatility control of microencapsulated Z11-16 acetate formulations.

[0126] Example 5. Volatility control of microencapsulated mixed pheromone formulations.

[0127] The pheromone encapsulation was achieved by forming microcapsules using only isocyanate monomers without the addition of amines. The isocyanate monomers self-polymerized. Capsules with different particle sizes (d90 from 9 μm to 34 μm) were prepared.

[0128] The table below provides the volatility control data for the prepared formulations. The volatility control of pheromones in the CS formulations was determined in a dark environment chamber with high airflow.

[0129] Encapsulation was found to improve volatility control of a mixture of (Z)-11-tetradecenyl acetate pheromones and (Z)-11-hexadecenyl acetate pheromones.

[0130] Table 5. Volatility control of microencapsulated mixed pheromone formulations.

[0131] Example 6. Volatility control of microencapsulated Z11-16 aldehyde formulation.

[0132] The pheromone encapsulation was achieved by using only isocyanate monomers without adding amines to form microcapsules. The isocyanate monomers self-polymerized. The formulation's d90 was determined to be 20 micrometers.

[0133] The table below provides volatility control data for the prepared formulations. The volatility control of the pheromone in the CS formulation was determined as described above. Encapsulation was found to improve the volatility control of the (Z)-11-hexadecenal pheromone.

[0134] Table 6. Volatility control of microencapsulated Z11-16 aldehyde formulations.

[0135] Example 7. Chemical stability of microencapsulated Z-11-16 aldehyde formulation.

[0136] The pheromone encapsulation was achieved by using only isocyanate monomers without adding amines to form microcapsules. The isocyanate monomers self-polymerized. The formulation's d90 was determined to be 20 micrometers.

[0137] The table below provides formulations and corresponding concentrations of 10-11 wt% Z-11-hexadecenal in CS formulations. It was found that microencapsulation using isocyanate self-polymerization did not degrade aldehyde pheromones.

[0138] Table 7. Chemical stability of microencapsulated Z11-16 aldehyde formulations.

[0139] Example 8. Chemical stability of microencapsulated Z-11-16 aldehyde formulation.

[0140] The pheromone is encapsulated by forming microcapsules using only isocyanate monomers without the addition of amines. The isocyanate monomers are self-polymerized.

[0141] The table below provides formulations and corresponding contents of formulations prepared from 5 wt% – 6 wt% Z-11-hexadecenal in CS formulations. It was found that microencapsulation using isocyanate self-polymerization did not degrade aldehyde pheromones.

[0142] Table 8. Chemical stability of microencapsulated Z11-16 aldehyde formulations.

[0143] Example 9. Comparison of the chemical stability of microencapsulated Z-11-16 aldehyde formulation.

[0144] Encapsulation of Z-11-16 aldehyde pheromones was achieved by using isocyanate monomers and adding amines to form microcapsules. The table below provides the formulation and its application at 54°C. o The C-aging study compared the corresponding contents before and after 2 weeks. It was found that up to 60% of the Z-11-16 aldehyde pheromone was lost during sample preparation. An additional 10%–30% of the pheromone was lost during aging. These unexpected results confirm the benefits of using the automated polymerization of isocyanate monomers to prepare microcapsules containing aldehyde pheromones.

[0145] Table 9. Comparison of the chemical stability of microencapsulated Z11-16 aldehyde formulations.

[0146] Surprisingly, this paper reveals that substantial improvements in the volatility control of pheromone compositions can be achieved using compositions comprising an antifreeze and microcapsules, wherein the microcapsules are small and contain co-encapsulated pheromones and solvents. The most significant improvements were observed for microcapsules having shells containing polymers generated through the autopolymerization of monomers, and for microcapsules with d90 values ​​less than about 40 μm.

[0147] This paper also surprisingly found that by using the automated polymerization of isocyanate monomers to prepare microcapsules, the chemical stability of encapsulated aldehyde pheromones can be significantly improved.

Claims

1. A composition comprising: Antifreeze; and Microcapsules, the microcapsules comprising: Core, the core comprising: Pheromones; and Solvent; and A shell encapsulating the core; The shell comprises a polymer produced by the autopolymerization of monomers; and The microcapsules have a d90 value of less than about 40 μm.

2. The composition according to claim 1, wherein the microcapsules have: The d90 value is approximately 5 μm to approximately 40 μm, preferably approximately 5 μm to approximately 25 μm. d50 values ​​from approximately 5 μm to approximately 25 μm; and / or d10 values ​​from approximately 1 μm to approximately 10 μm.

3. The composition according to any one of claims 1-2, wherein the composition further comprises excipients selected from the group consisting of dispersants, surfactants, emulsifiers, wetting agents, biocides, defoamers, antifreeze agents, rheology modifiers, solvents, stabilizers, UV stabilizers, UV absorbers, salts, excipients, antioxidants, and combinations thereof.

4. The composition according to any one of claims 1-3, wherein the composition is an agricultural chemical composition, preferably selected from premixes and tank mixes.

5. The composition according to any one of claims 1-4, wherein the composition is in the form of a CS formulation or a ZC formulation.

6. The composition according to any one of claims 1-5, wherein the shell comprises polyurea, isocyanate and / or polyisocyanate.

7. The composition according to any one of claims 1-6, wherein the pheromone is selected from aldehyde pheromones, acetate pheromones, alcohol pheromones, ketone pheromones, epoxide pheromones, hydrocarbon pheromones, and combinations thereof.

8. The composition according to any one of claims 1-7, wherein the pheromone is selected from: (Z)-5-decenyl acetate, dodecyl acetate, (Z)-7-dodecenyl acetate, (E)-7-dodecenyl acetate, (Z)-8-dodecenyl acetate, (E)-8-dodecenyl acetate, (Z)-9-dodecenyl acetate, (E)-9-dodecenyl acetate, (E)-10-dodecenyl acetate, 11-dodecenyl acetate, (Z)-9,11-dodecadienyl acetate, (E)-9,11-dodecadienyl acetate, etc. (Z)-11-tetratenyl acetate, (E)-11-tetratenyl acetate, tetradecyl acetate, (E)-7-tetradecenoyl acetate, (Z)-8-tetradecenoyl acetate, (E)-8-tetradecenoyl acetate, (Z)-9-tetradecenoyl acetate, (E)-9-tetradecenoyl acetate, (Z)-10-tetradecenoyl acetate, (E)-10-tetradecenoyl acetate, (Z)-11-tetradecenoyl acetate, (E)-11-tetradecenoyl acetate, (Z)-12-pentadecanenoyl acetate, (E)-12-pentadecanenoyl acetate Ester, hexadecyl acetate, (Z)-7-hexadecenyl acetate, (Z)-11-hexadecenyl acetate, (E)-11-hexadecenyl acetate, octadecyl acetate, (E,Z)-7,9-dodecadienyl acetate, (Z,E)-7,9-dodecadienyl acetate, (E,E)-7,9-dodecadienyl acetate, (Z,Z)-7,9-dodecadienyl acetate, (E,E)-8,10-dodecadienyl acetate, (E,Z)-9,12-dodecadienyl acetate, (E,Z)-4,7-tetracenedienyl acetate, ethyl acetate Acetic acid (E,E)-9,11-tetradecadienyl ester, acetate (Z,Z)-9,12-tetradecadienyl ester, acetate (Z,Z)-7,11-hexadecadienyl ester, acetate (E,Z)-7,11-hexadecadienyl ester, acetate (Z,E)-7,11-hexadecadienyl ester, acetate (E,E)-7,11-hexadecadienyl ester, acetate (Z,E)-3,13-octadecadienyl ester, acetate (E,Z)-3,13-octadecadienyl ester, acetate (E,E)-3,13-octadecadienyl ester, 3-methylbutyric acid (Z)-5-decenyl ester, (+) cis-7,8-epoxy-2-methyloctadecane, (E,Z)-2,4-decadienoic acid methyl ester, 2,6,10-trimethyltetrazoic acid methyl ester, citral, geranialdehyde, neraldehyde, tetradecane-1-aldehyde, pentadecane-1-aldehyde, pentadecene-1-aldehyde, hexadecane-1-aldehyde, (Z)-9-hexadecene-1-aldehyde, (Z)-11-hexadecene-1-aldehyde, (7E,9E)-undecane-7,9-diene-1-aldehyde, (11Z,(13Z)-hexadecadien-1-aldehyde, (9Z,12E)-tetradecadien-1-aldehyde, (8E,10E)-dodecadien-1-aldehyde, (11Z)-hexadecadien-1-aldehyde, (9Z)-tetradecen-1-aldehyde, 6,10-dimethyl-5,9-undecadien-2-ol, (6E)-7,11-dimethyl-3-methylene-1,6,10-dodecanetriene, [1S-(1a,2b,5a)]-4,6,6-trimethyl-bicyclo[3.1.1]hept-3-en-2-ol, 10-hexadecenal, (Z)-10-hexadecenal, (E)-10-hexadecenal, and combinations thereof.

9. The composition according to any one of claims 1-8, wherein the antifreeze is selected from propylene glycol, glycerin, glycol, ethylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, methanol, ethanol, propanol, butanol, and combinations thereof.

10. The composition according to any one of claims 1-9, wherein the solvent is selected from hydrophobic solvents, high flash point solvents, methylated seed oils, methyl oleate oils, methyl linoleate oils, mineral oils, paraffin oils, tall oils, fatty acid-based solvents, aromatic solvents, aromatic ester solvents, polybutene, fatty acid methyl esters, 2-acetyl tributyl citrate, alkylamides, benzyl acetate, wax esters, and combinations thereof.

11. A method for preparing a composition, the method comprising: A mixture is formed, the mixture comprising: antifreeze; and Microcapsules, the microcapsules comprising: Core, the core comprising: Pheromones; and Solvent; and A shell encapsulating the core; The shell comprises a polymer produced by the autopolymerization of monomers; and The microcapsules have a d90 value of less than about 40 μm.

12. The method of claim 11, wherein the method further comprises encapsulating the pheromone and the solvent in the microcapsules prior to forming the mixture.

13. A method for controlling pests, the method comprising contacting the pest or its environment with a bioactive amount of a composition, the composition comprising: Antifreeze; and Microcapsules, the microcapsules comprising: Core, the core comprising: Pheromones; and Solvent; and A shell encapsulating the core; The shell comprises a polymer produced by the autopolymerization of monomers; and The microcapsules have a d90 value of less than about 40 μm.

14. The method of claim 14, wherein the pest is selected from invertebrate pests, insects, arthropods, and combinations thereof.

15. The method according to any one of claims 13-14, wherein the environment is selected from farmland, orchard, forest, and combinations thereof.

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