Granular formulation for insecticide

Abstract

The subject matter provided herein provides a microplastic-free granular formulation compositions containing a water-soluble active ingredient with a high ratio of filler over binder by weight. The subject matter provided herein makes granule pastes easy to be extruded via multiple extrusion technologies across multiple variations in component lots, process scale and conditions, and provides high active suspensibility (≥93%) when diluted with water.

Description

GRANULAR FORMULATION FOR INSECTICIDECROSS-REFERENCES TO RELATED APPLICATIONS

[0001] This application claims the benefit of, and priority from, U.S. provisional applications serial number 63 / 639,061, filed on April 26, 2024.FIELD OF THIS DISCLOSURE

[0002] The subject matter provided herein provides a microplastic-free granular formulation compositions containing a water-soluble active ingredient with a high ratio of filler over binder by weight. The subject matter provided herein makes granule pastes easy to be extruded via multiple extrusion technologies across multiple variations in component lots, process scale and conditions, and provides high active suspensibility (>93%) when diluted with water.BACKGROUND

[0003] Despite high water solubility of an active ingredient, the desired formulation type for a targeted market could be granular. Granular formulations of water-soluble agriculture active ingredients were proposed. However, challenges associated with current protocols include maximizing active suspensibility, dissolving active ingredient in extrudable paste creation, and relatively low active loading.SUMMARY

[0004] A granular insecticidal formulation is provided. This provides a microplastic-free granular formulation compositions containing a water-soluble active ingredient with a high ratio of filler over binder by weight. The subject matter provided herein makes granule pastes easy to be extruded via multiple extrusion technologies across variations in component lots, process scale and conditions, and yields high active suspensibility (>93%) when diluted with water.

[0005] An aspect of the disclosure provides a granular insecticidal formulation comprising (a) at least one water-soluble active ingredient, where water solubility of the active ingredient is from about 0.3 grams per liter (g / L) to about 30 g / L at 25 °C; (b) a filler from about 15% to about 65% by weight; and (c) a binder, where the filler and the binder are present at a weight ratio of (b):(c) from about 1.5 to about 6.0. In some embodiments, the active ingredient is A-[4-chloro-2-(pyridin-3-yl)-l,3-thiazol-5-yl]- / V-ethyl-3- (methanesulfonyl)propanamide. In some embodiments, the active ingredient further comprises a nicotinic acetylcholine receptor (nAChR) competitive modulator comprising sulfoxaflor, triflumezopyrim, acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiamethoxam, nicotine or flupyradifurone. In some embodiments, the granular insecticidal formulation comprises the active ingredient from about 5% to about 60% by weight. In some embodiments, the filler comprises sand, limestone, gypsum, clays, montmorillonite, starch, or combination thereof. In some embodiments, the binder comprises gelatin, gum acacia, gum tragacanth, guar gum, sucrose, glucose, lactose monohydrate, starch, polyvinylpyrrolidone (PVP), PVP -polyvinyl acetate (PVA) copolymer, partially gelatinized starches (PGS), cellulose ethers, or combination thereof. In some embodiments, the granular insecticidal formulation comprises the binder (c) from about 5% to about 25% by weight. In some embodiments, the granular insecticidal formulation further comprises a wetting agent, a dispersant agent, a pH modifier, adjuvant agents, or combination thereof. In some embodiments, the granular insecticidal formulation comprises the wetting agent from about 0.5% to about 8.0% by weight. In some embodiments, the granular insecticidal formulation comprises the dispersant agent from about 3% to about 20% by weight. In some embodiments, the granule die is from about 0.5 mm to about 1.5 mm by dome extrusion or basket extrusion.DETAILED DESCRIPTION

[0006] While various embodiments of the invention have been shown and described herein, it will be obvious to those skilled in the art that such embodiments are provided by way of example only. Numerous variations, changes, and substitutions may occur to those skilled inthe art without departing from the invention. It should be understood that various alternatives to the embodiments of the invention described herein may be employed.

[0007] The use of the terms “a”, “an”, “the”, “at least one” and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The use of the term “at least one” followed by a list of one or more items (for example, “at least one of A and B”) is to be construed to mean one item selected from the listed items (A or B) or any combination of two or more of the listed items (A and B), unless otherwise indicated herein or clearly contradicted by context. The term "about" when referring to a number or a numerical range means that the number or numerical range referred to is an approximation within experimental variability (or within statistical experimental error), and thus the number or numerical range, in some instances, will vary between 1% and 15% of the stated number or numerical range. The terms “comprising,” “having,” “including,” and “containing” are to be construed as open-ended terms (i.e., meaning “including, but not limited to,”) unless otherwise noted. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.

[0008] The phrase “active ingredient” means a material having activity useful in controlling pests, and / or that is useful in helping other materials have better activity in controlling pests. Examples of such materials include, but are not limited to, acaricides, algicides, antifeedants, avicides, bactericides, bird repellents, chemosterilants, fungicides, herbicide safeners, herbicides, insect attractants, insect repellents, insecticides, mammal repellents, mating disrupters,molluscicides, nematicides, plant activators, plant growth regulators, rodenticides, synergists, and virucides (see alanwood.net).

[0009] The term “carrier” in an agricultural formulation is a material added to the pesticide to give a product of the required strength. Generally, carriers are materials with high absorptive capacities, while generally, diluents are materials with low absorptive capacities. Generally, carriers and diluents are used in the formulation of dusts, wettable powders, granules, and water- dispersible granules.

[0010] Recognized herein is an ongoing need for an effective granular formulation. The subject matter provided herein provides a microplastic-free granular formulation composition containing a water-soluble active ingredient with a high ratio of filler over binder by weight. The subject matter provided herein makes granule pastes easy to be extruded via multiple extrusion technologies across variations in component lots, process scale and conditions and provides high active suspensibility (>93%) when diluted with water.Water solubility

[0011] In one aspect, provided herein is a granular insecticidal formulation comprising an active ingredient. Water solubility of insecticides may be classified as low (less than 0.01 grams per liter (g / L) or 10 parts per million (ppm)), moderate (0.01 to 1 g / L or 10 to 1,000 ppm), or high (more than 1 g / L or 1,000 ppm) at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is moderate or high.

[0012] In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 0.3 g / L to about 30 g / L at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 0.3 g / L to about 0.4 g / L, from about 0.3 g / L to about 0.5 g / L, from about 0.3 g / L to about 0.6 g / L, from about 0.3 g / L to about 0.8 g / L, from about 0.3 g / L to about 1.0 g / L, from about 0.3 g / L to about 1.2 g / L, from about 0.3 g / L to about 1.4 g / L, from about 0.3 g / L to about 1.6 g / L, from about 0.3 g / L to about 1.8 g / L, from about 0.3 g / L to about 2.0 g / L, from about 0.3 g / L to about 2.2 g / L, from about 0.3 g / L to about 2.4 g / L, from about 0.3 g / L to about 2.6 g / L, from about 0.3 g / L to about 2.8 g / L, from about 0.3 g / L to about 3.0 g / L, from about 0.3 g / L to about 3.5 g / L,from about 0.3 g / L to about 4.0 g / L, from about 0.3 g / L to about 4.5 g / L, from about 0.3 g / L to about 5.0 g / L, from about 0.3 g / L to about 6.0 g / L, from about 0.3 g / L to about 7.0 g / L, from about 0.3 g / L to about 8.0 g / L, from about 0.3 g / L to about 9.0 g / L, from about 0.3 g / L to about 10.0 g / L, from about 0.3 g / L to about 12.0 g / L, from about 0.3 g / L to about 14.0 g / L, from about 0.3 g / L to about 16.0 g / L, from about 0.3 g / L to about 18.0 g / L, from about 0.3 g / L to about 20.0 g / L, from about 0.3 g / L to about 22.0 g / L, from about 0.3 g / L to about 24.0 g / L, from about 0.3 g / L to about 26.0 g / L, from about 0.3 g / L to about 28.0 g / L, or from about 0.3 g / L to about 30.0 g / L at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 0.4 g / L to about 0.5 g / L, from about 0.4 g / L to about 0.6 g / L, from about 0.4 g / L to about 0.8 g / L, from about 0.4 g / L to about 1.0 g / L, from about 0.4 g / L to about 1.2 g / L, from about 0.4 g / L to about 1.4 g / L, from about 0.4 g / L to about 1.6 g / L, from about 0.4 g / L to about 1.8 g / L, from about 0.4 g / L to about 2.0 g / L, from about 0.4 g / L to about 2.2 g / L, from about 0.4 g / L to about 2.4 g / L, from about 0.4 g / L to about 2.6 g / L, from about 0.4 g / L to about 2.8 g / L, from about 0.4 g / L to about 3.0 g / L, from about 0.4 g / L to about 3.5 g / L, from about 0.4 g / L to about 4.0 g / L, from about 0.4 g / L to about 4.5 g / L, from about 0.4 g / L to about 5.0 g / L, from about 0.4 g / L to about 6.0 g / L, from about 0.4 g / L to about 7.0 g / L, from about 0.4 g / L to about 8.0 g / L, from about 0.4 g / L to about 9.0 g / L, from about 0.4 g / L to about 10.0 g / L, from about 0.4 g / L to about 12.0 g / L, from about 0.4 g / L to about 14.0 g / L, from about 0.4 g / L to about 16.0 g / L, from about 0.4 g / L to about 18.0 g / L, from about 0.4 g / L to about 20.0 g / L, from about 0.4 g / L to about 22.0 g / L, from about 0.4 g / L to about 24.0 g / L, from about 0.4 g / L to about 26.0 g / L, from about 0.4 g / L to about 28.0 g / L, or from about 0.4 g / L to about 30.0 g / L at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 0.5 g / L to about 0.6 g / L, from about 0.5 g / L to about 0.8 g / L, from about 0.5 g / L to about 1.0 g / L, from about 0.5 g / L to about 1.2 g / L, from about 0.5 g / L to about 1.4 g / L, from about 0.5 g / L to about 1.6 g / L, from about 0.5 g / L to about 1.8 g / L, from about 0.5 g / L to about 2.0 g / L, from about 0.5 g / L to about 2.2 g / L, from about 0.5 g / L to about 2.4 g / L, from about 0.5 g / L to about 2.6 g / L, from about 0.5 g / L to about 2.8 g / L, from about 0.5 g / L to about 3.0 g / L, from about 0.5 g / L to about 3.5 g / L, from about 0.5 g / L to about 4.0 g / L, from about 0.5 g / L to about 4.5 g / L, from about 0.5 g / L to about 5.0 g / L, from about 0.5 g / L toabout 6.0 g / L, from about 0.5 g / L to about 7.0 g / L, from about 0.5 g / L to about 8.0 g / L, from about 0.5 g / L to about 9.0 g / L, from about 0.5 g / L to about 10.0 g / L, from about 0.5 g / L to about 12.0 g / L, from about 0.5 g / L to about 14.0 g / L, from about 0.5 g / L to about 16.0 g / L, from about 0.5 g / L to about 18.0 g / L, from about 0.5 g / L to about 20.0 g / L, from about 0.5 g / L to about 22.0 g / L, from about 0.5 g / L to about 24.0 g / L, from about 0.5 g / L to about 26.0 g / L, from about 0.5 g / L to about 28.0 g / L, or from about 0.5 g / L to about 30.0 g / L at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 0.6 g / L to about 0.8 g / L, from about 0.6 g / L to about 1.0 g / L, from about 0.6 g / L to about 1.2 g / L, from about 0.6 g / L to about 1.4 g / L, from about 0.6 g / L to about 1.6 g / L, from about 0.6 g / L to about 1.8 g / L, from about 0.6 g / L to about 2.0 g / L, from about 0.6 g / L to about 2.2 g / L, from about 0.6 g / L to about 2.4 g / L, from about 0.6 g / L to about 2.6 g / L, from about 0.6 g / L to about2.8 g / L, from about 0.6 g / L to about 3.0 g / L, from about 0.6 g / L to about 3.5 g / L, from about 0.6 g / L to about 4.0 g / L, from about 0.6 g / L to about 4.5 g / L, from about 0.6 g / L to about 5.0 g / L, from about 0.6 g / L to about 6.0 g / L, from about 0.6 g / L to about 7.0 g / L, from about 0.6 g / L to about 8.0 g / L, from about 0.6 g / L to about 9.0 g / L, from about 0.6 g / L to about 10.0 g / L, from about 0.6 g / L to about 12.0 g / L, from about 0.6 g / L to about 14.0 g / L, from about 0.6 g / L to about 16.0 g / L, from about 0.6 g / L to about 18.0 g / L, from about 0.6 g / L to about 20.0 g / L, from about 0.6 g / L to about 22.0 g / L, from about 0.6 g / L to about 24.0 g / L, from about 0.6 g / L to about 26.0 g / L, from about 0.6 g / L to about 28.0 g / L, or from about 0.6 g / L to about 30.0 g / L at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 0.8 g / L to about 1.0 g / L, from about 0.8 g / L to about 1.2 g / L, from about 0.8 g / L to about 1.4 g / L, from about 0.8 g / L to about 1.6 g / L, from about 0.8 g / L to about1.8 g / L, from about 0.8 g / L to about 2.0 g / L, from about 0.8 g / L to about 2.2 g / L, from about 0.8 g / L to about 2.4 g / L, from about 0.8 g / L to about 2.6 g / L, from about 0.8 g / L to about 2.8 g / L, from about 0.8 g / L to about 3.0 g / L, from about 0.8 g / L to about 3.5 g / L, from about 0.8 g / L to about 4.0 g / L, from about 0.8 g / L to about 4.5 g / L, from about 0.8 g / L to about 5.0 g / L, from about 0.8 g / L to about 6.0 g / L, from about 0.8 g / L to about 7.0 g / L, from about 0.8 g / L to about 8.0 g / L, from about 0.8 g / L to about 9.0 g / L, from about 0.8 g / L to about 10.0 g / L, from about 0.8 g / L to about 12.0 g / L, from about 0.8 g / L to about 14.0 g / L, from about 0.8 g / L to about 16.0g / L, from about 0.8 g / L to about 18.0 g / L, from about 0.8 g / L to about 20.0 g / L, from about 0.8 g / L to about 22.0 g / L, from about 0.8 g / L to about 24.0 g / L, from about 0.8 g / L to about 26.0 g / L, from about 0.8 g / L to about 28.0 g / L, or from about 0.8 g / L to about 30.0 g / L at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 1.0 g / L to about 1.2 g / L, from about 1.0 g / L to about 1.4 g / L, from about 1.0 g / L to about 1.6 g / L, from about 1.0 g / L to about 1.8 g / L, from about 1.0 g / L to about 2.0 g / L, from about 1.0 g / L to about 2.2 g / L, from about 1.0 g / L to about 2.4 g / L, from about 1.0 g / L to about 2.6 g / L, from about 1.0 g / L to about 2.8 g / L, from about 1.0 g / L to about 3.0 g / L, from about 1.0 g / L to about 3.5 g / L, from about 1.0 g / L to about 4.0 g / L, from about 1.0 g / L to about 4.5 g / L, from about 1.0 g / L to about 5.0 g / L, from about 1.0 g / L to about 6.0 g / L, from about 1.0 g / L to about 7.0 g / L, from about 1.0 g / L to about 8.0 g / L, from about 1.0 g / L to about 9.0 g / L, from about 1.0 g / L to about 10.0 g / L, from about 1.0 g / L to about 12.0 g / L, from about 1.0 g / L to about 14.0 g / L, from about 1.0 g / L to about 16.0 g / L, from about 1.0 g / L to about 18.0 g / L, from about 1.0 g / L to about 20.0 g / L, from about 1.0 g / L to about 22.0 g / L, from about 1.0 g / L to about 24.0 g / L, from about 1.0 g / L to about 26.0 g / L, from about 1.0 g / L to about 28.0 g / L, or from about 1 .0 g / L to about 30.0 g / L at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 1.2 g / L to about 1.4 g / L, from about 1.2 g / L to about 1.6 g / L, from about 1.2 g / L to about 1.8 g / L, from about 1.2 g / L to about 2.0 g / L, from about 1.2 g / L to about 2.2 g / L, from about 1.2 g / L to about 2.4 g / L, from about 1.2 g / L to about 2.6 g / L, from about 1.2 g / L to about 2.8 g / L, from about 1.2 g / L to about 3.0 g / L, from about 1.2 g / L to about 3.5 g / L, from about 1.2 g / L to about 4.0 g / L, from about 1.2 g / L to about 4.5 g / L, from about 1.2 g / L to about 5.0 g / L, from about 1.2 g / L to about 6.0 g / L, from about 1.2 g / L to about 7.0 g / L, from about 1.2 g / L to about 8.0 g / L, from about 1.2 g / L to about 9.0 g / L, from about 1.2 g / L to about 10.0 g / L, from about 1.2 g / L to about 12.0 g / L, from about 1.2 g / L to about 14.0 g / L, from about 1.2 g / L to about 16.0 g / L, from about 1.2 g / L to about 18.0 g / L, from about 1.2 g / L to about 20.0 g / L, from about 1.2 g / L to about 22.0 g / L, from about 1.2 g / L to about 24.0 g / L, from about 1.2 g / L to about 26.0 g / L, from about 1.2 g / L to about 28.0 g / L, or from about 1.2 g / L to about 30.0 g / L at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 1.4 g / L toabout 1.6 g / L, from about 1.4 g / L to about 1.8 g / L, from about 1.4 g / L to about 2.0 g / L, from about 1.4 g / L to about 2.2 g / L, from about 1.4 g / L to about 2.4 g / L, from about 1.4 g / L to about 2.6 g / L, from about 1.4 g / L to about 2.8 g / L, from about 1.4 g / L to about 3.0 g / L, from about 1.4 g / L to about 3.5 g / L, from about 1.4 g / L to about 4.0 g / L, from about 1.4 g / L to about 4.5 g / L, from about 1.4 g / L to about 5.0 g / L, from about 1.4 g / L to about 6.0 g / L, from about 1.4 g / L to about 7.0 g / L, from about 1.4 g / L to about 8.0 g / L, from about 1.4 g / L to about 9.0 g / L, from about 1.4 g / L to about 10.0 g / L, from about 1.4 g / L to about 12.0 g / L, from about 1.4 g / L to about 14.0 g / L, from about 1.4 g / L to about 16.0 g / L, from about 1.4 g / L to about 18.0 g / L, from about 1.4 g / L to about 20.0 g / L, from about 1.4 g / L to about 22.0 g / L, from about 1.4 g / L to about 24.0 g / L, from about 1.4 g / L to about 26.0 g / L, from about 1.4 g / L to about 28.0 g / L, or from about 1.4 g / L to about 30.0 g / L at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 1.6 g / L to about 1.8 g / L, from about 1.6 g / L to about 2.0 g / L, from about 1.6 g / L to about 2.2 g / L, from about 1.6 g / L to about 2.4 g / L, from about 1.6 g / L to about 2.6 g / L, from about 1.6 g / L to about 2.8 g / L, from about 1.6 g / L to about 3.0 g / L, from about 1.6 g / L to about 3.5 g / L, from about 1.6 g / L to about 4.0 g / L, from about 1 .6 g / L to about 4.5 g / L, from about 1 .6 g / L to about 5.0 g / L, from about 1 .6 g / L to about 6.0 g / L, from about 1.6 g / L to about 7.0 g / L, from about 1.6 g / L to about 8.0 g / L, from about 1.6 g / L to about 9.0 g / L, from about 1.6 g / L to about 10.0 g / L, from about 1.6 g / L to about 12.0 g / L, from about 1.6 g / L to about 14.0 g / L, from about 1.6 g / L to about 16.0 g / L, from about 1.6 g / L to about 18.0 g / L, from about 1.6 g / L to about 20.0 g / L, from about 1.6 g / L to about 22.0 g / L, from about 1.6 g / L to about 24.0 g / L, from about 1.6 g / L to about 26.0 g / L, from about 1.6 g / L to about 28.0 g / L, or from about 1.6 g / L to about 30.0 g / L at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 1.8 g / L to about 2.0 g / L, from about 1.8 g / L to about 2.2 g / L, from about 1.8 g / L to about 2.4 g / L, from about 1.8 g / L to about 2.6 g / L, from about 1.8 g / L to about 2.8 g / L, from about 1.8 g / L to about 3.0 g / L, from about 1.8 g / L to about 3.5 g / L, from about 1.8 g / L to about 4.0 g / L, from about 1.8 g / L to about 4.5 g / L, from about 1.8 g / L to about 5.0 g / L, from about 1.8 g / L to about 6.0 g / L, from about 1.8 g / L to about 7.0 g / L, from about 1.8 g / L to about 8.0 g / L, from about 1.8 g / L to about 9.0 g / L, from about 1.8 g / L to about 10.0 g / L, from about 1.8 g / L toabout 12.0 g / L, from about 1.8 g / L to about 14.0 g / L, from about 1.8 g / L to about 16.0 g / L, from about 1.8 g / L to about 18.0 g / L, from about 1.8 g / L to about 20.0 g / L, from about 1.8 g / L to about 22.0 g / L, from about 1.8 g / L to about 24.0 g / L, from about 1.8 g / L to about 26.0 g / L, from about 1.8 g / L to about 28.0 g / L, or from about 1.8 g / L to about 30.0 g / L at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 2.0 g / L to about 2.2 g / L, from about 2.0 g / L to about 2.4 g / L, from about 2.0 g / L to about 2.6 g / L, from about 2.0 g / L to about 2.8 g / L, from about 2.0 g / L to about 3.0 g / L, from about 2.0 g / L to about 3.5 g / L, from about 2.0 g / L to about 4.0 g / L, from about 2.0 g / L to about 4.5 g / L, from about 2.0 g / L to about 5.0 g / L, from about 2.0 g / L to about 6.0 g / L, from about 2.0 g / L to about 7.0 g / L, from about 2.0 g / L to about 8.0 g / L, from about 2.0 g / L to about 9.0 g / L, from about 2.0 g / L to about 10.0 g / L, from about 2.0 g / L to about 12.0 g / L, from about 2.0 g / L to about 14.0 g / L, from about 2.0 g / L to about 16.0 g / L, from about 2.0 g / L to about 18.0 g / L, from about 2.0 g / L to about 20.0 g / L, from about 2.0 g / L to about 22.0 g / L, from about 2.0 g / L to about 24.0 g / L, from about 2.0 g / L to about 26.0 g / L, from about 2.0 g / L to about 28.0 g / L, or from about 2.0 g / L to about 30.0 g / L at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 2.2 g / L to about 2.4 g / L, from about 2.2 g / L to about 2.6 g / L, from about 2.2 g / L to about 2.8 g / L, from about 2.2 g / L to about 3.0 g / L, from about 2.2 g / L to about 3.5 g / L, from about 2.2 g / L to about 4.0 g / L, from about 2.2 g / L to about 4.5 g / L, from about 2.2 g / L to about 5.0 g / L, from about 2.2 g / L to about 6.0 g / L, from about 2.2 g / L to about 7.0 g / L, from about 2.2 g / L to about 8.0 g / L, from about 2.2 g / L to about 9.0 g / L, from about 2.2 g / L to about 10.0 g / L, from about 2.2 g / L to about 12.0 g / L, from about 2.2 g / L to about 14.0 g / L, from about 2.2 g / L to about 16.0 g / L, from about 2.2 g / L to about 18.0 g / L, from about 2.2 g / L to about 20.0 g / L, from about 2.2 g / L to about 22.0 g / L, from about 2.2 g / L to about 24.0 g / L, from about 2.2 g / L to about 26.0 g / L, from about 2.2 g / L to about 28.0 g / L, or from about 2.2 g / L to about 30.0 g / L at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 2.4 g / L to about 2.6 g / L, from about 2.4 g / L to about 2.8 g / L, from about 2.4 g / L to about 3.0 g / L, from about 2.4 g / L to about 3.5 g / L, from about 2.4 g / L to about 4.0 g / L, from about 2.4 g / L to about 4.5 g / L, from about 2.4 g / L to about 5.0 g / L, from about 2.4 g / L to about 6.0 g / L, from about 2.4g / L to about 7.0 g / L, from about 2.4 g / L to about 8.0 g / L, from about 2.4 g / L to about 9.0 g / L, from about 2.4 g / L to about 10.0 g / L, from about 2.4 g / L to about 12.0 g / L, from about 2.4 g / L to about 14.0 g / L, from about 2.4 g / L to about 16.0 g / L, from about 2.4 g / L to about 18.0 g / L, from about 2.4 g / L to about 20.0 g / L, from about 2.4 g / L to about 22.0 g / L, from about 2.4 g / L to about 24.0 g / L, from about 2.4 g / L to about 26.0 g / L, from about 2.4 g / L to about 28.0 g / L, or from about 2.4 g / L to about 30.0 g / L at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 2.6 g / L to about 2.8 g / L, from about 2.6 g / L to about 3.0 g / L, from about 2.6 g / L to about 3.5 g / L, from about 2.6 g / L to about 4.0 g / L, from about 2.6 g / L to about 4.5 g / L, from about 2.6 g / L to about 5.0 g / L, from about 2.6 g / L to about 6.0 g / L, from about 2.6 g / L to about 7.0 g / L, from about 2.6 g / L to about 8.0 g / L, from about 2.6 g / L to about 9.0 g / L, from about 2.6 g / L to about 10.0 g / L, from about 2.6 g / L to about 12.0 g / L, from about 2.6 g / L to about 14.0 g / L, from about 2.6 g / L to about 16.0 g / L, from about 2.6 g / L to about 18.0 g / L, from about 2.6 g / L to about 20.0 g / L, from about 2.6 g / L to about 22.0 g / L, from about 2.6 g / L to about 24.0 g / L, from about 2.6 g / L to about 26.0 g / L, from about 2.6 g / L to about 28.0 g / L, or from about 2.6 g / L to about 30.0 g / L at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 2.8 g / L to about 3.0 g / L, from about 2.8 g / L to about 3.5 g / L, from about 2.8 g / L to about 4.0 g / L, from about 2.8 g / L to about 4.5 g / L, from about 2.8 g / L to about 5.0 g / L, from about 2.8 g / L to about 6.0 g / L, from about 2.8 g / L to about 7.0 g / L, from about 2.8 g / L to about 8.0 g / L, from about 2.8 g / L to about 9.0 g / L, from about 2.8 g / L to about 10.0 g / L, from about 2.8 g / L to about 12.0 g / L, from about 2.8 g / L to about 14.0 g / L, from about 2.8 g / L to about 16.0 g / L, from about 2.8 g / L to about 18.0 g / L, from about 2.8 g / L to about 20.0 g / L, from about 2.8 g / L to about 22.0 g / L, from about 2.8 g / L to about 24.0 g / L, from about 2.8 g / L to about 26.0 g / L, from about 2.8 g / L to about 28.0 g / L, or from about 2.8 g / L to about 30.0 g / L at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 3.0 g / L to about 3.5 g / L, from about 3.0 g / L to about 4.0 g / L, from about 3.0 g / L to about 4.5 g / L, from about 3.0 g / L to about 5.0 g / L, from about 3.0 g / L to about 6.0 g / L, from about 3.0 g / L to about 7.0 g / L, from about 3.0 g / L to about 8.0 g / L, from about 3.0 g / L to about 9.0 g / L, from about 3.0 g / L to about 10.0 g / L, from about 3.0 g / L to about 12.0 g / L,from about 3.0 g / L to about 14.0 g / L, from about 3.0 g / L to about 16.0 g / L, from about 3.0 g / L to about 18.0 g / L, from about 3.0 g / L to about 20.0 g / L, from about 3.0 g / L to about 22.0 g / L, from about 3.0 g / L to about 24.0 g / L, from about 3.0 g / L to about 26.0 g / L, from about 3.0 g / L to about 28.0 g / L, or from about 3.0 g / L to about 30.0 g / L at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 3.5 g / L to about 4.0 g / L, from about 3.5 g / L to about 4.5 g / L, from about 3.5 g / L to about 5.0 g / L, from about 3.5 g / L to about 6.0 g / L, from about 3.5 g / L to about 7.0 g / L, from about 3.5 g / L to about 8.0 g / L, from about 3.5 g / L to about 9.0 g / L, from about 3.5 g / L to about 10.0 g / L, from about3.5 g / L to about 12.0 g / L, from about 3.5 g / L to about 14.0 g / L, from about 3.5 g / L to about 16.0 g / L, from about 3.5 g / L to about 18.0 g / L, from about 3.5 g / L to about 20.0 g / L, from about 3.5 g / L to about 22.0 g / L, from about 3.5 g / L to about 24.0 g / L, from about 3.5 g / L to about 26.0 g / L, from about 3.5 g / L to about 28.0 g / L, or from about 3.5 g / L to about 30.0 g / L at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 4.0 g / L to about 4.5 g / L, from about 4.0 g / L to about 5.0 g / L, from about 4.0 g / L to about 6.0 g / L, from about 4.0 g / L to about 7.0 g / L, from about 4.0 g / L to about 8.0 g / L, from about 4.0 g / L to about 9.0 g / L, from about 4.0 g / L to about 10.0 g / L, from about 4.0 g / L to about 12.0 g / L, from about 4.0 g / L to about 14.0 g / L, from about 4.0 g / L to about 16.0 g / L, from about 4.0 g / L to about 18.0 g / L, from about 4.0 g / L to about 20.0 g / L, from about 4.0 g / L to about 22.0 g / L, from about 4.0 g / L to about 24.0 g / L, from about 4.0 g / L to about 26.0 g / L, from about 4.0 g / L to about 28.0 g / L, or from about 4.0 g / L to about 30.0 g / L at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 4.5 g / L to about 5.0 g / L, from about 4.5 g / L to about 6.0 g / L, from about 4.5 g / L to about 7.0 g / L, from about 4.5 g / L to about 8.0 g / L, from about 4.5 g / L to about 9.0 g / L, from about 4.5 g / L to about 10.0 g / L, from about 4.5 g / L to about 12.0 g / L, from about4.5 g / L to about 14.0 g / L, from about 4.5 g / L to about 16.0 g / L, from about 4.5 g / L to about 18.0 g / L, from about 4.5 g / L to about 20.0 g / L, from about 4.5 g / L to about 22.0 g / L, from about 4.5 g / L to about 24.0 g / L, from about 4.5 g / L to about 26.0 g / L, from about 4.5 g / L to about 28.0 g / L, or from about 4.5 g / L to about 30.0 g / L at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 5.0 g / L to about 6.0g / L, from about 5.0 g / L to about 7.0 g / L, from about 5.0 g / L to about 8.0 g / L, from about 5.0 g / L to about 9.0 g / L, from about 5.0 g / L to about 10.0 g / L, from about 5.0 g / L to about 12.0 g / L, from about 5.0 g / L to about 14.0 g / L, from about 5.0 g / L to about 16.0 g / L, from about 5.0 g / L to about 18.0 g / L, from about 5.0 g / L to about 20.0 g / L, from about 5.0 g / L to about 22.0 g / L, from about 5.0 g / L to about 24.0 g / L, from about 5.0 g / L to about 26.0 g / L, from about 5.0 g / L to about 28.0 g / L, or from about 5.0 g / L to about 30.0 g / L at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 6.0 g / L to about 7.0 g / L, from about 6.0 g / L to about 8.0 g / L, from about 6.0 g / L to about 9.0 g / L, from about 6.0 g / L to about 10.0 g / L, from about 6.0 g / L to about 12.0 g / L, from about 6.0 g / L to about 14.0 g / L, from about 6.0 g / L to about 16.0 g / L, from about 6.0 g / L to about 18.0 g / L, from about 6.0 g / L to about 20.0 g / L, from about 6.0 g / L to about 22.0 g / L, from about 6.0 g / L to about 24.0 g / L, from about 6.0 g / L to about 26.0 g / L, from about 6.0 g / L to about 28.0 g / L, or from about 6.0 g / L to about 30.0 g / L at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 7.0 g / L to about 8.0 g / L, from about 7.0 g / L to about 9.0 g / L, from about 7.0 g / L to about 10.0 g / L, from about 7.0 g / L to about 12.0 g / L, from about 7.0 g / L to about 14.0 g / L, from about 7.0 g / L to about 16.0 g / L, from about 7.0 g / L to about 18.0 g / L, from about 7.0 g / L to about 20.0 g / L, from about 7.0 g / L to about 22.0 g / L, from about 7.0 g / L to about 24.0 g / L, from about 7.0 g / L to about 26.0 g / L, from about 7.0 g / L to about 28.0 g / L, or from about 7.0 g / L to about 30.0 g / L at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 8.0 g / L to about 9.0 g / L, from about 8.0 g / L to about 10.0 g / L, from about 8.0 g / L to about 12.0 g / L, from about 8.0 g / L to about 14.0 g / L, from about 8.0 g / L to about 16.0 g / L, from about 8.0 g / L to about 18.0 g / L, from about 8.0 g / L to about 20.0 g / L, from about 8.0 g / L to about 22.0 g / L, from about 8.0 g / L to about 24.0 g / L, from about 8.0 g / L to about 26.0 g / L, from about 8.0 g / L to about 28.0 g / L, or from about 8.0 g / L to about 30.0 g / L at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 9.0 g / L to about 10.0 g / L, from about 9.0 g / L to about 12.0 g / L, from about 9.0 g / L to about 14.0 g / L, from about 9.0 g / L to about 16.0 g / L, from about 9.0 g / L to about 18.0 g / L, from about 9.0 g / L to about 20.0 g / L, from about 9.0 g / L to about 22.0 g / L, from about 9.0 g / L toabout 24.0 g / L, from about 9.0 g / L to about 26.0 g / L, from about 9.0 g / L to about 28.0 g / L, or from about 9.0 g / L to about 30.0 g / L at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 10.0 g / L to about 12.0 g / L, from about 10.0 g / L to about 14.0 g / L, from about 10.0 g / L to about 16.0 g / L, from about 10.0 g / L to about 18.0 g / L, from about 10.0 g / L to about 20.0 g / L, from about 10.0 g / L to about 22.0 g / L, from about 10.0 g / L to about 24.0 g / L, from about 10.0 g / L to about 26.0 g / L, from about 10.0 g / L to about 28.0 g / L, or from about 10.0 g / L to about 30.0 g / L at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 12.0 g / L to about 14.0 g / L, from about 12.0 g / L to about 16.0 g / L, from about 12.0 g / L to about 18.0 g / L, from about 12.0 g / L to about 20.0 g / L, from about 12.0 g / L to about 22.0 g / L, from about 12.0 g / L to about 24.0 g / L, from about 12.0 g / L to about 26.0 g / L, from about 12.0 g / L to about 28.0 g / L, or from about 12.0 g / L to about 30.0 g / L at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 14.0 g / L to about 16.0 g / L, from about 14.0 g / L to about 18.0 g / L, from about 14.0 g / L to about 20.0 g / L, from about 14.0 g / L to about 22.0 g / L, from about 14.0 g / L to about 24.0 g / L, from about 14.0 g / L to about 26.0 g / L, from about 14.0 g / L to about 28.0 g / L, or from about 14.0 g / L to about 30.0 g / L at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 16.0 g / L to about 18.0 g / L, from about 16.0 g / L to about 20.0 g / L, from about 16.0 g / L to about 22.0 g / L, from about 16.0 g / L to about 24.0 g / L, from about 16.0 g / L to about 26.0 g / L, from about 16.0 g / L to about 28.0 g / L, or from about 16.0 g / L to about 30.0 g / L at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 18.0 g / L to about 20.0 g / L, from about 18.0 g / L to about 22.0 g / L, from about 18.0 g / L to about 24.0 g / L, from about 18.0 g / L to about 26.0 g / L, from about 18.0 g / L to about 28.0 g / L, or from about 18.0 g / L to about 30.0 g / L at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 20.0 g / L to about 22.0 g / L, from about 20.0 g / L to about 24.0 g / L, from about 20.0 g / L to about 26.0 g / L, from about 20.0 g / L to about 28.0 g / L, or from about 20.0 g / L to about 30.0 g / L at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 22.0 g / L to about 24.0g / L, from about 22.0 g / L to about 26.0 g / L, from about 22.0 g / L to about 28.0 g / L, or from about 22.0 g / L to about 30.0 g / L at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 24.0 g / L to about 26.0 g / L, from about 24.0 g / L to about 28.0 g / L, or from about 24.0 g / L to about 30.0 g / L at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 26.0 g / L to about 28.0 g / L, or from about 26.0 g / L to about 30.0 g / L at 25 °C. In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is from about 28.0 g / L to about 30.0 g / L at 25 °C.

[0013] In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is at most about 30.0 g / L, at most about 28.0 g / L, at most about 26.0 g / L, at most about 24.0 g / L, at most about 22.0 g / L, at most about 20.0 g / L, at most about 18.0 g / L, at most about 16.0 g / L, at most about 14.0 g / L, at most about 12.0 g / L, at most about 10.0 g / L, at most about 9.0 g / L, at most about 8.0 g / L, at most about 7.0 g / L, at most about 6.0 g / L, at most about 5.0 g / L, at most about 4.5 g / L, at most about 4.0 g / L, at most about 3.5 g / L, at most about 3.0 g / L, at most about 2.8 g / L, at most about 2.6 g / L, at most about 2.4 g / L, at most about 2.2 g / L, at most about 2.0 g / L, at most about 1 .8 g / L, at most about 1 .6 g / L, at most about 1 .4 g / L, at most about 1.2 g / L, at most about 1.0 g / L, at most about 0.8 g / L, at most about 0.6 g / L, at most about 0.5 g / L, at most about 0.4 g / L, or at most about 0.3 g / L at 25 °C.

[0014] In some embodiments, water solubility of the active ingredient in the granular insecticidal formulation is about 0.3 g / L, about 0.4 g / L, about 0.5 g / L, about 0.6 g / L, about 0.8 g / L, about 1.0 g / L, about 1.2 g / L, about 1.4 g / L, about 1.6 g / L, about 1.8 g / L, about 2.0 g / L, about 2.2 g / L, about 2.4 g / L, about 2.6 g / L, about 2.8 g / L, about 3.0 g / L, about 3.5 g / L, about 4.0 g / L, about 4.5 g / L, about 5.0 g / L, about 6.0 g / L, about 7.0 g / L, about 8.0 g / L, about 9.0 g / L, about 10.0 g / L, about 12.0 g / L, about 14.0 g / L, about 16.0 g / L, about 18.0 g / L, about 20.0 g / L, about 22.0 g / L, about 24.0 g / L, about 26.0 g / L, about 28.0 g / L, or about 30.0 g / L at 25 °C.Active ingredient

[0015] In one aspect, provided herein is a granular insecticidal formulation comprising (a) a water-soluble active ingredient. In some embodiments of the granular insecticidal formulation,assuming that water solubility of the active ingredient is moderate or high, the active ingredient may be selected from the class of acetylcholinesterase (ACHE) inhibitors (IRAC Group 1, In some embodiments, the active ingredient is selected from the class ofcarbamates (IRAC Group 1A) comprising alanycarb, aldicarb, bendiocarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, trimethacarb, XMC, or xylylcarb. In some embodiments, the active ingredient is selected from the class of organophosphates (IRAC Group IB) comprising acephate, azamethiphos, azinphos-methyl, cadusafos, chlorfenvinphos, chlormephos, cyanophos, demeton-S-methyl, diazinon, dichlorvos (DDVP), dicrotophos, dimethoate, dimethylvinphos, disulfoton, famphur, fenamiphos, fenthion, fosthiazate, heptenophos, malathion, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, phenthoate, phosmet, phosphamidon, propetamphos, pyridaphenthion, terbufos, thiometon, trichlorfon, or vamidothion.

[0016] In some embodiments of the granular insecticidal formulation, assuming that water solubility of the active ingredient is moderate or high, the active ingredient may be selected from the class of sodium channel modulators (IRAC Group 3). In some embodiments, the active ingredient may be selected from the class of pyrethroids and pyrethrins (IRAC Group 3A). In some embodiments, the active ingredient is selected from the class of sodium channel modulators comprising bifenthrin.

[0017] In some embodiments of the granular insecticidal formulation, assuming that water solubility of the active ingredient is moderate or high, the active ingredient may be selected from the class of nicotinic acetylcholine receptor (nAChR) competitive modulators (IRAC Group 4). In some embodiments of the granular insecticidal formulation, assuming that water solubility of the active ingredient is moderate or high, the active ingredient is selected from the nicotinic acetylcholine receptor competitive modulators class of neonicotinoids (Group 4A) comprising acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, or thiamethoxam. In some embodiments of the granular insecticidal formulation, assuming that water solubility of the active ingredient is moderate or high, the active ingredient is selected from the nicotinicacetylcholine receptor competitive modulators class of nicotine (Group 4B) comprising nicotine. In some embodiments of the granular insecticidal formulation, assuming that water solubility of the active ingredient is moderate or high, the active ingredient is selected from the nicotinic acetylcholine receptor competitive modulators class of the sulfoximines (Group 4C) comprising sulfoxaflor. In some embodiments of the granular insecticidal formulation, assuming that water solubility of the active ingredient is moderate or high, the active ingredient is selected from the nicotinic acetylcholine receptor competitive modulators class of the butenolides (Group 4D) comprising flupyradifurone. In some embodiments of the granular insecticidal formulation, assuming that water solubility of the active ingredient is moderate or high, the active ingredient is selected from the nicotinic acetylcholine receptor competitive modulators class of the mesoionics (Group 4E) comprising triflumezopyrim.

[0018] In some embodiments of the granular insecticidal formulation, assuming that water solubility of the active ingredient is moderate or high, the active ingredient may be selected from the class of miscellaneous non-specific (multi-site) inhibitors (IRAC Group 8). In some embodiments of the granular insecticidal formulation, assuming that water solubility of the active ingredient is moderate or high, the active ingredient is selected from the class of alkyl halides (IRAC Group 8A) comprising methyl bromide or 1,3-dichloropropene. In some embodiments of the granular insecticidal formulation, assuming that water solubility of the active ingredient is moderate or high, the active ingredient is selected from the class of chloropicrin (IRAC Group 8B) comprising chloropicrin. In some embodiments of the granular insecticidal formulation, assuming that water solubility of the active ingredient is moderate or high, the active ingredient is selected from the class of fluorides (IRAC Group 8C) comprising cryolite or sulfuryl fluoride. In some embodiments of the granular insecticidal formulation, assuming that water solubility of the active ingredient is moderate or high, the active ingredient is selected from the class of borates (IRAC Group 8D) comprising borax, boric acid, disodium octaborate, sodium borate, or sodium metaborate. In some embodiments of the granular insecticidal formulation, assuming that water solubility of the active ingredient is moderate or high, the active ingredient is selected from the class of tartar emetic (IRAC Group 8E) comprising tartar emetic. In some embodiments of the granular insecticidal formulation,assuming that water solubility of the active ingredient is moderate or high, the active ingredient is selected from the class of methyl isothiocyanate generators (IRAC Group 8F) comprising dazomet, metam, or methyl isothiocyanate.

[0019] In some embodiments of the granular insecticidal formulation, assuming that water solubility of the active ingredient is moderate or high, the active ingredient may be selected from the class of chordotonal organ TRPV channel modulators (IRAC Group 9). In some embodiments of the granular insecticidal formulation, assuming that water solubility of the active ingredient is moderate or high, the active ingredient is selected from the class of pyridine azomethine derivatives (IRAC Group 9B) comprising pymetrozine.

[0020] In some embodiments of the granular insecticidal formulation, assuming that water solubility of the active ingredient is moderate or high, the active ingredient may be selected from the class of mitochondrial complex IV electron transport inhibitors (IRAC Group 24). In some embodiments, the active ingredient is selected from the class of phosphides (IRAC Group 24A) comprising phosphine, or zinc phosphide. In some embodiments, the active ingredient is selected from the class of cyanides (IRAC Group 24B) comprising calcium cyanide, potassium cyanide, or sodium cyanide.

[0021] In some embodiments of the granular insecticidal formulation, assuming that water solubility of the active ingredient is moderate or high, the active ingredient may be selected from the class of chordotonal organ nicotinamidase inhibitors (IRAC Group 29) comprising flonicamid.

[0022] In some embodiments of the granular insecticidal formulation, assuming that water solubility of the active ingredient is moderate or high, the active ingredient may be selected from the group comprising acetamiprid, acetoprole, avermectin, emamectin benzoate, ethiprole, or thiacl oprid.

[0023] In some embodiments, the water-soluble active ingredient (a) is selected from the group comprising aldicarb, acetamiprid, butoxy carb oxi m, carbofuran, ethiofencarb, metolcarb, pirimicarb, propoxur, azamethiphos, heptenophos, naled, demeton-S-methyl, dimethoate, A-[4- chloro-2-(pyridin-3-yl)-l,3-thiazol-5-yl]-JV-ethyl-3-(methanesulfonyl)propanamide, clothianidin,imidacloprid, thiamethoxam, flupyradifurone, methyl bromide, 1,3-dichloropropene, chloropicrin, sulfuryl fluoride, methyl isothiocyanate, or flonicamid.

[0024] In one aspect, provided herein is the granular insecticidal formulation comprising the active ingredient (a) from about 5% to about 60% by weight. In some embodiments, the granular formulation comprises active ingredient from about 5% to about 6%, from about 5% to about 7%, from about 5% to about 8%, from about 5% to about 9%, from about 5% to about 10%, from about 5% to about 11%, from about 5% to about 12%, from about 5% to about 13%, from about 5% to about 14%, from about 5% to about 15%, from about 5% to about 16%, from about 5% to about 17%, from about 5% to about 18%, from about 5% to about 19%, from about 5% to about 20%, from about 5% to about 21%, from about 5% to about 22%, from about 5% to about 23%, from about 5% to about 24%, from about 5% to about 25%, from about 5% to about 26%, from about 5% to about 27%, from about 5% to about 28%, from about 5% to about 29%, from about 5% to about 30%, from about 5% to about 35%, from about 5% to about 40%, from about 5% to about 45%, from about 5% to about 50%, from about 5% to about 55%, or from about 5% to about 60% by weight. In some embodiments, the granular formulation comprises active ingredient (a) from about 6% to about 7%, from about 6% to about 8%, from about 6% to about 9%, from about 6% to about 10%, from about 6% to about 11%, from about 6% to about 12%, from about 6% to about 13%, from about 6% to about 14%, from about 6% to about 15%, from about 6% to about 16%, from about 6% to about 17%, from about 6% to about 18%, from about 6% to about 19%, from about 6% to about 20%, from about 6% to about 21%, from about 6% to about 22%, from about 6% to about 23%, from about 6% to about 24%, from about 6% to about 25%, from about 6% to about 26%, from about 6% to about 27%, from about 6% to about 28%, from about 6% to about 29%, from about 6% to about 30%, from about 6% to about 35%, from about 6% to about 40%, from about 6% to about 45%, from about 6% to about 50%, from about 6% to about 55%, or from about 6% to about 60% by weight. In some embodiments, the granular formulation comprises the active ingredient (a) from about 7% to about 8%, from about 7% to about 9%, from about 7% to about 10%, from about 7% to about 11%, from about 7% to about 12%, from about 7% to about 13%, from about 7% to about 14%, from about 7% to about 15%, from about 7% to about 16%, from about 7% to about 17%, from about 7% to about 18%,from about 7% to about 19%, from about 7% to about 20%, from about 7% to about 21%, from about 7% to about 22%, from about 7% to about 23%, from about 7% to about 24%, from about 7% to about 25%, from about 7% to about 26%, from about 7% to about 27%, from about 7% to about 28%, from about 7% to about 29%, from about 7% to about 30%, from about 7% to about 35%, from about 7% to about 40%, from about 7% to about 45%, from about 7% to about 50%, from about 7% to about 55%, or from about 7% to about 60% by weight. In some embodiments, the granular formulation comprises the active ingredient (a) from about 8% to about 9%, from about 8% to about 10%, from about 8% to about 11%, from about 8% to about 12%, from about 8% to about 13%, from about 8% to about 14%, from about 8% to about 15%, from about 8% to about 16%, from about 8% to about 17%, from about 8% to about 18%, from about 8% to about 19%, from about 8% to about 20%, from about 8% to about 21%, from about 8% to about 22%, from about 8% to about 23%, from about 8% to about 24%, from about 8% to about 25%, from about 8% to about 26%, from about 8% to about 27%, from about 8% to about 28%, from about 8% to about 29%, from about 8% to about 30%, from about 8% to about 35%, from about 8% to about 40%, from about 8% to about 45% by weight, from about 8% to about 50%, from about 8% to about 55%, or from about 8% to about 60%. In some embodiments, the granular formulation comprises the active ingredient (a) from about 9% to about 10%, from about 9% to about 11%, from about 9% to about 12%, from about 9% to about 13%, from about 9% to about 14%, from about 9% to about 15%, from about 9% to about 16%, from about 9% to about 17%, from about 9% to about 18%, from about 9% to about 19%, from about 9% to about 20%, from about 9% to about 21%, from about 9% to about 22%, from about 9% to about 23%, from about 9% to about 24%, from about 9% to about 25%, from about 9% to about 26%, from about 9% to about 27%, from about 9% to about 28%, from about 9% to about 29%, from about 9% to about 30%, from about 9% to about 35%, from about 9% to about 40%, from about 9% to about 45%, from about 9% to about 50%, from about 9% to about 55%, or from about 9% to about 60% by weight. In some embodiments, the granular formulation comprises the active ingredient (a) from about 10% to about 11%, from about 10% to about 12%, from about 10% to about 13%, from about 10% to about 14%, from about 10% to about 15%, from about 10% to about 16%, from about 10% to about 17%, from about 10% to about 18%, from about 10% to about 19%, fromabout 10% to about 20%, from about 10% to about 21%, from about 10% to about 22%, from about 10% to about 23%, from about 10% to about 24%, from about 10% to about 25%, from about 10% to about 26%, from about 10% to about 27%, from about 10% to about 28%, from about 10% to about 29%, from about 10% to about 30%, from about 10% to about 35%, from about 10% to about 40%, from about 10% to about 45%, from about 10% to about 50%, from about 10% to about 55%, or from about 10% to about 60% by weight. In some embodiments, the granular formulation comprises the active ingredient (a) from about 11% to about 12%, from about 11% to about 13%, from about 11% to about 14%, from about 11% to about 15%, from about 11% to about 16%, from about 11% to about 17%, from about 11% to about 18%, from about 11% to about 19%, from about 11% to about 20%, from about 11% to about 21%, from about 11% to about 22%, from about 11% to about 23%, from about 11% to about 24%, from about 11% to about 25%, from about 11% to about 26%, from about 11% to about 27%, from about 11% to about 28%, from about 11% to about 29%, from about 11% to about 30%, from about 11% to about 35%, from about 11% to about 40%, from about 11% to about 45%, from about 11% to about 50%, from about 11% to about 55%, or from about 11% to about 60% by weight. In some embodiments, the granular formulation comprises the active ingredient (a) from about 12% to about 13%, from about 12% to about 14%, from about 12% to about 15%, from about 12% to about 16%, from about 12% to about 17%, from about 12% to about 18%, from about 12% to about 19%, from about 12% to about 20%, from about 12% to about 21%, from about 12% to about 22%, from about 12% to about 23%, from about 12% to about 24%, from about 12% to about 25%, from about 12% to about 26%, from about 12% to about 27%, from about 12% to about 28%, from about 12% to about 29%, from about 12% to about 30%, from about 12% to about 35%, from about 12% to about 40%, from about 12% to about 45%, from about 12% to about 50%, from about 12% to about 55%, or from about 12% to about 60% by weight. In some embodiments, the granular formulation comprises the active ingredient (a) from about 13% to about 14%, from about 13% to about 15%, from about 13% to about 16%, from about 13% to about 17%, from about 13% to about 18%, from about 13% to about 19%, from about 13% to about 20%, from about 13% to about 21%, from about 13% to about 22%, from about 13% to about 23%, from about 13% to about 24%, from about 13% to about 25%, fromabout 13% to about 26%, from about 13% to about 27%, from about 13% to about 28%, from about 13% to about 29%, from about 13% to about 30%, from about 13% to about 35%, from about 13% to about 40%, from about 13% to about 45% by weight, from about 13% to about 50%, from about 13% to about 55%, or from about 13% to about 60%. In some embodiments, the granular formulation comprises the active ingredient (a) from about 14% to about 15%, from about 14% to about 16%, from about 14% to about 17%, from about 14% to about 18%, from about 14% to about 19%, from about 14% to about 20%, from about 14% to about 21%, from about 14% to about 22%, from about 14% to about 23%, from about 14% to about 24%, from about 14% to about 25%, from about 14% to about 26%, from about 14% to about 27%, from about 14% to about 28%, from about 14% to about 29%, from about 14% to about 30%, from about 14% to about 35%, from about 14% to about 40%, from about 14% to about 45%, from about 14% to about 50%, from about 14% to about 55%, or from about 14% to about 60% by weight. In some embodiments, the granular formulation comprises the active ingredient (a) from about 15% to about 16%, from about 15% to about 17%, from about 15% to about 18%, from about 15% to about 19%, from about 15% to about 20%, from about 15% to about 21%, from about 15% to about 22%, from about 15% to about 23%, from about 15% to about 24%, from about 15% to about 25%, from about 15% to about 26%, from about 15% to about 27%, from about 15% to about 28%, from about 15% to about 29%, from about 15% to about 30%, from about 15% to about 35%, from about 15% to about 40%, from about 15% to about 45%, from about 15% to about 50%, from about 15% to about 55%, or from about 15% to about 60% by weight. In some embodiments, the granular formulation comprises the active ingredient (a) from about 16% to about 17%, from about 16% to about 18%, from about 16% to about 19%, from about 16% to about 20%, from about 16% to about 21%, from about 16% to about 22%, from about 16% to about 23%, from about 16% to about 24%, from about 16% to about 25%, from about 16% to about 26%, from about 16% to about 27%, from about 16% to about 28%, from about 16% to about 29%, from about 16% to about 30%, from about 16% to about 35%, from about 16% to about 40%, from about 16% to about 45%, from about 16% to about 50%, from about 16% to about 55%, or from about 16% to about 60% by weight. In some embodiments, the granular formulation comprises the active ingredient (a) from about 17% to about 18%, fromabout 17% to about 19%, from about 17% to about 20%, from about 17% to about 21%, from about 17% to about 22%, from about 17% to about 23%, from about 17% to about 24%, from about 17% to about 25%, from about 17% to about 26%, from about 17% to about 27%, from about 17% to about 28%, from about 17% to about 29%, from about 17% to about 30%, from about 17% to about 35%, from about 17% to about 40%, from about 17% to about 45%, from about 17% to about 50%, from about 17% to about 55%, or from about 17% to about 60% by weight. In some embodiments, the granular formulation comprises the active ingredient (a) from about 18% to about 19%, from about 18% to about 20%, from about 18% to about 21%, from about 18% to about 22%, from about 18% to about 23%, from about 18% to about 24%, from about 18% to about 25%, from about 18% to about 26%, from about 18% to about 27%, from about 18% to about 28%, from about 18% to about 29%, from about 18% to about 30%, from about 18% to about 35%, from about 18% to about 40%, from about 18% to about 45%, from about 18% to about 50%, from about 18% to about 55%, or from about 18% to about 60% by weight. In some embodiments, the granular formulation comprises the active ingredient (a) from about 19% to about 20%, from about 19% to about 21%, from about 19% to about 22%, from about 19% to about 23%, from about 19% to about 24%, from about 19% to about 25%, from about 19% to about 26%, from about 19% to about 27%, from about 19% to about 28%, from about 19% to about 29%, from about 19% to about 30%, from about 19% to about 35%, from about 19% to about 40%, from about 19% to about 45%, from about 19% to about 50%, from about 19% to about 55%, or from about 19% to about 60% by weight. In some embodiments, the granular formulation comprises the active ingredient (a) from about 20% to about 21%, from about 20% to about 22%, from about 20% to about 23%, from about 20% to about 24%, from about 20% to about 25%, from about 20% to about 26%, from about 20% to about 27%, from about 20% to about 28%, from about 20% to about 29%, from about 20% to about 30%, from about 20% to about 35%, from about 20% to about 40%, from about 20% to about 45%, from about 20% to about 50%, from about 20% to about 55%, or from about 20% to about 60% by weight. In some embodiments, the granular formulation comprises the active ingredient (a) from about 21% to about 22%, from about 21% to about 23%, from about 21% to about 24%, from about 21% to about 25%, from about 21% to about 26%, from about 21% to about 27%, fromabout 21% to about 28%, from about 21% to about 29%, from about 21% to about 30%, from about 21% to about 35%, from about 21% to about 40%, from about 21% to about 45%, from about 21% to about 50%, from about 21% to about 55%, or from about 21% to about 60% by weight. In some embodiments, the granular formulation comprises the active ingredient (a) from about 22% to about 23%, from about 22% to about 24%, from about 22% to about 25%, from about 22% to about 26%, from about 22% to about 27%, from about 22% to about 28%, from about 22% to about 29%, from about 22% to about 30%, from about 22% to about 35%, from about 22% to about 40%, from about 22% to about 45%, from about 22% to about 50%, from about 22% to about 55%, or from about 22% to about 60% by weight. In some embodiments, the granular formulation comprises the active ingredient (a) from about 23% to about 24%, from about 23% to about 25%, from about 23% to about 26%, from about 23% to about 27%, from about 23% to about 28%, from about 23% to about 29%, from about 23% to about 30%, from about 23% to about 35%, from about 23% to about 40%, from about 23% to about 45%, from about 23% to about 50%, from about 23% to about 55%, or from about 23% to about 60% by weight. In some embodiments, the granular formulation comprises the active ingredient (a) from about 24% to about 25%, from about 24% to about 26%, from about 24% to about 27%, from about 24% to about 28%, from about 24% to about 29%, from about 24% to about 30%, from about 24% to about 35%, from about 24% to about 40%, from about 24% to about 45%, from about 24% to about 50%, from about 24% to about 55%, or from about 24% to about 60% by weight. In some embodiments, the granular formulation comprises the active ingredient (a) from about 25% to about 26%, from about 25% to about 27%, from about 25% to about 28%, from about 25% to about 29%, from about 25% to about 30%, from about 25% to about 35%, from about 25% to about 40%, from about 25% to about 45%, from about 25% to about 50%, from about 25% to about 55%, or from about 25% to about 60% by weight. In some embodiments, the granular formulation comprises the active ingredient (a) from about 26% to about 27%, from about 26% to about 28%, from about 26% to about 29%, from about 26% to about 30%, from about 26% to about 35%, from about 26% to about 40%, from about 26% to about 45%, from about 26% to about 50%, from about 26% to about 55%, or from about 26% to about 60% by weight. In some embodiments, the granular formulation comprises the active ingredient (a) fromabout 27% to about 28%, from about 27% to about 29%, from about 27% to about 30%, from about 27% to about 35%, from about 27% to about 40%, from about 27% to about 45%, from about 27% to about 50%, from about 27% to about 55%, or from about 27% to about 60% by weight. In some embodiments, the granular formulation comprises the active ingredient (a) from about 28% to about 29%, from about 28% to about 30%, from about 28% to about 35%, from about 28% to about 40%, from about 28% to about 45%, from about 28% to about 50%, from about 28% to about 55%, or from about 28% to about 60% by weight. In some embodiments, the granular formulation comprises the active ingredient (a) from about 29% to about 30%, from about 29% to about 35%, from about 29% to about 40%, from about 29% to about 45%, from about 29% to about 50%, from about 29% to about 55%, or from about 29% to about 60% by weight. In some embodiments, the granular formulation comprises the active ingredient (a) from about 30% to about 35%, from about 30% to about 40%, from about 30% to about 45%, from about 30% to about 50%, from about 30% to about 55%, or from about 30% to about 60% by weight. In some embodiments, the granular formulation comprises the active ingredient (a) from about 35% to about 40%, from about 35% to about 45%, from about 35% to about 50%, from about 35% to about 55%, or from about 35% to about 60% by weight. In some embodiments, the granular formulation comprises the active ingredient (a) from about 40% to about 45%, from about 40% to about 50%, from about 40% to about 55%, or from about 40% to about 60% by weight. In some embodiments, the granular formulation comprises the active ingredient (a) from about 45% to about 50%, from about 45% to about 55%, or from about 45% to about 60% by weight. In some embodiments, the granular formulation comprises the active ingredient (a) from about 50% to about 55%, or from about 50% to about 60% by weight. In some embodiments, the granular formulation comprises the active ingredient (a) from about 55% to about 60% by weight.

[0025] In some embodiments, the granular formulation comprises the active ingredient (a) about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about13%, about 14%, about 15%, about 16%, about 17%, about 18%, about 19%, about 20%, about21%, about 22%, about 23%, about 24%, about 25%, about 26%, about 27%, about 28%, about29%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, or about 60% byweight. In some embodiments, the granular formulation comprises the active ingredient (a) at least about 5%, at least about 6%, at least about 7%, at least about 8%, at least about 9%, at least about 10%, at least about 11%, at least about 12%, at least about 13%, at least about 14%, at least about 15%, at least about 16%, at least about 17%, at least about 18%, at least about 19%, at least about 20%, at least about 21%, at least about 22%, at least about 23%, at least about 24%, at least about 25%, at least about 26%, at least about 27%, at least about 28%, at least about 29%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, at least about 50%, at least about 55%, or at least about 60% by weight. In some embodiments, the granular formulation comprises the active ingredient (a) at most about 60%, at most about 55%, at most about 50%, at most 45%, at most about 40%, at most about 35%, at most about 30%, at most about 29%, at most about 28%, at most about 27%, at most about 26%, at most about 25%, at most about 24%, at most about 23%, at most about 22%, at most about 21%, at most about 20%, at most about 19%, at most about 18%, at most about 17%, at most about 16%, at most about 15%, at most about 14%, at most about 13%, at most about 12%, at most about 11%, at most about 10%, at most about 9%, at most about 8%, at most about 7%, at most about 6%, or at most about 5% by weight.Filler

[0026] In one aspect, provided herein is a granular insecticidal formulation. In some embodiments, the granular formulation is a water dispersible granule (WG) formulation. In some embodiments, the granular formulation is a wettable granule. In some embodiments, the granular formulation is an emulsifiable granule.

[0027] In one aspect, provided herein is a granular insecticidal formulation comprising (b) a filler. Fillers may be applied in granule formulations, to provide structural support and aid in application of the active ingredient. Fillers may be applied to provide the foundation upon which the formulation is constructed, to support the overall integrity and stability of the granules. Fillers may be applied to impact the ease of handling and administration of the insecticidal formulation. Fillers may be applied to affect the visual appearance of the granules, such as color, texture, and overall aesthetics.

[0028] In some embodiments, the filler in the granular insecticidal formulation provided herein comprises mineral earths, clays, fertilizers, natural products of vegetable origin, synthetic polymeric materials, or combinations thereof. In some embodiments, the filler in the granular insecticidal formulation provided herein comprises mineral earths and clays comprising sand, kaolin, bentonite, kieselguhr, Fuller's earth, attapulgite, diatomaceous earth, bole, loess, talc, chalk, dolomite, limestone, lime, calcium carbonate, powdered magnesia, magnesium oxide, magnesium sulfate, sodium chloride, gypsum, calcium sulfate, pyrophyllite, silicic acid, silicates, silica gels, montmorillonite, or combination thereof. In some embodiments, the fdler in the granular insecticidal formulation provided herein comprises fertilizers comprising ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, or combination thereof. In some embodiments, the filler in the granular insecticidal formulation provided herein comprises natural products of vegetable origin comprising grain meals and flours, starch, bark meals, wood meals, nutshell meals, cellulosic powders, or combination thereof. In some embodiments, the filler in the granular insecticidal formulation provided herein comprises synthetic polymeric materials comprising ground or powdered plastics, resins, or combination thereof.

[0029] In one aspect, provided herein is the granular insecticidal formulation comprising the filler (b) from about 15% to about 65% by weight. In some embodiments, the granular insecticidal formulation comprises the filler (b) from about 15% to about 20%, from about 15% to about 25%, from about 15% to about 30%, from about 15% to about 35%, from about 15% to about 40%, from about 15% to about 45%, from about 15% to about 50%, from about 15% to about 55%, from about 15% to about 60%, or from about 15% to about 65% by weight. In some embodiments, the granular insecticidal formulation comprises the filler (b) from about 20% to about 25%, from about 20% to about 30%, from about 20% to about 35%, from about 20% to about 40%, from about 20% to about 45%, from about 20% to about 50%, from about 20% to about 55%, from about 20% to about 60%, or from about 20% to about 65% by weight. In some embodiments, the granular insecticidal formulation comprises the filler (b) from about 25% to about 30%, from about 25% to about 35%, from about 25% to about 40%, from about 25% to about 45%, from about 25% to about 50%, from about 25% to about 55%, from about 25% to about 60%, or from about 25% to about 65% by weight. In some embodiments, the granularinsecticidal formulation comprises the filler (b) from about 30% to about 35%, from about 30% to about 40%, from about 30% to about 45%, from about 30% to about 50%, from about 30% to about 55%, from about 30% to about 60%, or from about 30% to about 65% by weight. In some embodiments, the granular insecticidal formulation comprises the filler (b) from about 35% to about 40%, from about 35% to about 45%, from about 35% to about 50%, from about 35% to about 55%, from about 35% to about 60%, or from about 35% to about 65% by weight. In some embodiments, the granular insecticidal formulation comprises the filler (b) from about 40% to about 45%, from about 40% to about 50%, from about 40% to about 55%, from about 40% to about 60%, or from about 40% to about 65% by weight. In some embodiments, the granular insecticidal formulation comprises the filler (b) from about 45% to about 50%, from about 45% to about 55%, from about 45% to about 60%, or from about 45% to about 65% by weight. In some embodiments, the granular insecticidal formulation comprises the filler (b) from about 50% to about 55%, from about 50% to about 60%, or from about 50% to about 65% by weight. In some embodiments, the granular insecticidal formulation comprises the filler (b) from about 55% to about 60%, or from about 55% to about 65% by weight. In some embodiments, the granular insecticidal formulation comprises the filler (b) from about 60% to about 65% by weight.

[0030] In some embodiments, the granular insecticidal formulation comprising the filler (b) about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, or about 65% by weight. In some embodiments, the granular insecticidal formulation comprising the filler (b) at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, at least about 50%, at least about 55%, at least about 60%, or at least about 65% by weight. In some embodiments, the granular insecticidal formulation comprising the filler (b) at most about 65%, at most about 60%, at most about 55%, at most about 50%, at most about 45%, at most about 40%, at most about 35%, at most about 30%, at most about 25%, at most about 20%, or at most about 15% by weight.Binder

[0031] In one aspect, provided herein is a granular insecticidal formulation comprising (c) a binder. Binders or granulating agents may be applied in wet granulation, to help appropriate surface wetting ability, to ensure adhesion and cohesion between inter-particulate surfaces in the wet state, as well as excellent plasticity, compactibility and binding ability.

[0032] In some embodiments, the binder in the granular insecticidal formulation provided herein comprises natural polymers comprising gelatin, gum acacia, gum tragacanth, guar gum, glucose, fructose, galactose, lactose monohydrate, maltose, mannose, ribose, sucrose, trehalose, dextrose, raffinose, stachyose, maltotriose, lactulose, isomaltose, melibiose, starch, monosaccharides, disaccharides, oligosaccharides, polysaccharides, treacle, or combinations thereof. In some embodiments, the binder in the granular insecticidal formulation provided herein comprises cellulose derivatives, vinyl pyrrolidone derivatives, modified starches. In some embodiments, the binder in the granular insecticidal formulation provided herein comprises povidone (also known as polyvinylpyrrolidone, PVP), copovidone (PVP-polyvinyl acetate (PVA) copolymer), partially gelatinized starch (PGS), cellulose ethers such as hydroxypropyl cellulose (HPC), methyl cellulose (MC), hypromellose (also known as hydroxypropylmethyl cellulose, HPMC), sodium carboxymethyl cellulose (NaCMC), or combinations thereof.

[0033] In one aspect, provided herein is the granular insecticidal formulation comprising the binder (c) from about 5% to about 25% by weight. In some embodiments, the granular insecticidal formulation comprises the binder (c) from about 5% to about 10%, from about 5% to about 15%, from about 5% to about 20%, or from about 5% to about 25% by weight. In some embodiments, the granular insecticidal formulation comprises the binder (c) from about 10% to about 15%, from about 10% to about 20%, or from about 10% to about 25% by weight. In some embodiments, the granular insecticidal formulation comprises the binder (c) from about 15% to about 20%, or from about 15% to about 25% by weight. In some embodiments, the granular insecticidal formulation comprises the binder (c) from about 20% to about 25% by weight.

[0034] In some embodiments, the granular insecticidal formulation comprises the binder (c) about 5%, about 10%, about 15%, about 20%, or about 25% by weight. In some embodiments, the granular insecticidal formulation comprises the binder (c) at least about 5%, at least about 10%, at least about 15%, at least about 20%, or at least about 25% by weight. In someembodiments, the granular insecticidal formulation comprises the binder (c) at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5% by weight.

[0035] In one aspect, provided herein is the granular insecticidal formulation comprising the filler (b) and the binder (c) at a weight ratio of (b):(c) from about 1.5 to about 6.0. In some embodiments, the granular insecticidal formulation comprises the weight ratio of (b) :(c) is from about 1.5 to about 1.6, from about 1.5 to about 1.7, from about 1.5 to about 1.8, from about 1.5 to about 1.9, from about 1.5 to about 2.0, from about 1.5 to about 2.2, from about 1.5 to about 2.4, from about 1.5 to about 2.6, from about 1.5 to about 2.8, from about 1.5 to about 3.0, from about1.5 to about 3.2, from about 1.5 to about 3.4, from about 1.5 to about 3.6, from about 1.5 to about3.8, from about 1.5 to about 4.0, from about 1.5 to about 4.2, from about 1.5 to about 4.4, from about 1.5 to about 4.6, from about 1.5 to about 4.8, from about 1.5 to about 5.0, from about 1.5 to about 5.5, or from about 1.5 to about 6.0. In some embodiments, the granular insecticidal formulation comprises the weight ratio of (b):(c) is from about 1.6 to about 1.7, from about 1.6 to about 1.8, from about 1.6 to about 1.9, from about 1.6 to about 2.0, from about 1.6 to about 2.2, from about 1.6 to about 2.4, from about 1.6 to about 2.6, from about 1.6 to about 2.8, from about1 .6 to about 3.0, from about 1 .6 to about 3.2, from about 1 .6 to about 3.4, from about 1 .6 to about 3.6, from about 1.6 to about 3.8, from about 1.6 to about 4.0, from about 1.6 to about 4.2, from about 1.6 to about 4.4, from about 1.6 to about 4.6, from about 1.6 to about 4.8, from about 1.6 to about 5.0, from about 1.6 to about 5.5, or from about 1.6 to about 6.0. In some embodiments, the granular insecticidal formulation comprises the weight ratio of (b):(c) is from about 1.7 to about1.8, from about 1.7 to about 1.9, from about 1.7 to about 2.0, from about 1.7 to about 2.2, from about 1.7 to about 2.4, from about 1.7 to about 2.6, from about 1.7 to about 2.8, from about 1.7 to about 3.0, from about 1.7 to about 3.2, from about 1.7 to about 3.4, from about 1.7 to about 3.6, from about 1.7 to about 3.8, from about 1.7 to about 4.0, from about 1.7 to about 4.2, from about1.7 to about 4.4, from about 1.7 to about 4.6, from about 1.7 to about 4.8, from about 1.7 to about 5.0, from about 1.7 to about 5.5, or from about 1.7 to about 6.0. In some embodiments, the granular insecticidal formulation comprises the weight ratio of (b):(c) is from about 1.8 to about1.9, from about 1.8 to about 2.0, from about 1.8 to about 2.2, from about 1.8 to about 2.4, from about 1.8 to about 2.6, from about 1.8 to about 2.8, from about 1.8 to about 3.0, from about 1.8 toabout 3.2, from about 1.8 to about 3.4, from about 1.8 to about 3.6, from about 1.8 to about 3.8, from about 1.8 to about 4.0, from about 1.8 to about 4.2, from about 1.8 to about 4.4, from about1.8 to about 4.6, from about 1.8 to about 4.8, from about 1.8 to about 5.0, from about 1.8 to about5.5, or from about 1.8 to about 6.0. In some embodiments, the granular insecticidal formulation comprises the weight ratio of (b):(c) is from about 1.9 to about 2.0, from about 1.9 to about 2.2, from about 1.9 to about 2.4, from about 1.9 to about 2.6, from about 1.9 to about 2.8, from about1.9 to about 3.0, from about 1.9 to about 3.2, from about 1.9 to about 3.4, from about 1.9 to about3.6, from about 1.9 to about 3.8, from about 1.9 to about 4.0, from about 1.9 to about 4.2, from about 1.9 to about 4.4, from about 1.9 to about 4.6, from about 1.9 to about 4.8, from about 1.9 to about 5.0, from about 1.9 to about 5.5, or from about 1.9 to about 6.0. In some embodiments, the granular insecticidal formulation comprises the weight ratio of (b):(c) is from about 2.0 to about 2.2, from about 2.0 to about 2.4, from about 2.0 to about 2.6, from about 2.0 to about 2.8, from about 2.0 to about 3.0, from about 2.0 to about 3.2, from about 2.0 to about 3.4, from about 2.0 to about 3.6, from about 2.0 to about 3.8, from about 2.0 to about 4.0, from about 2.0 to about 4.2, from about 2.0 to about 4.4, from about 2.0 to about 4.6, from about 2.0 to about 4.8, from about 2.0 to about 5.0, from about 2.0 to about 5.5, or from about 2.0 to about 6.0. In some embodiments, the granular insecticidal formulation comprises the weight ratio of (b):(c) is from about 2.2 to about 2.4, from about 2.2 to about 2.6, from about 2.2 to about 2.8, from about 2.2 to about 3.0, from about 2.2 to about 3.2, from about 2.2 to about 3.4, from about 2.2 to about 3.6, from about 2.2 to about 3.8, from about 2.2 to about 4.0, from about 2.2 to about 4.2, from about 2.2 to about 4.4, from about 2.2 to about 4.6, from about 2.2 to about 4.8, from about 2.2 to about 5.0, from about 2.2 to about 5.5, or from about 2.2 to about 6.0. In some embodiments, the granular insecticidal formulation comprises the weight ratio of (b):(c) is from about 2.4 to about2.6, from about 2.4 to about 2.8, from about 2.4 to about 3.0, from about 2.4 to about 3.2, from about 2.4 to about 3.4, from about 2.4 to about 3.6, from about 2.4 to about 3.8, from about 2.4 to about 4.0, from about 2.4 to about 4.2, from about 2.4 to about 4.4, from about 2.4 to about 4.6, from about 2.4 to about 4.8, from about 2.4 to about 5.0, from about 2.4 to about 5.5, or from about 2.4 to about 6.0. In some embodiments, the granular insecticidal formulation comprises the weight ratio of (b):(c) is from about 2.6 to about 2.8, from about 2.6 to about 3.0, from about 2.6to about 3.2, from about 2.6 to about 3.4, from about 2.6 to about 3.6, from about 2.6 to about3.8, from about 2.6 to about 4.0, from about 2.6 to about 4.2, from about 2.6 to about 4.4, from about 2.6 to about 4.6, from about 2.6 to about 4.8, from about 2.6 to about 5.0, from about 2.6 to about 5.5, or from about 2.6 to about 6.0. In some embodiments, the granular insecticidal formulation comprises the weight ratio of (b):(c) is from about 2.8 to about 3.0, from about 2.8 to about 3.2, from about 2.8 to about 3.4, from about 2.8 to about 3.6, from about 2.8 to about 3.8, from about 2.8 to about 4.0, from about 2.8 to about 4.2, from about 2.8 to about 4.4, from about2.8 to about 4.6, from about 2.8 to about 4.8, from about 2.8 to about 5.0, from about 2.8 to about5.5, or from about 2.8 to about 6.0. In some embodiments, the granular insecticidal formulation comprises the weight ratio of (b):(c) is from about 3.0 to about 3.2, from about 3.0 to about 3.4, from about 3.0 to about 3.6, from about 3.0 to about 3.8, from about 3.0 to about 4.0, from about 3.0 to about 4.2, from about 3.0 to about 4.4, from about 3.0 to about 4.6, from about 3.0 to about4.8, from about 3.0 to about 5.0, from about 3.0 to about 5.5, or from about 3.0 to about 6.0. In some embodiments, the granular insecticidal formulation comprises the weight ratio of (b):(c) is from about 3.2 to about 3.4, from about 3.2 to about 3.6, from about 3.2 to about 3.8, from about 3.2 to about 4.0, from about 3.2 to about 4.2, from about 3.2 to about 4.4, from about 3.2 to about4.6, from about 3.2 to about 4.8, from about 3.2 to about 5.0, from about 3.2 to about 5.5, or from about 3.2 to about 6.0. In some embodiments, the granular insecticidal formulation comprises the weight ratio of (b):(c) is from about 3.4 to about 3.6, from about 3.4 to about 3.8, from about 3.4 to about 4.0, from about 3.4 to about 4.2, from about 3.4 to about 4.4, from about 3.4 to about 4.6, from about 3.4 to about 4.8, from about 3.4 to about 5.0, from about 3.4 to about 5.5, or from about 3.4 to about 6.0. In some embodiments, the granular insecticidal formulation comprises the weight ratio of (b):(c) is from about 3.6 to about 3.8, from about 3.6 to about 4.0, from about 3.6 to about 4.2, from about 3.6 to about 4.4, from about 3.6 to about 4.6, from about 3.6 to about 4.8, from about 3.6 to about 5.0, from about 3.6 to about 5.5, or from about 3.6 to about 6.0. In some embodiments, the granular insecticidal formulation comprises the weight ratio of (b):(c) is from about 3.8 to about 4.0, from about 3.8 to about 4.2, from about 3.8 to about 4.4, from about 3.8 to about 4.6, from about 3.8 to about 4.8, from about 3.8 to about 5.0, from about3.8 to about 5.5, or from about 3.8 to about 6.0. In some embodiments, the granular insecticidalformulation comprises the weight ratio of (b):(c) is from about 4.0 to about 4.2, from about 4.0 to about 4.4, from about 4.0 to about 4.6, from about 4.0 to about 4.8, from about 4.0 to about 5.0, from about 4.0 to about 5.5, or from about 4.0 to about 6.0. In some embodiments, the granular insecticidal formulation comprises the weight ratio of (b) : (c) is from about 4.2 to about 4.4, from about 4.2 to about 4.6, from about 4.2 to about 4.8, from about 4.2 to about 5.0, from about 4.2 to about 5.5, or from about 4.2 to about 6.0. In some embodiments, the granular insecticidal formulation comprises the weight ratio of (b):(c) is from about 4.4 to about 4.6, from about 4.4 to about 4.8, from about 4.4 to about 5.0, from about 4.4 to about 5.5, or from about 4.4 to about 6.0. In some embodiments, the granular insecticidal formulation comprises the weight ratio of (b):(c) is from about 4.6 to about 4.8, from about 4.6 to about 5.0, from about 4.6 to about 5.5, or from about 4.6 to about 6.0. In some embodiments, the granular insecticidal formulation comprises the weight ratio of (b):(c) is from about 4.8 to about 5.0, from about 4.8 to about 5.5, or from about 4.8 to about 6.0. In some embodiments, the granular insecticidal formulation comprises the weight ratio of (b):(c) is from about 5.0 to about 5.5, or from about 5.0 to about 6.0. In some embodiments, the granular insecticidal formulation comprises the weight ratio of (b):(c) is from about 5.5 to about 6.0.

[0036] In some embodiments, the granular insecticidal formulation comprises the weight ratio of (b):(c) is about 1.5, about 1.6, about 1.7, about 1.8, about 1.9, about 2.0, about 2.2, about 2.4, about 2.6, about 2.8, about 3.0, about 3.2, about 3.4, about 3.6, about 3.8, about 4.0, about4.2, about 4.4, about 4.6, about 4.8, about 5.0, about 5.5, or about 6.0. In some embodiments, the granular insecticidal formulation comprises the weight ratio of (b):(c) is at least about 1.5, at least about 1.6, at least about 1.7, at least about 1.8, at least about 1.9, at least about 2.0, at least about 2.2, at least about 2.4, at least about 2.6, at least about 2.8, at least about 3.0, at least about3.2, at least about 3.4, at least about 3.6, at least about 3.8, at least about 4.0, at least about 4.2, at least about 4.4, at least about 4.6, at least about 4.8, at least about 5.0, at least about 5.5, or at least about 6.0. In some embodiments, the granular insecticidal formulation comprises the weight ratio of (b):(c) is at most about 6.0, at most about 5.5, at most about 5.0, at most about 4.8, at most about 4.6, at most about 4.4, at most about 4.2, at most about 4.0, at most about 3.8, at most about 3.6, at most about 3.4, at most about 3.2, at most about 3.0, at most about 2.8, at mostabout 2.6, at most about 2.4, at most about 2.2, at most about 2.0, at most about 1.9, at most about 1.8, at most about 1.7, at most about 1.6, or at most about 1.5.Dispersant

[0037] In one aspect, provided herein is a granular insecticidal formulation further comprising a dispersant. Dispersants may be used to disperse solid particles in a liquid (such as a colloid or emulsion) to improve the separation of the particles and prevent them from agglomerating or settling. In some embodiments, the dispersant may be used to disperse the active ingredient in the granular formulation.

[0038] Generally, the dispersion process may include the following steps: wetting of the solid particles; breakdown of the solid particles; and stabilization of the dispersion. Dispersant may be used to help wet the solid particle and eliminate air between the solid particles and liquid medium. Dispersants may be absorbed on the surface of the particles with the other end of the molecule exposed and usually charged. Like charges repel, and the independently coated particles repel each other, maintaining uniform dispersity.

[0039] Dispersant molecules may contain ionic water-loving (hydrophilic) and oil-loving (lipophilic) groups. The hydrophobic (lipophilic) part of the molecule may be attracted to the particle and the particle is surrounded with an ionic layer. For example, in aqueous systems, dispersants are applied to disperse the particles and form an affiliation between the particles and the dispersing medium. Hydrophilic-lipophilic balance (HLB) is the balance of the size and strength of the hydrophilic and lipophilic moieties of a dispersant molecule. HLB may represent the oil and water solubility of a dispersant. The balance between the hydrophobic and hydrophilic properties of the molecules may determine the performance of a dispersant agent, for instance the type of emulsion formed.

[0040] In some embodiments, the granular formulation provided herein comprises dispersant to improve the wetting of the active ingredient and enhance stable suspension. Dispersants may be adsorbed onto the active ingredients and hinder close approach of the particles by charge repulsion effects or by steric effects. Examples of ionic dispersants comprise hydroxy functionalgroups, polyacrylates, polyurethane, fatty acid modified esters, polyacrylic acids, polycarboxylic copolymers, lignins, naphthalene, alkyl sulfates, alkylbenzene sulfonates, or alkyl ether sulfates.

[0041] In some embodiments, the granular formulation provided herein comprises an anionic dispersant. Anionic dispersants may contain anionic functional groups in the molecules.Examples of anionic dispersant comprise sulfonate, phosphate, carboxylate, lignin, naphthalene, humic acid, or polycarboxylic acids. In some embodiments, the anionic dispersant is selected from groups comprising naphthalene sulfonate condensate, lignosulfonate, acrylate copolymer, polymethylmethacrylate or ethoxylated phosphate ester.

[0042] In one aspect, provided herein is the granular insecticidal formulation further comprising dispersant agent from about 3% to about 20% by weight. In some embodiments, the granular formulation further comprises dispersant agent from about 3% to about 4%, from about 3% to about 5%, from about 3% to about 6%, from about 3% to about 7%, from about 3% to about 8%, from about 3% to about 9%, from about 3% to about 10%, from about 3% to about 11%, from about 3% to about 12%, from about 3% to about 13%, from about 3% to about 14%, from about 3% to about 15%, from about 3% to about 16%, from about 3% to about 17%, from about 3% to about 18%, from about 3% to about 19%, or from about 3% to about 20% by weight. In some embodiments, the granular formulation further comprises dispersant agent from about 4% to about 5%, from about 4% to about 6%, from about 4% to about 7%, from about 4% to about 8%, from about 4% to about 9%, from about 4% to about 10%, from about 4% to about 11%, from about 4% to about 12%, from about 4% to about 13%, from about 4% to about 14%, from about 4% to about 15%, from about 4% to about 16%, from about 4% to about 17%, from about 4% to about 18%, from about 4% to about 19%, or from about 4% to about 20% by weight. In some embodiments, the granular formulation further comprises dispersant agent from about 5% to about 6%, from about 5% to about 7%, from about 5% to about 8%, from about 5% to about 9%, from about 5% to about 10%, from about 5% to about 11%, from about 5% to about 12%, from about 5% to about 13%, from about 5% to about 14%, from about 5% to about 15%, from about 5% to about 16%, from about 5% to about 17%, from about 5% to about 18%, from about 5% to about 19%, or from about 5% to about 20% by weight. In some embodiments, the granular formulation further comprises dispersant agent from about 6% to about 7%, from about6% to about 8%, from about 6% to about 9%, from about 6% to about 10%, from about 6% to about 11%, from about 6% to about 12%, from about 6% to about 13%, from about 6% to about 14%, from about 6% to about 15%, from about 6% to about 16%, from about 6% to about 17%, from about 6% to about 18%, from about 6% to about 19%, or from about 6% to about 20% by weight. In some embodiments, the granular formulation further comprises dispersant agent from about 7% to about 8%, from about 7% to about 9%, from about 7% to about 10%, from about 7% to about 11%, from about 7% to about 12%, from about 7% to about 13%, from about 7% to about 14%, from about 7% to about 15%, from about 7% to about 16%, from about 7% to about 17%, from about 7% to about 18%, from about 7% to about 19%, or from about 7% to about 20% by weight. In some embodiments, the granular formulation further comprises dispersant agent from about 8% to about 9%, from about 8% to about 10%, from about 8% to about 11%, from about 8% to about 12%, from about 8% to about 13%, from about 8% to about 14%, from about 8% to about 15%, from about 8% to about 16%, from about 8% to about 17%, from about 8% to about 18%, from about 8% to about 19%, or from about 8% to about 20% by weight. In some embodiments, the granular formulation further comprises dispersant agent from about 9% to about 10%, from about 9% to about 1 1%, from about 9% to about 12%, from about 9% to about 13%, from about 9% to about 14%, from about 9% to about 15%, from about 9% to about 16%, from about 9% to about 17%, from about 9% to about 18%, from about 9% to about 19%, or from about 9% to about 20% by weight. In some embodiments, the granular formulation further comprises dispersant agent from about 10% to about 11%, from about 10% to about 12%, from about 10% to about 13%, from about 10% to about 14%, from about 10% to about 15%, from about 10% to about 16%, from about 10% to about 17%, from about 10% to about 18%, from about 10% to about 19%, or from about 10% to about 20% by weight. In some embodiments, the granular formulation further comprises dispersant agent from about 11% to about 12%, from about 11% to about 13%, from about 11% to about 14%, from about 11% to about 15%, from about 11% to about 16%, from about 11% to about 17%, from about 11% to about 18%, from about 11% to about 19%, or from about 11% to about 20% by weight. In some embodiments, the granular formulation further comprises dispersant agent from about 12% to about 13%, from about 12% to about 14%, from about 12% to about 15%, from about 12% toabout 16%, from about 12% to about 17%, from about 12% to about 18%, from about 12% to about 19%, or from about 12% to about 20% by weight. In some embodiments, the granular formulation further comprises dispersant agent from about 13% to about 14%, from about 13% to about 15%, from about 13% to about 16%, from about 13% to about 17%, from about 13% to about 18%, from about 13% to about 19%, or from about 13% to about 20% by weight. In some embodiments, the granular formulation further comprises dispersant agent from about 14% to about 15%, from about 14% to about 16%, from about 14% to about 17%, from about 14% to about 18%, from about 14% to about 19%, or from about 14% to about 20% by weight. In some embodiments, the granular formulation further comprises dispersant agent from about 15% to about 16%, from about 15% to about 17%, from about 15% to about 18%, from about 15% to about 19%, or from about 15% to about 20% by weight. In some embodiments, the granular formulation further comprises dispersant agent from about 16% to about 17%, from about 16% to about 18%, from about 16% to about 19%, or from about 16% to about 20% by weight. In some embodiments, the granular formulation further comprises dispersant agent from about 17% to about 18%, from about 17% to about 19%, or from about 17% to about 20% by weight. In some embodiments, the granular formulation further comprises dispersant agent from about 18% to about 19%, or from about 18% to about 20% by weight. In some embodiments, the granular formulation further comprises dispersant agent from about 19% to about 20% by weight.

[0043] In some embodiments, the granular formulation further comprises dispersant agent about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, about 15%, about 16%, about 17%, about 18%, about 19%, or about 20% by weight. In some embodiments, the granular formulation further comprises dispersant agent at least about 3%, at least about 4%, at least about 5%, at least about 6%, at least about 7%, at least about 8%, at least about 9%, at least about 10%, at least about 11%, at least about 12%, at least about 13%, at least about 14%, at least about 15%, at least about 16%, at least about 17%, at least about 18%, at least about 19%, or at least about 20% by weight. In some embodiments, the granular formulation further comprises dispersant agent at most about 20%, at most about 19%, at most about 18%, at most about 17%, at most about 16%, at most about 15%, at most about 14%, at most about 13%, at most about 12%, at most about 11%, at most about10%, at most about 9%, at most about 8%, at most about 7%, at most about 6%, at most about 5%, at most about 4%, or at most about 3% by weight.Wetting agent

[0044] In one aspect, provided herein is a granular insecticidal formulation further comprising a wetting agent. Wetting agents may be applied as surface-active molecules to reduce the surface tension of water. Wetting agents may be used to aid in the disintegration of granule matrices when added to water. Wetting agents may be used to facilitate the distribution of water within the premix used to form a granule. Wetting agents belong to a class of surfactants. Surfactants are surface active which make them prone to adsorb at air-liquid or liquid-liquid interfaces. They help to reduce the surface tension by penetrating in between the water molecules and thus reducing the cohesion between them.

[0045] Surfactants may contain hydrophilic "heads" and hydrophobic "tails" in structures. Surfactant molecules will migrate to air / water and solid / water interfaces and orientate in such a fashion as to minimize the contact between their hydrophobic groups and the water. This process is referred to as adsorption. An alternative way of limiting the contact between the hydrophobic groups and the water is for the surfactant molecules to aggregate in the bulk solution with the hydrophilic head groups oriented towards the aqueous phase. These aggregates of surfactant molecules vary in shape depending on concentration and range in shape from spherical to cylindrical to lamellar (sheets / layers). The aggregation process is called micellization and the aggregates are known as micelles. Micelles begin to form at a distinct and frequently very low concentration known as the critical micelle concentration (CMC).

[0046] The hydrophilic head of many surfactants comprises acetylenic, amino carboxylate, amine oxide, ammonium, carboxylate, diethanolamine, ether carboxylate, ether phosphate, ethoxylate, monoethanolamide, polyglucoside, sulfate, or sulfonate groups. The hydrophobic tails of most surfactants may comprise hydrocarbon, fluorocarbon or siloxane chains, which may be branched, linear, or aromatic. Non-limiting examples of hydrophobic groups include alkylbenzene, linear or branched alkyl, branched alkyl phenyl, polyoxypropylene, and polysiloxane.

[0047] The hydrophilic heads of surfactants are polar and may carry a negative or positive charge, both positive and negative charge or no charge at all. Generally, surfactants are classified according to the composition of their heads: anionic, cationic, amphoteric, or non-ionic. In some embodiments, the wetting agent in the granular insecticidal formulation provided herein comprises anionic surfactant, non-ionic surfactant, or combination thereof.

[0048] Anionic surfactants carry a net negative charge on the hydrophilic head and may generate significant foaming in solutions above their critical micelle concentration (CMC), which may be a desirable attribute in most cleansing applications. In some embodiments, the wetting agent in the granular insecticidal formulation provided herein comprises an anionic surfactant. Anionic surfactants may contain anionic polar functional groups at their head, comprising sulfate, sulfonate, phosphate ester, carboxylates, soaps, isethionates, or taurates. Non-limiting examples of sulfate anionic surfactants include alkyl sulfates, like ammonium lauryl sulfate (ALS), sodium lauryl sulfate (SLS), sodium dodecyl sulfate (SDS), alkyl-ether sulfates, like sodium laureth sulfate (sodium lauryl ether sulfate or SLES), and sodium myreth sulfate. Non-limiting examples of sulfonate anionic surfactants include alkylbenzene sulfonates, a-olefin sulfonates, paraffin sulfonates, sulfonated methyl esters, sulfonated fatty acids and sulfosuccinates. Other example anionic surfactants may include alkyl-aryl ether phosphates, alkyl ether phosphates, sodium stearate, sodium lauroyl sarcosinate, soap, ether carboxylates, alkyl phthalamates, taurates, isethionates, carboxylate-based fluorosurfactants, such as perfluorononanoate (PFOA), or perfluorooctanoate (PFO).

[0049] Cationic surfactants carry a net positive charge on the hydrophilic head and may be widely applied as the active ingredient in fabric softeners. Cationic surfactants may contain cationic functional groups at their head, including quaternary ammonium salts and pH-dependent primary, secondary, or tertiary amines. Nonlimiting examples of cationic surfactants may include cetrimonium bromide (CTAB), cetylpyridinium chloride (CPC), benzalkonium chloride (BAC), benzethonium chloride (BZT), dimethyldioctadecylammonium chloride, dioctadecyldimethylammonium bromide (DODAB), or octenidine dihydrochloride.

[0050] Amphoteric (or zwitterionic) surfactants have both cationic and anionic centers attached to the hydrophilic groups in the same molecule and may allow to both donate and acceptprotons. Amphoteric surfactants may behave as either an acid or a base, depending on the pH of the solution. The hydrophilic groups may change between anionic properties, the isoelectric neutral stage, and the cationic properties depending on the pH value. The cationic part may be formed by primary, secondary, or tertiary amines or quaternary ammonium cations. The anionic part may be variable and include sulfonates, as in the sultaines CHAPS (3-[(3-cholamidopropyl) dimethylammonio]-! -propanesulfonate) and cocamidopropyl hydroxy sultaine. Nonlimiting examples of amphoteric hydrophilic groups include amino acids, bicarbonate, dihydrogen phosphate, hydrogensulfate, or cocamidopropyl betaine. Nonlimiting examples of amphoteric hydrophobic groups include aminopropionates, iminodipropionates, imidazoline-based amphoteric surfactants, betaine surfactants, phospholipids phosphatidylserine, phosphatidylethanolamine, phosphatidylcholine, sphingomyelins, lauryldimethylamine oxide or myristamine oxide.

[0051] Nonionic surfactants are neutral and do not have charge in their molecular structure of the hydrophilic head. Nonionic surfactants may have covalently bonded oxygen-containing hydrophilic groups, which may form hydrogen bonds with water. In some embodiments, the wetting agent in the granular insecticidal formulation provided herein comprises a nonionic surfactant. In some embodiments, the nonionic surfactant in the granular insecticidal formulation provided herein comprises ethoxylates, fatty alcohol ethoxylates, 2-ethyl hexanol ethylene oxide / propylene oxide (EO / PO), fatty linear alcohol EO / PO, fatty alcohol Cl 2- 15 EO / PO, EO / PO block copolymer, alcohols C6-C12 and C 10-16 EO / PO, alkyl phenol ethoxylates (APEs or APEOs), fatty acid ethoxylates, ethoxylated fatty esters and oils, amine ethoxylates, fatty acid amides, ethylene oxide / propylene oxide block copolymers, fatty acid esters of polyhydroxy compounds, fatty acid esters of glycerol, fatty acid esters of sorbitol, fatty acid esters of sucrose, or alkyl poly-glucosides.

[0052] In some embodiments, the granular insecticidal formulation further comprises the wetting agent about 0.5%, about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, or about 8% by weight. In some embodiments, the granular insecticidal formulation further comprises the wetting agent at most about 8%, at most about 7%, at most about 6%, at most about 5%, at most about 4%, at most about 3%, at most about 2%, at most about 1%, or at mostabout 0.5% by weight. In some embodiments, the granular insecticidal formulation further comprises the wetting agent at least about 0.5%, at least about 1%, at least about 2%, at least about 3%, at least about 4%, at least about 5%, at least about 6%, at least about 7%, or at least about 8% by weight.

[0053] In one aspect, provided herein is the granular insecticidal formulation further comprising the wetting agent from about 0.5% to about 8% by weight. In some embodiments, the granular insecticidal formulation further comprises the wetting agent from about 0.5% to about 1%, from about 0.5% to about 2%, from about 0.5% to about 3%, from about 0.5% to about 4%, from about 0.5% to about 5%, from about 0.5% to about 6%, from about 0.5% to about 7%, or from about 0.5% to about 8% by weight. In some embodiments, the granular insecticidal formulation further comprises the wetting agent from about 1% to about 2%, from about 1% to about 3%, from about 1% to about 4%, from about 1% to about 5%, from about 1% to about 6%, from about 1% to about 7%, or from about 1% to about 8% by weight. In some embodiments, the granular insecticidal formulation further comprises the wetting agent from about 2% to about 3%, from about 2% to about 4%, from about 2% to about 5%, from about 2% to about 6%, from about 2% to about 7%, or from about 2% to about 8% by weight. In some embodiments, the granular insecticidal formulation further comprises the wetting agent from about 3% to about 4%, from about 3% to about 5%, from about 3% to about 6%, from about 3% to about 7%, or from about 3% to about 8% by weight. In some embodiments, the granular insecticidal formulation further comprises the wetting agent from about 4% to about 5%, from about 4% to about 6%, from about 4% to about 7%, or from about 4% to about 8% by weight. In some embodiments, the granular insecticidal formulation further comprises the wetting agent from about 5% to about 6%, from about 5% to about 7%, or from about 5% to about 8% by weight. In some embodiments, the granular insecticidal formulation further comprises the wetting agent from about 6% to about 7%, or from about 6% to about 8% by weight. In some embodiments, the granular insecticidal formulation further comprises the wetting agent from about 7% to about 8% by weight.

[0054] In some embodiments, the granular insecticidal formulation further comprises a pH modifier agent. In some embodiments, the pH modifier in the granular insecticidal formulationprovided herein comprises acetic acid, citric acid, fumaric acid, hydrochloric acid, lactic acid, malic acid, nitric acid, phosphoric acid, propionic acid, sulfuric acid, tartaric acid, ammonia, ammonium carbonate, diethanolamine, monoethanolamine, potassium hydroxide, sodium bicarbonate, sodium borate, sodium carbonate, sodium hydroxide, sodium phosphate dibasic, trolamine, acetate buffer, bicarbonate buffer, citrate buffer, phosphate buffer, Tris-HCl buffer, or combinations thereof.Adjuvant

[0055] In one aspect, provided herein is the granular insecticidal formulation further comprising adjuvants. An adjuvant may be added as a supplemental substance to an insecticidal formulation to enhance the performance and / or physical properties of the active ingredient. In some embodiments, the adjuvant in the granular insecticidal formulation provided herein comprises antifreeze agents, antifoam agents, thickening agents, antimicrobial agents, or mixtures thereof.

[0056] Exemplary agriculturally acceptable adjuvants comprise polyether polysiloxane, crop oil concentrates (e.g., 85% mineral oil + 15% emulsifiers), nonylphenol ethoxylates, benzylcocoalkyldimethyl quaternary ammonium salts, blends of petroleum hydrocarbon, alkyl esters, organic acids, anionic surfactants, C9-C11 alkylpolyglycoside, phosphate alcohol ethoxylates, natural primary alcohol (C12-C16) ethoxylate, di-sec-butylphenol ethylene oxide / propylene oxide (EO-PO) block copolymers, polysiloxane-methyl cap, mixture of nonylphenol ethoxylate urea ammonium nitrates, emulsified methylated seed oils, tridecyl alcohol (synthetic) ethoxylates (e.g., 8 EO), tallow amine ethoxylates (e.g., 15 EO), or PEG(400) dioleate-99.

[0057] Exemplary agriculturally acceptable adjuvants include, but are not limited to, thickening agents (i.e., thickeners). Exemplary thickeners comprise polysaccharides (e.g., xanthan gum), guar gum, locust bean gum, polyvinylpyrrolidones (PVP), polyvinyl acetates, polyvinyl alcohols, gelatin, carboxy methyl cellulose, sodium carboxymethyl cellulose,hydroxyethyl cellulose, sodium polyacrylate, modified starch attapulgite clay, bentonite clay, organic and inorganic sheet minerals, or mixtures thereof.

[0058] Exemplary agriculturally acceptable adjuvants include, but are not limited to, antifreeze agents. Exemplary antifreeze agents comprise ethylene glycol, propylene glycol, propane diols, glycol (e.g., monoethylene glycol, diethylene glycol, polypropylene glycol, polyethylene glycol), glycerin, urea, magnesium sulfate heptahydrate, sodium chloride, or mixtures thereof.

[0059] Exemplary agriculturally acceptable adjuvants include, but are not limited to, antifoam agents. Exemplary antifoam agents comprise silicone emulsions, long-chain alcohols, fatty acids, fatty acid salts, polydimethylsiloxane, organofluorine compounds, or mixtures thereof.

[0060] Exemplary agriculturally acceptable adjuvants include, but are not limited to, antimicrobial agents. Exemplary antimicrobial agents comprise bactericides based on dichlorophen and benzyl alcohol hemiformal, isothiazolinone derivatives, such as methylchloroisothiazolinone, alkylisothiazolinones and benzisothiazolinones, or mixtures thereof.Granule extrusion

[0061] In one aspect, provided herein is a granular insecticidal formulation. In some embodiments, granules are created by a paste extrusion. In some embodiments, the paste extrusion comprises dome extrusion or basket extrusion.

[0062] In basket extrusion, the wet-mass is gravity-fed, assisted by a set of blades towards an impeller which pushes the material radially outwards through a vertical screen / die. In dome extrusion, the material is fed using a horizontal screw and is pushed against a hemispherical dome screen / die creating granules of comparably high strength. Granule diameter may be controlled by extruder die selection. In some embodiments, granule die of the granular insecticidal formulation is from about 0.5 mm to about 1.5 mm. In some embodiments, granule die of the granular insecticidal formulation is from about 0.5 mm to about 0.6 mm, from about 0.5 mm to about 0.7 mm, from about 0.5 mm to about 0.8 mm, from about 0.5 mm to about 0.9mm, from about 0.5 mm to about 1.0 mm, from about 0.5 mm to about 1.1 mm, from about 0.5 mm to about 1.2 mm, from about 0.5 mm to about 1.3 mm, from about 0.5 mm to about 1.4 mm, or from about 0.5 mm to about 1.5 mm. In some embodiments, granule die of the granular insecticidal formulation is from about 0.6 mm to about 0.7 mm, from about 0.6 mm to about 0.8 mm, from about 0.6 mm to about 0.9 mm, or from about 0.6 mm to about 1.0 mm, from about 0.6 mm to about 1.1 mm, from about 0.6 mm to about 1.2 mm, from about 0.6 mm to about 1.3 mm, from about 0.6 mm to about 1.4 mm, or from about 0.6 mm to about 1.5 mm. In some embodiments, granule die of the granular insecticidal formulation is from about 0.7 mm to about 0.8 mm, from about 0.7 mm to about 0.9 mm, from about 0.7 mm to about 1.0 mm, from about 0.7 mm to about 1.1 mm, from about 0.7 mm to about 1.2 mm, from about 0.7 mm to about 1.3 mm, from about 0.7 mm to about 1.4 mm, or from about 0.7 mm to about 1.5 mm. In some embodiments, granule die of the granular insecticidal formulation is from about 0.8 mm to about 0.9 mm, from about 0.8 mm to about 1.0 mm, from about 0.8 mm to about 1.1 mm, from about 0.8 mm to about 1.2 mm, from about 0.8 mm to about 1.3 mm, from about 0.8 mm to about 1.4 mm, or from about 0.8 mm to about 1.5 mm. In some embodiments, granule die of the granular insecticidal formulation is from about 0.9 mm to about 1 .0 mm, from about 0.9 mm to about 1.1 mm, from about 0.9 mm to about 1.2 mm, from about 0.9 mm to about 1.3 mm, from about 0.9 mm to about 1.4 mm, or from about 0.9 mm to about 1.5 mm. In some embodiments, granule die of the granular insecticidal formulation is from about 1.0 mm to about 1.1 mm, from about 1.0 mm to about 1.2 mm, from about 1.0 mm to about 1.3 mm, from about 1.0 mm to about 1.4 mm, or from about 1.0 mm to about 1.5 mm. In some embodiments, granule die of the granular insecticidal formulation is from about 1.1 mm to about 1.2 mm, from about 1.1 mm to about 1.3 mm, from about 1.1 mm to about 1.4 mm, or from about 1.1 mm to about 1.5 mm. In some embodiments, granule die of the granular insecticidal formulation is from about 1.2 mm to about1.3 mm, from about 1.2 mm to about 1.4 mm, or from about 1.2 mm to about 1.5 mm. In some embodiments, granule die of the granular insecticidal formulation is from about 1.3 mm to about1.4 mm, or from about 1.3 mm to about 1.5 mm. In some embodiments, granule die of the granular insecticidal formulation is from about 1.4 mm to about 1.5 mm.

[0063] In some embodiments, granule die of the granular insecticidal formulation is at least about 0.5 mm, at least about 0.6 mm, at least about 0.7 mm, at least about 0.8 mm, at least about 0.9 mm, at least about 1.0 mm, at least about 1.1 mm, at least about 1.2 mm, at least about 1.3 mm, at least about 1.4 mm, or at least about 1.5 mm. In some embodiments, granule die of the granular insecticidal formulation is at most about 1.5 mm, at most about 1.4 mm, at most about 1.3 mm, at most about 1.2 mm, at most about 1.1 mm, at most about 1.0 mm, at most about 0.9 mm, at most about 0.8 mm, at most about 0.7 mm, at most about 0.6 mm, or at most about 0.5 mm.EXAMPLES

[0064] The following examples further illustrate the invention but, of course, should not be construed as in any way limiting its scope.EXAMPLE 1 : Granular formulation.

[0065] As illustrated in Table 1, the granular insecticidal formulation is listed.Table 1. Granular insecticidal formulationEXAMPLE 2: Granule formation by basket and dome extrusion.

[0066] Granular formulations were prepared to contain active ingredient of 300 grams per kilogram (g / kg), an anionic / nonionic surfactant blend wetting agent, a sodium lignosulfonate dispersant, a clay filler and lactose monohydrate binder, with a weight ratio of 2.67 for filler overbinder. Components of each formulation were combined and milled with a Micronizer® Jet Mill (Sturtevant Inc., US) outfitted with an AccuRate® feeder (Schenck Process LLC, US). All samples were milled until target particle size of D90 < 12 pm was reached. All particle size measurements were conducted using the Malvern Mastersizer® 3000 with Aero S (Malvern Instruments Limited, UK).

[0067] Water was added to the milled powder in a planetary mixer (Hobart Corp., US) until an extrudable paste was achieved. The amount of water needed to achieve an extrudable paste was noted and moisture content was calculated on a dry basis. Paste was extruded through a screen / die via basket extrusion using a NiroPharma Extruder EMO (GEA Group, Germany) or dome extrusion with a MG-55 extruder (LCI Corporation, US). Resulting granules were tray dried in an oven (Kason Industries Inc., US) until residual moisture content was less than 2%, measured with a Halogen Moisture Analyzer HX204 (Mettler Toledo LLC, US). The dried granules were passed through an 8-mesh sieve to remove any clumped product and then sieved using a 40-mesh screen to remove any fine particles. Granules collected in the 40-mesh sieve were used in subsequent testing.

[0068] Active suspensibility of the granulated product was assessed in accordance with CIPAC method MT 184.1 Suspensibility of Formulations Forming Suspensions on Dilution with Water, following the methods described for solid formulations and chemical analysis. Room temperature water with a hardness of 342 ppm was used in active suspensibility testing.

[0069] As illustrated in Table 2, moisture in paste were kept at the same level across granule extrusions of basket and dome, with various die sizes. Active Suspensibility was over 93% after storage over 2 weeks at room temperature (RT), or at 54 °C for both basket and dome extrusion with various die sizes. Active Suspensibility was over 91% after storage over 8 weeks at 40 °C for basket extrusion on two die sizes.Table 2. Granule formation.EXAMPLE 3: Granulation score.

[0070] Granular formulations were prepared to contain total active ingredient(s) from 5% to 60% by weight, an anionic / nonionic surfactant blend wetting agent (Geropon® L-Wet Max), a sodium lignosulfonate dispersant (Polyfon® T), a clay filler (aluminum silicate hydroxide) and lactose monohydrate as the binder. The weight ratio for filler over binder was kept from 1.53 to 5.67. All components of each formulation were combined and milled with a Jet-O-Mizer® Jet Mill (Fluid Energy Processing and Equipment Company, US). All samples were milled until target particle size of D90 < 12 pm was reached. All particle size measurements were conducted via laser diffraction using the Helos / BR (Sympatec, US) for particle size distribution.

[0071] Water was added to the milled powder in a food processer (Kitchen Aid, US) until an extrudable paste was achieved. The amount of water needed to achieve an extrudable paste was noted and moisture content was calculated on a dry basis. Paste was extruded through a screen / die via basket extrusion using a KAR-75 benchtop granulator (LCI Corporation, US). Resulting granules were tray dried in an oven (Fisher Scientific, US) until residual moisture content was less than 2%, as measured by a Computrac® Moisture Analyzer (Arizona Instrument LLC, US). The dried granules were passed through an 8-mesh sieve to remove any clumped product and then sieved using a 40-mesh screen to remove any fine particles. Granules collected in the 40-mesh sieve were used in subsequent testing.

[0072] Active suspensibility of the granulated product was assessed in accordance with CIPAC method MT 184.1 Suspensibility of Formulations Forming Suspensions on Dilution with Water, following the methods described for solid formulations and chemical analysis. Room temperature water with a hardness of 342 ppm was used in active suspensibility testing.

[0073] Granulation score is an observation-based evaluation of how the paste behaved throughout the granulation process, about the completeness of the granulation and the number of granules produced. Scores were selected from the phrases “very good”, “good”, “fair”, “poor”, and “impossible”.

[0074] All amounts of Active ingredient (A-[4-chloro-2-(pyri din-3 -yl)- 1,3 -thiazol-5-yl]-7V- ethyl-3-(methanesulfonyl)propenamide as Al and sulfoxaflor as A2), filler, wetting agent, dispersant, binder were listed as percentage (%) by weight in Table 3. As illustrated in Table 3, Granulation scores varied among the weight ratios of filler over binder. Very good and good scores were observed for the weight ratios greater than 2.4 and between 1.5 to 1.6. Active suspensibility was over 90% for formulations with the weight ratios greater than 2. 1.Table 3. Granulation scores of granular formulations.

[0075] All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.

[0076] Preferred embodiments of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Variations of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.

Claims

Claims1. A granular insecticidal formulation comprising(a) At least one water-soluble active ingredient, wherein water solubility of the active ingredient is from about 0.3 g / L to about 30 g / L at 25 °C;(b) a filler from about 15% to about 65% by weight; and(c) a binder; wherein the filler and the binder are present at a weight ratio of (b):(c) from about 1.5 to about 6.0.

2. The granular insecticidal formulation of claim 1, wherein the active ingredient is A-[4- chloro-2-(pyridin-3-yl)-l,3-thiazol-5-yl]-7V-ethyl-3-(methanesulfonyl)propanamide.

3. The granular insecticidal formulation of claim 1 or 2, an optional second active ingredient further comprises a nicotinic acetylcholine receptor (nAChR) competitive modulator comprising sulfoxaflor, triflumezopyrim, acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiamethoxam, nicotine or flupyradifurone.

4. The granular insecticidal formulation of any one of claims 1-3, comprises the active ingredient from about 5% to about 60% by weight.

5. The granular insecticidal formulation of any one of claims 1-4, wherein the filler comprises sand, limestone, gypsum, clays, montmorillonite, starch, or combination thereof.

6. The granular insecticidal formulation of any one of claims 1-4, wherein the binder comprises gelatin, gum acacia, gum tragacanth, guar gum, sucrose, glucose, lactose monohydrate, starch, polyvinylpyrrolidone (PVP), PVP-polyvinyl acetate (PVA) copolymer, partially gelatinized starches (PGS), cellulose ethers, or combination thereof.

7. The granular insecticidal formulation of any one of claims 1-6, comprises the binder (c) from about 5% to about 25% by weight.

8. The granular insecticidal formulation of any one of claims 1-7, further comprises a wetting agent, a dispersant agent, a pH modifier, adjuvant agents, or combination thereof.Corteva Docket 212201-WO-SEC-l9. The granular insecticidal formulation of any one of claims 1-8, comprises the wetting agent from about 0.5% to about 8.0% by weight.

10. The granular insecticidal formulation of any one of claims 1-9, comprises the dispersant agent from about 3% to about 20% by weight.

11. The granular insecticidal formation of any one of claims 1-10, wherein the granule die is from about 0.5 mm to about 1.5 mm by dome extrusion or basket extrusion.

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