WO2024254039A1 - Microencapsulated pheromone formulations - Google Patents

Abstract

Described herein are compositions including microencapsulated pheromones. Also described herein are methods of making compositions including microencapsulated pheromones. Also described herein are methods for controlling pests with the compositions.

Description

MICROENCAPSULATED PHEROMONE FORMULATIONS

CROSS-REFERENCE TO RELATED APPLICATIONS

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

FIELD OF THE DISCLOSURE

[2] Described herein are compositions including microencapsulated pheromones. Also described herein are methods of making compositions including microencapsulated pheromones. Also described herein are methods for controlling pests with the compositions.

BACKGROUND OF THE DISCLOSURE

[3] Pheromone compositions are difficult to formulate for numerous reasons, including reactions with other ingredients in formulation matrices, degradation of the pheromones overtime, and unfavorable release rates of pheromones from formulations. This is particularly true where the pheromones are active agrochemical ingredients and must be delivered at certain release rates over time. Therefore, there is a need in the art for compositions including pheromones that have improved release rate and degradation properties.

[4] Microencapsulation provides a means of formulating pheromones for application to large areas in the control of insect populations by disruption of pheromone- mediated communication. Microencapsulation also helps to control the volatility of the pheromone. However, although microencapsulation of pheromones has been previously demonstrated, there remains a need for improved formulations including microencapsulated pheromones.

[5] The present disclosure provides formulations including microencapsulated pheromones. The formulations possess improved properties compared to conventional formulations including microencapsulated pheromones. The present disclosure enables formulations of pheromones that may be used in spray able agricultural formulations. Such sprayable formulations are essential for row crop applications. [6] Formulations including microencapsulated pheromones according to the present disclosure may be manufactured by known methods of interfacial polymerization and they may be applied over large areas with conventional spray equipment. They possess numerous variables that may be manipulated to control the release characteristics (capsule wall composition, capsule wall thickness, capsule size and internal composition).

BRIEF DESCRIPTION OF THE DISCLOSURE

[7] In one embodiment, the present disclosure is directed to a composition comprising: an antifreeze agent; and a microcapsule comprising: a core comprising: a pheromone; and a solvent; and a shell encapsulating the core; wherein the shell comprises a polymer produced by autopolymerization of a monomer; and wherein the microcapsule has a d90 value less than about 40 pm.

[8] In another embodiment, the present disclosure is directed to a method of making a composition, the method comprising: forming a mixture comprising: an antifreeze agent; and a microcapsule comprising: a core comprising: a pheromone; and a solvent; and a shell encapsulating the core; wherein the shell comprises a polymer produced by autopolymerization of a monomer; and wherein the microcapsule has a d90 value less than about 40 pm.

[9] In yet another embodiment, the present disclosure is directed to a method for controlling a pest comprising contacting the pest or its environment with a biologically effective amount of a composition comprising: an antifreeze agent; and a microcapsule comprising: a core comprising: a pheromone; and a solvent; and a shell encapsulating the core; wherein the shell comprises a polymer produced by autopolymerization of a monomer; and wherein the microcapsule has a d90 value less than about 40 pm.

DETAILED DESCRIPTION OF THE DISCLOSURE

[10] This written description uses examples to illustrate the present disclosure, including the best mode, and also to enable any person skilled in the art to practice the disclosure, including making and using any compositions or systems and performing any incorporated methods. The patentable scope of the disclosure is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be 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 with insubstantial differences from the literal language of the claims.

[11] As used herein, the terms ‘'comprises,” ‘'comprising,” “includes,” “including,” “has,” “having,” '‘contains”, “containing,” “characterized by” or any other variation thereof, are intended to cover anon-exclusive inclusion, subject to any limitation explicitly indicated. For example, a composition, mixture, process or method that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process or method.

[12] The transitional phrase “consisting of’ excludes any element, step, or ingredient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase “consisting of’ appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.

[13] The transitional phrase “consisting essentially of’ is used to define a composition or method that includes materials, steps, features, components, or elements, in addition to those literally disclosed, provided that these additional materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention. The term “consisting essentially of’ occupies a middle ground between “comprising” and “consisting of’. The use of “consisting essentially of’ herein allows the applicant, as lexicographer, to define the invention being claimed by excluding any material, step, feature . . . that is considered by the applicant to be non-critical to the claimed invention, but which may be known in the prior art and otherwise can be included in the invention being claimed, whether or not such inclusion or exclusion is specifically described in the specification. Exclusion of any material, step, feature . . . by the applicant may be for the sole purpose of excluding elements of the prior art that affect the novelty and, therefore, the patentability of the invention being claimed. As such, the use of '‘consisting essentially of’ herein does not require explicit support from the specification to exclude any element of the prior art from the invention being claimed if inclusion of said element is detrimental to patentability of the invention claimed. [14] Where an invention or a portion thereof is defined with an open-ended term such as ‘'comprising,” it should be readily understood that (unless otherwise stated) the description should be interpreted to also describe such an invention using the terms “consisting essentially of’ or “consisting of.”

[15] Further, unless expressly stated to the contrary, “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present). A is false (or not present) and B is true (or present), and both A and B are true (or present).

[16] Also, the indefinite articles “a” and “an” preceding an element or component of the invention are intended to be nonrestrictive regarding the number of instances (i.e. occurrences) of the element or component. Therefore “a” or “an” should be read to include one or at least one, and the singular word form of the element or component also includes the plural unless the number is obviously meant to be singular.

[17] 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, where the estimated value is reasonable when taken in context with the description of the invention and in view of what is known from information available to the public, as such information would be understood or interpreted by a person of ordinary skill in the art. Generally, the term “about” as used herein means that the estimated value will fall within plus or minus 10% of the associated value. The term “about” may be further defined by context, and it is within the applicant’s rights as lexicographer to define how “about” should be interpreted within the specific context in which it is used in describing the invention.

[18] As used herein, “wt%” refers to the weight percent of the recited component relative to the total weight of the recited composition.

[19] As used herein, '‘substantially free” generally refers to no more than 2 wt%. In some embodiments, “substantially free” refers to no more than 1.5 wt%, no more than 1.0 wt%, no more than 0.5 wt%, or no more than 0. 1 wt%.

[20] As used herein, a “dlO value” means that the portion of particles with diameters smaller than this value is 10%. [21] As used herein, a '‘d50 value” means that the portion of particles with diameters smaller than this value is 50%.

[22] As used herein, a “d90 value” means that the portion of particles with diameters smaller than this value is 90%.

[23] Particle size measurements can be made with a variety of different methods, techniques, and equipment. As described in the present disclosure, the particle sizes are not limited by any measurement method, technique, or equipment. In some embodiments, the particle sizes are measured with a technique selected from light scattering, static light scattering, dynamic light scattering, and combinations thereof. In some embodiments, the particle sizes are measured with a particle size analyzer. In some embodiments, the particle sizes are measured with a particle size analyzer configured to calculate particle size with a Fraunhofer approximation of light scattering. In some embodiments, the particle sizes are measured with a particle size analyzer selected from a Malvern Mastersizer 2000, a Malvern Mastersizer 3000, a HELOS/BR Sucell, and combinations thereof.

[24] As used herein, '‘antifreeze” refers to a substance that can be added to water or an aqueous mixture to lower the freezing point of the water or aqueous mixture.

[25] In the context of this disclosure “invertebrate pest control” means inhibition of invertebrate pest development (including mortality, feeding reduction, and/or mating disruption), and related expressions are defined analogously.

[26] As referred to in this disclosure, the term “invertebrate pest” includes arthropods, gastropods, nematodes and helminths of economic importance as pests. The term “arthropod” includes insects, mites, spiders, scorpions, centipedes, millipedes, pill bugs and symphylans. The term “gastropod” includes snails, slugs and other Stylommatophora. The term “nematode” includes members of the phylum Nematoda, such as phytophagous nematodes and helminth nematodes parasitizing animals. The term “helminth” includes all of the parasitic worms, such as roundworms (phylum Nematoda), heartworms (phylum Nematoda, class Secementea), flukes (phylum Platyhelminthes, class Tematoda), acanthocephalans (phylum Acanthocephala), and tapeworms (phylum Platyhelminthes, class Cestoda). [27] The term “agronomic’’ refers to the production of field; crops such as for food and fiber and includes the growth of maize or com, soybeans and other legumes, rice, cereal (e.g., wheat, oats, barley, rye and rice), leafy vegetables (e.g., lettuce, cabbage, and other cole crops), fruiting vegetables (e.g., tomatoes, pepper, eggplant, crucifers and cucurbits), potatoes, sweet potatoes, grapes, cotton, tree fruits (e.g., pome, stone and citrus), small fruit (e.g., berries and cherries) and other specialty crops (e.g., canola, sunflower and olives).

[28] The term “nonagronomic” refers to other than field crops, such as horticultural crops (e.g., greenhouse, nursery or ornamental plants not grown in a field), residential, agricultural, commercial and industrial structures, turf (e.g., sod farm, pasture, golf course, lawn, sports field, etc.), wood products, stored product, agro-forestry and vegetation management, public health (i.e. human) and animal health (e.g., domesticated animals such as pets, livestock and poultry, undomesticated animals such as wildlife) applications.

[29] The term “crop vigor” refers to rate of growth or biomass accumulation of a crop plant. An “increase in 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 return on crop material, in terms of both quantity and quality, obtained after harvesting a crop plant. An “increase in crop yield” refers to an increase in crop yield relative to an untreated control crop plant.

[30] The term “biologically effective amount” refers to the amount of a biologically active compound sufficient to produce the desired biological effect when applied to (i.e. contacted with) an invertebrate pest to be controlled or its environment, or to a plant, the seed from which the plant is grown, or the locus of the plant (e.g., growth medium) to protect the plant from injury by the invertebrate pest or for other desired effect (e.g., increasing plant vigor).

[31] Nonagronomic applications include protecting an animal from an invertebrate parasitic pest by administering a parasiticidally effective (i.e. biologically effective) amount of a biologically active compound of the disclosure, typically in the form of a composition formulated for veterinary' use, to the animal to be protected. As referred to in the present disclosure and claims, the terms “parasiticidal” and “parasiticidally” refers to observable effects on an invertebrate parasite pest to provide protection of an animal from the pest. Parasiticidal effects typically relate to diminishing the occurrence or activity of the target invertebrate parasitic pest. Such effects on the pest include necrosis, death, retarded grow th, diminished mobility or lessened ability to remain on or in the host animal, reduced feeding and inhibition of reproduction. These effects on invertebrate parasite pests provide control (including prevention, reduction or elimination) of parasitic infestation or infection of the animal.

[32] It was surprisingly discovered herein that substantial improvements in volatility control of pheromone compositions could be achieved with compositions including an antifreeze and microcapsules, where the microcapsules are relatively small and contain co-encapsulated pheromones and solvents. The most substantial improvements were observed with microcapsules having shells including a polymer produced by autopolymerization of a monomer and microcapsules having a d90 value less than about 40 pm.

[33] In some embodiments, described herein is a composition including: an antifreeze agent; and a microcapsule including: a core including: a pheromone; and a solvent; and a shell encapsulating the core. The shell includes a polymer produced by autopolymerization of a monomer and the microcapsule has a d90 value less than about 40 pm.

[34] Generally, compositions according to the present disclosure may include microcapsules of any suitable size know n in the art that facilitate the compositions described herein. The size of the microcapsules affects the various characteristics of the encapsulant, as its size indicates the amount of carrier material from which the encapsulant is constructed. 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 application of the product. The formulations according to the present disclosure surprisingly exhibit good release rate characteristics for the pheromone and the capsules do not sediment in accelerated storage stability studies.

[35] In some embodiments, the microcapsule has a d90 value in a range of from about 10 pm to about 40 pm. In some embodiments, the microcapsule has a d90 value in a range of from about 10 pm to about 25 pm. [36] In some embodiments, the microcapsule has a d90 value of at least 10 pm, at least 11 pm, at least 12 pm, at least 13 pm, at least 14 pm, at least 15 pm, at least 16 pm, at least 17 pm, at least 18 pm, at least 19 pm, at least 20 pm, at least 21 pm, at least 22 pm, at least 23 pm, at least 24 pm, at least 25 pm, at least 26 pm, at least 27 pm, at least 28 pm, at least 29 pm, at least 30 pm, at least 31 pm, at least 32 pm, at least 33 pm, at least 34 pm, at least 35 pm, at least 36 pm, at least 37 pm, at least 38 pm, or at least 39 pm. In some embodiments, the microcapsule has a d90 value of at most 11 pm, at most 12 pm, at most 13 pm, al most 14 pm, at most 15 pm, at most 16 pm, at most 17 pm, at most 18 pm, al most

19 pm. at most 20 pm. at most 21 pm. at most 22 pm. at most 23 pm, at most 24 pm, at most

25 pm, at most 26 pm, at most 27 pm, at most 28 pm, at most 29 pm, at most 30 pm, at most

31 pm, at most 32 pm, at most 33 pm, at most 34 pm, at most 35 pm, at most 36 pm, at most

37 pm, at most 38 pm, at most 39 pm. or at most 40 pm.

[37] In some embodiments, the microcapsule has a d50 value in a range of from about 5 pm to about 25 pm. In some embodiments, the microcapsule has a d50 value in a range of from about 5 pm to about 24 pm.

[38] In some embodiments, the microcapsule has a dlO value in a range of from about 1 pm to about 10 pm.

[39] Generally, compositions according to the present disclosure may include any suitable auxiliary known in the art that facilitates the compositions described herein. The compositions may include an encapsulated auxiliary and/or anon-encapsulated auxiliary. In some embodiments, the composition includes at least one auxiliary. In some embodiments, the composition includes at least two auxiliaries. In some embodiments, the composition includes at least three auxiliaries. In some embodiments, the composition includes at least four auxiliaries.

[40] In some embodiments, the auxiliary is selected from dispersants, surfactants, emulsifiers, wetting agents, biocides, antifoamers, antifreeze agents, rheology modifiers, solvents, stabilizers, UV stabilizers, UV absorbers, salts, excipients, antioxidants, and combinations thereof. [41] In some embodiments, the auxiliary comprises a rheology modifier selected from xanthan gum (e.g., Rhodopol 23, Kelzan S), clays, smectite clays, bentonite clays, hectorite clays, magnesium aluminosilicate clays (e.g., Acti-Gel 208, Veegum R), organically modified hectorite clays (e.g.. Bentone LF), silica (e.g., Aerosil 200), hydrophobically modified ethoxylated urethane (HEUR), anionic polyacrylate copolymer hydrophobically modified (HASE), anionic polyacrylate copolymer (ASE), rheology modifiers useful for aqueous systems (e.g., Rheovis rheology modifiers), and combinations thereof.

[42] Generally, compositions according to the present disclosure may include any suitable pheromone known in the art that facilitates the compositions described herein. In some embodiments, the pheromone is selected from aldehyde pheromones, acetate pheromones, alcohol pheromones, ketone pheromones, epoxide pheromones, hydrocarbon pheromones, ester pheromones, and combinations thereof. In some embodiments, the pheromone does not comprise an aldehyde pheromone. 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-Methylenebutanal; 3-Methyl-2-butenal; 3-Methyl-3-butenal; 3- Methylbutanal; Butanal; (E)-2-Pentenal; 2-Methylenepentanal; 2-Pentenal; 3-Methyl-l- (vinyloxy)-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- Hexenoxy)-hexanal; 3,5-Dimethylhexanal; 3-Ethoxyhexanal; 3-Hydroxybenzaldehyde; 3- Hydroxyhexanal: 4-Hydroxy-3,5-dimethoxybenzaldehyde; 4-Hydroxybenzaldehyde; 5- Methylhexanal; Hexanal; (lR,2S,5R)-2-Methyl-5-((R)-l-oxopropan-2-yl)- cyclopentanecarbaldehyde; (lR,2S,5S)-2-Methyl-5-((R)-l-oxopropan-2-yl)- cyclopentanecarbaldehyde; (lR,5S)-6,6-Dimethylbicyclo[3. 1. l]hept-2-ene-2-carbaldehyde; (lS,2S,5R)-2-Methyl-5-((R)-l-oxopropan-2-yl)-cyclopentanecarbaldehyde; (3S,8R)-2- Methyl-5-(l-formylethyl)-l-cyclopentene-l-carbaldehyde; (3S,8S)-2-Methyl-5-(l- formylethyl)-l -cyclopentene- 1-carbaldehy de; (5S,8S)-2-Methyl-5-(l -formylethyl)-! - cyclopentene-1 -carbaldehyde; (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-l-en-2-yl)-cyclohex-l-enecarbaldehyde; (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-l- cyclopentenecarboxaldehyde; 2-Methyl-2-heptenal; 2-Methyl-5-(l-oxopropan-2-yl)- cyclopentanecarbaldehyde; 2-Methylcy cl opent-1 -enecarbaldehyde; 3,3-Dimethyl-5-oxo-7- oxabicyclo[4.1.0]heptane-l -carbaldehy de; 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-Hydroxybenzene-l,2-dicarbaldehyde; 3 -Methylbenzaldehyde; 4- (Heptyloxy)-butanal; 4-Methoxybenzaldehyde; 5-(l-Formylethyl)-2-methyl-2- cyclopentene-l-carbaldehyde; 6-Methyl-5-heptenal; 6-Methylheptanal; Benzaldehyde; Cartilagineal; Cyclohexanedial; Heptanal; Taxifolial D; (lR,2S)-cis-2-Isopropenyl-l - methylcyclobutaneethanal; (1 S,2R,3S)-2-(l -Formylvinyl)-5- methylcyclopentanecarbaldehyde; (1 S,2S,3S)-2-(l -Formylvinyl)-5- methylcyclopentanecarbaldehyde; (2Z,6E)-8-Chloro-6-chloromethyl-2-methyl-2,6- octadienal; (4S)-(3-Oxoprop-l-en-2-yl)-cyclohex-l -enecarbaldehyde; (E)-(3,3-Dimethyl)- cyclohexylideneacetaldehyde; (E)-2-(3,3-Dimethylcyclohexylidene)-acetaldehyde; (E)-2- (4-Methyl-3-pentenyl)-butenedial; (E)-2-(4-Methyl-3-pentenylidene)-butanedial; (E)-2,7- Octadienal; (E)-2-Methyl-2-octenal; (E)-2-Methyl-5-(3-furyl)-2-pentenal; (E)-2-Octenal; (E)-3,7-Dimethyl-2,6-octadienal; (E)-3,7-Dimethyl-2,6-octadienal; (E)-3-Octenal; (E)-4- oxo-2-Octenal; (E)-7-Methyl-2-octenal; (E,E)-2,4-Octadienal; (E,E)-2,6-Dimethyl-8- hydroxy-2,6-octadienal; (E,E)-2,6-Octadienal; (E,E)-2,6-Octadienedial; (E,Z)-2,4- Octadienal; (E,Z)-2,6-Octadienal; (R)-l, 2-Dimethyl-3-methylenecy cl openly 1-acetaldehyde; (R)-3,7-Dimethyl-6-octenal; (Z)-(3.3-Dimethyl)-cyclohexylideneacetaldehyde; (Z)-2-(3,3- Dimethylcyclohexylidene)-acetaldehyde; (Z)-3,7-Dimethyl-2,6-octadienal; (Z,E)-3,7- Dimethyl-2,6-octadienal; 1-Octenal; 2-( 1 -Formyl vinyl)-5- methylcyclopentanecarbaldehyde; 2-(3,4-Dihydroxyphenyl)-2-oxoacetaldehyde; 2,6,6- Trimethy 1- 1 -cyclohexene- 1 -carbaldehy de; 2-Ethyloctanal; 2-Hy droxy-6- methylbenzaldehyde; 2-Methyl benzaldehyde; 2-Methyl-5-(l -formylethyl)-! -cyclopentene- 1 -carbaldehy de; 2-Octenal; 2-Phenylacetaldehyde; 2-Phenylpropenal; 3,4- Dihydroxyphenylglyoxal; 3,7-Dimethyl-6-octenal; 3-Ethoxy-4-hydroxybenzaldehyde; 3- Ethyl benzaldehyde; 3-Isopropyl-6-methyl benzaldehyde; 3-Octenal; 3-oxo-4- Isopropylidene- 1 -cyclohexene- 1 -carboxyaldehy de; 4-Ethylbenzaldehy de; 4-Hy droxy-2- methyl benzaldehyde; 4-Hydroxy-3-methoxybenzaldehyde; 4-Isopropenyl-l-cyclohexene-

1-carbaldehyde; 4-Isopropenyl-3-oxo-l-cyclohexene-l -carboxyaldehyde; 4S-4-

Isopropenyl-3-oxo-l -cyclohexene-1 -carboxyaldehyde; 5 -Ethyl cy cl opent- 1 -ene- carbaldehyde; 6,6-Dimethylbicyclo[3.Ll]hept-2-ene-2-carbaldehyde; 6-Methyloctanal; 7- Methyloctanal; Anisomorphal; cis-2-Isopropenyl-l -methylcyclobutaneethanal; Octanal; Peruphasmal; (lR.2S.6R)-2.6-Dimethyl-3-oxabicyclo|4.2.0]octane-2-carbaldehyde; (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; (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-methylcyclopenteneacetaldehyde; 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-Ethyl benzaldehyde; 7,7-Dimethylbicyclo[4.1.0]hept-3-ene- 3-carbaldehyde; 7-Methylnonanal; 8-Methylnonanal; 9-Acetyloxynonanal; Gibepyrone C; Nonanal; (4R,8R)-4,8-Dimethyldecanal; (4R,8S)-4,8-Dimethyldecanal; (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-Ethyldecanal; 3-(2,3-Dibromo-4,5- dihydroxyphenyl)-2-methylpropanal; 4,5-Dimethyldecanal; 4,8-Dimethyldecanal; Caraibical; Decanal; Rogiolal; (2E,4E)-2,6,10-Trimethylundeca-2.4.9-trienal; (2E,4E,7Z)- 2,6.10-Trimethylundeca-2.4.7.9-tetraenal; (5E)-2,6, 10-Trimethylundeca-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-oxoundeca-2,6-dienal; 5-Methyl-

2-phenyl-2-hexenal; 8-Isopropyl-5-methyl-3,4,4a,5.6,7,8,8a-octahydronaphthalene-2- carbaldehyde; Austrodoral; Oxytoxin 1; syn-4,6-Dimethylundecanal; Taxifolial A; Taxifolial B; Taxifolial C; Undecanal; (lR,6R,7S,10R)-l-Hydroxy-4-cadinen-15-al; (2R,7S,1 lR)-7-Acetoxy-2-hydroxynardosin-l(10)-en-12-al; (3R,5R,9R)-3,5,9- Trimethyldodecanal; (3S,6E)-7-Ethyl-3, 11 -dimethyldodeca-6,10-dienal; (9R)-3,5,9- Trimethyldodecanal; (E)-lO-Dodecenal; (E)-2-Dodecenal; (E)-3,7,l l-Trimethyl-6,10- dodecadienal; (E)-5-Dodecenal; (E)-6-Dodecenal; (E)-7-Dodecenal; (E)-8-Dodecenal: (E)- 9, 11 -Dodecadi enal; (E)-9-Dodecenal; (E.E)-3,7,1 l-Trimethyl-2,6,10-dodecatrienal; (E.E)- 7-Ethyl-3,l l-dimethyl-2,6, 10-dodecatrienal; (E,E)-8,10-Dodecadienal; (E,E,E)-3,7- Dimethyl-8,1 l-dioxo-2,6,9-dodecatrienal; (E,E,Z)-3,7-Dimethy 1-8,1 l-dioxo-2,6,9- dodecatrienal; (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; (S,E)-3,7,1 l-Trimethyl-6,10- dodecadienal; (Z)-2-Methyl-5-((lR,5R,6S)-2,6-dimethylbicyclo|3.1.1]hept-2-en-6-yl)-pent- 2-enal; (Z)-5-Dodecenal; (Z)-7-Dodecenal; (Z)-9,11-Dodecadienal; (Z)-9-Dodecenal; (Z,E)-

3.7.1 l-Trimethyl-2,6,10-dodecatrienal; (Z,E)-5,7-Dodecadienal; (Z,E)-7-Ethyl-3,l l- dimethyl-2,6.10-dodecatrienal; (Z,E)-8,10-Dodecadienal; (Z,Z)-5.7-Dodecadienal; 10- Methyldodecanal; 2.10-Dibromo-3-chloro-7-chamigrene; 2-Dodecenal; 2-Ethyldodecanal; 2-Formylguaiazulene; 3,7,1 l-Trimethyl-(E)-6,10-dodecadienal; 5-Hydroxy-8- methoxycalamanen-15-al; 5-Hydroxy-8-methoxycalamenene-15-al; Aplysinal; Debromoaplysinal; Dodecanal; Parahigginol D; Polygodial; Sclerosporal: Sinuketal; syn- 4,6-Dimethyldodecanal; trans-Calamenen-13-al; (3R.5S,9R,7E,11E)-3,5,9,11-Tetramethyl- 7, 11 -tridecadi enal; (3 S,4R,6E, 10Z)-3,4,7, 11 -Tetramethyl-6, 10-tridecadienal; (E,E)-

3.5.9.1 l-Tetramethyltrideca-7,l l-dienal; (Z)-4-Tridecenal; 13, 14,15, 16-Tetranorcl erod-3 - en-12-al; 13-Acetyloxytridecanal; 4,6-bis(4-Methylpent-3-en-l-yl)-6-methylcyclo-l,3- hexadienecarbaldehyde; Acanthodoral; Ancistrodial; Cespitulin F; Isoacanthodoral; Tndecanal; (E)-l l,13-Tetradecadienak (E)-l l-Tetradecenal; (E,E)-8,10-Tetradecadienal; (E,Z)-4,9-Tetradecadienal; (E,Z)-8,10-Tetradecadienal; (Z)-l l,13-Tetradecadienal; (Z)-l l- Tetradecenal; (Z)-5-Tetradecenal; (Z)-7-Tetradecenal; (Z)-8-Tetradecenal; (Z)-9,13- Tetradecadien-l l-ynal; (Z)-9-Tetradecenal; (Z,E)-9,11,13-Tetradecatrienal; (Z,E)-9,11- Tetradecadienal; (Z,E)-9,12-Tetradecadienal; (Z.Z)-5,8-Tetradecadienal; (Z,Z)-8,10- Tetradecadienal; (Z,Z)-9,l l-Tetradecadienal; 10,12-Tetradecadienal; 2,4-Tetradecadienal; 2-Ethyltetradecanal; 3-oxo-13-Tetradecenal; 3-oxo-Tetradecanal; 5,8-Tetradecadienal; 5- Tetradecenal; Norasperenal A; Norasperenal B; Norasperenal C; Norasperenal D; Sargasal I; Sargasal II; Tetradecanal; (6R)-6-Acetoxidichotoma-3,14-diene-l, 17-dial; (6R)-6- Hydroxydichotoma-3,14-diene-l, 17-dial; (E,E)-3,7,l l,15-Tetramethyl-6,10,14- hexadecatrienal; (E,Z)-6,8-Pentadecadienal; (E,Z)-9,l l-Pentadecadienal; (E,Z,Z)-2,6,9- Pentadecatrienal; (Z)-lO-Pentadecenal; (Z)-2-Chloropentadec-2-enak (Z)-6,14- Pentadecadienal; (Z,Z)-6,9-Pentadecadienal; (Z,Z)-9, 11 -Pentadecadi enal; 2-Hexyl-2- decenal; Azamial A; Azamial B; Isopachydictyolak Pentadecanal; Sinularial A; Umbellacin A; Xeniafaraunol A; (IR)-Pimaral; (E)-lO-Hexadecenal; (E)-l l-Hexadecenal; (E)-14- Hexadecenal; (E)-14-Methyl-8-hexadecenal; (E)-3,7,l l,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-Hexadecatrienal; (E,E,E)-3,7, 11,15- tetramethyl-2,6, 10.14-hexadecatetraenal; (E,E,Z)- 10, 12, 14-Hexadecatrienal; (E,E,Z)- 4.6.11-Hexadecatrienal; (E.E,Z,Z)-4.6.11,13-Hexadecatetraenak (E,Z)-10.12- Hexadecadienal; (E,Z)-11,13-Hexadecadienal; (E,Z)-4,6-Hexadecadienal; (E,Z)-6,11- Hexadecadienal; (E,Z)-8, 11 -Hexadecadi enal; (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)-lO-Hexadecenal; (Z)-l 1-Hexadecenal; (Z)-12-Hexadecenal; (Z)-13-Hexadecen-1 1 -ynal; (Z)-14-Methyl-8-hexadecenal; (Z)- 3,7,1 l,15-Tetramethyl-2-hexadecenal; (Z)-3-oxo-9-Hexadecenal; (Z)-7-Hexadecenal; (Z)- 9-Hexadecenal; (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-Hexadecatrienal; 11-Hexadecenal; 11-Hexadecynal; 13(16), 14-Spongiadien- 19-al; 2-Methylhexadecanal; 7-Hexadecenal; 9-Hexadecenal; Deacetyl-dihydro-nor-thuridillonal; Dictyodial A: Dihydro-nor-thuridillonak Hexadecanal; Keikipukalide A; Keikipukalide B; Keikipukalide C; Keikipukalide D; Keikipukalide E; Nor-thuridillonak Pseudoplexaurak Pukalide aldehyde; Sanadaol; (E)-2-Tridecyl-2- heptadecenal; (Z)-9-Heptadecenal; 1-Heptadecenal; 2-Heptadecenal; Globostelletin C; Globostelletin D: Heptadecanal; (E)-l 1-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)-6,1 1 -Octadecadi enal; (Z)-l l- Octadecenal; (Z)-13-Octadecenal; (Z)-9-Octadecenal; (Z,E)-13,15-Octadecadienal; (Z,Z)-

11.13-Octadecadi enal; (Z,Z)-13,15-Octadecadienal; (Z,Z)-3,13-Octadecadienal; (Z,Z)-9,12- Octadecadienal; (Z,Z,Z)-9,12.15-Octadecatrienal; 11-Octadecenal; 13,15-Octadecadienal; 13-Octadecenal; 16-Methyloctadecanal; 1-Octadecenal; 3,6-Dihydroxy-24-nor-9-oxo-9,l l- secocholesta-7,22-dien-l l-al; 9-Octadecenal; Methyloctadecanal; Octadecanal; Panicein B2; Panicein B3; Panicein C; (Z)-l O-Nonadecenal; (Z)-9-Nonadecenal; 9(1 1)-Pargueren- 16- al; Hyrtiosal; Nonadecanal; (2E,6Z,9Z)-2-Methyl-2,6,9-eicosatrienal; (Z)-l 1-Eicosenal; 11- Eicosenal; 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-Eicosenal; 1-Eicosenal; 3-Deacetyl-22,23-dihydro-24,28-dehydroluffasterol B; 3-Deacetylluffasterol B; 9- Eicosenal; Anthogorgiene B; Deacetylscalaradial; Eicosadienal; Eicosanal; Mooloolabene A; Mooloolabene B; Scalaradial; and combinations thereof.

[43] Of note pheromones include (Z)-5-decenyl acetate, dodecanyl 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)-lO-dodecenyl acetate, 11- dodecenyl acetate. (Z)-9, l 1 -dodecadi enyl acetate, (E)-9.11- dodecadienyl acetate, (Z)-l l- tridecenyl acetate, (E)- 11 -tridecenyl acetate, tetradecanyl acetate, (E)-7-tetradecenyl acetate, (Z)-8-tetradecenyl acetate, (E)-8-tetradecenyl acetate, (Z)-9-tetradecenyl acetate, (E)-9- tetradecenyl acetate, (Z)-lO-tetradecenyl acetate. (E)-lO-tetradecenyl acetate, (Z)-l l- tetradecenyl acetate, (E)-l 1 -tetradecenyl acetate, (Z)-12-pentadecenyl acetate. (E)-12- pentadecenyl acetate, hexadecanyl acetate, (Z)-7-hexadecenyl acetate, (Z)-l 1 -hexadecenyl acetate, (E)- 11 -hexadecenyl acetate, octadecanyl 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- tridecadienyl acetate, (E,E)-9, 11 -tetradecadienyl acetate, (Z,Z)-9,12-tetradecadienyl acetate, (Z,Z)-7,11 -hexadecadienyl acetate, (E,Z)-7, 11 -hexadecadi enyl acetate, (Z,E)-7,11- hexadecadienyl acetate, (E,E)-7, 11 -hexadecadienyl acetate, (Z,E)-3,13-octadecadienyl acetate. (E,Z)-3,13-octadecadienyl acetate, (E,E)-3,13-octadecadienyl acetate, decanol, (Z)- 6-nonenol, (E)-6-nonenol, dodecanol, (Z)-5-decenol, 11-dodecenol. (Z)-7-dodecenol. (E)-7- dodecenol, (Z)-8-dodecenol, (E)-8-dodecenol, (E)-9-dodecenol, (Z)-9-dodecenol, (E)-9,l l- dodecadienol, (Z)-9, 11 -dodecadienol, (Z,E)-5,7-dodecadienol, (E,E)-5,7-dodecadienol, (E,E)-8,10-dodecadien-l-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)-lO-tetradecenol, (Z)-l l- tetradecenol, (E)-l l-tetradecenol, (Z)- 11 -hexadecenol, (Z,E)-9, 11 -tetradecadi enol, (Z,E)- 9,12-tetradecadienol, (Z,Z)-9,12- tetradecadi enol, (Z, Z)-10,12-tetradecadienol, (Z,Z)-7,11- hexadecadienol, (Z,E)-7, 11 -hexadecadi enol, (E)-14-methyl-8- hexadecen-l-ol, (Z)-14- methyl-8-hexadecen-l-ol, (E,E)-10, 12-hexadecadienol, (E,Z)-10, 12-hexadecadienol, dodecanal, (Z)-9-dodecanal, tetradecanal. (Z)-7- tetradecenal, (Z)-9-tetradecenal, (Z)-l l- tetradecenal, (E)- 11 -tetradecenal. (E)-l l,13-tetradecadienal, (E.E)-8,10-tetradecadienal, (Z,E)-9,11 -tetradecadi enal, (Z,E)-9,12- tetradecadienal, hexadecanal, (Z)-8-hexadecenal, (Z)-9-hexadecenal, (Z)-lO-hexadecenal, (E)-lO-hexadecenal, (Z)-l l-hexadecenal, (E)- hexadecenal, (Z)-12-hexadecenal, (Z)-13-hexadecenal, (Z)-14-methyl-8-hexadecenal, (E)- 14-methyl-8-hexadecenal, (Z.Z)-7,l l-hexadecadienal, (Z,E)-7,l l-hexadecadienal, (Z,E)- 9.11-hexadecadienal. (E.E)-10.12-hexadecadienal. (E.Z)-10.12-hexadecadienal, (Z.E)- 10,12-hexadecadienal, (Z,Z)- 10, 12-hexadecadienal, (Z,Z)- 11,13 -hexadecadienal, octadecenal, (Z)-l l-octadecenal, (E)-13-octadecenal, (Z)-13-octadecenal, (Z)-5-decenyl 3- methylbutanoate. (+) cis-7,8-epoxy-2 -methyloctadecane

[44] Also of note pheromones include citral; geranial; neral; tetradecan-1 -al; pentadecan-l-al; pentadecen-l-al; hexadecan- 1 -al; (Z)-9-hexadecen-l-al; (Z)-l l- hexadecen-l-al; (7E,9E)-undeca-7,9-dien-l-al; (11Z, 13Z)-hexadecadien-l-al; (9Z,12E)- tetradecadien-l-al; (8E,10E)-dodecadien-l-al; (1 lZ)-hexadecadien-l-al; (9Z)-tetradecen-l- al; 6,10-dimethyl-5,9-undecadien-2-ol; (6E)-7,11 -dimethyl -3 -methylene- 1,6, 10- dodecatriene; [lS-(la,2b,5 a)]- 4,6,6-trimethyl-Bicyclo[3.1.1]hept-3-en-2-ol; 10-

Hexadecenal; (Z)-lO-hexadecenal; (E)-lO-hexadecenal; and combinations thereof.

[45] In some embodiments, the pheromone is selected from (Z)-5-decenyl acetate, dodecanyl 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,l l- dodecadienyl acetate, (Z)- 11 -tridecenyl acetate, (E)- 11 -tri decenyl acetate, tetradecanyl acetate, (E)-7-tetradecenyl acetate, (Z)-8-tetradecenyl acetate, (E)-8-tetradecenyl acetate, (Z)-9-tetradecenyl acetate, (E)-9-tetradecenyl acetate, (Z)-lO-tetradecenyl acetate, (E)-10- tetradecenyl acetate, (Z)- 11 -tetradecenyl acetate. (E)-l 1 -tetradecenyl acetate, (Z)-12- pentadecenyl acetate, (E)-12-pentadecenyl acetate, hexadecanyl acetate, (Z)-7-hexadecenyl acetate, (Z)-l 1 -hexadecenyl acetate, (E)-l 1 -hexadecenyl acetate, octadecanyl 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-tridecadienyl acetate, (E,E)-9,11 -tetradecadienyl acetate, (Z,Z)-9, 12- tetradecadienyl acetate, (Z,Z)-7, 11 -hexadecadienyl acetate, (E,Z)-7, 11 -hexadecadienyl acetate, (Z,E)-7, 11 - hexadecadienyl acetate, (E,E)-7, 11 -hexadecadienyl acetate, (Z,E)-3,13- octadecadienyl acetate. (E,Z)-3,13-octadecadienyl acetate, (E,E)-3.13-octadecadienyl acetate, (Z)-5-decenyl 3-methylbutanoate, (+) AS-7.8-epoxy-2-methyloctadecane. methyl (E,Z)-2,4-decadi enoate, methyl 2,6,10-trimethyltridecanoate, and combinations thereof.

[46] In some embodiments, the loading level of the pheromone relative to the entire formulation is in a range of from about 5 wt.% to about 30 wt.%. In some embodiments, the loading level of the pheromone relative to the entire formulation is in a range of from about 5 wt.% to about 15 wt.%. The loading level is achieved by in situ autopolymerization of isocyanate monomers, which forms a polymeric membrane.

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

[48] In some embodiments, the percentage of the pheromone in the organic phase is in a range of from about 10 wt.% to about 100 wt.%. In some embodiments, the percentage of the pheromone in the organic phase is in arange of from about 50 wt.% to about 100 wt.%. In some embodiments, the percentage of the pheromone in the organic phase is in a range of from about 70 wt.% to about 100 wt.%.

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

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

[51] In some embodiments, the percentage of the wall material (e.g., isocyanate) relative to the organic phase is at least about 3 wt.%, at least about 4 wt.%, at least about 5 wt.%, at least about 6 wt.%. at least about 7 wt.%, at least about 8 wt.%, at least about 9 wt.%, at least about 10 wt.%, at least about 11 wt.%, at least about 12 wt.%, at least about 13 wt.%, at least about 14 wt.%, at least about 15 wt.%, at least about 16 wt.%, at least about 17 wt.%, at least about 18 wt.%, or at least about 19 wt.%. In some embodiments, the percentage of the wall material (e.g., isocyanate) relative to the organic phase is at most about 4 wt.%, at most about 5 wt.%, at most about 6 wt.%, at most about 7 wt.%, at most about 8 wt.%, at most about 9 wt.%, at most about 10 wt.%, at most about 11 wt.%, at most about 12 wt.%, at most about 13 wt.%, at most about 14 wt.%, at most about 15 wt.%, at most about 16 wt.%, at most about 17 wt.%, at most about 18 wt.%, at most about 19 wt.%, or at most about 20 wt.%.

[52] Generally, compositions according to the present disclosure may include any suitable solvent known in the art that facilitates 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 flashpoint-type solvents, methylated seed oils, methyl oleate methyl ester oil, methyl linoleate methyl ester oil, mineral oils, paraffinic oil, tall oil fatty acid-based solvents, aromatic solvents (e.g., Aromatic 200, Aromatic 200ND), aromatic ester solvents, polybutenes, methyl esters of fatty acids, tributyl 2-acetate citrate, alkyl amides (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 methyl ester oil and methyl linoleate methyl ester oil and a solvent selected from hydrophobic solvents including high flashpoint-type solvents, methylated seed oils, mineral oils, paraffinic oil, tall oil fatty acid-based solvents, aromatic solvents, aromatic ester solvents, polybutenes, methyl esters of fatty acids, tributyl 2-acetate citrate, alkyl amides, benzy l acetate, wax esters, and combinations thereof.

[53] In some embodiments, the pheromone and the solvent are each encapsulated. 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 auxiliary.

[54] Generally, compositions according to the present disclosure may include any suitable antifreeze agent known in the art that facilitates the compositions described herein. In some embodiments, the antifreeze agent is selected from propylene glycol, glycerin, glycols, ethylene glycol, 1,2-butane diol, 1,3-butane diol, 2,3-butanediol, 1,4-butanediol, methanol, ethanol, propanol, butanol, and combinations thereof. In some embodiments, the antifreeze agent is non-encapsulated. In some embodiments, a portion of the antifreeze agent is encapsulated. [55] In many embodiments, the shell comprises polyurea, isocyanate, and/or polyisocyanate. Suitable isocyanates include polyisocyanates and polyisocyanate prepolymers such as polymethylene polyphenyl isocyanates (e.g., PAPI 27), polymeric diphenyl methane diisocyanate (MDI) (e.g., Rubinate M or Suprasec 5025). isocyanates based on xylylene diisocyanate (XDI), including but not limited to, Takenate™ 500 (XDI), Takenate™ 600 (hydrogenated XDI), Takenate™ D-l 10N (an adduct of XDI and trimethylol propane), Takenate™ D-131N (an XDI-trimer), and Takenate™ D-120 (an adduct of hydrogenated XDI and trimethylol propane), polyisocyanate-polyol adducts, polyfunctional aliphatic isocyanates, and the like. In these embodiments, the shell is formed without an additionally added amine. In some embodiments, the shell is formed via in situ autopolymerization. When the shell comprises polyurea, the polyurea is formed from an in situ autopolymerization of isocyanate monomers. Without being bound to any particular theory, it is believed that isocyanate monomers may react with water in an aqueous phase to form carbamic acid which then converts to an amine and carbon dioxide. This amine then reacts with isocyanate monomers to form a polyurea.

[56] In some embodiments, the composition is an agrochemical composition. In some embodiments, the composition is in a form selected from a premix and a tank mix. In some embodiments, the composition is a sprayable composition.

[57] Compositions according to the present disclosure may be in any suitable form of compositions known in the art that facilitates the compositions described herein. Particularly preferred formulations of compositions in accordance with the present disclosure are capsule suspension concentrates (CS), mixed formulations (ZC) that include mixtures of suspension concentrates (SC) and capsule suspension concentrates (CS), mixed formulations (ZW) that include mixtures of emulsions, oil-in-water (EW) and capsule suspension concentrates (CS), and mixed formulations (ZE) that include mixtures of suspoemulsions (SE) and capsule suspension concentrates (CS).

[58] In some embodiments, the composition is in a form of a CS formulation, a ZC formulation, a ZW formulation, or a ZE formulation. [59] Sprayable formulations are typically extended in a suitable medium before spraying. Such formulations are formulated to be readily diluted in the spray medium, usually water, but occasionally another suitable medium like an aromatic or paraffinic hydrocarbon or vegetable oil. Spray volumes can range from about one to several thousand liters per hectare, but more ty pical ly are in the range from about ten to several hundred liters per hectare. Sprayable formulations can be tank mixed with water or another suitable medium for foliar treatment by aerial or ground application, or for application to the growing medium of the plant. Formulations can be metered directly into drip irrigation systems or metered into the furrow during planting. Formulations can be applied onto seeds of crops and other desirable vegetation as seed treatments before planting to protect developing roots and other subterranean plant parts and/or foliage through systemic uptake.

[60] The compositions according to the present disclosure may be delivered by an autonomous vehicle. The autonomous vehicle may be a grounded vehicle. The autonomous vehicle may operate during the day and/or night.

[61] The compositions according to the present disclosure may be aerially delivered. The compositions according to the present disclosure may be delivered by an unmanned vehicle or an unmanned aerial vehicle (UAV). The compositions according to the present disclosure may be delivered by a helicopter or fixed-wing airplane.

[62] Generally, compositions according to the present disclosure may be made according to any suitable method know n in the art that facilitates the compositions described herein.

[63] In some embodiments, described herein is a method of making a composition, the method comprising: forming a mixture comprising: an antifreeze agent; and a microcapsule comprising: a core comprising: a pheromone; and a solvent; and a shell encapsulating the core. The shell includes a polymer produced by autopolymerization of a monomer and the microcapsule has a d90 value less than about 40 pm.

[64] In some embodiments, the method further includes encapsulating the pheromone and the solvent in the microcapsule prior to forming the mixture. In these embodiments, the microcapsule is added to the mixture. [65] In some embodiments, the method includes encapsulating the pheromone and the solvent in the microcapsule in the mixture. In these embodiments, the microcapsule is formed in situ in the mixture by known methods of interfacial polymerization. Microencapsulated formulations prepared by interfacial polymerization are beneficial for at least three reasons: i) they are easily manufactured on a large scale using known technology; ii) they are easily applied over large areas with conventional spray equipment; and iii) they possess numerous variables that can be manipulated to control the release characteristics (e.g. capsule wall thickness, capsule wall composition, capsule size and internal composition).

[66] Generally, compositions according to the present disclosure may be used according to any suitable purpose know n in the art that facilitates the compositions described herein.

[67] In some embodiments, described herein is a method for controlling a pest comprising contacting the pest or its environment with a biologically effective amount of a composition comprising: an antifreeze agent; and a microcapsule comprising: a core comprising: a pheromone; and a solvent; and a shell encapsulating the core. The shell includes a polymer produced by autopolymerization of a monomer and the microcapsule has a d90 value less than about 40 pm.

[68] Compositions of this disclosure are useful for controlling a wide spectrum of invertebrate pests. These pests include invertebrates inhabiting a variety of environments such as, for example, plant foliage, roots, soil, harvested crops or other foodstuffs, building structures or animal integuments. These pests include, for example, invertebrates feeding on foliage (including leaves, stems, flowers and fruits), seeds, wood, textile fibers or animal blood or tissues, and thereby causing injury or damage to, for example, growing or stored agronomic crops, forests, greenhouse crops, ornamentals, nursery crops, stored foodstuffs or fiber products, or houses or other structures or their contents, or being harmful to animal health or public health. Those skilled in the art will appreciate that not all compositions are equally effective against all growth stages of all pests.

[69] These present compositions are thus useful agronomically for protecting field crops from phytophagous invertebrate pests, and also nonagronomically for protecting other horticultural crops and plants from phytophagous invertebrate pests. This utility includes protecting crops and other plants (i.e. both agronomic and nonagronomic) that contain genetic material introduced by genetic engineering (i.e. transgenic) or modified by mutagenesis to provide advantageous traits. Examples of such traits include tolerance to herbicides, resistance to phytophagous pests (e.g., insects, mites, aphids, spiders, nematodes, snails, plant-pathogenic fungi, bacteria and viruses), improved plant growth, increased tolerance of adverse growing conditions such as high or low temperatures, low or high soil moisture, and high salinity, increased flowering or fruiting, greater harvest yields, more rapid maturation, higher quality and/or nutritional value of the harvested product, or improved storage or process properties of the harvested products. Transgenic plants can be modified to express multiple traits. Examples of plants containing traits provided by genetic engineering or mutagenesis include varieties of com, cotton, soybean and potato expressing an insecticidal Bacillus thuringiensis toxin such as YIELD GARD®, KNOCKOUT®, STARLINK®, BOLLGARD®, NuCOTN® and NEWLEAF®, INVICTA RR2 PRO™, and herbicide-tolerant varieties of com, cotton, soybean and rapeseed such as ROUNDUP READY®, LIBERTY LINK®, IMI®, STS® and CLEARFIELD®, as well as crops expressing A-acetyl transferase (GAT) to provide resistance to glyphosate herbicide, or crops containing the HRA gene providing resistance to herbicides inhibiting acetolactate synthase (ALS). The present compositions may exhibit enhanced effects with traits introduced by genetic engineering or modified by mutagenesis, thus enhancing phenotypic expression or effectiveness of the traits or increasing the invertebrate pest control effectiveness of the present compounds and compositions. In particular, the present compositions may exhibit enhanced effects with the phenotypic expression of proteins or other natural products toxic to invertebrate pests to provide greater-than-additive control of these pests.

[70] Compositions of this disclosure can also optionally comprise plant nutrients, e.g., a fertilizer composition comprising at least one plant nutrient selected from nitrogen, phosphorus, potassium, sulfur, calcium, magnesium, iron, copper, boron, manganese, zinc, and molybdenum. Of note are compositions comprising at least one fertilizer composition comprising at least one plant nutrient selected from nitrogen, phosphorus, potassium, sulfur, calcium and magnesium. Compositions of the present disclosure which further comprise at least one plant nutrient can be in the form of liquids or solids. Of note are solid formulations in the form of granules, small sticks or tablets. Solid formulations comprising a fertilizer composition can be prepared by mixing the composition of the present disclosure with the fertilizer composition together with formulating 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 a composition of the present disclosure in a volatile solvent onto a previous prepared fertilizer composition in the form of dimensionally stable mixtures, e.g., granules, small sticks or tablets, and then evaporating the solvent.

[71] Nonagronomic uses refer to invertebrate pest control in the areas other than fields of crop plants. Nonagronomic uses of the present compositions include control of invertebrate pests in stored grains, beans and other foodstuffs, and in textiles such as clothing and carpets. Nonagronomic uses of the present compositions also include invertebrate pest control in ornamental plants, forests, in yards, along roadsides and railroad rights of way, and on turf such as lawns, golf courses and pastures. Nonagronomic uses of the present compositions also include invertebrate pest control in houses and other buildings which may be occupied by humans and/or companion, farm, ranch, zoo or other animals. Nonagronomic uses of the present compositions also include the control of pests such as termites that can damage wood or other structural materials used in buildings.

[72] Nonagronomic uses of the present compositions also include protecting human and animal health by controlling invertebrate pests that are parasitic or transmit infectious diseases. The controlling of animal parasites includes controlling external parasites that are parasitic to the surface of the body of the host animal (e.g., shoulders, armpits, abdomen, inner part of the thighs) and internal parasites that are parasitic to the inside of the body of the host animal (e.g., stomach, intestine, lung, veins, under the skin, 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 helminths. Compositions of the present disclosure are suitable for systemic and/or non- systemic control of infestation or infection by parasites on animals. Compositions of the present disclosure are suitable for combating external parasitic or disease transmitting pests. Compositions of the present disclosure are suitable for combating parasites that infest agricultural working animals, such as cattle, sheep, goats, horses, pigs, donkeys, camels, buffalos, rabbits, hens, turkeys, ducks, geese and bees; pet animals and domestic animals such as dogs, cats, pet birds and aquarium fish; as well as so-called experimental animals, such as hamsters, guinea pigs, rats and mice. By combating these parasites, fatalities and performance reduction (in terms of meat, milk, wool, skins, eggs, honey, etc.) are reduced, so that applying a composition of the present disclosure allows more economic and simple husbandry of animals.

[73] Examples of agronomic or nonagronomic invertebrate pests include eggs, larvae and adults of the order Lepidoptera, such as armyworms, cutworms, loopers, and heliothines in the family Noctuidae (e.g., pink stem borer (Sesamia inferens Walker), com stalk borer (Sesamia nonagrioides Lefebvre), southern armyworm (Spodoptera eridania Cramer), fall army worm (Spodoptera frugiperda J. E. Smith), beet army worm (Spodoptera exigua Hubner), cotton leafworm (Spodoptera littoralis Boisduval), yellowstriped armyworm (Spodoptera ornithogalli Guenee), black cutworm (Agrotis ipsilon Hufhagel), velvetbean caterpillar (Anticarsia gemmatalis Hubner), green fruitworm (Lithophane antennata Walker), cabbage armyworm (Barathra brassicae Linnaeus), soybean looper (Pseudoplusia includens Walker), cabbage looper (Trichoplusia ni Hubner), tobacco budworm (Heliothis virescens Fabricius)); borers, casebearers, webworms, coneworms, cabbageworms and skeletonizers from the family Pyralidae (e.g., European com borer (Ostrinia nubilalis Hubner), navel orangeworm (Amyelois transitella Walker), com root webworm (Crambus caliginosellus Clemens), sod webworms (Pyralidae: Crambinae) such as sod worm (Herpetogramma licarsisalis Walker), sugarcane stem borer (Chilo infuscatellus Snellen), tomato small borer (Neoleucinodes elegantalis Guenee), green leafroller (Cnaphalocrocis medinalis Guenee), grape leaffolder (Desmia funeralis Hubner), pickleworm (Diaphania nitidalis Stoll), cabbage center grub (Hellula hydralis Guenee), yellow stem borer (Scirpophaga incertulas Walker), white stem borer (Scirpophaga innotata Walker), top shoot borer (Scirpophaga nivella Fabricius). dark-headed rice borer (Chilo polychrysus Meyrick), striped riceborer (Chilo suppressalis Walker), cabbage cluster caterpillar (Crocidolomia binotalis Zeller)); leafrollers, budworms, seed worms, and fruit worms in the family Tortricidae (e.g., codling moth (Cydia pomonella Linnaeus), grape berry moth (Paralobesia viteana Clemens), oriental fruit moth (Grapholita molesta Busck), citrus false codling moth (Cryptophlebia leucotreta Meyrick), citms borer (Gymnandrosoma aurantianum Lima), redbanded leafroller (Argyrotaenia velutinana Walker), obliquebanded leafroller (Choristoneura rosaceana Harris), light brown apple moth (Epiphyas postvittana Walker), European grape berry moth (Eupoecilia ambiguella Hiibner), apple bud moth (Pandemis pyrusana Kearfott), omnivorous leafroller (Platynota stultana Walsingham), barred fruit-tree tortrix (Pandemis cerasana Hiibner), apple brown tortrix Pandemis heparana Denis & Schiffermtiller)); and many other economically important lepidoptera (e.g., diamondback moth (Plutella xylostella Linnaeus), pink bollworm (Pectinophora gossypiella Saunders), gypsy moth (Lymantria dispar Linnaeus), peach fruit borer (Carposina niponensis Walsingham), peach twig borer (Anarsia lineatelia Zeller), potato tuberworm (Phthorimaea operculella Zeller), spotted teniform leafminer (Phyllonorycter blancardella Fabricius), Asiatic apple leafminer (Lithocolletis ringoniella Matsumura), rice leaffolder (Lerodea eufala Edwards), apple leafminer (Leucoptera scitella Zeller)); eggs, nymphs and adults of the order Blattodea including cockroaches from the families Blattellidae and Blattidae (e.g., oriental cockroach (Blatta orientalis Linnaeus), Asian cockroach (Blatella asahinai Mizukubo), German cockroach (Blattella germanica Linnaeus), brownbanded cockroach (Supella longipalpa Fabricius), American cockroach (Periplaneta americana Linnaeus), brown cockroach (Periplaneta brunnea Burmeister), Madeira cockroach (Leucophaea maderae Fabricius)), smoky brown cockroach (Periplaneta fuliginosa Serville). Australian Cockroach (Periplaneta australasiae Fabr.), lobster cockroach (Nauphoeta cinerea Olivier) and smooth cockroach (Symploce pollens Stephens)); eggs, foliar feeding, fruit feeding, root feeding, seed feeding and vesicular tissue feeding larvae and adults of the order Coleoptera including weevils from the families Anthribidae, Bruchidae, and Curculionidae (e.g., boll weevil (Anthonomus grandis Boheman). rice water weevil (Lissorhoptrus oryzophilus Kuschel), granary weevil (Sitophilus granarius Linnaeus), rice weevil (Sitophilus oryzae Linnaeus)), annual bluegrass weevil (Listronotus maculicollis Dietz), bluegrass billbug (Sphenophorus parvulus Gyllenhal), hunting billbug (Sphenophorus venatus vestitus Chittenden), Rocky Mountain billbug (Sphenophorus cicatristriatus Fahraeus)); flea beetles, cucumber beetles, rootworms, leaf beetles, potato beetles, and leafminers in the family Chrysomelidae (e.g., Colorado potato beetle (Leptinotarsa decemlineata Say), western com rootworm (Diabrotica virgifera LeConte)); chafers and other beetles from the family Scarabaeidae (e.g., Japanese beetle (Popillia japonica Newman), oriental beetle (Anomala orientalis Waterhouse, northern masked chafer (Cyclocephala borealis Arrow), southern masked chafer (Cyclocephala immaculata Olivier or C. lurida Bland), dung beetle and white grub (Aphodius spp.), black turfgrass ataenius (Ataenius spretulus Haldeman), green June beetle (Cotinis nitida Linnaeus), Asiatic garden beetle (Maladera castanea Arrow), May/June beetles (Phyllophaga spp.) and European chafer (Rhizotrogus majalis Razoumowsky)); carpet beetles from the family Dermestidae; wireworms from the family Elateridae; bark beetles from the family Scolytidae and flour beetles from the family Tenebrionidae.

[74] In addition, agronomic and nonagronomic pests include: eggs, adults and larvae of the order Dermaptera including earwigs from the family Forficulidae (e.g., European earwig (Forficula auricularia Linnaeus), black earwig (Chelisoches morio Fabricius)); eggs, immatures, adults and nymphs of the order Hemiptera such as, plant bugs from the family Miridae, cicadas from the family Cicadidae, leafhoppers (e.g. Empoasca spp.) from the family Cicadellidae, bed bugs (e.g., Cimex lectularius Linnaeus) from the family Cimicidae, planthoppers from the families Fulgoridae and Delphacidae, treehoppers from the family Membracidae, psyllids from the families Liviidae, Psyllidae, and Triozidae, whiteflies from the family Aleyrodidae, aphids from the family Aphididae, phylloxera from the family Phylloxeridae, mealybugs from the family Pseudococcidae, scales from the families Coccidae, Diaspididae and Margarodidae, lace bugs from the family Tingidae, stink bugs from the family Pentatomidae, chinch bugs (e g., hairy chinch bug (Blissus leucopterus hirtus Montandon) and southern chinch bug (Blissus insularis Barber)) and other seed bugs from the family Lygaeidae, spittlebugs from the family Cercopidae squash bugs from the family Coreidae, and red bugs and cotton stainers from the family Pyrrhocoridae.

[75] Agronomic and nonagronomic pests also include : eggs, larvae, nymphs and adults of the order Acari (mites) such as spider mites and red mites in the family Tetranychidae (e.g., European red mite (Panonychus ulmi Koch), twospotted spider mite (Tetranychus urticae Koch), McDaniel spider mite (Tetranychus mcdanieli McGregor)); flat mites in the family Tenuipalpidae (e.g., citrus flat mite (Brevipalpus lewisi McGregor)); rust and bud mites in the family Eriophyidae and other foliar feeding mites and mites important in human and animal health, i.e. dust mites in the family Epidermoptidae, follicle mites in the family Demodecidae, grain mites in the family Glycyphagidae; ticks in the family Ixodidae, commonly known as hard ticks (e.g., deer tick (Ixodes scapularis Say), Australian paralysis tick (Ixodes holocyclus Neumann), American dog tick (Dermacentor variabilis Say), lone star tick (Amblyomma americanum Linnaeus)) and ticks in the family Argasidae, commonly known as soft ticks (e.g., relapsing fever tick (Ornithodoros turicata Duges), common fowl tick (Argas radiatus Raillet)); scab and itch mites in the families Psoroptidae, Pyemotidae, and Sarcoptidae; eggs, adults and immatures of the order Orthoptera including grasshoppers, locusts and crickets (e.g., migratory grasshoppers (e.g., Melanoplus sanguinipes Fabricius, M. dijferentialis Thomas), American grasshoppers (e.g., Schistocerca americana Drury), desert locust (Schistocerca gregaria Forsskal), migratory locust (Locusta migratoria Linnaeus), bush locust (Zonocerus spp.), house cricket (Acheta domesticus Linnaeus), mole crickets (e.g., tawny mole cricket (Scapteriscus vicinus Scudder) and southern mole cricket (Scapteriscus borelhi Giglio-Tos)); eggs, adults and immatures of the order Diptera including leafminers (e.g., Liriomyza spp. such as serpentine vegetable leafminer (Liriomyza sativae Blanchard)), midges, fruit flies (Tephritidae), frit flies (e.g., Oscinella frit Linnaeus), soil maggots, house flies ( .g.. Musca domestica Linnaeus), lesser house flies (e.g., Fannia canicularis Linnaeus. F. femoralis Stein), stable flies (e.g., Stomoxys calcitrans Linnaeus), face flies, horn flies, blow' flies (e g., Chrysomya spp., Phormia spp.), and other muscoid fly pests, horse flies (e.g., Tabanus spp.), hot flies (e.g., Gasterophilus spp., Oestrus spp.), cattle grubs (e.g., Hypoderma spp.), deer flies (e.g., Chrysops spp.), keds (e.g., Melophagus ovinus Linnaeus) and other Brachycera, mosquitoes (e.g., Aedes spp., Anopheles spp., Culex spp.), black flies (e.g., Prosimulium spp., Simulium spp.), biting midges, sand flies, sciarids, and other Nematocera; eggs, adults and immatures of the order Thysanoptera including onion thrips (Thrips tabaci Lindeman), flower thrips (Frankliniella spp.), and other foliar feeding thrips; insect pests of the order Hymenoptera including ants of the Family Formicidae including the Florida carpenter ant (Camponotus floridanus Buckley), red carpenter ant (Camponotus ferrugineus Fabricius), black carpenter ant (Camponotus pennsylvanicus De Geer), white-footed ant (Technomyrmex albipes F. Smith), big headed ants (Pheidole sp.), ghost ant (Tapinoma melanocephalum Fabricius); Pharaoh ant (Monomorium pharaonis Linnaeus), little fire ant (Wasmannia auropunctata Roger), fire ant (Solenopsis geminata Fabricius), red imported fire ant (Solenopsis invicta Buren), Argentine ant (Iridomyrmex humilis Mayr), crazy ant (Paratrechina longicornis Latreille), pavement ant (Tetramorium caespitum Linnaeus), cornfield ant (Lasius alienus Forster) and odorous house ant (Tapinoma sessile Say). Other Hymenoptera including bees (including carpenter bees), hornets, yellow jackets, wasps, and sawflies (Neodiprion spp.; Cephus spp.); insect pests of the order Isoptera including termites in the Termitidae (e.g., Macrotermes sp., Odontotermes obesus Rambur), Kalotermitidae (e.g., Cryptotermes sp.), and Rhinotermitidae (e.g., Reticulitermes sp., Coptotermes sp., Heterotermes tenuis Hagen) families, the eastern subterranean termite (Reticulitermes flavipes Kollar), western subterranean termite (Reticulitermes hesperus Banks), Formosan subterranean termite (Coptotermes formosanus Shiraki), West Indian drywood termite (Incisitermes immigrans Snyder), powder post termite (Cryptotermes brevis Walker), drywood termite (Incisitermes snyderi Light), southeastern subterranean termite (Reticulitermes virginicus Banks), western dry wood termite (Incisitermes minor Hagen), arboreal termites such as Nasutitermes sp. and other termites of economic importance; insect pests of the order Thysanura such as silverfish (Lepisma saccharina Linnaeus) and firebrat (Thermobia domestica Packard); insect pests of the orders Mallophaga and Phthiraptera, and including the head louse (Pediculus humanus capitis De Geer), body louse (Pediculus humanus Linnaeus), chicken body louse (Menacanthus stramineus Nitzsch). dog biting louse (Trichodectes canis De Geer), fluff louse (Goniocotes gallinae De Geer), sheep body louse (Bovicola ovis Schrank), short-nosed cattle louse (Haematopinus eurysternus Nitzsch), long-nosed cattle louse (Linognathus vituli Linnaeus) and other sucking and chewing parasitic lice that attack man and animals; insect pests of the order Siphonoptera including the oriental rat flea (Xenopsylla cheopis Rothschild), cat flea Ctenocephalides felis Bouche), dog flea (Ctenocephalides canis Curtis), hen flea (Ceratophyllus gcdlinae Schrank), sticktight flea (Echidnophaga gcdlinacea Westwood), human flea (Pulex irritans Linnaeus) and other fleas afflicting mammals and birds. Additional arthropod pests covered include: spiders in the order Araneae such as the brown recluse spider (Loxosceles reclusa Gertsch & Mulaik) and the black widow spider (Latrodectus mactans Fabricius), and centipedes in the order Scutigeromorpha such as the house centipede (Scutigera coleoptrata Linnaeus).

[76] Examples of invertebrate pests of stored grain include larger grain borer (Prostephanus truncatus Hom), lesser grain borer (Rhyzopertha dominica Fabricius), rice weevil (Sitophilus oryzae Linnaeus), maize weevil (Sitophilus zeamais Motschulsky). cowpea weevil (Calio sobruchus maculatus Fabricius), red flour beetle (Tribolium castaneum Herbst), granary weevil (Sitophilus granarius Linnaeus). Indian meal moth (Plodia interpunctella Htibner), Mediterranean flour beetle (Ephestia kuehniella Zeller) and flat or rusty grain beetle (Cryptolestes ferrugineus Stephens). [77] Compositions of the present disclosure may be useful 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 in the genus Meloidogyne, lesion nematodes in the genus Pratylenchus , stubby root nematodes in the genus Trichodorus , etc.) and animal and human health pests (i.e. all economically important flukes, tapeworms, and roundworms, such as Strongylus vulgaris in horses. Toxocara cants in dogs, Haemonchus contortus in sheep, Dirofllaria immitis Leidy in dogs. Anoplocephala perfoliata in horses, Fasciola hepatica Linnaeus in ruminants, etc.).

[78] Compositions of the disclosure may be useful to control pests in the order Lepidoptera (e.g., Alabama argillacea Htibner (cotton leaf worm), Archips argyrospila Walker (fruit tree leaf roller), A. rosana Linnaeus (European leaf roller) and other Arch ips species, Chilo suppressalis Walker (rice stem borer), Cnaphalocrocis medinalis Guenee (rice leaf roller), Crambus caliginosellus Clemens (com root webworm), Crambus teterrellus Zincken (bluegrass webworm), Cydia pomonella Linnaeus (codling moth). Earias insulana Boisduval (spiny bollworm), Earias vittella Fabricius (spotted bollworm), Helicoverpa armigera Htibner (Old World bollworm), Helicoverpa zea Boddie (com earworm), Heliothis virescens Fabricius (tobacco budworm). Herpetogramma licarsisalis Walker (sod webworm). Lobesia botrana Denis & Schiffermuller (grape berry moth). Pectinophora gossypiella Saunders (pink bollworm), Phyllocnistis citrella Stainton (citrus leafminer), Pieris brassicae Linnaeus (large white butterfly), Pieris rapae Linnaeus (small white butterfly), Plutella xylostella Linnaeus (diamondback moth), Spodoptera exigua Htibner (beet army worm), Spodoptera litura Fabricius (tobacco cutworm, cluster caterpillar), Spodoptera frugiperda J. E. Smith (fall armyworm). Trichoplusia ni Htibner (cabbage looper) and Tina absoluta Meyrick (tomato leafminer)).

[79] Compositions of the disclosure may be useful to control members from the order Hemiptera including: Acyrthosiphon pisum Harris (pea aphid), Aphis craccivora Koch (cowpea aphid), Aphis fabae Scopoli (black bean aphid), Aphis gossypii Glover (cotton aphid, melon aphid), Aphis pomi De Geer (apple aphid), Aphis spiraecola Patch (spirea aphid), Aulacorthum solani Kaltenbach (foxglove aphid), Chaetosiphon fragaefolii Cockerell (strawberry aphid), Diuraphis noxia Kurdjumov/Mordvilko (Russian wheat aphid), Dysaphis plantaginea Passerini (rosy apple aphid), Eriosomci lanigerum Hausmann (woolly apple aphid), Hyalopterus pruni Geoffrey (mealy plum aphid). Lipaphis pseudobrassicae Davis (turnip aphid), Metopolophium dirrhodum Walker (rose-grain aphid), Macrosiphum euphorbiae Thomas (potato aphid), Myzus persicae Sulzer (peachpotato aphid, green peach aphid), Nasonovia ribisnigri Mosley (lettuce aphid), Pemphigus spp. (root aphids and gall aphids), Rhopalosiphum maidis Fitch (com leaf aphid), Rhopalosiphum padi Linnaeus (bird cherry-oat aphid), Schizaphis graminum Rondani (greenbug). Sitobion avenae Fabricius (English grain aphid), Therioaphis maculata Buckton (spotted alfalfa aphid), Toxoptera aurantii Boyer de Fonscolombe (black citrus aphid), and Toxoptera citricidus Kirkaldy (brown citrus aphid); Adelges spp. (adelgids); Phylloxera devastatrix Pergande (pecan phylloxera); Bemisia tabaci Gennadius (tobacco whitefly, sweetpotato whitefly), Bemisia argentifolii Bellows & Perring (silverleaf whitefly), Dialeurodes citri Ashmead (citrus whitefly) and Trialeurodes vaporariorum Westwood (greenhouse whitefly); Empoasca fabae Harris (potato leafhopper), Laodelphax striatellus Fallen (smaller brown planthopper), Macrosteles quadrilineatus Forbes (aster leafhopper), Nephotettix cincticeps Uhler (green rice leafhopper), Nephotettix nigropictus Stal (rice leafhopper), Nilaparvata lugens Stal (brown planthopper), Peregrinus maidis Ashmead (com planthopper), Sogatella furcifera Horvath (white-backed planthopper), Tagosodes orizicolus Muir (rice delphacid), Typhlocyba pomaria McAtee (white apple leafhopper), Erythroneura spp. (grape leafhoppers); Magicidada septendecim Linnaeus (periodical cicada); Icerya purchasi Maskell (cottony cushion scale), Quadraspidiotus perniciosus Comstock (San Jose scale); Planococcus citri Risso (citms mealybug); Pseudococcus spp. (other mealybug complex); Cacopsylla pyricola Foerster (pear psylla), Trioza diospyri Ashmead (persimmon psylla).

[80] Compositions of this disclosure may be useful to control members from the order Hemiptera including: Acrosternum hilare Say (green stink

Anasa tristis De Geer (squash bug). Blissus leucopterus leucopterus Say (chinch bug). Cimex lectularius Linnaeus (bed bug) Corythucha gossypii Fabricius (cotton lace bug), Cyrtopeltis modesta Distant (tomato bug), Dysdercus suturellus Herrich-Schaffer (cotton stainer), Euschistus servus Say (brown stink bug), Euschistus variolarius Palisot de Beauvois (one-spotted stink bug), Graptostethus spp. (complex of seed bugs), Halyomorpha halys Stal (brown marmorated stink bug), Leptoglossus corculus Say (leaf-footed pine seed bug), Lygus lineolaris Palisot de Beauvois (tarnished plant bug), Nezara viridula Linnaeus (southern green stink bug), Oebalus pugnax Fabricius (rice stink bug), Oncopeltus fasciatus Dallas (large milkweed bug), Pseudatomoscelis seriatus Reuter (cotton fleahopper). Other insect orders controlled by compositions of the disclosure include Thysanoptera (e.g., Frankliniella occidentalis Pergande (western flower thrips), Scirtothrips citri Moulton (citrus thrips), Scirtothrips variabilis Beach (soybean thrips), and Thrips tcibaci Lindeman (onion thrips); and the order Coleoptera (e.g., Leptinotarsa decemlineata Say (Colorado potato beetle), Epilachna varivestis Mulsant (Mexican bean beetle) and wireworms of the genera Agriotes. Athous or Timonins').

[81] In some embodiments, the pest is selected from the group consisting of invertebrate pests, insects, arthropods, and combinations thereof.

[82] In some embodiments, the environment is selected from the group consisting of agricultural fields, orchards, forests, and combinations thereof.

[83] The composition embodiments of this disclosure may be combined with the method embodiments of this disclosure in any manner. Similarly, the method embodiments of this disclosure may be combined in any manner. The following embodiments are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever.

[84] Aspects of the present disclosure are provided by the subject matter of the following clauses:

[85] 1. A composition comprising: an antifreeze agent; and a microcapsule comprising: a core comprising: a pheromone; and a solvent; and a shell encapsulating the core; wherein the shell comprises a polymer produced by autopolymerization of a monomer; and wherein the microcapsule has a d90 value less than about 40 pm.

[86] 2. The composition in accordance with the preceding clause, wherein the microcapsule has a d90 value in a range of from about 5 pm to about 40 pm.

[87] 3. The composition in accordance with any preceding clause, wherein the microcapsule has a d90 value in a range of from about 5 pm to about 25 pm.

[88] 4. The composition in accordance with any preceding clause, wherein the microcapsule has a d50 value in a range of from about 5 pm to about 25 pm.

[89] 5. The composition in accordance with any preceding clause, wherein the microcapsule has a dlO value in a range of from about 1 pm to about 10 pm.

[90] 6. The composition in accordance with any preceding clause, wherein the composition further comprises an auxiliary selected from dispersants, surfactants, emulsifiers, wetting agents, biocides, antifoamers, antifreeze agents, rheology modifiers, solvents, stabilizers, UV stabilizers, UV absorbers, salts, excipients, antioxidants, and combinations thereof.

[91] 7. The composition in accordance with any preceding clause, wherein the composition is an agrochemical composition.

[92] 8. The composition in accordance with any preceding clause, wherein the composition is in a form selected from a premix and a tank mix.

[93] 9. The composition in accordance with any preceding clause, wherein the composition is in a form of a CS formulation or a ZC formulation. [94] 10. The composition in accordance with any preceding clause, wherein the shell comprises polyurea, isocyanate, and/or poly isocyanate.

[95] 11. The composition in accordance with any preceding clause, wherein the pheromone is selected from aldehyde pheromones, acetate pheromones, alcohol pheromones, ketone pheromones, epoxide pheromones, hydrocarbon pheromones, and combinations thereof.

[96] 12. The composition in accordance with any preceding clause, wherein the pheromone does not comprise an aldehyde pheromone.

[97] 13. The composition in accordance with any preceding clause, wherein the pheromone is selected from (Z)-5-decenyl acetate, dodecanyl 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)-lO-dodecenyl acetate, 11 -dodecenyl acetate, (Z)-9, 11 -dodecadienyl acetate, (E)-9, 11- dodecadienyl acetate, (Z)- 11 -tridecenyl acetate, (E)-l 1 -tridecenyl acetate, tetradecanyl acetate, (E)-7-tetradecenyl acetate, (Z)-8-tetradecenyl acetate, (E)-8-tetradecenyl acetate, (Z)-9-tetradecenyl acetate, (E)-9-tetradecenyl acetate, (Z)-lO-tetradecenyl acetate, (E)-lO-tetradecenyl acetate, (Z)-l l-tetradecenyl acetate, (E)-l l- tetradecenyl acetate, (Z)-12-pentadecenyl acetate, (E)-12-pentadecenyl acetate, hexadecanyl acetate. (Z)-7-hexadecenyl acetate, (Z)-l 1 -hexadecenyl acetate. (E)-l 1 -hexadecenyl acetate, octadecanyl 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-tri decadienyl acetate, (E,E)-9, 11 -tetradecadienyl acetate. (Z.Z)-9,12-tetradecadienyl acetate, (Z,Z)-7, 11 -hexadecadienyl acetate, (E,Z)-7,11- hexadecadienyl acetate, (Z,E)-7,11- hexadecadienyl acetate, (E,E)-7, 11 -hexadecadienyl acetate, (Z,E)-3,13-octadecadienyl acetate, (E,Z)-3,13-octadecadienyl acetate, (E,E)-3,13- octadecadienyl acetate, (Z)-5-decenyl 3-methylbutanoate, (+) cis-1 ,8-epoxy-2- methyloctadecane, methyl (E,Z)-2,4-decadi enoate, methyl 2,6, 10-trimethyltri decanoate, citral, geranial, neral, tetradecan- 1 -al, pentadecan-1 -al, pentadecen-l-al, hexadecan- 1 -al, (Z)-9-hexadecen-l-al, (Z)-l 1-hexadecen-l-al, (7E,9E)-undeca-7,9-dien-l-al, (11Z, 13Z)- hexadecadien-l-al, (9Z,12E)-tetradecadien-l-al, (8E,10E)-dodecadien-l-al, (11Z)- hexadecadien-l-al, (9Z)-tetradecen-l-al, 6,10-dimethyl-5,9-undecadien-2-ol, (6E)-7,11- dimethyl-3-methylene-1.6.10-dodecatriene, [lS-(la,2b,5 a)]- 4,6,6-trimethyl- Bicyclo[3.1.1]hept-3-en-2-ol, 10-Hexadecenal, (Z)-lO-hexadecenal, (E)-l O-hexadecenal, and combinations thereof.

[98] 14. The composition in accordance with any preceding clause, wherein the antifreeze agent is selected from propylene glycol, glycerin, glycols, ethylene glycol, 1,2- butane diol, 1,3-butane diol, 2,3-butanediol, 1,4-butanediol, methanol, ethanol, propanol, butanol, and combinations thereof.

[99] 15. The composition in accordance with any preceding clause, wherein the solvent is selected from hydrophobic solvents, high flashpoint-tj pe solvents, methylated seed oils, methyl oleate methyl ester oil. methyl linoleate methyl ester oil, mineral oils, paraffinic oil, tall oil fatty acid-based solvents, aromatic solvents, aromatic ester solvents, polybutenes, methyl esters of fatty acids, tributyl 2-acetate citrate, alkylamide, benzyl acetate, wax esters, and combinations thereof.

[100] 16. A method of making a composition, the method comprising: forming a mixture comprising: an antifreeze agent; and a microcapsule comprising: a core comprising: a pheromone; and a solvent; and a shell encapsulating the core; wherein the shell comprises a polymer produced by autopolymerization of a monomer; and wherein the microcapsule has a d90 value less than about 40 pm. [101] 17. The method in accordance with the preceding clause, wherein the method further comprises encapsulating the pheromone and the solvent in the microcapsule prior to forming the mixture.

[102] 18 A method for controlling a pest comprising contacting the pest or its environment with a biologically effective amount of a composition comprising: an antifreeze agent; and a microcapsule comprising: a core comprising: a pheromone; and a solvent; and a shell encapsulating the core; wherein the shell comprises a polymer produced by autopolymerization of a monomer; and wherein the microcapsule has a d90 value less than about 40 pm.

[103] 19. The method in accordance with any preceding clause, wherein the pest is selected from invertebrate pests, insects, arthropods, and combinations thereof.

[104] 20. The method in accordance with any preceding clause, wherein the environment is selected from agricultural fields, orchards, forests, and combinations thereof.

[105] Without further elaboration, it is believed that one skilled in the art using the preceding descnption can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. EXAMPLES

[106] Example 1. Solvent Screen.

[107] Solvents with different chemistries were used to prepare emulsion-in-water (EW) formulations containing Z9-14 acetate pheromone. A control, solvent-free EW formulation, was also prepared and evaluated. Table 1 summarizes the volatility and chemical stability of the EW formulations and the results were sorted to list the best performing sample last according to the best volatility control. An EW formulation using Steposol ME (a methyl oleate/methyl linoleate methyl ester oil from Stepan) outperformed other EW formulations in this series. Formulations not including a solvent exhibited the worst performance.

[108] To measure the chemical stability, EW formulations were placed inside tightly sealed scintillation vials and then the vials were 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 associated with chemical degradation. Chemical stability was measured as the remaining wt.% of Z9- 14 acetate pheromone.

[109] To measure the volatility, EW formulations were placed in uncapped vials and then the vials were 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 measured as the remaining wt.% of Z9-14 acetate pheromone.

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

[111] Example 2. Volatility control of non-encapsulated emulsion-in-water (EW) pheromone formulations.

[112] To prepare emulsion-in-water (EW) formulations, pheromones (Z-l l-16 aldehyde and Z-l 1-16 acetate), butylated hydroxy toluene (BEIT), and 1.6-hexanediol were dissolved in a solvent (Steposol ME) and combined with the oil soluble emulsifier (Atlox 4916). In a different vessel, an aqueous phase was created by combining water with water soluble emulsifiers (Toximul SEE 340 with Toximul 8320 or Atlas G5000). The organic phase was then slowly charged into the aqueous phase and followed by a high shear step to create the concentrated emulsion. In a final step, biocide, rheology modifier and antifreeze were added. [113] The table below provides volatility control data for the prepared EW formulations. Volatility of final formulations was studied in a dark environmental chamber with high air flow.

[114] Samples were diluted to appropriate concentration. An appropriate amount of HPLC grade water was added to form lOOOppm spray solutions. For the initial (0 hr) samples, 3.0 ml of acetone was added to a scintillation vial and then 30 microliter of the 1000 ppm spray solution was added. For the remaining aged samples (24h. 48 h), 30 microliter was spotted on German glass coverslips in 24 well Falcon plates at 1000 ppm concentration. These were placed in an environmental chamber at 25 °C and 50% humidity. The samples were extracted by placing the glass slip into a scintillation vial with 3 ml of acetone and sonicating on ice in two 30 minutes cycles. Extracts were then transferred to autosampler vials. They were analyzed by GC-FID using DB5ms column splitless 2 microliter injections.

[115] Poor volatility control was achieved for these non-encapsulated pheromones.

[116] Table 2. Volatility control of non-encapsulated emulsion-in-water (EW) pheromone formulations.

[117] Example 3. Volatility control of microencapsulated Z9-14 acetate formulations.

[118] Encapsulation of the pheromone was achieved by forming microcapsule shells using isocyanate monomers only, without the addition of an amine. The isocyanate monomers self-polymerized. Capsules with different particle size were prepared (d90 ranging between 14 and 50 microns).

[119] The below table provides volatility control data for the prepared formulations. Volatility control for the pheromone in a CS formulation was measured as follows. Tn the photolysis PEACH Drop Method, aqueous spray solutions of formulated material were applied as droplets on glass. After desired time periods passed in a solar simulating light (0 - 99 hours), the glass was extracted in a solvent. The extract was analyzed by GC for amount of pheromone remaining on the glass. T24hr. T44hr. T46hr, and T99hr represent 24 hours, 44 hours, 46 hours, and 99 hours, respectively, in a solar simulating light chamber w ith continuous light on. Each 24 hours of solar simulating light is equivalent to 2.5 days of sunlight. [120] It was discovered that encapsulation improved volatility control of (Z)-l l - tetradecenyl acetate pheromone. The best volatility control was achieved with the formulation having capsules with a d90 values of about 14.5 pm.

[121] Table 3. Volatility control of microencapsulated Z9-14 acetate formulations.

[122] Example 4. Volatility control of microencapsulated Zl l-16 acetate formulations.

[123] Encapsulation of the pheromone was achieved by forming microcapsule shells using isocyanate monomers only, without the addition of an amine. The isocyanate monomers self-polymerized. Capsules with different particle size were prepared (d90 ranging between 19 and 38 microns). [124] The below table provides volatility control data for the prepared formulations. Volatility control for the pheromone in a CS formulation was measured as described above.

[125] It was discovered that encapsulation improved volatility control of (Z)-l 1 - hexadecenyl acetate pheromone. The best volatility control was achieved with the formulation having capsules with a d90 values of about 19.7 pm.

[126] Table 4. Volatility control of microencapsulated Zl l-16 acetate formulations.

[127] Example 5. Volatility control of microencapsulated mixed pheromone formulations. [128] Encapsulation of the pheromone was achieved by forming microcapsule shells using isocyanate monomers only, without the addition of an amine. The isocyanate monomers self-polymerized. Capsules with different particle size were prepared (d90 ranging between 9 and 34 microns).

[129] The below table provides volatility' control data for the prepared formulations. Volatility control for the pheromone in a CS formulation was measured in a dark environmental chamber with high air flow.

[130] It was discovered that encapsulation improved volatility’ control of a mixture of (Z)- 11 -tetradecenyl acetate pheromone and (Z)- 11 -hexadecenyl acetate pheromone.

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

[132] Example 6. Volatility control of microencapsulated Z 11-16 aldehyde formulation.

[133] Encapsulation of the pheromone was achieved by forming microcapsule shells using isocyanate monomers only, without the addition of an amine. The isocyanate monomers self-polymerized. The d90 of the formulation was measured to be 20 microns.

[134] The below table provides volatility control data for the prepared formulation. Volatility control for the pheromone in a CS formulation was measured as described above. It was discovered that encapsulation improved volatility control of (Z)-l l-hexadecenal pheromone.

[135] Table 6. Volatility control of microencapsulated Zl l-16 aldehyde formulation.

[136] Example 7. Chemical stability of the microencapsulated Z-l l-16 aldehyde formulations.

[137] Encapsulation of the pheromone was achieved by forming microcapsule shells using isocyanate monomers only, without the addition of an amine. The isocyanate monomers self-polymerized. The d90 of the formulation was measured to be 20 microns.

[138] The below table provides the recipes and corresponding assays for the prepared formulations at 10-11 wt% Z-l l-hexadecenal in CS formulations. It was discovered that microencapsulation using the self-polymerization of isocyanate does not degrade the aldehyde pheromones.

[139] Table 7. Chemical stability of microencapsulated Zl l-16 aldehyde formulations.

[140] Example 8. Chemical stability of the microencapsulated Z-l l-16 aldehyde formulations.

[141] Encapsulation of the pheromone was achieved by forming microcapsule shells using isocyanate monomers only, without the addition of an amine. The isocyanate monomers self-polymerized.

[142] The below table provides the recipes and corresponding assays for the prepared formulations at 5-6 wt% Z- 11 -hexadecenal in the CS formulations. It was discovered that the microencapsulation using the self-polymerization of isocyanate does not degrade the aldehyde pheromones.

[143] Table 8. Chemical stability of microencapsulated Zl l-16 aldehyde formulations.

[144] Example 9. Chemical stability of comparative microencapsulated Z-l l -16 aldehyde formulations.

[145] Encapsulation of the Z-l 1-16 aldehyde pheromone was achieved by forming microcapsule shells using isocyanate monomers with the addition of an amine. The below table provides the recipes and corresponding assays for the formulations before and after aging studies at 54°C for 2 weeks. It was discovered that up to 60% of Z-l l-16 aldehyde pheromone is lost during sample preparation. An additional 10-30% pheromone is lost during aging. These unexpected results confirm the benefit of preparing microcapsules containing aldehyde pheromones using the autopolymerization of isocyanate monomers.

[146] Table 9. Chemical stability of comparative microencapsulated Zl l-16 aldehyde formulations.

[147] It was surprisingly discovered herein that substantial improvements in volatility control of pheromone compositions could be achieved with compositions including an antifreeze and microcapsules, where the microcapsules are relatively small and contain co-encapsulated pheromones and solvents. The most substantial improvements were observed with microcapsules having shells including a polymer produced by autopolymerization of a monomer and microcapsules having a d90 value less than about 40 pm.

[148] It was also surprisingly discovered herein that substantial improvements in chemical stability for encapsulated aldehyde pheromones could be achieved by preparing microcapsules using the autopolymerization of isocyanate monomers.

Claims

WHAT TS CLAIMED IS:

1. A composition comprising: an antifreeze agent; and a microcapsule comprising: a core comprising: a pheromone; and a solvent; and a shell encapsulating the core; wherein the shell comprises a polymer produced by autopolymerization of a monomer; and wherein the microcapsule has a d90 value less than about 40 pm.

2. The composition of claim 1, wherein the microcapsule has: a d90 value in a range of from about 5 pm to about 40 pm, preferably in a range of from about 5 pm to about 25 pm; a d50 value in a range of from about 5 pm to about 25 pm; and/or a dlO value in a range of from about 1 pm to about 10 pm.

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

4. The composition of any of claims 1 -3, wherein the composition is an agrochemical composition, preferably in a form selected from a premix and a tank mix.

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

6. The composition of any of claims 1-5, wherein the shell comprises poly urea, isocyanate, and/or polyisocyanate.

7. The composition of any 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 of any of claims 1-7, wherein the pheromone is selected from (Z)-5- decenyl acetate, dodecanyl 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)-lO-dodecenyl acetate, 11 -dodecenyl acetate, (Z)-9, 11 -dodecadienyl acetate, (E)- 9, 11 - dodecadienyl acetate, (Z)-l 1 -tridecenyl acetate, (E)-l 1 -tridecenyl acetate, tetradecanyl acetate. (E)- 7 -tetradecenyl acetate, (Z)-8-tetradecenyl acetate. (E)-8-tetradecenyl acetate, (Z)-9-tetradecenyl acetate, (E)-9-tetradecenyl acetate, (Z)-lO-tetradecenyl acetate, (E)-10- tetradecenyl acetate, (Z)-l 1 -tetradecenyl acetate, (E)-l l -tetradecenyl acetate, (Z)-12- pentadecenyl acetate, (E)-12-pentadecenyl acetate, hexadecanyl acetate, (Z)-7 -hexadecenyl acetate. (Z)-l 1 -hexadecenyl acetate, (E)-l 1 -hexadecenyl acetate, octadecanyl 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-tridecadienyl acetate, (E,E)-9, 11 -tetradecadienyl acetate, (Z,Z)-9,12- tetradecadienyl acetate, (Z,Z)-7, 11 -hexadecadienyl acetate, (E,Z)-7, 11 -hexadecadienyl acetate. (Z.E)-7,11- hexadecadienyl acetate, (E,E)-7, 11 -hexadecadienyl acetate, (Z,E)-3,13- octadecadienyl acetate, (E,Z)-3,13-octadecadienyl acetate, (E,E)-3, 13-octadecadienyl acetate, (Z)-5-decenyl 3-methylbutanoate, (+) c .s-7.8-epo\y-2-methyloctadecane. methyl (E,Z)-2,4-decadienoate, methyl 2,6, 10-trimethyltri decanoate, citral, geranial, neral, tetradecan- 1 -al, pentadecan- 1 -al, pentadecen-l-al, hexadecan-1 -al, (Z)-9-hexadecen-l-al, (Z)-l 1-hexadecen-l-al, (7E,9E)-undeca-7,9-dien-l-al, (HZ, 13Z)-hexadecadien-l-al, (9Z,12E)-tetradecadien-l-al, (8E,10E)-dodecadien-l-al, (HZ)-hexadecadien-l-al, (9Z)- tetradecen-l-al, 6,10-dimethyl-5,9-undecadien-2-ol, (6E)-7,1 l-dimethyl-3-methylene- 1,6.10-dodecatriene, [lS-(la,2b,5 a)]- 4,6,6-trimethyl-Bicyclo[3.1.1]hept-3-en-2-ol, 10- Hexadecenal, (Z)-lO-hexadecenal. (E)-lO-hexadecenal, and combinations thereof.

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

10. The composition of any of claims 1 -9, wherein the solvent is selected from hydrophobic solvents, high flashpoint-type solvents, methylated seed oils, methyl oleate methyl ester oil, methyl linoleate methyl ester oil, mineral oils, paraffinic oil, tall oil fatty acid-based solvents, aromatic solvents, aromatic ester solvents, polybutenes, methyl esters of fatty acids, tributyl 2-acetate citrate, alkylamide, benzyl acetate, wax esters, and combinations thereof.

11. A method of making a composition, the method comprising: forming a mixture comprising: an antifreeze agent; and a microcapsule comprising: a core comprising: a pheromone; and a solvent; and a shell encapsulating the core; wherein the shell comprises a polymer produced by autopolymerization of a monomer; and wherein the microcapsule has a d90 value less than about 40 pm.

12. The method of claim 1 1, wherein the method further comprises encapsulating the pheromone and the solvent in the microcapsule prior to forming the mixture.

13. A method for controlling a pest comprising contacting the pest or its environment with a biologically effective amount of a composition comprising: an antifreeze agent; and a microcapsule comprising: a core comprising: a pheromone; and a solvent; and a shell encapsulating the core; wherein the shell comprises a polymer produced by autopolymerization of a monomer; and wherein the microcapsule has a d90 value less than about 40 pm.

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

15. The method of any of claims 13-14, wherein the environment is selected from agricultural fields, orchards, forests, and combinations thereof.