Agrochemical formulations containing sulfonic polymers

Abstract

The present disclosure describes agrochemical formulations comprising an optional rosin, one or more agrochemical active ingredients, and a sulfopolymer, such as a sulfopolyester. The present disclosure also describes methods of making and using such formulations in agriculture.

Description

Technical Field

[0001] The present disclosure relates to agricultural formulations comprising sulfopolymers such as sulfopolyesters and optionally rosin. More particularly, the present disclosure relates to suspension formulations and compositions comprising sulfopolymers and optionally rosin, and methods of using the same. Background Art

[0002] Although there are many adjuvants and surfactants for use in the agricultural industry, the increase of continuous regulatory changes and formulation complexity requires the development of new adjuvants. In addition, the development of new active compounds and combinations of active compounds has led to very difficult formulation challenges. Simplifying the composition while increasing the feasible active ingredient load is considered to be important for any future adjuvant development. In the industry, the continued need to improve the stability of agricultural chemical formulations under high loads.

[0003] Existing adjuvants are designed to perform specific functions, such as wetting, spreading, adhesion, reducing evaporation, reducing volatility, buffering, emulsification, dispersion, reducing spray drift or reducing foaming. Many adjuvants cannot perform multiple functions. In this case, compatible adjuvants can be combined in some cases to perform multiple functions simultaneously.

[0004] Because most existing adjuvants are designed to play a specific function, the end user of this type of adjuvant usually needs to buy, store and prepare several different adjuvants, which is expensive and time-consuming. Specific adjuvants also require different formulations usually. Incompatible mixtures of adjuvants can cause formulation instability. Based on considerations as mentioned above, there is still a clear business and industrial demand for the development of adjuvants that can play multiple functions in the agricultural industry.

[0005] As the agricultural industry turns more to blends of active ingredients due to the high cost and lengthy process of obtaining registration for new active ingredients, the complexity of formulations continues to increase. It is not uncommon for two active ingredients to require different sets of adjuvants, which may be incompatible when combined, leading to crystallization, gelation, or some other form of formulation failure. An adjuvant that is functional and effective across a wide range of formulation types would be advantageous. Summary of the Invention

[0006] This Summary is provided to introduce some concepts in a simplified form that are further described below in the Detailed Description. This Summary is not intended to identify all key features or essential features of the claimed subject matter, nor is it intended to be used solely as an aid in determining the scope of the claimed subject matter.

[0007] Sulfopolymers are described herein as being particularly effective as adjuvants in a variety of agrochemical formulations. More specifically, sulfopolyesters are demonstrated to provide a variety of adjuvant functions to agrochemical formulations.

[0008] Provided herein are agricultural compositions comprising at least one sulfopolymer that provide stable formulations for the agricultural industry. While polymeric surfactants and ionic surfactants are known, surprisingly, the sulfopolymers described herein, particularly sulfopolyesters, such as those comprising a sulfoisophthalate moiety derived, for example, from sodium sulfoisophthalic acid (5-SSIPA) or its esters or amides, provide stable formulations for various agricultural chemicals (agrochemicals) when used as agricultural adjuvants. In one embodiment, or in combination with any of the aforementioned embodiments, the agricultural composition may further comprise rosin.

[0009] In a first embodiment, or in combination with any of the aforementioned embodiments, the present disclosure provides an agricultural chemical formulation comprising: at least one agricultural chemical active ingredient, and an unlyophilized sulfopolymer. In one embodiment, or in combination with any of the aforementioned embodiments, the agricultural formulation can further comprise rosin.

[0010] Another embodiment, or in combination with any of the aforementioned embodiments, is an agrochemical concentrate formulation comprising: at least one agrochemical active ingredient, and a sulfopolymer that has not been lyophilized. In one embodiment, or in combination with any of the aforementioned embodiments, the formulation can further comprise rosin.

[0011] Also provided is an agrochemical concentrate formulation comprising: 5 wt% to 90 wt% of an agrochemical active ingredient or a mixture of two or more agrochemical active ingredients, and up to 15 wt% of an unlyophilized sulfopolymer. In one embodiment, or in combination with any of the above embodiments, the formulation may further comprise 0.1 wt% to 10 wt% of rosin.

[0012] Another embodiment, or in combination with any of the aforementioned embodiments, is an agrochemical concentrate formulation comprising: at least one agrochemical active ingredient; and no more than 15 wt% of an unlyophilized sulfopolymer; the formulation being characterized by one or more of: dispersibility and / or reliable redispersibility of the active ingredient; high active ingredient loading; and / or increased formulation stability. In one embodiment, or in combination with any of the aforementioned embodiments, the formulation can further comprise rosin.

[0013] Also described is an agrochemical composition for application comprising the formulation of any one of the above embodiments diluted in water.

[0014] Additional embodiments, or in combination with any of the aforementioned embodiments, include the use of an unfreeze-dried sulfopolyester to stabilize an agriculturally active agent in a formulation; the use of an unfreeze-dried sulfopolyester to uniformly disperse an agriculturally active agent in a formulation; and the use of an unfreeze-dried sulfopolyester as a surfactant adjuvant in an agrochemical formulation comprising an agriculturally active ingredient. In one embodiment, or in combination with any of the aforementioned embodiments, the formulation can further comprise rosin.

[0015] Also provided is the use of the concentrate formulation described herein in the preparation of an applied agrochemical composition for application to plants, plant parts or culture medium.

[0016] Another embodiment, or in combination with any of the aforementioned embodiments, is an agrochemical formulation in an applied state comprising: at least one agrochemical active ingredient and a sulfopolyester that has not been lyophilized. In one embodiment, or in combination with any of the aforementioned embodiments, the formulation can further comprise rosin.

[0017] Another embodiment, or in combination with any of the aforementioned embodiments, is an agrochemical formulation in an applied state comprising: at least one agrochemical active ingredient and a sulfopolymer that has not been lyophilized. In one embodiment, or in combination with any of the aforementioned embodiments, the formulation can further comprise rosin.

[0018] Also provided is an agrochemical formulation in an applied state comprising: 0.05 wt% to 20 wt% of an agrochemical active ingredient or a mixture of two or more agrochemical active ingredients, and up to 5 wt% of an unlyophilized sulfopolymer. In one embodiment, or in combination with any of the aforementioned embodiments, the formulation may further comprise rosin.

[0019] Another embodiment, or in combination with any of the aforementioned embodiments, is an agrochemical formulation for use, comprising: at least one insoluble or partially soluble agrochemical active ingredient; and no more than 15 wt% of an unlyophilized sulfopolymer; the formulation being characterized by one or more of: dispersibility and / or reliable redispersibility of the active ingredient; high active ingredient loading; and / or increased formulation stability. In one embodiment, or in combination with any of the aforementioned embodiments, the formulation may further comprise rosin.

[0020] Also provided are embodiments, or in combination with any of the mentioned embodiments, comprising the use of any of the herein described agrochemical compositions in an applied state or any of the herein described formulations for treating plants or culture media for agricultural purposes.

[0021] A final embodiment, or in combination with any of the aforementioned embodiments, is a method comprising: combining unlyophilized sulfopolymer and at least one agrochemical active ingredient with water to produce a mixture. In one embodiment, or in combination with any of the aforementioned embodiments, the method further comprises combining rosin to produce a mixture. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 are photographs of SC formulations from Examples 7-10 showing the amount of separation after 10 days at 54°C.

[0023] Figure 2 are photographs of SC formulations from Examples 7-10 showing dilutions after standing for 2 hours at room temperature.

[0024] Figure 3 are photographs of SC formulations from Examples 11-14 showing the dispersions after standing at room temperature for 1 hour.

[0025] Figure 4 are photographs of SC formulations from Examples 15-18 showing the amount of separation after 10 days at 54°C.

[0026] Figure 5 are photographs of SC formulations from Examples 15-18 showing dilutions after standing at room temperature for 8 hours.

[0027] Figure 6 are photographs of SC formulations from Examples 19-24 showing the amount of separation after 10 days at room temperature.

[0028] Figure 7 The method used to quantify the percentage of separated layer is shown. It is a photograph of the EW formulation from Example 31 showing the amount of separation after 1 hour at room temperature.

[0029] Figure 8 are photographs of EW formulations from Examples 47, 48, and 49 showing the amount of separation after 14 days at 54°C.

[0030] Figure 9 are photographs of EW formulations from Examples 47, 48, and 49 showing the dispersions immediately after dilution and before inversion at room temperature.

[0031] Figure 10 are photographs of EW formulations from Examples 47, 48, and 49 showing the dispersions 4 hours after dilution and tumbling at room temperature.

[0032] Figure 11 Shown is a photograph of petri dishes used to test wt% coverage of SC formulations at 1 wt.% dilution for Examples SC1-SC4.

[0033] Figure 12 Shown is a photograph of petri dishes used to test wt% coverage of SC formulations at 10 wt.% dilution for Examples SC1-SC4. DETAILED DESCRIPTION

[0034] Various aspects of the present disclosure will now be described with additional details and options to support the teachings of the present disclosure, as follows: (I) Selected Abbreviations; (II) Selected Definitions; (III) Sulfopolymers / Sulfopolyesters Useful in Formulations; (IV) Recovered Sulfopolyesters; (V) Additional Components in the Formulations (including (i) the active compound; (ii) optional rosin; and (iii) additional adjuvants); (VI) Additional Optional Ingredients); (VII) Exemplary Ranges of Components in Representative Formulations; (VIII) Methods of Making Concentrated Formulations; (IX) Characterization of Formulations; (X) Uses of Concentrated Formulations; (XI) Additional Disclosures; (XII) Examples; and (XIII) Concluding Paragraph.

[0035] (I) Select abbreviation

[0036] 5-SSIPA is sodium sulfoisophthalic acid; BO is banana oil; cp is centipoise; dg is geometric mean diameter; EC is emulsifiable concentrate; EDTA is ethylenediaminetetraacetic acid; EO is emulsion, water-in-oil; EW is emulsion, oil-in-water; Ex is excipient; HLB is hydrophile-lipophile balance; h is hours; HS is high shear; min is minutes; MSO is methylated seed oil; MW is molecular weight; OD is oil dispersion; PEG is polyethylene glycol; PWO is Petronas white oil; rpm is revolutions per minute; rt is room temperature; RTU is ready to use; SC is suspension concentrate (also known as flowable concentrate); SCMF is short-cut multicomponent fiber; sec is seconds; T g is the glass transition temperature; UAN is urea ammonium nitrate; UV is ultraviolet light.

[0037] (II) Selection Definition

[0038] The use of the words "exemplary" or "embodiment" or "desirably" in this document does not limit the definitions or language used for the words, and is intended to further illustrate in a non-limiting manner through the use of examples or specific embodiments within the scope of the definitions.

[0039] As used herein, activating agent refers to chemicals or compounds with specific biological activity.Activating agent can include chemicals or compounds with acaricidal activity, bactericidal activity, fungicidal activity, weeding activity, insecticidal activity, larvicidal activity, nematode activity, acaricidal activity, molluscicidal activity, fish killing activity, rodent killing activity, armyworm killing activity, or fertilizer, hormone and / or other growth regulator.Other active ingredient has been listed herein. In addition, activating agent can include chemicals or compounds that support or enhance plant growth.Activating agent can also be called active ingredient.

[0040] As used herein, adjuvant refers to an ingredient that promotes or alters the biological activity and / or physical properties of a formulation.

[0041] The use of agrochemical adjuvants generally falls into four categories: (1) activator adjuvants that generally enhance the performance of the formulation, (2) spray modifier adjuvants that generally affect the application performance of the spray solution (e.g., drift retarder, sticker, evaporation aid), (3) utility modifiers that generally minimize handling and improve application (e.g., defoamers), and (4) utility products that minimize application problems (e.g., foam markers and drum cleaners). The adjuvant kit or formulation can contain, and desirably contains, a surfactant. In one embodiment, the surfactant, or adjuvant, in the adjuvant kit or formulation comprises a sulfopolymer.

[0042] As used herein, an agriculturally acceptable adjuvant refers to a substance that enhances the performance of an active agent in a composition used to affect (ie, inhibit or enhance, as the case may be) the growth or cultivation of plants and / or plant parts.

[0043] As used herein, agrochemicals refer to any chemical used to help manage agricultural ecosystems, such as hormones or other growth regulators, pesticides (e.g., herbicides, insecticides, fungicides, nematicides, acaricides, larvicides, molluscicides, etc.), fertilizers, soil conditioners, liming agents, acidifiers, or any other growth agents.

[0044] As used herein, ambient temperature refers to the temperature at a location or in a room, or the temperature surrounding the object in question. The term is equivalent to "room temperature" (rt). By way of example, room temperature can be between 65°F and 78°F (approximately 18.3°C to 25.5°C); or between 68°F and 72°F (approximately 20°C to 22.2°C).

[0045] As used herein, antifreeze refers to a material that lowers the freezing point of a formulation.

[0046] As used herein, an aqueous dispersion refers to a water-based formulation in which a compound is dispersed. In specific embodiments, an aqueous dispersion of a sulfopolyester is a formulation in which the sulfopolyester compound has been dispersed in water. Aqueous dispersion formulations may have a continuous phase of water, as opposed to an organic solvent.

[0047] As used herein, bloom refers to the spontaneous dispersion of a concentrated formulation into a diluent such as water with minimal agitation. Bloom can refer to the dispersion of liquid droplets into a liquid diluent (e.g., for EC formulations) or to the dispersion of solid particles suspended in a liquid (e.g., for SC formulations).

[0048] As used herein, a colorant is any substance used to intentionally change the color of a formulation.

[0049] As used herein, a concentrated formulation (also known as a formulated concentrate) refers to a formulation containing at least one active agrochemical compound at a concentration that is at least twice that of the active agrochemical compound used in an application-state formulation, or higher than the active ingredient in a ready-to-use (RTU) formulation. Thus, the concentrated formulation is intended or intended to be diluted (e.g., with water or another acceptable carrier or diluent) before use or application. In representative embodiments, the concentrated formulation comprises at least one active ingredient at a concentration that is at least twice that of the ingredient used in an application-state or RTU formulation. The term concentrated formulation as used herein is liquid at 25° C. and 1 atmosphere. Although the concentrated formulation may contain dispersed solids, the formulation itself is still liquid because it is flowable at that temperature and pressure.

[0050] As used herein, contact angle refers to the measurement of the profile of a water droplet in contact with a solid surface; the flatter the droplet, the lower the contact angle reading. In particular embodiments, adjuvants (e.g., surfactants) can reduce surface tension, causing the water droplet to spread and reduce the contact angle.

[0051] As used herein, a control formulation is a formulation containing the same ingredients as the reference formulation but without any sulfopolymer. Alternatively, the control formulation may include an adjuvant in place of the sulfopolymer, such as an adjuvant recognized in the art that is believed to function similarly to the function of the sulfopolymer included in one embodiment of the reference formulation or in combination with any of the mentioned embodiments.

[0052] As used herein, stratification (crashing) refers to the dissociation of a liquid emulsion (partially or completely) into two layers. This can include the coalescence of droplets of the discontinuous phase into a non-dispersed phase, which is alternatively referred to as the "breaking" of the liquid in the liquid emulsion, which includes creaming, sedimentation and coalescence of one or two phases of the emulsion. For suspension formulations, stratification can include the caking, sedimentation, flocculation, crystallization or precipitation of solid (pre-dispersed and / or suspended) components from the formulation into a block (cake) or clay. Typically, stratified formulations cannot be easily redistributed.

[0053] As used herein, a diluent refers to a gas, liquid, or solid used to reduce the concentration of active ingredients in the formulation or application of an agrochemical composition.

[0054] As used herein, a dispersion refers to a system in which distributed particles of one material are uniformly dispersed in a continuous phase of another material. The particles to be distributed can be solid or liquid particles, which can be dispersed in a continuous liquid phase.

[0055] As used herein, dispersibility refers to the ability of one material to be uniformly dispersed in a continuous phase of another material. As used herein, redispersibility refers to the ability of particles to be dispersed in a mixture after separation, settling, or sedimentation of the particles.

[0056] Drift, as used herein, refers to the aerial movement of a compound from the application area to any unintended (e.g., off-target) sites. Drift can occur during agrochemical application, for example, when droplets or particles travel away from the target site. Drift can also occur after application, when some of the chemical becomes a vapor that can be displaced from the application site.

[0057] Drift includes anything that moves away from or away from the target site (plant, plant part, culture medium, etc.). Many phenomena contribute to drift, such as evaporation or sublimation, as well as off-target spray applications. These are the two main forms of drift generally considered in agricultural practices; both are important for controlling effects on adjacent fields. The two main forms are: particle or droplet drift (the movement of spray droplets produced upon application), which can be influenced by rheology modifiers that affect the size of the droplets exiting the sprayer; and vapor drift (the movement of mist / vapor after application of a volatile formulation), which can be influenced by changing the volatility of the formulation and by changing the environment in which the compound is applied.

[0058] Drift control as used herein refers to the action or effect of measurably reducing or preventing drift. In representative embodiments, drift control includes a statistically significant reduction in the drift of a detectable compound, such as in a comparison between preparations having a component that is different in presence or amount. Drift control agents are chemical reagents that reduce one or more of the following: wind drift experienced when spraying a barrel mix composition, or vapor drift. Exemplary drift control agents increase the droplet size in the preparation and / or reduce the ratio of driftable fine particles (less than 150 microns of droplets), such as by increasing the viscosity of the preparation.

[0059] There are standard methods recognized in the art to measure drift; for example, see U.S. Patent Publication 20160015033A1. However, it is also recognized that different formulators may demonstrate or measure drift in different ways. A common format for reporting drift reduction due to the inclusion of a drift control agent in a formulation is to provide results for an "improved formulation" compared to the same formulation without the improved formulation.

[0060] One method for observing particle / droplet drift control involves measuring droplet size using a spray test device. In one embodiment or in combination with any of the aforementioned embodiments, the optimized droplet size distribution is approximately 400 microns; droplets smaller than this value are generally considered to be driftable due to wind or temperature conditions at the time of spraying. Droplet size measurements can be performed using a laser system using techniques recognized in the art (similar to the methods used to determine the atomization properties of a formulation).

[0061] Vapor drift is often considered more difficult to measure or quantify, in part because the amount of volatilization loss of a compound / ingredient is usually quite low. Volatility is usually detected and measured in field trials, involving observation of phytotoxic effects (up to and including plant death) on nearby plants.

[0062] As used herein, effective dose refers to the amount that is enough to cause useful and / or desired result.For example, activeconstituents can be present in the preparation with the amount that effectively provides the desired effect relevant with this activeconstituents, and described desired effect is for example pesticide effect, fertilizer effect or any other agricultural chemicals effect.The amount that any activity or other composition is effectively used for its required purposes is usually subject to the influence of the composition used, the background (for example, other components in the preparation) using it, the method or mode of the composition using the composition etc..Can use art-recognized method to determine for any particular component and effective dose under various backgrounds.

[0063] As used herein, an emulsion concentrate (EC) (or emulsifiable concentrate) refers to a liquid formulation containing at least one active agrochemical compound (at a level at least twice the level used in an applied or RTU formulation), one or more water-immiscible organic solvents, and an emulsifier (e.g., a surfactant). In one embodiment or combination with any of the aforementioned embodiments, the emulsion concentrate includes at least some water or has an aqueous continuous phase. In one embodiment or combination with any of the aforementioned embodiments, the agrochemical active compound and the water-immiscible solvent may be the same compound. In another embodiment or combination with any of the aforementioned embodiments, the agrochemical active compound and the at least one water-immiscible compound are not the same compound. In a representative embodiment, the emulsifier is or includes a sulfopolymer, such as a sulfopolyester. When EC formulations are diluted with water, for example, in a spray tank, they desirably form an emulsion with minimal mixing. Even more desirably, they form an emulsion spontaneously without mixing. The formation of an emulsion upon dilution may be referred to as "clouding."

[0064] Diluted EC formulations contain small droplets of one liquid uniformly dispersed in another liquid. A common type of EC formulation contains the active ingredient dissolved in a non-aqueous (water-immiscible) solvent (e.g., oil, inorganic or organic solvent, fatty acid amide, or ester), which is uniformly dispersed in water. It is important that the water-immiscible droplet size remains small (e.g., 0.1 to 1.0 μm), otherwise the dispersion will collapse, producing a solvent / oil phase and an aqueous phase. To prevent this collapse, agrochemical formulations typically include a surfactant or emulsifier. Such emulsifiers interact with the solvent / oil phase and the aqueous phase to maintain equilibrium, thereby enabling a stable emulsion. As formulations become more complex, interactions with additional adjuvants have led to the need to find new dispersants to enable stable emulsions. Furthermore, as the concentration of active ingredients in formulations continues to increase, improved emulsifiers are needed. Stricter regulatory requirements are forcing the industry to search for new solvents for use in agricultural formulations. With the introduction of new oil-soluble solvents, the suite of emulsifiers required for stable EC formulations continues to evolve. Emulsion stability and testing are discussed in ParticleSciences Technical Brief 2011, vol. 2 (available online at particlesciences.com / docs / technical_briefs / TB_2011_2.pdf).

[0065] As used herein, an emulsion is a mixture created when one liquid is added to another and mixes with it but does not dissolve in it, resulting in a uniform dispersion of droplets dispersed in a continuous phase. An emulsion is prepared by combining two liquids that normally do not mix. The process of turning a liquid mixture into an emulsion is called emulsification.

[0066] As used herein, a flowable concentrate refers to a suspension of one or more solid active ingredients (at a level at least twice the level used in an application or RTU formulation) in water.

[0067] As used herein, culture medium refers to any natural or artificial solid, semi-solid or liquid suitable for germination, rooting and / or propagation of plants. Examples of culture medium include peat, vermiculite, perlite, bark, coconut shell, sawdust, certain types of fly ash, pumice, plastic particles, glass wool, asbestos and certain polymer-based foams. These are typically used alone or in various combinations with each other and / or natural soil (with or without soil amendments). Suitable soil amendments include ground natural minerals such as kaolin, clay, chalk and talc; ground synthetic minerals such as silicates and highly dispersed silica; anionic or nonionic emulsifiers; surfactants such as alkali metal salts of lignin sulfate and naphthalenesulfonic acid; and dispersants such as methylcellulose. Natural soil is also considered as culture medium herein, including in situ soil in fields. The term culture medium also particularly includes liquid media for growing hydroponic plants, and growth support materials / matrix used in combination with hydroponic methods.

[0068] As used herein, high loading refers to a concentration or level of active ingredient or solvent that (i) cannot be achieved in the absence of the sulfopolymer, or (ii) is at least 1 wt.% based on the weight of the liquid of the formulation (in a concentrated formulation). In one embodiment or in combination with any of the embodiments mentioned, the concentration (w / w%) can be 1-80%. In further embodiments, the concentration is 20-80%, or 30-80%, or 40-80%, or 50-80%, or 60-80%, or 20-70%, or 30-70%, or 40-70%, or 50-70%, or 20-30%, or 30-40%, 40-50%, 50-60%, 60-70%, or 70-80%. The target concentration depends on the specific active ingredient and / or solvent used in the formulation. The embodiments provided herein can increase the concentration of a control formulation by at least 10%, or at least 20%, or at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, or at least 80%, or at least 90%, or at least 100%, or more, relative to the industry-accepted standard stable concentration of the concentrated formulation. In some examples, the control formulation is the same formulation but lacks the sulfopolymer; in other examples, it is the same formulation lacking the sulfopolymer but with an industry-accepted alternative adjuvant in place of the sulfopolymer.

[0069] It will be understood that the phrase high-load formulation generally refers to a concentrated formulation; such formulations may be diluted for use as described herein.

[0070] High shear (mixing) as used herein refers to the production of high shear forces primarily by using a rotor rotating at high speed to direct the material outwards towards a fixed stator and thereby shear the mixed form of the material. Variable rotor speeds provide the ability to uniquely customize the amount of shear energy for each application. This technology can be used to mix liquids, solids or gases into liquids that are not usually easy to mix with them. High shear mixing can be used for homogenization, dispersion, emulsification or diameter reduction.

[0071] As used herein, an inert ingredient or component refers to any substance other than an active ingredient (e.g., an agrochemical active ingredient) that is intentionally included in a formulation. Non-limiting examples of inert ingredients include emulsifiers, solvents, carriers, adhesives, surfactants, drift control agents, drought control agents, fragrances, dyes, and adjuvants with spreader activity, rainfast activity, and the like.

[0072] As used herein, an inert kit refers to a premixed composition that provides one or more inert components for use in an agrochemical formulation. The inert kit is added to a formulation (e.g., a concentrated formulation) containing at least one active agrochemical ingredient, for example, while the formulation is being diluted for application to plants, plant parts, or culture media. One of ordinary skill in the art will recognize that different inert kits can be formulated to pair with different active ingredient formulations.

[0073] Inert packages can provide at least one adjuvant function, such as an emulsifier, a sticking agent, a drift control agent, a spreader, a rainfastness agent, etc. Other examples of inert packages provide two or more such adjuvant functions. A "complete" inert package provides all adjuvant functions required for use with a particular agrochemical formulation.

[0074] For example, the inert cover can include at least one sulfopolymer as described herein. In particular embodiments, the sulfopolymer in the inert cover is a sulfopolyester, such as a sulfopolyester comprising a sulfoisophthalate moiety derived, for example, from sodium sulfoisophthalic acid (5-SSIPA) or an ester or amide thereof.

[0075] As used herein, a lipophilic compound is a compound that tends to bind to or dissolve in lipids or fats. Typically, a lipophilic compound has a solubility in water that is in the "slightly soluble" range or lower. For a "slightly soluble in water" compound, the amount of water required to dissolve one gram of the compound will range from 30 ml to 100 ml or more. Compounds with a solubility less than "slightly soluble" in water will require a larger amount of water to dissolve the compound.

[0076] As used herein, loading refers to the amount of material in a given volume. For agricultural formulations, loading generally refers to the amount of active ingredient in the formulation, expressed as a percentage of g / liter.

[0077] Oil dispersion (OD) used herein refers to a system in which the distribution particles (liquid or solid) of the material are uniformly dispersed in the continuous phase of the oil. Water-sensitive active agents are usually mixed with solid dry preparations because they are hydrolytically unstable active agents. OD enables water-sensitive active agents to be mixed with liquid preparations. In OD, water-sensitive solid or liquid particles are uniformly suspended in the oil phase. The oil in the preparation has the additional features of strengthening and spraying the leaves on the blade by hydrophobic affinity. Because the oil dispersion is optionally water-free, it is not necessary to add a biocide as a preservative, which is the advantage of using the oil dispersion.

[0078] OD preparations may disintegrate before use and require stirring and energy to redisperse. For example, active ingredient can crystallize or settle out from oil solution. For example, solid component can fully settle out to form block, or liquid can settle out to form discrete layer. In the embodiment that provides, the composition and / or block of sedimentation can be easily resuspended. In order to avoid this disintegration, adjuvant can be added to promote or support dispersion. Sulfonic polymers as herein described are suggested to support OD dispersion and prevent or reduce the possibility of disintegration, and / or make preparation also easy to redisperse even when not significantly stirring. In one embodiment or in combination with any embodiment of mentioning, OD is diluted with water before using, for example, in the field.

[0079] In one embodiment, when OD is mixed with water, inversion can occur. For example, initially, the aqueous phase is dispersed as small droplets in the oil phase. Upon dissolution in water, the oil droplets are dispersed in the continuous aqueous phase. The sulfopolymers described can promote this type of inversion.

[0080] As used herein, an oil-in-water emulsion refers to a mixture in which oil is dispersed as very fine droplets in a continuous aqueous phase. Optionally, one or more active ingredients may also be included in the oil-in-water emulsion; depending on the active ingredient, it may be included in the oil phase, the aqueous phase, or both.

[0081] As used herein, a pest is any organism (including microorganisms) in an environment where the presence of the pest is undesirable. It will be appreciated that in illustrative examples, the pest is a plant (e.g., weeds), a microorganism (e.g., fungi, bacteria, nematodes, etc.), an insect (including any stage or life cycle of an insect, such as eggs, larvae, or adults), a mollusk (e.g., a slug or snail), or a larger animal (e.g., a rodent, bird, fish, etc.).

[0082] As used herein, pesticides include any substance or mixture of substances intended for use in preventing, destroying, repelling or mitigating any unwanted pest, wherein a pest is any organism that may have an effect on crops. There are many subclasses of pesticides, including: insecticides, herbicides, rodenticides, bactericides, fungicides, larvicides, acaricides, molluscicides, nematicides, etc.

[0083] As used herein, phase refers to the physically distinct forms of matter. While they are conventionally considered to be in the form of solids, liquids, gases, or plasmas, there are other phases that are important for mixtures. For example, in an emulsion, there are two phases: a continuous phase and a dispersed phase that occupies discrete regions of space. The dispersed phase can coalesce but remains the dispersed phase until and unless it coalesces to form a continuous connection throughout a given volume, at which point it becomes the continuous phase. The dispersed phase can be discrete droplets of liquid, solids, or bubbles within the continuous phase.

[0084] As used herein, phytotoxicity refers to any form of plant damage. Phytotoxicity can cause one or more of the following in plants: leaf tip or edge burn, general yellowing, stunting, leaflet size reduction, leaf curling, cupping and other distortions, dark green color (typical of triazole fungicides), mottling, delayed flowering, delayed rooting, delayed or reduced seed or fruit development, or plant death. A "substantially non-phytotoxic" substance, compound, composition, or formulation will not produce any of the aforementioned side effects when applied to a plant.

[0085] In a phytotoxicity test, a substance, compound, composition, or formulation is applied to a target plant and the plants are visually observed over a period of time, such as one hour, one day, one week, multiple weeks, one month, or an entire growing season. Phytotoxicity can be measured visually (e.g., leaf impact or overall plant health observation) or quantitatively (e.g., the amount of fruit or seeds produced). If the substance, compound, composition, or formulation is substantially non-phytotoxic, there will be no statistically relevant difference in appearance or yield relative to untreated plants.

[0086] Plant: As used herein, the term "plant" refers to the entire plant, including any root structure, vascular tissue, vegetative tissue, and reproductive tissue. "Plant part" includes any part of a plant. For example, when a tree is harvested, the tree separated from its roots becomes a plant part. Plant parts also include flowers, fruits, leaves, vegetables, stems, roots, branches, seeds, and combinations thereof that are less than the entire plant.

[0087] Powder as used herein refers to particles in the range of 0.5-5000 μM.

[0088] As used herein, a preservative is any chemical that inhibits or retards the decomposition of a product or formulation, such as an agrochemical formulation.

[0089] As used herein, rainfastness is a measure of how well a substance resists being washed away by rainfall or irrigation after application to a surface (e.g., a leaf surface). A formulation is considered rainfast after application when the formulation has dried sufficiently or been absorbed by plant tissue to remain effective after rainfall or irrigation. The degree of rainfastness of agrochemical formulations is highly variable.

[0090] This area recognizes the method for measuring or measuring the rain fastness of preparation.For example, test can be based on the visual determination of the amount of the marker dye residue on blade (or other test application surface) after " rain " or other washing.For example, before being applied to the surface, fluorescent dye or colored dye can be added in the preparation.After making the preparation drying, can visually or use fluorescence detector or colorimetric detector to determine the amount of dye.After raining or being exposed to water, blade or surface drying and again assess residual dye.The indication of the effective rain fastness of modified preparation is provided with the comparison of control preparation.

[0091] Rosin as used herein refers to a solid form of resin obtained from pine trees and some other plants, primarily conifers, which is produced by heating fresh liquid resin to evaporate the volatile liquid terpene components. Unrefined, it is translucent and varies in color from yellow to black; its softening point is generally below the boiling point of water. Rosin consists primarily of various resin acids, particularly abietic acid and pimaric acid. The three main categories / sources of rosin are tall oil rosin, gum rosin, and wood rosin. For commercial use, rosin is typically purified and / or derivatized to provide different properties. Derivatization can include disproportionation (which can provide improved stability), hydrogenation (which provides stability, different chemical compatibility, reduced odor, and / or enhanced transparency), or esterification (which increases stability, changes molecular weight and acid number, and can change softening / melting point and T g ) One or more of. Numerous commercially available rosins, including rosin esters and rosin resins, can be used in the formulations, compositions, and methods provided herein.

[0092] As used herein, solvent dispersion refers to a system in which distributed particles of a material are uniformly dispersed in a continuous phase of a substantially water-immiscible solvent. Oil dispersions are a variety of solvent dispersions.

[0093] As used herein, the term atomization refers to the ability of a liquid or gel to be driven or dispersed in the air as particles, droplets or droplets. The liquid or gel can be sprayed, blown or forced into or through the air in the form of droplets or aerosols, optionally through a nozzle, usually under pressure.

[0094] As used herein, spreading refers to the effect or ability of a formulation (e.g., a mixture, dispersion, or emulsion) to extend, distribute, cover, or coat a specific area. In specific embodiments, spreading more particularly refers to the effect or ability of a formulation to overcome at least a portion of the hydrophobicity of the surface of a plant or plant part, thereby allowing the formulation to obtain better contact and / or coverage with the formulation. The ability of a formulation to spread can be measured using standard tests known to those skilled in the art, such as contact angle measurements, droplet counts, or area % coverage.

[0095] The ability of a liquid composition to spread on a surface is related to the surface tension of the liquid. Thus, surfactants, detergents and other compounds that reduce surface tension can be used to increase spreading.

[0096] High spreading is a relative term that refers to a characteristic of a liquid composition that has a higher level of spreading (wetting) than a composition to which it is being compared. For example, if a formulation containing a spreader has higher spreading properties (better wetting) than a comparable formulation that does not contain a spreader, or contains less spreader, or contains another spreader that is less effective, then the spreader / agent provides higher spreading for the formulation containing it. For example, the contact angles of two compositions can be measured and compared using standard techniques. It is generally believed that a lower contact angle indicates better wetting (lower surface tension and higher coverage area). In one embodiment or in combination with any of the mentioned embodiments, there is now provided a formulation or composition that has a high coverage area or spreading / wetting, even with a high contact angle.

[0097] In another embodiment or in combination with any of the mentioned embodiments, the relative spreading of two formulations can be determined by measuring the actual coverage of each formulation when applied to a surface, such as a leaf surface or a test surface; for example, a high-spreading formulation will have at least 10%, or at least 20%, or at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, or at least 80%, or at least 90%, or at least 100%, or more than 100% greater coverage than a comparative formulation (e.g., a formulation containing a test spreader adjuvant compared to a formulation lacking a spreader, or a formulation containing a different spreader adjuvant compared to a formulation).

[0098] As used herein, stable refers to the ability of a system (e.g., an emulsion or suspension) to resist changes in its physicochemical properties over time. Formulation stability can be viewed as having one of the following aspects: initial stability (the ability of a formulation to resist phase separation) and redispersibility (the ability to readily undergo reverse phase separation when phase separation occurs). Thus, a "stable" formulation resists phase separation for at least the initial time period defined below; or is easily redispersed using the test method described below.

[0099] As used herein, a formulation (e.g., a formulation concentrate) is "stable" if it does not phase separate (as determined by the naked eye) when tested for uniform dispersion under the following conditions: 54°C and 1 atmosphere of pressure for 14 days in a container having a height (or shoulder, if present) to diameter ratio (H / D) of anywhere between 20 and 0.7 and a diameter of at least 0.5 inches. With respect to redispersion, a formulation or formulation concentrate is "stable" if it exhibits phase separation according to the above test method and can be redispersed manually using at least one and no more than 10 inversion cycles (inversion and return to its upright position being one cycle), each inversion cycle being completed within 2 seconds and without any other induced vibration, agitation, or shaking, and no visible phase separation is apparent to the naked eye after a standing period of 5 minutes thereafter.

[0100] For example, a redispersible stable formulation may undergo 50%, 40%, 30%, 20%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2% or 1% (in each case no more than) phase separation over a two week period when stored at 54°C and 1 atmosphere (e.g., Figure 7 and the measurements described in the corresponding text). Separation can be tested over shorter time periods, such as one hour, two hours, three hours, four hours, six hours, 12 hours, 18 hours, 20 hours, 24 hours, two days, three days, four days, five days, six days, seven days, eight days, nine days, ten days, eleven days, twelve days, or thirteen days. In those cases where the formulation shows phase separation within the first 14 days after its initial mixing, the formulation is still considered stable if it is redispersible according to the above method. In other embodiments, a formulation will be considered stable if it experiences less than 50%, less than 40%, less than 30%, less than 20%, less than 10%, or less than 5% separation, or no visible phase separation, under the test conditions for two weeks, or three weeks, or one month, or two months, or three months, or six months, or a period of time during the growing season; or if any phase separation is observed during this period, it can be reversed by redispersion.

[0101] Similarly, if the formulations can be redispersed according to the above test method, they are considered stable even if they phase separate. Redispersion can be performed by any of a variety of methods, such as simple mixing with or without high shear mixing, shaking, vibration, etc. To determine the ease of redispersion, a formulation is considered stable if it can be redispersed by the above method. In one embodiment, the formulation can be redispersed in the test method by as little as a single manual inversion, or no more than two inversions, or no more than three inversions, or no more than four inversions, or no more than five inversions, or no more than six inversions, or no more than seven inversions, or no more than eight inversions, or no more than nine inversions, or no more than 10 inversion cycles, and without any other induced vibration, agitation, or shaking. In one embodiment, after any of the above ranges of tumbling numbers, the formulation exhibits no phase separation evident to the naked eye when allowed to stand for a period of at least 10 minutes, or at least 15 minutes, or at least 30 minutes, or at least 60 minutes, or at least 90 minutes, or at least 120 minutes, or at least 3 hours, or at least 5 hours, or at least 10 hours, or at least 12 hours, or at least 16 hours, or at least 24 hours, or at least 36 hours, or at least 2 days, or at least 4 days, or at least 7 days, or 10 days after said number of tumblings.

[0102] In addition to stability at ambient temperature, in one embodiment or in combination with any of the mentioned embodiments, the formulation can be stable at low temperatures (e.g., 5°C for 2 weeks) (initial stability or redispersibility stability), or stable under temperature fluctuations (e.g., temperature cycling every 12 hours, every day, every 3-5 days, every 7 days, every two weeks, or seasonally) between higher and lower temperatures (e.g., between 2°C lower and 60°C higher (35.6°F to 140°F), or between 5°C lower and 54°C higher (41°F to 129.2°F), or between 4.4°C lower and 37.8°C higher (40°F to 100°F)). It should be understood that such fluctuating temperature stability measurements are intended to capture the stability of formulations that are intended to be maintained under realistic conditions in locations that do not have consistent temperature maintenance, such as in storage facilities or on farms. Thus, stability at variable temperatures can also be examined by selecting formulations, for example, by storing them for a period of at least 24 weeks, at least two weeks or more than two months (e.g., at least two weeks or more than two months), three months or more, six months or more, nine months or more, or one year or more) in an environment or in a facility without any (or reliable) temperature maintenance, so as to expose the formulation to natural temperature fluctuations. Natural temperature fluctuations herein refer to temperature variations during the day (within a day), temperature variations due to weather patterns, temperature variations due to the passage of seasons, and temperature variations due to natural climate cycles.

[0103] As used herein, a sticking agent or sticking adjuvant refers to a compound or ingredient used in an agrochemical formulation that affects the spraying properties of the formulation so that it "sticks" to a surface better than a formulation that does not contain the compound or ingredient. Sticking adjuvants provide one or more of the following: increased surface contact between the formulation and the surface to which it is sprayed; reduced runoff; and / or increased surface penetration. At least some sticking adjuvants exhibit surfactant activity.

[0104] As used herein, surface tension refers to the conditions that exist at the free surface of a liquid.Surface tension is a measure of the force required to pull a floating ring away from the surface of a liquid and is measured in dynes / cm.

[0105] As used herein, surfactant refers to a compound that reduces the surface tension (or interfacial tension) between two liquids, between a gas and a liquid, or between a liquid and a solid. Surfactants can serve as detergents, wetting agents, emulsifiers, foaming agents, and dispersants. Surfactants can be amphoteric, nonionic, and / or anionic. In agricultural chemical formulations, surfactants can affect one or more of the following: emulsification, dispersion, spreading, and / or wetting of active ingredients.

[0106] As used herein, a suspension refers to a heterogeneous mixture comprising solid particles dispersed in a liquid, wherein the solid particles are not completely dissolved in the liquid. The particles may be visible to the naked eye and may eventually settle, although the mixture is classified as a suspension only if the particles do not settle. It should be understood that if the formulation is redispersible as described above, the formulation continues to be classified as a suspension even if the particles have settled.

[0107] As used herein, a suspension concentrate (SC) refers to a suspension of small particles of a solid active ingredient (wherein the content of at least one active agrochemical compound / ingredient is at least twice the content used in the application state or RTU formulation) in a liquid phase (e.g., water) that is intended to be diluted with water before use. Suspension concentrate formulations (SC) may also be referred to as flowable concentrate formulations. The liquid phase of the SC may be based on a water-immiscible solvent (e.g., oil), or water, depending on the specific active ingredient and the application involved. The concentrate is typically diluted into a larger amount of water at the time of use, for example, on the farm (for agrochemical suspension concentrates).

[0108] When suspension concentrates are stored over time, it is common for at least some of the solid particles to settle to the bottom of the container. This settling can result in very hard lumps (lumps) at the bottom of the container that require significant stirring to break up and resuspend. In many cases, this settling results in an increase in particle size in the tank mix, which can clog or block nozzles and lines and render the formulation unusable. Some SC formulations require significant stirring to ensure that the solid particles are fully dispersed, thereby avoiding equipment blockage and enabling complete addition to the tank.

[0109] As used herein, ready-to-use refers to a formulation that does not require further dilution prior to administration.

[0110] As used herein, a tank mix refers to two or more chemical pesticides, inert ingredients, components or formulations that are mixed in a spray tank at or just prior to spray application.

[0111] As used herein, thickener refers to a material whose primary function is to increase the viscosity of a fluid.

[0112] Total water hardness refers to the amount of dissolved calcium and magnesium ions in a water sample. Total water hardness can be expressed in parts per million ("ppm").

[0113] As used herein, volatilization refers to the process of evaporating a dissolved sample or subliming a solid residue.

[0114] As used herein, water hardness is a measure of the amount of minerals present in water. Hardness is typically expressed as milligrams of dissolved calcium carbonate and magnesium carbonate per liter of water; however, other divalent and trivalent metal elements can contribute to water hardness.

[0115] As used herein, water-immiscible refers to a liquid, typically a solvent, that has limited or insignificant ability to mix with water or water under ambient conditions. That is, in the absence of a surfactant, a water-immiscible solvent that mixes with water will form two layers, although there may be slight solubility. The term is not absolute, and it is recognized that hydrophobic liquids (such as oils and other hydrophobic solvents) are actually capable of mixing with water to a limited extent. Therefore, in one embodiment or in combination with any of the embodiments mentioned, at approximately 25°C and approximately 1 atmosphere, the water-immiscible solvent will be less than 0.1wt%, less than 0.2wt%, less than 0.3wt%, less than 0.4wt%, less than 0.5wt%, less than 0.75wt%, less than 1wt%, less than 1.25wt%, less than 1.5wt%, less than 2wt%, less than 2.5wt%, less than 3wt%, less than 5wt%, less than 7wt%, less than 8wt%, or less than 9wt%, or 0.1-10wt% soluble in water / can be mixed with water. Examples of water-immiscible solvents include any of the active agents mentioned throughout this disclosure as being immiscible with water (or in other words, having a solubility / miscibility with water of less than 10 wt % at 25° C. and 1 atmosphere), or mineral oil, vegetable oil, seed oil, methylated seed oil, banana oil, white mineral spirits, toluene, benzene, xylene, SOLVESSO TM Aromatic 100, SOLVESSO TM Aromatic 150, SOLVESSO TM Aromatic 150 ND, SOLVESSOTM Aromatic 200 ND SOLVESSO TM Aromatic 200, SOLVESSO TM 100. SOLVESSO TM 150. SOLVESSO TM 150 ND, SOLVESSO TM 200、SOLVESSO TM 200 ND, acetophenone, isopropyl acetate, tert-butyl acetate, methyl n-acetone, propyl acetate, methyl isobutyl ketone, isobutyl acetate, n-propyl propionate, butyl acetate, methyl isoamyl ketone, amyl acetate, n-butyl propionate, methyl p-amyl acetate, n-amyl methyl ketone, isobutyl isobutyrate, cyclohexanone, diisobutyl ketone, n-amyl propionate, ethyl 3-ethoxypropionate, 2-ethylhexyl acetate, ethylene glycol monobutyl ether, isophorone, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, 2-heptanol, or 2-ethylhexanol.

[0116] As used herein, a water-in-oil emulsion refers to a mixture in which water is dispersed as very fine droplets in a continuous phase of oil or other water-immiscible solvent. Optionally, one or more active ingredients may also be included in the water-in-oil emulsion; depending on the active ingredient, it may be contained in the oil phase, the water phase, or both. A water-in-oil emulsion is an example of an emulsion of water in a water-immiscible solvent.

[0117] (III) Sulfopolymers / sulfopolyesters useful for formulations

[0118] The sulfopolymers described herein are water-dispersible sulfopolymers. The water-dispersible sulfopolymers can be any sulfopolymer comprising at least one sulfomonomer residue. In one embodiment or in combination with any of the embodiments mentioned, the sulfomonomer residue comprises a salt of a sulfoisophthalate moiety derived from, for example, sodium sulfoisophthalic acid (5-SSIPA) or an ester thereof. The sulfoisophthalate moiety can also be derived from other metal sulfoisophthalic acids and their esters. For example, the associated metal M is a monovalent metal, such as Na + 、Li + , or K + .

[0119]

[0120] In addition, salts of the sulfoisophthalate moiety can also be derived from non-metallic sulfoisophthalic acids and esters thereof. As an example, the metal sulfonate group can be replaced by an ammonium sulfonate group, such as a tertiary or quaternary ammonium cation, for example, ammonium, hydrazinyl, N-methylpyridinium, methylammonium, butylammonium, diethylammonium, triethylammonium, tetraethylammonium, and benzyltrimethylammonium.

[0121] In addition to the sulfoisophthalate moieties, the sulfopolymer may include residues of one or more of a diol monomer, a dicarboxylic acid monomer, and / or a diamine monomer.Examples of sulfopolymers include sulfopolyesters, sulfopolyamides, or sulfopolyesteramides.

[0122] In one embodiment or in combination with any of the aforementioned embodiments, the sulfopolymer can be a linear polymer having an average molecular weight (MW) of at least 2 kDa. In one embodiment or in combination with any of the aforementioned embodiments, the sulfopolymer has an average MW of 2-20 kDa, 4-18 kDa, 5-15 kDa, 5-12 kDa, or 7-10 kDa. Additionally, the sulfopolymer can have a T of at least 30°C. g In addition, the sulfopolymer may have a T ranging from 30°C to 120°C, 35°C to 100°C, 40°C to 90°C, 45°C to 80°C, and 50°C to 70°C. g .

[0123] The water-dispersible sulfopolyesters used in accordance with the present disclosure are prepared from monomer residues comprising dicarboxylic acid monomer residues, sulfomonomer residues, and diol monomer residues. The sulfomonomer can be a dicarboxylic acid, a diol, or a hydroxycarboxylic acid. Thus, the term "monomer residue" as used herein refers to the residue of a dicarboxylic acid, a diol, or a hydroxycarboxylic acid. As used herein, a "repeating unit" or "repeat unit" refers to an organic structure having two monomer residues bonded through a carbonyloxy group. The sulfopolyesters used in accordance with the present disclosure contain substantially equal molar amounts of acid residues (100 mole%) and diol residues (100 mole%) reacted in substantially equal proportions such that the total number of moles of repeat units equals 100 mole%.

[0124] Sulfopolyesters are high molecular weight amorphous polyesters that are typically dispersed directly in water without the need for the introduction of organic cosolvents, surfactants, or amines. Sulfopolyesters differ primarily in their chemical composition (i.e., they are composed of 5-sodium sulfoisophthalic acid (5-SSIPA) and various combinations of other materials, such as terephthalic acid (TPA), isophthalic acid (IPA), 1,4-cyclohexanedicarboxylic acid (1,4-CHDA), ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol (TEG), 1,4-cyclohexanedimethanol (CHDM), and / or neopentyl glycol (NPG). The sulfopolyesters described herein have a MW ranging from 2 kDa to 15 kDa. The temperature at which a glassy polymer becomes rubbery upon heating, and the temperature at which it becomes glassy upon cooling, is referred to as the "glass transition temperature (Tg). g )". Therefore, various sulfopolyester polymers have different average T g Sulfopolyesters are solid to semisolid polymers and require ample mixing time and warm water to prepare concentrated dispersions.

[0125] An exemplary sulfopolymer is sulfopolyester 2 (SPE2), which is a sulfopolyester that disperses directly in a mixture of ethanol and water at room temperature or in warm water without the aid of surfactants or other additives. Low viscosity aqueous dispersions can be prepared at polymer concentrations up to 30 wt%. The aqueous or hydroalcoholic dispersions have a water-like viscosity at polymer concentrations up to 20 wt%. The SPE2 polymer facilitates the dispersion of hydrophobic ingredients in water-based formulations, and films formed from the dispersions are clear and glossy at room temperature. SPE2 is more compatible with higher levels of alcohol than SPE1. The T of SPE2 is g is 48℃.

[0126] Another exemplary sulfopolymer is sulfopolyester 1 (SPE1), a sulfopolyester that disperses directly in hot water without the aid of amines, cosolvents, surfactants, or other additives. SPE1 polymer forms a transparent film from an aqueous dispersion at room temperature. g is 38°C. Because of its low T g , SPE1 forms a flexible membrane.

[0127] Typically, sulfopolymer dispersions, especially aqueous dispersions of sulfopolyesters, will have a neutral to slightly acidic pH, such as 5-7.5. Specific exemplary sulfopolymers will have a pH of 5.5 to 7, or 5.8 to 6.8, or 6.0 to 6.6, or 5.8 to 6.5.

[0128] The mole percentages provided in this disclosure can be based on the total moles of acid residues, the total moles of diol residues, or the total moles of repeating units. For example, a sulfopolyester containing 30 mole% of a sulfomonomer, which can be a dicarboxylic acid, diol, or hydroxycarboxylic acid, based on the total repeating units, means that the sulfopolyester contains 30 mole% of the sulfomonomer out of a total of 100 mole% of the repeating units. Thus, there are 30 moles of sulfomonomer residues per 100 moles of repeating units. Similarly, a sulfopolyester containing 30 mole% of a dicarboxylic acid sulfomonomer including a sulfoisophthalic acid moiety, based on the total acid residues, means that the sulfopolyester contains 30 mole% of the sulfomonomer out of a total of 100 mole% of the acid residues. Thus, in the latter case, there are 30 moles of sulfomonomer residues per 100 moles of the acid residues.

[0129] The sulfopolyesters described herein have an inherent viscosity, hereinafter abbreviated as "Ih.V.", of at least 0.1 dL / g, e.g., at least 0.2, at least 0.3 dL / g, or at least 0.4 dL / g, and up to 0.5 dL / g, measured in a 60 / 40 parts by weight phenol / tetrachloroethane solvent at 25° C. and a concentration of 0.5 g of sulfopolyester in 100 ml of solvent. The term "polyester" as used herein includes both "homopolyester" and "copolyester" and refers to a synthetic polymer prepared by the polycondensation of a difunctional carboxylic acid with a difunctional hydroxy compound. As used herein, the term "sulfopolyester" refers to any polyester comprising a sulfomonomer including a sulfoisophthalic acid moiety. Typically, the difunctional carboxylic acid is a dicarboxylic acid and the difunctional hydroxy compound is a dihydric alcohol, such as ethylene glycol and diol. Alternatively, the sulfopolyester contains a hydroxy acid monomer, such as p-hydroxybenzoic acid, and the difunctional hydroxy compound can be an aromatic nucleus with two hydroxy substituents, such as hydroquinone. As used herein, the term "residue" refers to any organic structure introduced into a polymer by a polycondensation reaction involving the corresponding monomer. Thus, a dicarboxylic acid residue can be derived from a dicarboxylic acid monomer or its related acid halide, ester, salt, anhydride, or mixtures thereof. Thus, as used herein, the term dicarboxylic acid is intended to include dicarboxylic acids and any derivatives of dicarboxylic acids, including their related acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, or mixtures thereof, which can be used in polycondensation processes with diols to prepare high molecular weight polyesters.

[0130] The sulfopolyesters of the present disclosure include one or more dicarboxylic acid residues. Depending on the type and concentration of the sulfomonomer, the dicarboxylic acid residues may comprise from 60 to 100 mole % of acid residues. Other examples of concentration ranges for dicarboxylic acid residues include from 60 to 95 mole % and from 70 to 95 mole %. Examples of dicarboxylic acids that may be used include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, or mixtures of two or more of these acids. Thus, suitable dicarboxylic acids include succinic acid; glutaric acid; adipic acid; azelaic acid; sebacic acid; fumaric acid; maleic acid; itaconic acid; 1,3-cyclohexanedicarboxylic acid; 1,4-cyclohexanedicarboxylic acid; diethylene glycol; 2,5-norbornanedicarboxylic acid; phthalic acid; terephthalic acid; 1,4-naphthalene dicarboxylic acid; 2,6-naphthalene dicarboxylic acid; biphenyl; 4,4'-dibenzoic acid; 4,4'-sulfonyldibenzoic acid; and isophthalic acid. Examples of dicarboxylic acid residues include isophthalic acid, terephthalic acid, and 1,4-cyclohexanedicarboxylic acid, or, if diesters are used, dimethyl terephthalate, dimethyl isophthalate, and dimethyl 1,4-cyclohexanedicarboxylate, with isophthalic acid and terephthalic acid residues being exemplary. Methyl dicarboxylates are specific exemplary embodiments; higher alkyl esters, such as ethyl, propyl, isopropyl, and butyl, are also acceptable. Aromatic esters, particularly phenyl esters, may also be used.

[0131] The sulfopolyester comprises from 4 to 40 mol % of the residue of at least one sulfomonomer having two functional groups and one or more sulfonate groups attached to an aromatic or alicyclic ring, wherein the functional groups are hydroxyl, carboxyl, or a combination thereof, based on the total repeating units. Further examples of concentration ranges for the sulfomonomer residues are from 4 to 35 mol %, from 8 to 30 mol %, and from 8 to 25 mol %, based on the total repeating units. The sulfomonomer can be a dicarboxylic acid or ester thereof containing a sulfonate group, a diol containing a sulfonate group, or a hydroxy acid containing a sulfonate group. The term "sulfonate" refers to a sulfonate having the structure "-SO3 - The term "sulfonate" is a salt of a sulfonic acid having the structure "-SO3M" where M is the cation of the sulfonate. The cation of the sulfonate can be a metal ion such as Li + 、Na + , K +etc. Alternatively, the cation of the sulfonate salt can be non-metallic, such as a nitrogenous base as described in U.S. Patent No. 4,304,901. The nitrogenous cation is derived from a nitrogenous base, which can be an aliphatic, alicyclic, or aromatic compound. Examples of such nitrogenous bases include ammonia, dimethylethanolamine, diethanolamine, triethanolamine, pyridine, morpholine, and piperidine. Because monomers containing nitrogenous sulfonates are generally thermally unstable under the conditions required to prepare polymers in melt form, the disclosed method for preparing sulfopolyesters containing nitrogenous sulfonate groups is to disperse, dissipate, or dissolve a polymer containing the desired amount of sulfonate groups in the form of its alkali metal salt in water and then exchange the alkali metal cations for the nitrogenous cations.

[0132] When monovalent alkali metal ions are used as the cation of the sulfonate, the resulting sulfopolyester is fully dispersible in water, with the rate of dispersion depending on the amount of sulfomonomer in the polymer, the temperature of the water, the surface area / thickness of the sulfopolyester, etc. When divalent metal ions are used, the resulting sulfopolyester is not readily dispersible by cold water but is more readily dispersible by hot water. The use of more than one counterion in a single polymer composition is possible and can provide a means of adjusting or fine-tuning the water responsiveness of the resulting article. Examples of sulfomonomer residues include monomer residues in which the sulfonate group is attached to an aromatic or alicyclic ring of an aromatic dicarboxylic acid or residue thereof, such as a benzene ring; naphthalene; biphenyl; oxybiphenyl; sulfonylbiphenyl; and methylenediphenyl or cycloaliphatic rings, such as cyclohexyl; cyclopentyl; cyclobutyl; cycloheptyl; and cyclooctyl. Other examples of sulfomonomer residues useful in the present disclosure are metal sulfonates of sulfophthalic acid, sulfoterephthalic acid, sulfoisophthalic acid, or combinations thereof. Other examples of sulfomonomers that may be used are 5-sodiosulfoisophthalic acid and its esters. If the sulfomonomer residue is derived from 5-sodiosulfoisophthalic acid, typical sulfomonomer concentrations range from 4 to 35 mole%, 8 to 30 mole%, and about 8 to 25 mole%, based on the total moles of acid residues.

[0133] The sulfomonomers used to prepare sulfopolyesters are known compounds and can be prepared using methods well known in the art. For example, sulfomonomers in which the sulfonate group is attached to an aromatic ring can be prepared by sulfonating an aromatic compound with oleum to obtain the corresponding sulfonic acid, which is then reacted with a metal oxide or a base, such as sodium acetate, to produce the sulfonate salt. Methods for preparing various sulfomonomers are described, for example, in U.S. Patents 3,779,993; 3,018,272; and 3,528,947.

[0134] When the polymer is in dispersed form, polyesters can also be prepared using, for example, sodium sulfonate and ion exchange methods to replace the sodium with a different ion, such as zinc. This type of ion exchange procedure is generally preferred over preparing polymers with divalent salts because sodium salts are generally more soluble in the polymer reactant melt phase.

[0135] The sulfopolyester comprises one or more diol residues, which may include aliphatic, cycloaliphatic, and / or aralkyl glycols. Examples include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, and polyalkylene glycols. Other suitable diols include cycloaliphatic diols having 6 to 20 carbon atoms and aliphatic diols having 3 to 20 carbon atoms. Specific examples of these diols are ethylene glycol, propylene glycol, 1,3-propylene glycol, 2,4-dimethyl-2-ethylhexane-1,3-diol, 2,2-dimethyl-1,3-propylene glycol, 2-ethyl-2-butyl-1,3-propylene glycol, 2-ethyl-2-isobutyl-1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethanol, 2,2,4-trimethyl-1,6-hexanedi-1-thiodiethanol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and terephthalate glycol. The sulfopolyester may also include a mixture of diols.

[0136] Diols also include multifunctional alcohols (polyols). Examples of polyols include neopentyl glycol; butanediol; 1,4-butanediol, hexanediol; 1,6-hexanediol; polyglycols such as diethylene glycol or triethylene glycol; triols such as glycerol, trimethylolethane, trimethylolpropane; and other higher functional alcohols such as pentaerythritol, sorbitol, mannitol, etc.

[0137] The diol residues may include from 25 mole % to 100 mole % of residues of poly(ethylene glycol) having the structure

[0138] H-(OCH2-CH2)n-OH

[0139] wherein n is an integer in the range of 2 to 500. Non-limiting examples of low molecular weight polyethylene glycols are diethylene glycol, triethylene glycol, and tetraethylene glycol, for example, where n is 2 to 6. Of these low molecular weight glycols, diethylene glycol and triethylene glycol are examples. Higher molecular weight polyethylene glycols (abbreviated herein as "PEG"), where n is 7 to 500, include those commercially available under the names PEG is a product of Dow Chemical Company (formerly Union Carbide). Typically, PEG is used in combination with other glycols such as diethylene glycol or ethylene glycol. Based on the value of n, which ranges from greater than 6 to 500, the molecular weight can range from greater than 300 to 22,000 g / mol. Molecular weight and mole % are inversely proportional to each other; specifically, as molecular weight increases, mole % will decrease to achieve a given degree of hydrophilicity. For example, an illustrative example of this concept is to consider that PEG with a molecular weight of 1000 can constitute up to 10 mole % of the total glycol, while PEG with a molecular weight of 10,000 is typically incorporated at a level of less than 1 mole % of the total glycol.

[0140] Due to side reactions that can be controlled by varying process conditions, certain dimers, trimers, and tetramer diols can be formed in situ. For example, varying amounts of diethylene glycol, triethylene glycol, and tetraethylene glycol can be formed from ethylene glycol via an acid-catalyzed dehydration reaction that readily occurs when the polycondensation reaction is carried out under acidic conditions. Buffer solutions well known to those skilled in the art can be added to the reaction mixture to delay these side reactions. However, if the buffer solution is omitted and the dimerization, trimerization, and tetramerization reactions are allowed to proceed, additional composition ranges are possible.

[0141] The sulfopolyesters of the present invention may include from 0 to 25 mole % of the residue of a branching monomer having three or more functional groups, based on the total repeat units, wherein the functional groups are hydroxyl, carboxyl, or a combination thereof. Non-limiting examples of branching monomers are 1,1,1-trimethylolpropane, 1,1,1-trimethylolethane, glycerol, pentaerythritol, erythritol, threitol, dipentaerythritol, sorbitol, trimellitic anhydride, pyromellitic dianhydride, dimethylolpropionic acid, or a combination thereof. Other examples of branching monomer concentration ranges are from 0 to 20 mole % and from 0 to 10 mole %. The presence of branching monomers can lead to many possible benefits of the sulfopolyesters of the present invention, such as the ability to adjust rheology, solubility, and tensile properties. For example, at a constant molecular weight, branched sulfopolyesters will also have a higher concentration of end groups than linear analogs, which can promote post-polymerization crosslinking reactions. However, at high concentrations of branching agents, the sulfopolyesters may tend to gel.

[0142] In one embodiment or in combination with any of the mentioned embodiments, the sulfopolyester described herein comprises the following structural formula (Formula I):

[0143]

[0144] Wherein A is a dicarboxylic acid repeating unit and G is a diol repeating unit. Examples of dicarboxylic acid repeating units A include, but are not limited to, terephthalic acid, isophthalic acid, and / or 1,4-cyclohexanedicarboxylic acid (1,4-CHDA). Examples of diol repeating units G include, but are not limited to, ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol (TEG), neopentyl glycol (NPG), and / or 1,4-cyclohexanedimethanol (CHDM). The following are exemplary monomer residues:

[0145]

[0146] As an example, a sulfopolyester may include the following structural formula:

[0147]

[0148] In one embodiment or in combination with any of the mentioned embodiments, the sulfopolyesters useful in the present disclosure have a glass transition temperature, abbreviated herein as "T g ", as measured on dry polymer using standard techniques well known to those skilled in the art, such as differential scanning calorimetry ("DSC"). The T of the sulfopolyesters of the present disclosure is g The measurements are made using "dry polymer", i.e. a polymer sample in which adventitious or absorbed water is driven off by heating the polymer to a temperature of 200°C and allowing the sample to return to room temperature. Typically, T is obtained by performing a first thermal scan in which the sample is heated to a temperature above the vaporization temperature of water, holding the sample at that temperature until vaporization of the absorbed water in the polymer is complete (as indicated by a large broad endotherm), cooling the sample to room temperature, and then performing a second thermal scan. g The sulfopolyester is measured while drying in a DSC apparatus. Further examples of glass transition temperatures exhibited by the sulfopolyesters are at least 30°C, at least 35°C, at least 40°C, at least 50°C, at least 60°C, at least 65°C, at least 80°C, and at least 90°C, and additionally or alternatively, at most 100°C, or at most 110°C or at most 120°C. Although other T g It is possible that typical glass transition temperatures for the dry sulfopolyesters of the present disclosure are 30°C, 48°C, 55°C, 65°C, 70°C, 75°C, 85°C, and 90°C.

[0149] In one embodiment or in combination with any of the mentioned embodiments, the sulfopolyester comprises:

[0150] (i) residues of one or more dicarboxylic acids;

[0151] (ii) 2 to 20 mole % of the residues of at least one sulfomonomer, based on the total moles of diacid or diol residues, said sulfomonomer having two functional groups and one or more sulfonate groups attached to an aromatic or alicyclic ring, wherein the functional groups are hydroxyl, carboxyl, or a combination thereof;

[0152] (iii) one or more diol residues, of which at least 25 mole % based on the total diol residues is poly(ethylene glycol) having the following structure:

[0153] H-(OCH2-CH2)n-OH

[0154] wherein n is an integer in the range of 2 to 500; and

[0155] (iv) 0 to 25 mole % of the residue of a branching monomer having 3 or more functional groups, based on the total repeating units, wherein the functional groups are hydroxyl groups, carboxyl groups, or a combination thereof.

[0156] In one embodiment or in combination with any of the mentioned embodiments, the sulfopolyester has a T of at least 25°C. g And includes:

[0157] (i) residues of one or more dicarboxylic acids;

[0158] (ii) 4 to 40 mole percent, based on the total repeating units, of the residue of at least one sulfonated monomer having two functional groups and one or more metal sulfonate groups attached to an aromatic or alicyclic ring, wherein the functional groups are hydroxyl, carboxyl, or a combination thereof;

[0159] (iii) one or more diol residues, of which at least 20 mole % based on the total diol residues is poly(ethylene glycol) having the following structure:

[0160] H-(OCH2-CH2)n-OH

[0161] wherein n is an integer in the range of 2 to 500;

[0162] (iv) 0 to 25 mole % of the residue of a branching monomer having 3 or more functional groups, based on the total repeating units, wherein the functional groups are hydroxyl groups, carboxyl groups, or a combination thereof.

[0163] In one embodiment or in combination with any of the mentioned embodiments, the sulfopolymer or sulfopolyester used in the agricultural formulation is not lyophilized.

[0164] As the agricultural industry turns more to blends of active ingredients (e.g., due to the high cost and low likelihood of obtaining registrations for new active ingredients), the complexity of formulations has increased significantly. It is not uncommon for two active ingredients to require different adjuvant sets that are incompatible when combined, leading to crystallization, gelation, or some other form of formulation failure. An adjuvant that is functional and effective across a wide range of formulation types would be advantageous. The sulfopolymers described herein (e.g., sulfopolyesters) have excellent properties as surfactants and can effectively emulsify or suspend countless different types of agrochemical formulations. The sulfopolymers disclosed herein have been shown to be effective in suspension concentrate and emulsion concentrate formulations, providing flexibility to the industry. In addition, the sulfopolymers disclosed herein have beneficial physical properties due to their polymer properties. As a result, once dried on the surface of a leaf or pest, they can improve the rain resistance of the pesticide, making the active ingredient more effective. Alternatively, due to the hydrophobic, hydrophilic nature of the polymer structure, they provide excellent adhesion of aqueous solutions to hydrophobic surfaces, such as the waxy surface of a leaf, thereby providing advantages as an adhesive adjuvant. Thus, unexpectedly but beneficially, the sulfopolymers of the present disclosure would be able to replace more than one adjuvant in a formulation, rendering the formulation stable, more broadly compatible, and / or more cost-effective without additional adjuvants.

[0165] (IV) Recovered sulfopolyester

[0166] The compositions, formulations, and methods described herein can be operated with fresh sulfopolyester or with recycled sulfopolyester. As an example, an exemplary method for recovering sulfopolyester from a composite material comprises: washing the composite material with a solvent composition to remove a portion of surface impurities, thereby forming a washed composite material; wherein the washing is conducted at a temperature at which less than 2% of the water-dispersible sulfopolyester is removed from the composite material; and wherein the composite material comprises a water-dispersible sulfopolyester and one or more water-non-dispersible polymers; opening the washed composite material with water at a temperature greater than 60° C. to produce an aqueous dispersion and the water-non-dispersible polymer; wherein the aqueous dispersion comprises the sulfopolyester; and recovering the sulfopolyester from the aqueous dispersion.

[0167] In one embodiment or in combination with any of the mentioned embodiments, a method of recovering a sulfopolyester comprises washing a material comprised of a sulfopolyester with a wash solvent composition at a temperature less than 60°C, opening the washed composite at a temperature greater than 60°C, and recovering the sulfopolyester from the aqueous dispersion as an aqueous dispersion, a concentrated aqueous dispersion, a solid, or a polymer melt.

[0168] The raw materials used in the methods described herein include a composite material (composite) composed of a sulfopolyester, and the sulfopolyester is recovered from the composite material. The term "composite" refers to a material made from two or more constituent materials having different physical and chemical properties. The individual components remain separate and distinct in the final material. In one embodiment or combination with any of the aforementioned embodiments, the components of the composite material described herein include a water-dispersible sulfopolyester and one or more water-non-dispersible polymers.

[0169] In one embodiment or in combination with any of the mentioned embodiments, the starting material is a composite material comprising fibers.The term "fibers" includes continuous fibers, short fibers, chopped fibers, long fibers, and multicomponent fibers.

[0170] The method for recovering sulfopolyester described herein comprises washing a composite material composed of sulfopolyester with a solvent composition (wash solvent) at a temperature below 60°C for a period of time to remove impurities on the surface of the composite material before opening the fibers.

[0171] Washing the composite material with the wash solvent composition produces a washed composite material and a wash liquor.After washing, the washed composite material is ready to be opened.

[0172] In one embodiment or in combination with any of the mentioned embodiments, the first and second mother liquors comprise aqueous dispersions of sulfopolyesters.

[0173] Water is then removed from the aqueous dispersion to recover the sulfopolyester. Water can be removed from the aqueous dispersion by evaporation or by precipitation to produce recovered sulfopolyester. The term "recovered sulfopolyester" refers to the sulfopolyester obtained by the methods described herein, including a washing step, and can be in the form of a solid containing some water or a concentrated sulfopolyester dispersion. The recovered sulfopolyester can also be in the form of a polymer melt.

[0174] Water can also be evaporated from the aqueous dispersion to obtain sulfopolyester solids. The term "sulfopolyester solids" refers to a solid form of the sulfopolyester that includes some water. The sulfopolyester solids have a moisture content of less than 5 wt.%, relative to the total weight of the solids. In one embodiment or combination with any of the aforementioned embodiments, the moisture content is less than 4 wt.%, or no more than 3 wt.%, or no more than 2 wt.%, or no more than 1 wt.%, or no more than 0.5 wt.%, relative to the total weight of the solids.

[0175] The term "concentrated sulfopolyester dispersion" refers to an aqueous dispersion that has been further processed to remove water to increase the concentration of the sulfopolyester. The sulfopolyester in the concentrated dispersion is from 1 wt.% to 40 wt.%, from 1 wt.% to 35 wt.%, from 5 wt.% to 30 wt.%, from 10 wt.% to 30 wt.%, from 15 wt.% to 30 wt.%, from 20 wt.% to 30 wt.%, or from 25 wt.% to 30 wt.%, relative to the total weight of the concentrated sulfopolyester dispersion.

[0176] In one embodiment or in combination with any of the mentioned embodiments, heat can be applied to the concentrated sulfopolyester dispersion to obtain a polymer melt. The polymer melt contains very little water and forms a solid sulfopolyester upon cooling.

[0177] In one embodiment or in combination with any of the embodiments, the recovered sulfopolyester is in the form of a dispersion comprising the recovered sulfopolyester and a solvent composition, and the dispersion comprises 0.01 wt.% to 5 wt.% impurities, relative to the total weight of the dispersion. The dispersion can be a concentrated recovered sulfopolyester dispersion. The dispersion can also be diluted with water in a volume ratio of 1:1, 1:2, 1:3, 1:4, 1:5, 1:10, 1:20, 1:30, 1:50, or 1:100.

[0178] In one embodiment or in combination with any of the aforementioned embodiments, the recycled sulfopolyester is a washed (pre-washed) recycled sulfopolyester dispersion comprising the recycled sulfopolyester and a solvent composition; wherein the dispersion has an impurity level in the range of 0.01 wt.% to 5 wt.% relative to the total weight of the dispersion. The term "washed recycled sulfopolyester" or "pre-washed recycled sulfopolyester" refers to a sulfopolyester that has been recovered from a material and the recovery process includes a washing (pre-washing) step prior to opening and / or mixing with treated water.

[0179] In one embodiment or combination with any of the mentioned embodiments, the amount of impurities in the dispersions described herein is 0.1 wt.% to 4.5 wt.%, 0.1 wt.% to 4.0 wt.%, 0.1 wt.% to 3.5 wt.%, 0.1 wt.% to 3.0 wt.%, 0.1 wt.% to 2.5 wt.%, 0.1 wt.% to 2.0 wt.%, 0.1 wt.% to 1.5 wt.%, 0.1 wt.% to 1.0 wt.%, 0.1 wt.% to 0.5 wt.%, 0.1 wt.% to 0.4 wt.%, 0.1 wt.% to 0.3 wt.%, or 0.1 wt.% to 0.2 wt.%, relative to the total weight of the dispersion.

[0180] In one embodiment or in combination with any of the mentioned embodiments, the recycled sulfopolyester is a washed (pre-washed) recycled sulfopolyester dispersion comprising a recycled sulfopolyester and a solvent composition, and the dispersion has a reduced impurity concentration of at least 80%, 82%, 85%, 87%, 90%, 92%, 95%, or 97% or more compared to a recycled sulfopolyester dispersion that has not been pre-washed.

[0181] In one embodiment or in combination with any of the embodiments, the recovered sulfopolyester is a washed (pre-washed) recovered sulfopolyester dispersion, wherein the dispersion essentially comprises a two-phase system. The dispersion primarily comprises an aqueous phase and a sulfopolyester phase. In one embodiment or in combination with any of the embodiments, the dispersion may contain impurities as described above. Depending on the impurity, for example, if the impurity is oil, there may be another phase containing a small amount of the impurity.

[0182] The recycled sulfopolyesters described herein include washed (or prewashed) sulfopolyesters in solid form containing 0.01 wt.% to 5 wt.% impurities or a reduced impurity concentration of at least 80% or more compared to a non-prewashed recycled sulfopolyester dispersion.

[0183] The washed (pre-washed) recovered sulfopolyester has a glass transition temperature (Tg) of 25°C to 120°C, 30°C to 120°C, 35°C to 120°C, 40°C to 120°C, 50°C to 120°C, 60°C to 120°C, 65°C to 120°C, 70°C to 120°C, 75°C to 120°C, or 80°C to 120°C. g ).

[0184] The recovered sulfopolyester is hydrophilic and hydrophobic. The recovered sulfopolyester comprises: (A) residues of one or more dicarboxylic acids; (B) 4 to 40 mole%, 5 to 30 mole%, 6 to 20 mole%, 7 to 15 mole%, or 8 to 10 mole%, based on the total repeating units, of residues of at least one sulfomonomer comprising two functional groups and one or more sulfonate groups attached to an aromatic or alicyclic ring, wherein the functional groups are hydroxyl, carboxyl, or a combination thereof; and (C) 10 to 100 mole%, 10 to 90 mole%, 10 to 80 mole%, 15 to 75 mole%, 20 to 60 mole%, 20 to 55 mole%, 20 to 50 mole%, or 20 to 40 mole%, based on the total diol residues, of one or more diol residues having the structure H(OCH2CH2) nwherein n is an integer in the range of 2 to 500, 2 to 100, 2 to 75, 2 to 50, 2 to 25, 2 to 20, 2 to 15, 2 to 10, 2 to 9, 2 to 8, 2 to 7, 2 to 6, 2 to 5, or 2 to 4; and 0 to 25 mole%, 0 to 20 mole%, 0 to 15 mole%, 0 to 10 mole%, 0 to 5 mole%, 0 to 4 mole%, 0 to 3 mole%, 0 to 2 mole%, or 0 to 1 mole% of the residue of a branching monomer having 3 or more functional groups, wherein the functional groups are hydroxyl, carboxyl, or a combination thereof. The dicarboxylic acid and the diol or hydroxyl-containing compound can be any of those mentioned in the present disclosure and can have the same type of repeating units as the sulfopolymer described above.

[0185] (V) Additional components in the formulation

[0186] In addition to the sulfopolymer component, the formulations provided herein may include one or more additional ingredients. For example, in one embodiment or in combination with any of the embodiments mentioned, these additional ingredients may include one or more of the following: active ingredients (e.g., pesticides, fertilizers, plant growth regulators and / or retardants, growth stimulants, flowering / fruiting inhibitors, harvest aids, defoliants, cracking inhibitors), rosin, adjuvants (e.g., emulsifiers, spreaders, stickers, drift control agents, rainfastness agents, surfactants, anti-caking agents, antifreeze agents, components that regulate respiration (water loss or dehydration)), a water-immiscible phase, and other additional optional ingredients (e.g., viscosity reducers, solubilizers, dispersants, defoamers, stabilizers, preservatives, antioxidants, pH adjusters, sequestrants / chelating agents, solvents, additional polymers, flavor enhancers, and colorants or other markers, such as foam markers).

[0187] Those of ordinary skill will recognize that individual active ingredients and other optional components are more or less easily included in different types of formulations. It is within the ordinary skill of the art to select which ingredient or which form of ingredient to use in, for example, a suspension formulation, an emulsion (oil-in-water or water-in-oil), or a solvent dispersion (e.g., an oil dispersion). The selection of one or more ingredients in any one formulation may be affected by the target application, the specific active ingredient used, other ingredients in the formulation, the environment in which the formulation will be used, etc. Similarly, those of ordinary skill in the art can determine, including through empirical studies, the appropriate amount of each additional component in the formulation.

[0188] (i) Active ingredient

[0189] In one embodiment or in combination with any of the embodiments mentioned, the formulations containing sulfopolymers provided herein include one or more agricultural chemical active ingredients. Generally speaking, this can be any chemical or compound with selected biological activity. For example, activating agents include chemicals, compounds and mixtures with acaricidal activity, bactericidal activity, fungicidal activity, herbicidal activity, insecticidal activity, larvicidal activity, nematicidal activity, acaricidal activity, molluscicide activity, fish killing activity, rodent killing activity or armyworm killing activity. Pest repellents are also contemplated. Other activating agents can include chemicals, compounds or mixtures that modify, support or enhance plant growth, such as fertilizers, hormones and / or other growth regulators. Other active ingredients are listed herein. The following paragraphs provide a non-exhaustive list of considered agricultural chemical active ingredients.

[0190] pesticide

[0191] Any formulation containing a sulfopolymer described herein may also optionally include one or more pesticides as active ingredients. Typically, a pesticide is a substance or mixture of substances used to eliminate, repel, or mitigate any unwanted pests, particularly any organisms that may have a negative impact on crops. The term pesticide describes a broad category that includes acaricides (to eradicate ticks and mites), bactericides, fungicides, herbicides, insecticides, larvicides, acaricides, molluscicides, nematicides, piscicides, rodenticides, and sticky fungicides (anti-slime agents). The following paragraphs provide non-limiting representative examples of various pesticides; those of ordinary skill in the art will recognize additional examples, including biological pesticide examples.

[0192] Algaecides: Any of the sulfopolymer-containing formulations described herein may also optionally include one or more algaecides as active ingredients for use in mitigating the effects of algal damage on agricultural production. Useful algaecides include becloxacin, copper dioctoate, copper sulfate, cyclobutanecarbonitrile, diclopyridine, dichlorophen, endosol, fentidine, hydrated lime, mancozeb, quinucamine, quinolamide, simazine, triphenyltin acetate, and triphenyltin hydroxide.

[0193] Bactericides: Any of the sulfopolymer-containing formulations described herein may also optionally include one or more bactericides as active ingredients to mitigate the effects of bacterial damage or predation on agriculture. Useful bactericides include copper hydroxide, copper octoate, copper oxychloride sulfate, copper sulfate pentahydrate, kasugamycin, sodium hypochlorite, and streptomycin sulfate.

[0194] Fungicides: Any of the sulfopolymer-containing formulations described herein may also optionally include one or more fungicides as active ingredients for reducing the effects of fungal damage or predation on agricultural production. Useful fungicides include azoxystrobin, trifloxystrobin, kresoxim-methyl, oxathiapiprolin, oxadiazon, pyraclostrobin, carbendazim, thiabendazole, dimethomorph, vinclozolin, iprodione, dithiocarbamate, imazalil, prochloraz, fluquinconazole, fluepoxiconazole, flutriafol, pentoconazole, bifenthionol, fuconazole, cyproconazole, difenoconazole, hexaconazole, paclobutrazol, propiconazole, tebuconazole, triadimefon, triazole, fenpropimorph, trimorph, fenpropidin, mancozeb, methanamide, chlorothalonil, metamizole, thiram, thiram zinc, captan, captan, folpet, fluazinam, flutolanil, flutolanil, rust The present invention also includes the following: metalaxyl, natural terpene extracts (e.g., carvacrol and thymol), metalaxyl, pyrimidine sulfonate, pyrimidine, orysastrobin, fluoxastrobin, orysastrobin, oxadiazole, prothioconazole, 8-(2,6-diethyl-4-methyl-phenyl)tetrahydropyrazolo[1,2-d][1,4,5]oxadiazepin-7,9-dione, 2,2,-dimethyl-propionic acid-8-(2,6-diethyl-4-methyl-phenyl)-9-oxo-1,2,4,5-tetrahydro-9H-pyrazolo[1,2d][1,4,5]oxadiazepin-7-yl ester and metalaxyl.

[0195] Herbicides: Any of the sulfopolymer-containing formulations described herein may also optionally include one or more herbicides as active ingredients to mitigate the effects of unwanted plant growth on agricultural production. Useful herbicides include fluzifop, mesotrione, fomesafen, tralkoxydim, napropamide, propanil, cyprodanil, pyrimethanil, chlordiazepoxide, tetrachloronitrobenzene, toclofos-methyl, and chloranil. methyl), chlorpyrifos M, 2,4-D, MCPA, mecoprop, clodinafop-butyl, cyhalofop-butyl, diclofop-butyl, fluazifop-butyl, quizalofop-ethyl, indole-3-acetic acid, 1-naphthylacetic acid, isopropylamine, chlorpyrifos, dimethyl chlorthalate, benomyl, furazolidone, dicamba, dichlorvos, chloranil, imidazolin, fluazolone, fluazifop-butyl, benomyl, acetochlor, alachlor, isopropyl metolachlor, pretilachlor, dimethenamid, chlorpyrifos, fluazifop-butyl, clodinafop-butyl, clethodim, cyclohexim, sethoxydim, pyraclostrobin, pendimethalin, dichlorvos, oxazolidinone, oxyfluorfen, trifluorfen, fluazifop-butyl, bromoxynil, iodine Benzonitrile, imazapic, imazapic, imazaquin, imazapic, imazapic, imazapic, imazapic, imazamox, fluazifop-butyl, fluazifop-butyl, picloram, ammoniasulfuron, chlorosulfuron, nicosulfuron, sulfonesulfuron, etherbensulfuron, wild wheat phthalate, glufosinate, atrazine, simazine, cyanazine, ametryn, prometryn, terbuthylazine, terbuthylazine, sulcotrione, isoproturon, linuron, fenuron, chlorotoluron, methoxuron, N-phosphonomethylglycine and its salts (glyphosate), glufosinate, chlormequat, paraquat, diquat, trifloxysulfuron, fomesafen, mesotrione, fenuron, 2,2-dichloropropionic acid, tromethamine, aminopyralid, sulfopropane, avermectin hydrochloride.

[0196] Insecticides: Any formulation containing a sulfonic polymer described herein may also optionally include one or more insecticides as active ingredients for reducing the effects of insect damage or predation on agricultural production. Useful insecticides include abamectin, acetamiprid, acralthrin, almectin, aldicarb, allethrin, α-cypermethrin, amitraz, azadirachtin, methylpyrifos, azinphos-methyl, benzocarb, benfuracarb, sulfamethoxam, β-cyfluthrin, β-cypermethrin, bifenthrin, bio-allethrin, bio-resmethrin, bistrifluan, borax, buprofen, butanone, cadusafos, carbaryl, chlorpyrifos, chlorpropham, thiophanate-methyl, chlorpyrifos ... Beefenac, cyfluthrin, cyhalothrin, cypermethrin, deltamethrin, diethofencarb, diflubenzuron, dinotefuran, emamectin, endosulfan, fenoxycarb, fenthion, cypermethrin, fipronil, benzylpyraclostrobin, heptachlor, hydrazone, imidacloprid, imiprofen, isoprocarb, lambda cyhalothrin, methamidophos, methiocarb, methomyl, nitenpyram, omethoate, permethrin, pirimicarb, cypermethrin, propoxur, tebufenozide, terpenes, thiamethoxam, thiodimethoate, thiofluanid, and methomyl.

[0197] Acaricides: Any of the sulfopolymer-containing formulations described herein may also optionally include one or more acaricides as active ingredients to mitigate the effects of mite damage or predation on agricultural production. Useful acaricides include antibiotic acaricides, carbamate acaricides, formamidine acaricides, mite growth regulators, organochlorines, permethrins, and organophosphate acaricides.

[0198] Molluscicides: Any of the sulfopolymer-containing formulations described herein may also optionally include one or more molluscicides as active ingredients for use in mitigating the effects of damage or predation by mollusks (e.g., slugs or snails) on agriculture. Useful molluscicides include metaldehyde, methiocarb, and methiocarb.

[0199] Nematicides: Any of the sulfopolymer-containing formulations described herein may also optionally include one or more nematicides as active ingredients to mitigate the effects of nematode damage or predation on agriculture. Useful nematicides include 1,3-dichloropropylene, neem extract, carbamates, garlic-derived polysulfides, and Tagetes extract.

[0200] Pheromones: Any formulation containing a sulfopolymer described herein may also optionally include one or more pheromones as active ingredients for use in reducing the effects of insect damage or predation on agricultural production. Useful pheromones include (Z)-9-tricosene, 14-methyl-1-octadecene, and the like, acetic acid compounds such as (E)-5-decenyl acetate, (E)-4-tridecenyl acetate, (Z)-7-dodecenyl acetate, (Z)-8-dodecenyl acetate, (Z)-9-dodecenyl acetate, (E)-9-dodecenyl acetate, 11-dodecenyl acetate, (E,Z)-7,9-dodecenyl acetate, (Z)-7-tetradecenyl acetate, (Z)-9-tetradecenyl acetate, (Z)-11-tetradecenyl acetate, (Z)-11-hexadecenyl acetate, (E,Z)-3,13-octadecenyl acetate, (E,Z)-2,13-octadecenyl acetate. Ester, (Z,Z)-3,13-octadecenyl acetate, (Z,E)-9,11-tetradecenyl acetate, (Z,E)-9,12-tetradecenyl acetate, (Z,Z / E)-7,11-hexadecenyl acetate, (Z)-7-tetradecenal, (Z)-9-tetradecenal, (Z)-11-tetradecenal, (Z)-7-hexadecenal, (Z)-9-hexadecenal, (Z)-aldehyde compound 11-hexadecenal, n-hexadecenal, (Z,Z)-11,13-hexadecenal, (Z)-13-octadecenal, and ketone compounds such as (Z)-13-eicos-10-one, and mixtures thereof and mixtures mainly consisting of them and other compounds.

[0201] fertilizer

[0202] Another class of active ingredients included in one embodiment of the provided agricultural formulations and compositions, or in combination with any of the aforementioned embodiments, is fertilizer. Thus, any of the sulfopolymer-containing formulations described herein may also optionally include one or more fertilizers as active ingredients. Fertilizers are natural or artificial substances that contain one or more chemical elements that improve plant growth and productivity. Fertilizers enhance the natural fertility of a culture medium (e.g., soil) or replace chemical elements previously acquired from the culture medium by crops. Modern chemical fertilizers contain one or more of the three most important elements (major macronutrients) in plant nutrition: nitrogen (N; particularly for leaf growth), phosphorus (P; particularly for root, flower, seed, and fruit development), and potassium (K; beneficial for strong stem growth, water mobilization, and promoting flowering and fruiting). Of secondary importance are the elements sulfur (S), magnesium (Mg), and calcium (Ca) (referred to as secondary macronutrients). Optionally, fertilizers may include one or more micronutrients: copper (Cu), iron (Fe), manganese (Mn), molybdenum (Mo), zinc (Zn), and boron (B). Of occasional importance are silicon (Si), cobalt (Co), and vanadium (V).

[0203] Nitrogen fertilizers can be obtained from synthetic ammonia (NH3); this compound is used as a gas or aqueous solution, or it can be converted into salts such as ammonium sulfate, ammonium nitrate, and ammonium phosphate. Ammonium can also be produced from waste streams such as farm waste, processed garbage, sewage, and manure. Phosphate fertilizers include calcium phosphates derived from phosphate rock or bone. Treatment of calcium phosphate with sulfuric acid and phosphoric acid, respectively, yields the more soluble superphosphate and triple superphosphate formulations. Potash fertilizers, namely potassium chloride and potassium sulfate, are mined from potash deposits. Mixed fertilizers contain one or more of the three main nutrients - nitrogen, phosphorus, and potassium. Mixed fertilizers can be formulated in countless ways known to those of ordinary skill in the art.

[0204] Particularly contemplated herein are fertilizer compositions and formulations intended for application as liquids. Examples of liquid fertilizers include one or more aqueous solutions of ammonia, ammonium nitrate, or urea; these concentrated nitrogenous products can be diluted with water to form concentrated liquid fertilizers (e.g., UAN). Advantages of the present invention are rapid fertilizer application and ease of coverage. Adding fertilizer to irrigation water is known as "fertigation." Foliar fertilizers are applied directly to leaves; foliar fertilization is commonly used to apply water-soluble nitrogen fertilizers, for example, to high-value crops such as fruit. Foliar fertilization has also gained popularity among home and amateur gardeners.

[0205] plant growth regulators

[0206] In representative examples, it is desirable to change the growth rate or development of desired plants by applying plant growth regulators, for example, to increase the stem thickness or growth rate of fruits and vegetables. Therefore, any formulation containing sulfopolymers as described herein may also optionally include one or more plant growth regulators as active ingredients. Compositions that can be used for this purpose may contain one or more growth stimulants or plant growth regulators, for example, cytokinins at the most 4wt.%, gibberellins at the most 4wt.%, growth hormones at the most 4wt.%, ethylene, abscisic acid at the most 4wt.%, or a combination thereof. When diluted to a concentration within the range of 0.01-0.04wt.%, these concentrations promote growth. When combined together in a ratio of 0.85:1.0 to 1:1, plant growth stimulants have similar effects, but these growth stimulants can be used alone or in combination. If the concentration of the plant growth stimulant increases 10 to 100 times from the listed concentrations, they can also be used as herbicides.

[0207] Plant growth retardants

[0208] In a representative example, it is desirable to slow the growth rate of many plants. Therefore, any formulation containing a sulfonium polymer described herein may also optionally include one or more plant growth regulators as active ingredients. Chemicals useful for this include compounds with quaternary ammonium, phosphonium, or sulfonium moieties, flurprimidol, paclobutrazol, uniconazole, pyrimidinol, acylcyclohexanediones (e.g., trinexapac-ethyl and prohexadione-calcium), daminozide, aminohydroxyethylglycine, brassinolide, forchlorfenuron, oxamyl, thiamethoxam), and other plant regulators (e.g., benzofluor, buminafos, carvone, ciobutide, androstrazine, cyanamide, cyclopropanesulfonamide, cycloheximide, epocholeone, indazole esters, pyridazinone acids (fenridazon), yield-increasing oximes, chloroethanesulfinic acid (holosulf), antineptasulf, karetazan, lead arsenate, sulfamethoxam, prohexadione, pydanon, sintofen, triapenthenol. Abscisic acid, pyrimidine alcohol, dimethoate, carbaryl, chlorpyrifos, chlorpropham, dimethoate, chlorfluanid, flusulfamide, phosphamidon, glyphosate, isopyrimol, jasmonic acid, maleic hydrazide, mepiquat, piproctanyl, propylhydrojasmone, propham, 2,3,5-triiodobenzoic acid), morphogens (chlorofluorene carboxylic acid, chlorofluorene, dichlorflurenol, flurenol), and tetracycline.

[0209] Growth stimulants

[0210] Any of the sulfopolymer-containing formulations described herein may also optionally include one or more growth stimulants as active ingredients, including, for example, aminooxyacetic acid, rhizobium toxin, methoxyvinylglycine, silver thiosulfate, 2,5-norbornadiene, brassinolide, forchlorfenuron, hymexazol, 2-amino-6-oxopurine derivatives, indolinone derivatives, 3,4-disubstituted maleimide derivatives, and fused azapine derivatives.

[0211] Flowering / fruiting inhibitors

[0212] Any of the sulfopolymer-containing formulations described herein may also optionally include one or more flowering and / or fruiting inhibitors as active ingredients, including, for example, copper sulfate, zinc sulfate, diallyl disulfide, dinitro-o-cresol, calcium cyanamide, hydrogen cyanamide, potassium nitrate, sodium azide, calcium ammonium nitrate, urea, thidiazuron, and thiourea as possible flowering and / or fruiting inhibitors.

[0213] Additional active ingredients

[0214] Other examples of active compounds for agricultural use, at least some of which fit into the categories listed above, include: 1,4-dimethylnaphthalene, 1-methylcyclopropene, 1-naphthaleneacetic acid (NAA), 2-hydroxybenzoic acid, 3-bromo-1-chloro-5,5-dimethylhydantoin, 8-hydroxyquinoline sulfate, Agrobacterium radiobacterium, aluminum phosphide, ammonium thiosulfate, azoxystrobin, Bacillus subtilis, Bacillus subtilis QST 713, Bacillus thuringiensis var. ayuzawa (Abbott 1857), Bacillus thuringiensis var. ayuzawa / Kustak, Bacillus thuringiensis var. kustak (H-3A, 3B HDL), Bacillus thuringiensis var. kustak (H-3A, 3B, HD 263), Bacillus thuringiensis var. kustak (H-3A, 3B, SA-1 1), Beauveria bassiana (k4b1), bensulfuron, benomyl, bentazon, benzalkonium chloride, bifenthrin, Bordeaux mixture, boscalid, brodifacoum, herbicide, bromadiolone, bromopyrene, bromoxynil, pyrimidine sulfonate, buprofen, calcium polysulfide, canola oil, captan, carbaryl, carbendazim, carboxin, mesotrione, chitosan, chloralose, ethephon, herbicide, chlorimuron, chlormequat, chloropicrin, chlorpropham, chlorpyrifos, clodinafop-propargyl, chlorsulfuron, chlorthal-dimethyl, Cholecalciferol, clethodim, clodinafop-propargyl, clofentezine, clomazone, clopyralid, clopyralid as clopyralid monoethanolamine, clothianidin, copper, copper oxide, cuprammonium acetate, copper hydroxide, copper oxychloride, copper sulfate, powder, coumatetralyl, cresols (all isomers), cyanazine, Salmonella granular disease virus, Mexican strain, cyfluthrin, cymoxanil, cypermethrin, cyproconazole, cyprodinil, cyromazine, cyromazine, diaminobenzamide, daminozide, dazomethanil, deltamethrin, betaine, diazinon, wheat straw Fear, dichlorvos, dichlorvos, dichlorvos, chloranil, dicofol, difenoconazole, diflubenzuron, dimethoate, dimethomorph, dimethoate, diquat, diquat in the form of diquat, dithianon, diuron, dodine, emamectin benzoate, endosulfan, cypermethrin, fluazifop, cypermethrin, ethoxyfuran, ethyl formate, clozolin, fatty acids, fatty acids (potassium salt), fenamidone, anilamidophos sulfone, chlorfenapyr, fenhexamid, fenothion, fenoxaprop-ethyl, fenpropidin, butyric acid Benzomorph, fenpyroximate, fipronil, fluazifop, fludioxonil, fluazifop-p-butyl, fluazinam, fludioxonil, fluchlorfenuron, broadleaf, fluoxastrobin, flupyr, flusilazole, sulfamethoxazole, flutriafol, folpet, forchlorfenuron, fosetyl-aluminum, oxazolidinone, furathiocarb, gibberellic acid, gibberellic acid a4 / a7, glufosinate, glyphosate, glyphosate in the form of glyphosate potassium and glyphosate triethanolamine, glyphosate in the form of glyphosate potassium, chlorpyrifos, haloxyfop,Gaifenone [(r)-isomer], hexazinone, hydrogen cyanamide, hydrocyanic acid, imazalil, imazapic acid, imidacloprid, indolebutyric acid, indoxacarb, iodocarb, iodosulfuron-methyl sodium salt, ioxynil, iprodione, isoprofenamide, ferric phosphate, sodium ferric EDTA, isoproturon, kresoxim-methyl, lambda-cyhalothrin, Verticillium lecanii (strain K4V1), Verticillium lecanii spores (strain K4V2), l-isopropyl thiocyanate, linuron, lubricating oil, petroleum, C15-30, hydrotreated neutral oil-based oil, solvent deasphalted residue, lufenuron, magnesium phosphide, malathion, maleic hydrazide, mancozeb, mandipropamide, MCPA, MCPB, mecoprop (mecoprop) rop), mecoprop-p, mepiquat-chloride, mesotrione, metalaxyl, meta-metalaxyl, metaldehyde, metamifentone, metamitron, benzylthiocarb, methamidophos, methiocarb, methomyl, methoxyfenozide, methyl bromide, methyl alcohol formate, metiram, metribuzin, metsulfuron-methyl, mebiprofen, mineral oil, myclobutanil, n6-benzyladenine, neem seed kernel extract, nicosulfuron, fluazifop, oil-mineral-insecticide, oleic acid, amoxicillin, oxadiazon, oxamyl, oxyfluorfen, paclobutrazol, palm oil-derived fatty acids, Pantoea agglomerans, strain P10c, paraffin oil, paraquat, paraquat in the form of paraquat dichloride, penconazole, pencycuron, pendimethalin, chlorpyrifos Pyrethroids, benzamidine, phorate, phosphorous acid, phosphorus, picloram, picloram in the form of picloram monoethanolamine, amiloride in the form of amiloride triethanolamine, picoxystrobin, pinone, pine oil, pinoxadone, piperonyl butoxide, pirimicarb, methyl pirimiphos, potassium bicarbonate, potassium cyanide, pyrimidin, prochloraz, procymidone, prohexadione-calcium, promethazine, pyraclostrobin, propazine, aproxil, propanil, propazine, aprofen, propiconazole, propineb, propyzamide, prothioconazole, prothiophos, pymetrozine, pyraclostrobin, pyrethrins, pyrimidine esters, pyrimethanil, phenoxyquin, pentachloronitrobenzene, quizalofop-p-ethyl, rabbit calicivirus (RCD), rotenone, Serratia entomophila (strain 626), sethoxydim, simazine, isopropylamine Alachlor, sodium cyanide, sodium fluoroacetate, sodium tetrathiocarbonate, ethyl spinetoram, spiromesifen, spirotetramat, spirocyclam, Steinernema, sulfentrazone, sulfur, sulfur in the form of polysulfide sulfur, fluvalinate, TCA, tebuconazole, tebuconazole, terbucid, terbufos, terbuthrin, terbutaline, thiabendazole, thiacloprid, thiamethoxam, thiadiazole, thifensulfuron, thiodimethoate, methyl thiophanate, thiram, thymol, methyl tolclofos, tolylfluanid, trimethylol, triadimefon, triadimenol, trichlorochloride, bensulfuron, trichlorfon, dark green Trichoderma (lc52), Trichoderma harzianum, Trichoderma harzianum Rifai (5 strains), triclopyr, ethyl clofos-butyl ester: triclopyr, trifloxystrobin, trifluralin, trinexapac-ethyl,Also contemplated are compounds or mixtures that affect respiration / water loss regulation, drought resistance, and fruit cracking resistance; see, for example, U.S. Patent No. 8,752,328.

[0215] (ii) Rosin

[0216] Rosin is a solid form of resin obtained from pine trees and some other plants (primarily conifers), which is produced by heating fresh liquid resin to evaporate the volatile liquid terpene components. Unrefined, it is translucent and varies in color from yellow to black; its softening point is generally below the boiling point of water. Rosin is mainly composed of various resin acids, especially abietic acid, neoabietic acid, palustric acid and pimaric acid, such as levorotatory pimaric acid. The acids can be free acids, dimers or trimers. Rosin can have a three-ring backbone of abietane, pimarane, isopimarane or bicyclolabdanum. The three main categories / sources of rosin resins are tall oil rosin, gum rosin and wood rosin. For commercial use, rosin is usually purified and / or derivatized to provide different properties. Derivatization may include disproportionation (which may provide improved stability), hydrogenation (which provides stability, different chemical compatibility, reduced odor, and / or enhanced clarity), or esterification (which increases stability, changes molecular weight and acid number, and may change softening / melting point and T g )

[0217] Numerous commercially available rosins can be used in the formulations, compositions, and methods provided herein. Examples of commercially available rosins include rosin esters (which are generally relatively more hydrophobic and generally more soluble in hydrocarbons), including methyl esters of rosin, glycerol esters of rosin, triethylene glycol esters of rosin, pentaerythritol esters of rosin, optionally any of which are hydrogenated before or after derivatization (e.g., esterification). Examples of specific rosins are those marketed as ABALYN TM DE, FORALYN TM 5020-F, 90 and 110, METALYN TM 200, EASTMAN TM Ester Gum 8D, PERMALYN 5095, 5110, 6110 and 8120STABELITE TM Esters 10-E, 5-E and 3-E, FORAL TM 85-E AND 105-E, PENTALYN TM Rosins sold under the name H-3; and rosin resins (which generally have relatively more carboxylic acids and are more hydrophilic), such as DYMEREX TM , STAYBELITE-E TM , FORAL TM AX-E, FORALYN TME, POLY-PALE TM ,ABITOL TM -E, and DRESINATE TM 91 and TX. Eastman Chemical (Kingsport, TN) produces and sells a variety of rosins; see online information available at eastman.com / Markets / Tackifier_Center / Tackifier_Families / Rosin_Resins / Pages / Rosin_Resins.aspx. Rosins from Florachem (Jacksonville, FL) are also contemplated, including: Non-hydrogenated resins: FloraRez TM DR95, FloraRez TM DR105, FloraRez TM DR115, FloraRez TM DR140、FloraRez TM G85、FloraRez TM PE100; and hydrogenated resin: FloraRez TM LRL, FloraRez TM PR, FloraRez TM HR, FloraRez TM 120AA、FloraRez TM 485、FloraRez TM 785、FloraRez TM 100H and FloraRez TM 440. Other commercially available rosins include: and other products manufactured by Pinova, Inc. (Brunswick, GA); Promax (Randers, Demark) rosin resins (e.g., Protex TM series); Specialty rosin resin (Xiamen, China); Novotrade rosin (Keemia, Estonia); DRT rosin (France); Kraton rosin (Belpre, OH); Arakawa Chemical Industries, Ltd. rosin (Osaka, Japan); etc.

[0218] In one embodiment or in combination with any of the referenced embodiments provided herein, the rosin component is provided in (e.g., contained in or included within) a water-immiscible or substantially water-immiscible phase, such as in a water-immiscible component of a kit or system for providing or producing an agrochemical formulation, or contained in a water-immiscible phase of an emulsion or suspension.

[0219] (iii) Additional adjuvants

[0220] The sulfopolymer component of the formulations provided herein generally acts as an adjuvant. In representative embodiments, it may be beneficial to include one or more additional agriculturally acceptable adjuvants to influence one or more properties of the formulation. One of ordinary skill will recognize adjuvants that can be used with the provided sulfopolymer-containing formulations. The following paragraphs provide exemplary adjuvant classes and specific exemplary adjuvants; these lists are not exhaustive.

[0221] emulsifiers

[0222] Any of the sulfopolymer-containing formulations described herein may also optionally include one or more emulsifiers. One of ordinary skill in the art will recognize that there are many agriculturally acceptable emulsifiers that can be used in an embodiment of the present disclosure or in combination with any of the embodiments mentioned. For example, emulsifiers can include: alkanoic and alkenoic acids, monoesters and diesters of α-hydrogen-ω-hydroxy poly(ethylene oxide), glyceryl monostearate, and / or sodium metasilicate.

[0223] Spreader

[0224] Any of the sulfopolymer-containing formulations described herein may also optionally include one or more spreaders. Those skilled in the art will recognize that there are several agriculturally acceptable spreader / wetting agent compounds that can be used in one embodiment of the present disclosure or in combination with any of the embodiments mentioned. By way of example, spreaders may include: alkylaryl polyethoxylates and other ethoxylated derivatives, fatty acids, and isopropyl alcohol.

[0225] Adhesive

[0226] Any of the sulfopolymer-containing formulations described herein may also optionally include one or more adhesives (adhesives). One of ordinary skill in the art will recognize that there are several agriculturally acceptable adhesives that can be used in an embodiment of the present disclosure or in combination with any of the embodiments mentioned. Examples of adhesives include latex-based products, rosindiene / terpene-based products, and long-chain polysaccharides such as gellan gum, guar gum, and xanthan gum. Alternatively, the adhesive can be a polymer or copolymer derived from polymer types such as polyacrylates and polyethylene, or polyetheramides, or imides.

[0227] Drift control agents

[0228] Any of the sulfopolymer-containing formulations described herein may also optionally include one or more drift control agents. Those skilled in the art will recognize that there are numerous agriculturally acceptable drift control agents that can be used in an embodiment of the present disclosure or in combination with any of the embodiments mentioned. Examples of drift control agents include lecithin and related derivatives, linear nonionic polymers having a molecular weight of at least 20 kDa, guar gum and its derivatives, and fatty alcohol alkoxylates.

[0229] Suitable lecithin derivatives are lecithin and its chemically modified derivatives. Such drift control agents are, for example, or Commercially available from Loveland Products.

[0230] Typical polymers currently used as drift control agents include viscoelastic polyacrylamide, polyethylene oxide, and poly(vinyl pyrrolidone), wherein polyacrylamide is a spray tank additive in the agricultural industry that reduces drift. Suitable linear nonionic polymers having a molecular weight of at least 20 kDa can be selected from polyacrylamide, polyacrylate, or polyethylene glycol. Nonionic polymers such as polyacrylamide and polyacrylate are also contemplated. In representative embodiments, the molecular weight of such nonionic polymers is at least 50 kDa, for example at least 100 kDa, and in a specific example at least 1000 kDa.

[0231] Suitable guar gums include, for example, those described in EP0660999 or can be used as DEP775 or DR 200 is commercially available from Rhodia. Hydroxypropyl guar and carboxymethyl hydroxypropyl guar are also examples.

[0232] Examples of fatty alcohol alkoxylates include fatty alcohol ethoxylates. The fatty alcohol may include C8-22, or C14-20, and in representative examples, C16-18 fatty alcohols. The fatty alcohol ethoxylate may contain 1 to 15, such as 1 to 8, and in some instances 2 to 6 equivalents of ethylene oxide. Suitable fatty alcohol ethoxylates are C14-20 fatty alcohols that include 2-6 equivalents of ethylene oxide. The hydrophilic-lipophilic balance (HLB) value of the drift control agent may be 4.0 to 11.0, such as 6.0 to 10.0, and in some instances 8.0 to 10.0. In another specific form, the drift control agent has an HLB of 5.0 to 8.0, or for example 6.0 to 7.0. HLB can be determined according to the Griffin method (Griffin, J Soc Cosmet Chem. 1(5): 311-326, 1949). In another exemplary form, the drift control agent is a fatty alcohol alkoxylate.

[0233] Also contemplated for use as drift control agents are hydroxyethyl cellulose (HEC), ethyl hydroxyethyl cellulose (EHEC), hydroxypropyl cellulose (HPC), hydroxybutyl methyl cellulose (HBMC), hydroxypropyl methyl cellulose (HPMC), methyl ethyl hydroxyethyl cellulose (MEHEC), and hydrophobically modified ethyl hydroxyethyl cellulose (HMEHEC).

[0234] Rainproof agent

[0235] Any of the sulfopolymer-containing formulations described herein may also optionally include one or more rainfast agents. One of ordinary skill in the art will recognize that there are several agriculturally acceptable rainfast agents that can be used in an embodiment of the present disclosure or in combination with any of the mentioned embodiments. Rainfast agents may include: ethyl hydroxyethyl cellulose (EHEC), hydroxypropyl cellulose (HPC), hydroxybutyl methyl cellulose (HBMC), hydroxypropyl methyl cellulose (HPMC), methyl ethyl hydroxyethyl cellulose (MEHEC), and hydrophobically modified ethyl hydroxyethyl cellulose (HMEHEC). Polyvinyl alcohol and organosiloxanes (e.g., trimethylchlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, hexamethyldisilazane, diphenylsilanediol, methyltrichlorosilane, octamethylcyclotetrasiloxane, diphenyldichlorosilane, dichloromethylsilane, vinyl silicone oil, trimethyl(bromodifluoromethyl)silane, tris-buffered saline, isopropoxymethylsilane, silicone ov-101, hydroxy silicone oil, silicone oil, affinity silane, tetrahydrosilane, hydroxytrimethylsilane, trimethoxychlorosilane 05 / 06 / 04, chlorophenylsilane 97, chloromethylsilane).

[0236] surfactants

[0237] Any formulation containing a sulfopolymer described herein may also optionally include one or more surfactants. One of ordinary skill in the art will recognize that there are several agriculturally acceptable surfactants that can be used in an embodiment of the present disclosure or in combination with any of the mentioned embodiments. The surfactant can include one or more of the following: a-(nonylphenyl)-oo-hydroxy poly(oxy-1,2-ethanediyl); polyethylene glycol ethers; mono(nonylphenyl) ether; polyethylene glycol nonylphenyl ether; polyoxyethylene (n)-nonylphenyl ether; nonylphenyl polyethylene glycol ether; nonylphenoxypolyethoxyethanol; and poly(oxy-1,2 ethanediyl)-a-(nonylphenol)-)-hydroxy, N-alkyl-N,N-dimethyl glycinate, such as coconut oil alkyl dimethyl-glycinate, N-acylaminopropyl-N,N-dimethyl glycinate, such as coconut oil Acylaminopropyldimethyl-ammonium glycinate and 2-alkyl-3-carboxymethyl-3-hydroxyethyl-imidazoline, in each case having 8 to 18 C atoms in the alkyl or acyl group, and cocoacylaminoethyl hydroxyethylcarboxymethyl glycinate, N-alkylglycinate, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropyl glycine, N-alkyltaurine, N-alkylsarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid, in each case having about 8 to 18 C atoms in the alkyl group. Exemplary amphoteric surfactants include N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C-acylsarcosine.

[0238] Nonionic surfactants include alkoxylates, such as alkoxylated alcohols, alkoxylated fatty acids, such as ethoxylates and their derivatives, including ethoxylated C8-C24 saturated and unsaturated, linear and branched fatty acids or fatty alcohols, alkoxylated block copolymers, alkoxylated aryl alkylphenols, especially ethoxylates and their derivatives, including alkylphenol ethoxylates, alkoxylated amines, alkoxylated oils, fatty esters, especially polyethylene glycol monoesters and diesters of C8-C24 saturated and unsaturated, linear and branched fatty acids, sorbitan derivatives, including esters and ethoxylates, alkyl polyglucosides, and the like.

[0239] Ionic surfactants include alkylaryl sulfonates, alkylaryl sulfonic acids, carboxylated alcohol ethoxylates and alkylphenol ethoxylates, carboxylic acids / fatty acids, diphenyl sulfonate derivatives, olefin sulfonates, phosphates, phosphorus-containing organic derivatives, quaternized surfactants, sulfates and sulfonates of oils and fatty acids, sulfates and sulfonates of ethoxylated alkylphenols, sulfates of ethoxylated alcohols, sulfates of fatty acids, sulfonates of dodecyl and tridecylbenzene, sulfonates of naphthalene and alkylnaphthalene, sulfonates of petroleum, sulfosuccinamates, alkanolamides, alkoxylated amines, N-acylsarcosinates, and the like.

[0240] Anti-caking agent

[0241] Any sulfopolymer-containing formulation described herein may also optionally include one or more anti-caking agents. One of ordinary skill in the art will recognize that there are several agriculturally acceptable anti-caking agents that can be used in an embodiment of the present disclosure or in combination with any of the mentioned embodiments. Anti-caking agents can include sodium carbonate, tricalcium phosphate, potassium carbonate, ammonium carbonate, magnesium carbonate, hydrochloric acid, potassium chloride, calcium chloride, ammonium chloride, magnesium chloride, stannous chloride, sulfuric acid, sodium sulfate, potassium sulfate, calcium sulfate, ammonium sulfate, magnesium sulfate, Epsom salts, copper sulfate, aluminum sulfate, sodium aluminum sulfate, potassium aluminum sulfate, ammonium aluminum sulfate, sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonium hydroxide, magnesium hydroxide, calcium oxide, magnesium oxide, sodium ferrocyanide, potassium ferrocyanide, calcium ferrocyanide, dicalcium diphosphate, sodium aluminum phosphate, sodium silicate, silicon dioxide, calcium silicate, magnesium silicate, magnesium trisilicate, talc, sodium aluminum silicate, potassium aluminum silicate, calcium aluminum silicate, bentonite, kaolin, stearic acid, magnesium stearate, calcium stearate, gluconic acid, glucono delta-lactone (gluconolactone), sodium gluconate, potassium gluconate, calcium gluconate, ferrous gluconate, ferrous lactate, polydimethylsiloxane.

[0242] antifreeze

[0243] Any of the sulfopolymer-containing formulations described herein may also optionally include one or more antifreeze agents. Those skilled in the art will recognize that there are several agriculturally acceptable antifreeze agents that can be used in an embodiment of the present disclosure or in combination with any of the embodiments mentioned. Urea antifreeze agents may include: glycols (i.e., propylene glycol), sorbitol, urea, glycerin, and solvents.

[0244] (VI) Additional optional ingredients

[0245] Optionally, the formulations and compositions described herein may include one or more other agriculturally acceptable ingredients. Representative examples of categories of optional ingredients are provided below; the lists provided herein are not intended to be exhaustive, but rather merely provide examples.

[0246] Water-immiscible phase

[0247] In solvent dispersions (or, more narrowly, oil dispersions, or OD), what is needed is a water-immiscible solvent, such as a saturated or unsaturated oil. Examples of saturated oils include saturated mineral oils. In one embodiment or in combination with any of the embodiments mentioned, highly unsaturated oils are used because they are liquid at room temperature. The trend towards using seed oils is clear, as the goal of OD is to claim to be "safer, more environmentally friendly, and gentler." Examples of vegetable and seed oils include refined sunflower oil, rapeseed / canola oil, soybean oil, corn oil, palm oil (liquid form), coconut (liquid form), banana oil, and other vegetable oils. Additional examples of water-immiscible solvents are described herein. Methylated seed oil (MSO) forms of all of these are also contemplated. In one embodiment or in combination with any of the embodiments mentioned, peanut oil and sesame oil are also feasible. In one embodiment or in combination with any of the embodiments mentioned, peanut oil and sesame oil are avoided in situations where the final product may come into contact with food or may itself be consumed.

[0248] Also contemplated are non-vegetable and non-seed oils and fats, including: petroleum oils, paraffinic oils, and unsaturated fatty acids (from any source).

[0249] Alternatively, fish oils, citrus oils, neem oil, tea tree oil, etc. may also be used; however, these are considered active ingredients because they have biological activity (e.g., as pesticides). These are not considered inert components.

[0250] Viscosity regulator

[0251] Any of the sulfopolymer-containing formulations described herein may also optionally include one or more viscosity modifiers. Viscosity modifiers may include glycerol, ethylene glycol, propylene glycol, and low molecular weight polyethylene glycol or polypropylene glycol.

[0252] solubilizer

[0253] Any of the sulfopolymer-containing formulations described herein may also optionally include one or more solubilizing agents. Such solubilizing agents may include sodium p-toluenesulfonate and sodium xylenesulfonate.

[0254] dispersants

[0255] Any of the sulfopolymer-containing formulations described herein may also optionally include one or more dispersants. Dispersants include, but are not limited to, sulfonated aromatic polymers or oligomers, low ethoxylate content PEG esters and diesters, ethylene oxide / propylene oxide block copolymers, and organosilicone.

[0256] defoaming agent

[0257] Any of the sulfopolymer-containing formulations described herein may also optionally include one or more defoaming agents. Defoaming agents can be used to prevent or reduce foaming that may occur during formulation or upon dilution. Those skilled in the art will recognize that there are several agriculturally acceptable defoaming agents that can be used in one embodiment of the present disclosure or in combination with any of the embodiments described herein. Defoaming agents may include: 20 polyethylene glycol 8000, polymethylsiloxane, dimethicone caprylic acid, and silicone oils and emulsions.

[0258] stabilizer

[0259] Any of the sulfopolymer-containing formulations described herein may also optionally include one or more stabilizers (stabilizers). One of ordinary skill in the art will recognize that there are several agriculturally acceptable stabilizers that can be used in an embodiment of the present disclosure or in combination with any of the embodiments mentioned. Stabilizers include xanthan gum, agar, alginic acid, alginates, calcium lactobionate, carrageenan, gellan gum, guar gum, diisopropanolamine, hydroxyethylidene diphosphonic acid, and silver nitrate.

[0260] preservative

[0261] Any of the sulfopolymer-containing formulations described herein may also optionally include one or more preservatives. One of ordinary skill in the art will recognize that there are several agriculturally acceptable preservatives available that can be used in an embodiment of the present disclosure or in combination with any of the mentioned embodiments. Preservatives can include weak acid preservatives such as sorbic acid, lactic acid, benzoic acid, propionic acid, citric acid, acetic acid, or alkali metal or alkaline earth metal salts thereof; inorganic acids such as hydrochloric acid; imidazoles such as imazalil. More generally, a "preservative component," if included in a composition, is any molecule that can be used to increase the field or shelf life of a formulation, or a plant or plant part to which the formulation is coated, including, for example, fruits, flowers, and vegetables. Exemplary ingredients that can be used as the preservative component include parabens, including methylparaben and propylparaben, sodium benzoate (and other benzoate salts), vanillin, sodium sorbate (and other salts of sorbic acid), vitamin E, tocopherol, alpha-tocopherol, vitamin E acetate, ethanol, butanol, ethylenediaminetetraacetic acid (EDTA) and all its salts, silicates such as calcium silicate, magnesium aluminum silicate, calcium aluminum silicate, magnesium silicate, sodium aluminum silicate, potassium aluminum silicate, sodium potassium aluminum silicate, other water-soluble silicates, and combinations of two or more thereof.

[0262] The preservative component can be included in the formulation at any concentration sufficient to increase shelf life. Generally, shelf life refers to the amount of time a particular formulation or plant part can be kept in a marketable condition. Similarly, field life refers to the amount of time a plant or plant part can be maintained in the field and still allow the plant part to be harvested in a marketable condition.

[0263] Those skilled in the art will be able to determine the appropriate concentration of the preservative component, such as by producing a test formulation with different amounts of the preservative component, optionally applying them to plants or plant parts, and measuring the shelf life or field life of the formulation or plant parts and the desired concentration. Exemplary concentrations of the preservative component in the composition include 0.001wt.% to 10.5wt.%, 0.01wt.% to 10wt.%, 0.02wt.% to 9wt.%, 0.05wt.% to 8wt.%, 0.07wt.% to 7wt.%, 0.10wt.% to 6wt.%, and 0.15wt.% to 5wt.%. If the preservative component is included in the composition, it can also increase the shelf life of the formulation during storage, transportation, display sales, and handling, which can occur before the end user uses the product for the purposes outlined herein for the compositions detailed herein.

[0264] antioxidants

[0265] In other examples, antioxidants can be included in the compositions and preparations provided herein. Antioxidants can be used to protect post-harvest fruits and vegetables from browning due to oxidation. In addition, antioxidants can be used to protect certain active ingredients from degradation due to contact with oxygen. Exemplary antioxidants include EDTA, glutathione, α-tocopherol, tocopherol, vitamin E acetate, vitamin E palmitate, zinc glycinate, ascorbic acid and its calcium, sodium and potassium salts, ascorbyl palmitate, calcium citrate, BHA, BHT, guaiac extract, gallic acid and methyl, ethyl, propyl, lauryl esters of gallic acid, phosphatidylcholine, propionic acid, sucrose, cyclodextrin, rosemary and cysteine ​​hydrochloride. Other antioxidants include amino acids (such as glycine, histidine, tyrosine, tryptophan) and derivatives thereof, imidazoles (such as urocanic acid) and derivatives thereof, vitamin C and derivatives thereof (such as ascorbyl palmitate and tetraisopalmityl ascorbyl ester, magnesium ascorbyl phosphate, ascorbyl phosphate, ascorbyl acetate), tocopherol and derivatives thereof (such as vitamin E-acetate), vitamin E, vitamin A and derivatives thereof (vitamin-A, palmitate and acetate), and coniferyl benzoate, rutin and derivatives thereof, α-glycosyl rutin, ferulic acid, furfurylglucitol, carnosine, 15 butylated hydroxytoluene, butylated hydroxyanisole and trihydroxybutyrophenone. In one embodiment or in combination with any of the embodiments mentioned, antioxidants can be included in a concentration of 0.01wt% to 1.0wt%. Compositions or preparations can include a combination of two or more different antioxidants.

[0266] pH adjusters

[0267] Any of the sulfopolymer-containing formulations described herein may also optionally include one or more compounds that affect or adjust pH, such as buffers, acidifiers, alkalizers, and the like. One of ordinary skill in the art will recognize that there are several agriculturally acceptable pH-adjusting compounds that can be used in one embodiment of the present disclosure or in combination with any of the aforementioned embodiments. Examples of pH adjusters include ethanolamine, phosphoric acid, triethanolamine, acetic acid, diethylamine, monoethylamine, and monoisopropylamine.

[0268] Masking agents / chelating agents

[0269] The term "sequestrant" refers to a compound that can remove or inactivate another substance by chelation. Chelants (or chelating agents) are therefore more general terms than sequestrants. Examples of sequestrants include those used to complex metal ions (e.g., EDTA or gluconate). On the other hand, sequestrants can be used more widely, for example, to determine metal ion concentrations (e.g., neocuprous acid) or to form very important / useful compounds (e.g., chlorophyll, copper phthalocyanine) by colorimetry. Therefore, if a sequestrant is present, it can be expected that the sequestrant will complex several ions, while some applications of sequestrants may involve intentional chelation of only one type of ion.

[0270] Any of the sulfopolymer-containing formulations described herein may also optionally include one or more masking agents or chelating agents, for example, to adjust the amount of metal suspended in the formulation. Those skilled in the art will recognize that there are several agriculturally acceptable chelating and masking agents that can be used in one embodiment of the present disclosure or in combination with any of the embodiments mentioned. Examples of chelating agents include sodium polyphosphate, sodium polyacrylate, sodium lignin sulfonate, citric acid, sodium citrate, sodium gluconate / glucoheptonate, EDTA, disodium salts, and diammonium salts.

[0271] For example, it is well-known that well water often has high concentrations of Ca ++ ions. This can lead to the formation of gels, precipitates or solids during the preparation or dilution of agrochemical formulations. In some cases, such as in places or regions where water is particularly hard, softened water (such as can be provided by an in-line water softener) or the addition of chelated Ca ++ Sequestrants of all ions are useful. Alternatively, such sequestrant(s) may be a tank mix, for example one formulated to take into account region-specific water hardness.

[0272] It is generally recognized in the art that water hardness is a measure of the amount of salt present in water and is typically expressed in milligrams of dissolved calcium carbonate and magnesium carbonate per liter of water. Water hardness varies greatly between agricultural sites and regions, and those skilled in the art recognize that water hardness affects the biophysical properties (e.g., specific gravity, evaporation rate) and chemical properties (e.g., pH, ionic strength) of solutions, including those used in agriculture. For example, in solutions comprising sulfopolymers, water hardness can change the precipitation rate and pH, and affect the solubility of pesticides and change the atomization properties of the solution. Those skilled in the art also recognize that changes in the biophysical and chemical properties of solutions due to water hardness affect the effectiveness of common pesticides. For example, those skilled in the art recognize that reducing water hardness can reduce the phytotoxicity of glyphosate. Water hardness is commonly addressed in numerous ways, including but not limited to using water softeners in water lines (e.g., replacing calcium with sodium) or adding chelating agents (e.g., EDTA, citric acid) to holding tanks.

[0273] solvent

[0274] Any formulation containing a sulfopolymer described herein may also optionally include one or more (organic) solvents. Solvents may be used to increase the solubility of one or more active ingredients, inhibit freezing or crystallization, reduce viscosity, and enhance pourability (change rheology), etc. Solvents may include: ethylene dichloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, xylene, trichloroethylene, N-methyl-2-pyrrolidone, polychlorinated methanes, chlorinated volatile organic compounds, and isopropyl alcohol. Mineral oil, vegetable oil, seed oil, methylated seed oil, banana oil, white mineral oil, mineral spirits, toluene, benzene, xylene, SOLVESSO TM Aromatic 100, SOLVESSO TM Aromatic 150, SOLVESSO TM Aromatic 150 ND, SOLVESSO TM Aromatic 200 ND SOLVESSO TM Aromatic 200, SOLVESSO TM 100. SOLVESSO TM 150. SOLVESSO TM 150 ND、SOLVESSO TM 200、SOLVESSO TM200 ND, acetophenone, isopropyl acetate, tert-butyl acetate, methyl n-acetone, propyl acetate, methyl isobutyl ketone, isobutyl acetate, n-propyl propionate, butyl acetate, methyl isoamyl ketone, amyl acetate, n-butyl propionate, methyl p-amyl acetate, n-amyl methyl ketone, isobutyl isobutyrate, cyclohexanone, diisobutyl ketone, n-amyl propionate, ethyl 3-ethoxypropionate, 2-ethylhexyl acetate, ethylene glycol monobutyl ether, isophorone, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, 2-heptanol, 2-ethylhexanol.

[0275] Other polymers

[0276] Any of the sulfopolymer-containing formulations described herein may also optionally include one or more additional polymers (in addition to the sulfopolymer). For example, the polymers may include semisynthetic polymeric materials such as diethylaminoethyl (DEAE) cellulose, nitrocellulose, carboxymethyl cellulose, quaternary amine-substituted celluloses, and celluloses derivatized with phosphonic and sulfonic acids. Such polymers can be prepared from common and inexpensive large-scale materials, including cellulose, dextran, ethylene glycol, polyethyleneimine, vinyl compounds, acetates, amides, and the like.

[0277] flavor enhancers

[0278] Any of the sulfopolymer-containing formulations described herein may also optionally include one or more flavor enhancers, for example, to mask the aroma of other components of the formulation or to provide a flavor identifier or label. Those skilled in the art will recognize that there are numerous agriculturally acceptable flavor enhancers available that can be used in an embodiment of the present disclosure or in combination with any of the embodiments described herein. For example, a non-exhaustive list of flavor enhancers can be found in U.S. Patent Publication No. 2009 / 0163449.

[0279] Colorants

[0280] Any preparation containing sulfopolymer described herein can also optionally include one or more colorants, for example, so that product identification and anti-counterfeiting are provided, and for health and safety reasons, identify a particular product. Colorant can also be used for showing where to have applied otherwise substantially transparent preparation, for example, to ensure complete coverage and repeat coverage minimum. Those of ordinary skill in the art will recognize that there are several agriculturally acceptable colorants, which can be used in an embodiment of the present disclosure or in combination with any of the embodiments mentioned. Representative colorant examples include FD&C Blue No. 1, FD&C Red No. 40, and the proprietary colorant that can be obtained from Pylam Dyes (Tempe, Arizona), Vipul Organics Ltd (Mumbai, India) and other commercial producers.

[0281] (VII) Exemplary Component Ranges in Representative Formulations

[0282] The compositions and formulations described herein can be used in a variety of applications, including but not limited to suspensions, emulsions (oil-in-water and water-in-oil), and solvent dispersions. For example, many types of active ingredients used in agriculture can be suspended in solutions that can improve the dispersibility of the active ingredients on crops. In addition, emulsification is an important aspect of combining different chemicals and / or liquid mixtures. In addition, uniformly distributing the material particles in a continuous phase that is substantially immiscible with a water-immiscible solvent is also an important aspect of ensuring adequate mixing. Taking into account the chemical and biophysical properties of different organic and inorganic chemicals, the precise composition of suspensions, emulsions (water-in-oil and oil-in-water), and solvent dispersions can vary depending on the precise compound used.

[0283] suspension

[0284] In suspension formulations (including suspension concentrates SC), sulfopolymers, such as sulfopolyesters containing a sulfoisophthalate moiety derived, for example, from sodium sulfoisophthalic acid (5-SSIPA) or an ester thereof, provide excellent dispersion of the active ingredient in water, providing an unexpectedly high loading of solid active compound to be easily suspended in water. In addition to the direct benefits of high loading and easy dispersion, the formulation is stable. Minimal sedimentation was observed relative to the control formulation. After standing for several weeks at room temperature, sedimentation was observed at the bottom of both the control (lacking SPE1 or SPE2 polymer) and the SPE formulation. The suspension containing the sulfopolymer can be redispersed by simple inversion.

[0285] Another important feature of SC formulations is their ability to disperse with minimal agitation upon dilution (simulating a bucket mix by an end user, such as a farmer). Here, too, formulations based on sulfopolymers (e.g., sulfopolyesters, such as polymers containing sulfoisophthalate moieties, such as those derived from sodium sulfoisophthalic acid (5-SSIPA) or its esters) can be dispersed unmixed into a graduated cylinder containing tap water upon dilution. If the dispersion settles after standing, the sulfopolymer-containing system can be redispersed with minimal mixing, such as low-shear mixing and / or tumbling, and without visually observable undispersible residue.

[0286] Suspending the active ingredient in a suspension improves the distribution of the active ingredient on the crop during delivery of the active ingredient by a number of delivery mechanisms, such as spraying. The sulfopolymer improves the suspension properties, as described herein. Representative suspension formulations will contain the components at the concentrations provided in the table below, based on the weight percentages of the composition. The exact amount of any component used can be affected by the component used, the other components used, the intended use of the formulation, and other factors well known to those of ordinary skill in the art. Typically, the concentrate will be diluted 1:1 to 1:1000 times before use. Exemplary component ranges for suspension concentrates

[0287]

[0288] *Optional component.

[0289] More generally, common components of SCs are: active ingredient (solid or liquid; which provides a biological function): 200-600 g / L; wetting agent / co-dispersant (which can be used to facilitate the milling process): 5-20 g / L; dispersant (which helps disperse the active ingredient in the concentrate and / or dilute in water): 20-60 g / L; optionally one or more adjuvants (which increase the efficacy of the active ingredient): the amount of which varies depending on the adjuvant chosen and its function; rheology modifier (which provides and / or modifies the structure of the formulation): 1-10 g / L; optionally, an antifreeze (which reduces the likelihood of the formulation freezing): 50-80 g / L; a biocide (which eliminates, reduces or prevents the growth of unwanted bacteria in the formulation): 1-5 g / L; an antifoaming agent (to reduce the tendency of the formulation to entrap air during manufacture and transport): 1-20 g / L; and a diluent, typically water (which serves as the continuous phase): to form a final volume of 1 L.

[0290] SC formulations generally have one or more of the following positive features: they are water-based, so they offer good safety and user convenience; they are suitable for many active ingredients with low water solubility; they are dust-free; they do not contain flammable liquids; they have a small particle size of the active ingredient; and adjuvants can optionally be built in for bioenhancement. However, SC is also generally considered to have the following limitations: they are incompatible with water-soluble active ingredients; if the active ingredient is partially soluble in water, crystal growth can be a problem; some SC formulations may have long-term stability issues (caking in the tank); some SC formulations may have stability issues when diluted (sedimentation in the barrel); and some SC formulations may require stirring during application. The various sulfopolymer-containing formulations provided herein address some or all of these limitations.

[0291] Emulsion / emulsion

[0292] Typically, the emulsion may contain the following components: active ingredient (solid or liquid, which provides the biological function): 50-800 g / L; water-immiscible solvent / oil (which dissolves or suspends the active ingredient to improve biological activity): 30-600 g / L; emulsifier / emulsifier system (which stabilizes the concentrated emulsion and promotes emulsification upon dilution in water): 1-200 g / L; rheology modifier (which provides and / or modifies the structure of the formulation): 1-5 g / L; optionally, an antifreeze (which reduces the likelihood of the formulation freezing): 5-100 g / L; a biocide (which eliminates, reduces or prevents the growth of unwanted bacteria in the formulation): 1-3 g / L; an antifoaming agent (to reduce the tendency of the formulation to entrap air during manufacture and transport): 1-20 g / L; and a continuous phase, typically water: to form a final volume of 1 L.

[0293] Prior to the present disclosure, in order to obtain high solvent / oil content EWs, emulsifier systems were typically blends of different products and needed to be present in the formulation at high concentrations, which affected the price and overall functionality of the formulation. The various sulfopolymer-containing formulations provided herein address this problem, for example, by providing a multi-featured adjuvant component that can stabilize the emulsion formulation and provide it with various functionalities.

[0294] In general, EW formulations often have one or more of the following beneficial properties: simple manufacturing (one-pot high-shear mixing); high biological activity; generally good chemical stability; some formulations exhibit spontaneous emulsification upon dilution; and are considered a safer and more environmentally friendly alternative to emulsifiable concentrates (ECs). However, EWs are generally considered to have the following limitations: they traditionally use expensive solvents containing hazardous VOCs; solvents can affect plastics and rubber in sprayers; the active ingredient requires a certain temperature range to fully dissolve in the solvent; and the use of water-miscible solvents can cause crystallization of the active ingredient upon dilution. However, new, milder solvents, such as mineral oil, lemon oil, MSO, etc., have allowed EWs to be manufactured at a lower overall cost, with lower toxicity and reduced chemical damage to equipment.

[0295] Water-in-water emulsions with water-immiscible solvents

[0296] Emulsifying water in a water-immiscible solvent (e.g., oil; the continuous phase) allows water to mix into solvents that it would not normally mix in. As described herein, the use of sulfopolymers in water-in-oil emulsions improves the emulsification characteristics and stability of the resulting emulsion.

[0297] Representative water-in-solvent emulsion formulations contain the components at the concentrations provided in the table below, based on weight percentages of the composition. The exact amount of any component used may be affected by the component used, the other ingredients used, the intended use of the formulation, and other factors known to those of ordinary skill in the art. Typically, the concentrate will be diluted 1:1 to 1:1000 times before use.

[0298] Exemplary composition ranges for water-in-oil emulsion concentrates

[0299]

[0300] *Optional component.

[0301] **This substance may be the same compound as the water-immiscible solvent, in which case the minimum amount is the amount specified in the water-immiscible solvent column, and the maximum amount is the sum of the amounts specified in the active ingredient column and the amount specified in the water-immiscible solvent column.

[0302] ***"To 100%" refers to the remaining percentage of water, with the sum of all ingredients being 100%.

[0303] Water-in-water immiscible solvent emulsion

[0304] A water-immiscible solvent (e.g., oil)-in-water emulsion (or concentrated aqueous emulsion or simply emulsion, "EW") is a dispersion of a water-immiscible liquid (the discontinuous phase) in water (the continuous phase). Examples of such emulsions contain a liquid or solid active ingredient dissolved in a water-immiscible solvent. Sometimes, the water-immiscible phase itself is the active ingredient (e.g., NEEM and other biologically active oils). Emulsifying oil in water allows the oil (or, using any water-immiscible solvent) to mix into water where oils would not normally mix.

[0305] EW formulations are gaining popularity as companies avoid using solvents such as toluene and aromatic compounds for formulation. The concept is to use oils, such as fatty acid esters, to dissolve water-insoluble (i.e., essentially water-immiscible) active ingredients and then emulsify them into water. Surfactants are important for these systems to function and remain stable in the formulation, including in the applied formulation.

[0306] The sulfopolymer systems described herein were tested at very high levels of methylated soybean oil (MSO) (65 wt.% oil in water). Using 1% SPE1 or SPE2 polymer, the oil dispersed easily to provide a stable milky white dispersion. The formulation was stable under accelerated stability testing, showing no cracking after two weeks at 54°C. When mixed with water, for example, at the location where the diluted (applied state) formulation is to be applied, such as on a farm, the formulation can be easily dispersed. Using the 65% oil in water formulation, dilution into water provided a system that dispersed very well. The sulfopolymers not only enable the system to be stable at significantly high concentrations, but also, upon dilution, in some embodiments, the phases can flip to provide a stable diluted (e.g., applied state) oil-in-water mixture.

[0307] As described herein, the use of sulfopolymers in oil-in-water emulsions improves the emulsification properties and stability of the resulting emulsions. A representative oil-in-water formulation will contain the components at the concentrations provided in the table below, based on weight percentages of the composition. The precise amount of any component used may be affected by the component used, the other ingredients used, the intended use of the formulation, and other factors known to those of ordinary skill in the art. Typically, the concentrate will be diluted 1:1 to 1:1000 prior to use.

[0308] Exemplary Component Ranges for Oil-in-Water Emulsion Concentrates

[0309]

[0310]

[0311] *Optional component.

[0312] **This substance may be the same compound as the water-immiscible solvent, in which case the minimum amount is the amount specified in the water-immiscible solvent column, and the maximum amount is the sum of the amounts specified in the active ingredient column and the amount specified in the water-immiscible solvent column.

[0313] ***"To 100%" refers to the remaining percentage of water, with the sum of all ingredients being 100%.

[0314] Solvent dispersion

[0315] The water-immiscible solvent is typically dispersed throughout the solution in the continuous phase. As described herein, the use of sulfopolymers in solvent dispersions improves the solvent dispersion properties and the stability of the resulting emulsion. Representative solvent dispersion formulations will contain the components at the concentrations provided in the table below, based on weight percentages of the composition. The precise amount of any component used may be affected by the component used, other components used, the intended use of the formulation, and other factors known to those of ordinary skill in the art. Typically, the concentrate will be diluted 1:1 to 1:1000 times prior to use.

[0316] Exemplary composition ranges for solvent dispersion concentrates

[0317]

[0318]

[0319] *Optional component.

[0320] **This substance may be the same compound as the water-immiscible solvent, in which case the minimum amount is the amount specified in the water-immiscible solvent column, and the maximum amount is the sum of the amounts specified in the active ingredient column and the amount specified in the water-immiscible solvent column.

[0321] ***"To 100%" refers to the remaining percentage of water, with the sum of all ingredients being 100%.

[0322] (VIII) Method for preparing concentrated preparation

[0323] The sulfopolymer-containing formulations, compositions, and systems described herein are rendered new, unique, and useful because they include a sulfopolymer (e.g., a sulfopolyester) in an agrochemical formulation. However, the formulations, including concentrate formulations, can generally be prepared in a conventional manner. That is, the inclusion of a sulfopolymer in a suspension formulation, a solvent-in-water emulsion formulation, a water-in-solvent emulsion formulation, or a solvent / oil dispersion does not significantly alter the manner in which the formulation is prepared.

[0324] Provided herein are representative methods for preparing formulations, including concentrated formulations. In one embodiment or in combination with any of the aforementioned embodiments, the ingredients of the desired formulation can be simply mixed together—typically all simultaneously using moderate to high shear mixing—particularly when the sulfopolyester is introduced into the mixture as a liquid dispersion (e.g., using a 10 wt% to 40 wt% stock dispersion of the sulfopolymer). In one embodiment or in combination with any of the aforementioned embodiments, where the sulfopolymer is first introduced as a solid (powder or pellets or flakes), the sulfopolymer is dispersed into water at an elevated temperature (e.g., above 40°C, such as at least 45°C, at least 50°C, at least 55°C, at least 60°C, at least 65°C, at least 70°C, at least 75°C, at least 80°C, or above 80°C) under moderate to high shear mixing. The elevated temperature can be provided by adding hot water to the mixture; by heating the mixture; or a combination of both methods. Dispersion of the solid sulfopolymer can occur before or after the active ingredient or other components are added to the liquid, with heat-labile active ingredients or other components advantageously being added only after the sulfopolymer has been dispersed and the composition has cooled, for example, to ambient temperature.

[0325] While most other components can be simply mixed into the formulation, it should be noted that high shear mixing may be required to add the rosin to ensure uniform incorporation. Alternatively, in representative embodiments, the rosin (if included in the final formulation) is provided in a water-immiscible component of the formulation. For example, the rosin is provided in the water-immiscible solvent aspect of the exemplary system or kit embodiments. Alternatively, in one embodiment or in combination with any of the aforementioned embodiments, the rosin is provided in a container that is phase-separated from the water (sulfopolymer-containing) and the water-immiscible phase.

[0326] (IX) Characterization of Formulations

[0327] General Considerations in Agricultural Formulations: Phase separation is commonly observed in nearly all crop formulations. However, useful aspects of these formulations include the ability to form a stable, diluted formulation within a certain time after dilution in a bucket with water, e.g., long enough to allow spray application. This time requirement is influenced by the active ingredient in the formulation, the formulation type (e.g., suspension, emulsion, dispersion), and the spray application conditions. For oil-containing formulations, a typical requirement is that no free oil phase is observed within a certain time period (e.g., 6 hours) under stirring. Creaming or sedimentation can occur in tanks and buckets; however, the original properties are restored after shaking.

[0328] Preparations as herein described can be inspected and characterized using any art-recognized system for detecting and / or measuring the function or behavior of the preparation that may be affected. These characteristics may include, for example, solubility, viscosity, pH, density, stability (including short-term, long-term and at various temperatures), turbidity, dispersibility, redispersibility, atomization, drift, coverage, efficacy (including in the field), etc. Representative methods and systems for carrying out such measurements are provided herein. In addition, for example, standard methods can be found in the handbook of the Collaborative International Pesticides Analytical Council (CIPAC), which can be accessed online at (cipac.org / index.php / methods-publications / handbooks).

[0329] (X) Use of concentrated preparations

[0330] Provided herein are concentrated formulations, i.e., formulations containing a level of active ingredient higher than the level of the ingredient in the applied state, which concentrate is diluted before application or use. Concentrates are considered beneficial, for example, because they can be more efficiently transported and stored (because they take up less volume than diluted formulations). However, in order to avoid waste, to avoid toxicity that may result from using an active ingredient or other component higher than the recommended level, to avoid phytotoxic effects caused by unbalanced formulation components, and to avoid environmental pollution and / or user health effects, it is important that the concentrated formulation be diluted before use. Methods for diluting concentrated formulations are recognized in the art; the following discussion is intended to be a guide only and not a limitation.

[0331] Methods for diluting concentrated preparations

[0332] A concentrated sulfopolymer-containing formulation can be diluted by adding the desired amount of the concentrated formulation (generally, a stock solution) to a certain amount of diluent / solvent (e.g., water). The resulting solution contains the amount of each component originally obtained from the concentrated formulation (stock solution), but dispersed in a larger volume. As a result, the final concentration of the solvent is lower; the final solution (e.g., the formulation in the state of administration) is less concentrated and more dilute.

[0333] There are many ways to express concentrates and dilutions. Exemplary methods of expressing concentrates and dilutions are described below, but are not intended to be exhaustive.

[0334] Use C1V1=C2V2: To prepare a fixed amount of dilute solution from a stock solution, the following formula can be used:

[0335] C1V1=C2V2

[0336] in:

[0337] V1 = Volume of stock solution required to prepare new solution

[0338] C1 = concentration of stock solution

[0339] V2 = Final volume of new solution

[0340] C2 = Final concentration of the new solution

[0341] Using the dilution factor: To prepare a diluted solution without calculating the concentration, you can use a derivative of the above formula (which can also be used in terms of mass):

[0342] (Final volume / concentrate volume) = dilution factor.

[0343] The dilution factor (DF) can be used alone or as the denominator of a fraction. For example, a DF of 10 represents a 1:10 dilution, or 1 part concentrate + 9 parts diluent, for a total of 10 parts. This is different from the "dilution ratio," which typically refers to the ratio of parts solute to parts solvent, for example, 1:9 using the previous example. The dilution factor is related to the dilution ratio because DF is equal to parts solvent + 1 part.

[0344] Step Dilution: If the dilution factor is greater than the desired final volume, or the concentrate stock is too small to be easily measured and dispensed, one or more intermediate dilutions may be necessary. The formula Final DF = DF1 * DF2 * DF3, etc., can be used until the product reaches the appropriate final dilution.

[0345] Concentrates can be prepared in a variety of viscosities, from non-flowable, viscous concentrates to lower viscosity flowable concentrates. Furthermore, dilutions of such concentrates can be prepared by any of the aforementioned or other known methods, typically by measuring and dispensing the desired amount of concentrate into a mixing vessel or container containing, or subsequently adding, the desired diluent (e.g., water). For example, a more viscous concentrate can be measured by scooping a portion of the concentrate into a measuring vessel until the desired amount of concentrate has been deposited into the measuring vessel, and emptying the measured amount of thick ice from the measuring vessel into the mixing vessel or container using a scoop or spatula-like device. Alternatively, the desired amount of concentrate can be deposited directly into the mixing vessel or container by squeezing or cutting the desired amount of concentrate into the mixing vessel or container. Flowable concentrates of lower viscosity can be measured by simply pouring or otherwise depositing the measured desired amount of concentrate into the mixing vessel or container. Water or other diluent / solvent can then be added until the desired dilution concentration (e.g., the intended use concentration) is reached. Optionally, the concentrate / solvent mixture can be stirred and / or heated, for example, to facilitate dissolution of the concentrate, wherein more stirring or heating may be required for more viscous concentrates. In a representative embodiment, the only stirring required is provided by jostling the drum or container containing the diluted formulation as it is transported to the site of administration.

[0346] Also contemplated are embodiments in which the concentrated formulation is provided in pre-measured amounts, e.g., in an amount suitable for dilution to a desired (e.g., application state) concentration in a set final volume. For example, a concentrated formulation intended for dilution 1:1000 in water can be provided as a 1 gallon, pre-measured container that is mixed with water into a 1000 gallon container.

[0347] In addition, in all dilution embodiments, it will be understood that the amount of diluent used can reduce the volume of other admixture components (e.g., adjuvants, e.g., tank-mixed adjuvants) to be added to the final administration state formulation. It is within the scope of ordinary skill to provide for the inclusion of such tank-mixed adjuvants in the final administration state (diluted) formulation.

[0348] Representative methods for field application

[0349] Once the sulfopolymer-containing formulation is prepared at an appropriate concentration (RTU or "ready-to-use" composition), the formulation can be sprayed onto the soil where the plant or crop is being planted, grown, harvested, or any combination of the foregoing, or directly onto the plant at any stage of growth. Methods of distributing or applying the sulfopolymer-containing formulation can include broadcast spraying or spreading or targeted application. Broadcast spreading is typically used when the product needs to be distributed over a larger area, such as across a field so that the product can be spread across the field. Broadcast spreading can take various forms, such as by hand-held sprayers, tractors, airplanes, or other devices. In contrast, targeted application is typically used when it is desired to apply the product to a specific area of ​​a field or crop. Targeted application can be applied by a tractor or other spraying device.

[0350] For example, the sulfopolymer-containing formulation can be stored in a barrel or other container. The barrel can then be sealed and optionally pressurized, at which point it can be connected to any desired dispensing device (e.g., a sprayer, tractor, or airplane) and applied to the soil or crops as desired. Alternatively, the product can be applied to the soil by injection before or during sowing of the field. Another method can include mixing the product with irrigation water, wherein the product is dispensed during irrigation.

[0351] In one embodiment or in combination with any of the embodiments mentioned, the sulfopolymer-containing formulation is applied to edible plant parts, such as leaves, stems, roots, corms, bulbs, rhizomes, fruits, and / or vegetables. Such application can be carried out at any time during the plant's growth cycle, depending on the active ingredient being applied and the field application conditions. In a specific embodiment, the sulfopolymer-containing formulation is applied before or during the bud stage, before or during the flowering stage, or once fruit begins to develop or has developed, or at any time during any of these periods. The sulfopolymer-containing formulation can be applied, for example, by spraying.

[0352] The following additional disclosures and examples are included to illustrate specific embodiments of the present disclosure. Those of ordinary skill in the art will recognize that, in light of the present disclosure, many changes can be made to the specific embodiments disclosed herein without departing from the spirit and scope of the present disclosure and still achieve the same or similar results.

[0353] (XI) Additional Disclosures

[0354] Provided herein are agricultural formulations and compositions comprising sulfopolymers (eg, sulfopolyesters), and methods of using the same. In one embodiment, or in combination with any of the mentioned embodiments, the formulation or composition further comprises a rosin.

[0355] A first embodiment, or in combination with any of the above embodiments, is an agrochemical formulation comprising: at least one agrochemical active ingredient; and a sulfopolymer that has not been lyophilized. For example, the at least one agrochemical active ingredient is present in an amount at least twice as high as that in the applied form. In one embodiment, or in combination with any of the above embodiments, the formulation further comprises rosin.

[0356] Also provided is an agrochemical concentrate formulation comprising: at least one agrochemical active ingredient and a sulfopolymer that has not been freeze-dried. The formulation may further comprise rosin.

[0357] The sulfopolymers in the compositions described herein have an average molecular weight of 2 kDa to 20 kDa, 4 kDa to 18 kDa, 5 kDa to 15 kDa, 5 kDa to 12 kDa, 5 kDa to 11 kDa, 5 kDa to 10 kDa, 5 kDa to 9 kDa, 5 kDa to 8 kDa, or 5 kDa to 7 kDa.

[0358] The sulfopolymers in the compositions described herein include a glass transition temperature (Tg) of 30°C to 120°C, 30°C to 100°C, 40°C to 90°C, 40°C to 80°C, or 50°C to 70°C. g ).

[0359] In one embodiment or in combination with any of the mentioned embodiments, the sulfopolymer has a charge density of at least 0.3 meq / g, or at least 0.5 meq / g, or at least 0.7 meq / g, or at least 0.9 meq / g. Additionally or alternatively, the charge density can be at most 1.5 meq / g, or at most 1.0 meq / g, or at most 0.9 meq / g, or at most 0.8 meq / g, or at most 0.7 meq / g. In one embodiment or in combination with any of the mentioned embodiments, the sulfopolymer has a charge density of 0.3 to 1.5 meq / g, 0.3 to 0.5 meq / g, 0.5 to 0.7 meq / g, 0.7 to 1.0 meq / g, 0.9 to 1.5 meq / g, 0.5 to 1.0 meq / g, 0.6 to 1.0 meq / g, or 0.8 meq / g to 1.0 meq / g. In any of these embodiments, the sulfopolymer can be a sulfopolyester or a sulfopolyesteramide.The charge density can be calculated according to the method disclosed in US Publication No. 2014 / 0357789, which is incorporated herein by reference.

[0360] In one embodiment or in combination with any of the mentioned embodiments, there is provided a concentrate formulation, composition, combination of compositions, emulsion or mixture containing no more than 5 wt% sulfopolymer, or no more than 3 wt% sulfopolymer, or no more than 2.75 wt% sulfopolymer; or no more than 2.5 wt% sulfopolymer, or no more than 2.25 wt% sulfopolymer, or no more than 2 wt% sulfopolymer; or no more than 1.75 wt.% sulfopolymer, or no more than 1.5 wt.% sulfopolymer, or no more than 1.25 wt.% sulfopolymer; or no more than 1 wt% sulfopolymer, or no more than 0.75 wt% sulfopolymer, in each case based on the weight of the concentrate formulation. Additionally or alternatively, the concentrate, composition, combination of compositions, emulsion, or mixture contains at least 0.05 wt% sulfopolymer; or at least 0.075 wt% sulfopolymer; or at least 0.1 wt% sulfopolymer; or at least 0.2 wt% sulfopolymer; or at least 0.3 wt% sulfopolymer; or at least 0.4 wt% sulfopolymer; or at least 0.5 wt% sulfopolymer; or at least 0.75 wt% sulfopolymer; at least 0.9 wt% sulfopolymer; or at least 1 wt% sulfopolymer; or at least 1.25 wt% sulfopolymer; or at least 1.5 wt% sulfopolymer, in each case based on the weight of the concentrate, composition, combination of compositions, emulsion, or mixture. In one embodiment or in combination with any of the aforementioned embodiments, the described amount of sulfopolymer at a level of less than 3 wt% is particularly beneficial in the emulsion.

[0361] In one embodiment or in combination with any of the mentioned embodiments, a formulation is provided containing less than 10 wt.%, or no more than 9 wt.% sulfopolymer, or no more than 8 wt.% sulfopolymer, or no more than 7 wt.% sulfopolymer, or no more than 6 wt.% sulfopolymer, or no more than 5 wt.% sulfopolymer, or no more than 4 wt.% sulfopolymer, or no more than 3 wt.% sulfopolymer, or no more than 2.5 wt.% sulfopolymer, or no more than 2 wt.% sulfopolymer, or no more than 1.5 wt.% sulfopolymer, in each case based on the weight of the sulfopolymer and all water-insoluble or partially water-soluble agrochemical active ingredients in the formulation, composition, combination of compositions, emulsion or mixture. Additionally or alternatively, the formulation, composition, combination of compositions, emulsion or mixture contains at least 1 wt% sulfopolymer, or at least 1.5 wt% sulfopolymer, or at least 2 wt% sulfopolymer, or at least 3 wt% sulfopolymer, or at least 4 wt% sulfopolymer, or at least 5 wt% sulfopolymer, or at least 6 wt% sulfopolymer, in each case based on the weight of the sulfopolymer and all water-insoluble or partially water-soluble agrochemical active ingredients in the formulation, composition, combination of compositions, emulsion or mixture.

[0362] In one embodiment or in combination with any of the recited embodiments, provided is a formulation, concentrate, composition, combination of compositions, emulsion, or mixture having a high loading of a water-insoluble or partially water-soluble agrochemical active ingredient relative to the weight of the formulation, concentrate, composition, combination of compositions, emulsion, or mixture. In one embodiment or in combination with any of the mentioned use embodiments, the formulation, concentrate, composition, combination of compositions, emulsion or mixture comprises: 0.0001 wt.% to 5 wt.% of the active ingredient; at least 0.005 wt.% of the active ingredient; at least 0.01 wt.% of the active ingredient; at least 0.5 wt.% of the active ingredient; at least 1 wt.% of the active ingredient; at least 1.5 wt.% of the active ingredient; at least 2 wt.% of the active ingredient, at least 2.5 wt.% of the active ingredient; at least 3 wt.% of the active ingredient, at least 3.5 wt.% of the active ingredient; at least 4 wt.% of the active ingredient; at least 4.5 wt.% of the active ingredient; at least 5 wt.% of the active ingredient; at least 8 wt.% of the active ingredient; at least 10 wt.% of the active ingredient; at least 15 wt.% of the active ingredient; at least 20 wt.% of the active ingredient; at least 25 wt.% of the active ingredient. t.% active ingredient; at least 30 wt.% active ingredient; at least 35 wt.% active ingredient; at least 40 wt.% active ingredient; at least 45 wt.% active ingredient; or at least 50 wt.% active ingredient; for example, 5 to 75 wt.% active ingredient; 15 to 70 wt.% active ingredient; 30 to 70 wt.% active ingredient; 30 to 60 wt.% active ingredient; or 25 to 70 wt.% active ingredient; or 30 to 70 wt.% active ingredient; or 35 to 70 wt.% active ingredient; or 40 to 70 wt.% active ingredient; or 45 to 70 wt.% active ingredient; or not more than 50 wt.% active ingredient, based on the weight of the formulation, concentrate, composition, combination of compositions, emulsion or mixture.

[0363] The sulfopolymers can be used to reduce the total amount or type of surfactants relative to the total amount of a formulation, concentrate, composition, combination of compositions, emulsion, or mixture; or relative to the total amount of active ingredient in a formulation, concentrate, composition, combination of compositions, emulsion, or mixture. In one embodiment or in combination with any of the recited embodiments, there is provided a formulation, concentrate, composition, combination of compositions, emulsion, or mixture containing an agrochemical active ingredient and a sulfopolymer and containing no more than 3 wt.% surfactants in total, or no more than 2.9 wt.% surfactants, or no more than 2.75 wt.% surfactants; or no more than 2.5 wt.% surfactants, or no more than 2.25 wt.% surfactants, or no more than 2 wt.% surfactants; or no more than 1.75 wt.% surfactants, or no more than 1.5 wt.% surfactants, or no more than 1.25 wt.% surfactants, or no more than 1 wt.% surfactants, or no more than 0.75 wt.% surfactants, in each case based on the weight of the formulation, concentrate, composition, combination of compositions, emulsion, or mixture, and wherein the surfactants are determined including the sulfopolymer. Additionally or alternatively, the formulation, concentrate, composition, combination of compositions, emulsion, or mixture contains at least 0.05 wt.% surfactant; or at least 0.075 wt.% surfactant; or at least 0.1 wt.% surfactant; or at least 0.2 wt.% surfactant; or at least 0.3 wt.% surfactant; or at least 0.4 wt.% surfactant; or at least 0.5 wt.% surfactant; or at least 0.75 wt.% surfactant; at least 0.9 wt.% surfactant; or at least 1 wt.% surfactant; or at least 1.25 wt.% surfactant; or at least 1.5 wt.% surfactant, in each case based on the weight of the formulation, concentrate, composition, combination of compositions, emulsion, or mixture. These amounts can apply to any agrochemical active loading mentioned herein, or to any sulfopolymer concentration relative to other surfactants mentioned.

[0364] Often, multiple surfactants must be used in a single formulation to obtain multiple effects; or multiple different types of surfactants must be used that are specific for one class of agrochemical active ingredients. The sulfopolymer can be used as the primary surfactant that can provide multiple effects in the same formulation, or it can be the same surfactant across two or more formulations, each with a different type of agrochemical active ingredient. In one embodiment or in combination with any of the mentioned embodiments, there is provided a formulation, concentrate, composition, combination of compositions, emulsion or mixture comprising (i) the agrochemical active ingredient and (ii) one or more sulfopolymers present in an amount greater than 50 wt.%, or at least 60 wt.%, or at least 65 wt.%, or at least 70 wt.%, or at least 75 wt.%, or at least 80 wt.%, or at least 85 wt.%, or at least 90 wt.%, or at least 92 wt.%, or at least 95 wt.%, or at least 98 wt.%, or at least 99 wt.% or 100 wt.%, based on the amount present in the formulation, concentrate, or combination of the sulfopolymers. % of the total surfactants (including sulfopolymers) in the formulation, concentrate, composition, combination of compositions, emulsion, or mixture; or the weight ratio of sulfopolymer to all other surfactants (excluding sulfopolymers) is greater than 1:1, or at least 1.5:1, or at least 2:1, or at least 2.5:1, or at least 3:1, or at least 3.5:1, or at least 4:1, or at least 5:1, or at least 7:1, or at least 10:1, or at least 15:1, or at least 20:1, or at least 30:1, or at least 50:1, or at least 100:1, or at least 125:1, or at least 150:1, or at least 200:1, or at least 500:1. The formulation may optionally contain no more than the above amounts of total surfactants (including sulfopolymers) in the formulation, concentrate, composition, combination of compositions, emulsion, or mixture; for example, no more than 3 wt.% total of surfactants (including sulfopolymers) based on the weight of the formulation, concentrate, composition, combination of compositions, emulsion, or mixture, etc. The formulation, concentrate, composition, combination of compositions, emulsion or mixture may be of any loading, particularly high loading.

[0365] In one embodiment or in combination with any of the mentioned embodiments, there is provided a formulation, concentrate, composition, combination of compositions, emulsion, or mixture comprising an agrochemical active ingredient and one or more sulfopolymers, and the formulation, concentrate, composition, combination of compositions, emulsion, or mixture does not contain any other surfactant, or contains no more than 5 wt.%, or no more than 4.5 wt.%, or no more than 4 wt.%, or no more than 3.5 wt.%, or no more than 3 wt.%, or no more than 2.5 wt.%, or no more than 2 wt.%, or no more than 1.5 wt.%, or no more than 1 wt.%, or no more than 0.75 wt.%, or no more than 0.5 wt.% of other surfactants, based on the weight of the formulation, concentrate, composition, combination of compositions, emulsion, or mixture, especially a high-load concentrate.

[0366] In one embodiment or in combination with any of the embodiments mentioned, a method for preparing a plurality (two or more) of formulations is provided, wherein at least two of the formulations contain different agrochemical active ingredients, and each of the at least two formulations contains a sulfopolymer or the same sulfopolymer, optionally in any amount recited throughout this disclosure and optionally having any of the effects recited throughout this disclosure. In one embodiment or in combination with any of the embodiments described, the sulfopolymers in the at least two formulations containing different agrochemical active ingredients produce at least one common effect, such as stability, wettability, redispersibility, etc. The agrochemical active ingredient can be any of those mentioned herein.

[0367] Sulfonic polymers can have the advantage of providing two or more effects (in addition to phytotoxicity) with a single surfactant, optionally with at least one effect being a stable dispersion. In one embodiment or in combination with any of the embodiments mentioned, the sulfopolymer provides a stable dispersion and good spreadability or wettability, or a stable dispersion and low particle drift, or a stable dispersion and low vapor drift, or a stable dispersion and rainfastness, or a stable dispersion and viscosity. In one embodiment or in combination with any of the embodiments mentioned, the sulfopolymer exhibits a non-phytotoxic effect. In each of these cases, the extent of the effect can be any of the extents mentioned in the present disclosure. The amount of sulfopolymer, the amount of surfactant, and the loading in the formulation can be any of those mentioned in the present disclosure.

[0368] In other embodiments of the present invention, the weight ratio of the oil phase to the sulfopolymer in the formulation can be 500:1 to 1:1, or 400:1 to 1:1, or 300:1 to 1:1, or 250:1 to 1:1, or 200:1 to 1:1, or 150:1 to 1:1, or 100:1 to 1:1, or 90:1 to 1:1, or 80:1 to 1:1, or 70:1 to 1:1, or 60:1 to 1:1, or 50:1 to 1:1, or 40:1 to 1:1, or 30:1 to 1:1, or 100:1 to 30:1, or 100:1 to 40:1, or 100:1 to 50:1, or 100:1 to 60:1 , or 100:1 to 70:1, or 100:1 to 80:1, or 90:1 to 30:1, or 90:1 to 40:1, or 90:1 to 50:1, or 90:1 to 60:1, or 90:1 to 70:1, or 90:1 to 80:1, or 90:1 to 30:1, or 80:1 to 60:1, or 80:1 to 70:1, or 85:1 to 80:1, or 70:1 to 30:1, or 70:1 to 40:1, or 70:1 to 50:1, or 70:1 to 60:1, or 75:1 to 70:1, or 60:1 to 40:1, or 60:1 to 50:1, or 60:1 to 50:1. In other embodiments of the present invention, the emulsion formulation weight ratio of oil phase to sulfopolymer can be at least 30: 1, or at least 35: 1, or at least 40: 1, or at least 50: 1, or at least 60: 1, or at least 70: 1, or at least 80: 1, or at least 90: 1, or at least 100: 1, or at least 500: 1. In one embodiment or any of the mentioned embodiments, the formulation in which these ratios are applied is an emulsion, a ready-to-use emulsion, an emulsion concentrate, or an oil-in-water emulsion concentrate.

[0369] In other embodiments of the present invention, the ratio of the agrochemical active to the sulfopolymer in the formulation may be 500:1 to 1:1, or 400:1 to 1:1, or 300:1 to 1:1, or 250:1 to 1:1, or 200:1 to 1:1, or 150:1 to 1:1, or 100:1 to 1:1, or 90:1 to 1:1, or 80:1 to 1:1, or 70:1 to 1:1, or 60:1 to 1:1, or 50:1 to 1:1, or 40:1 to 1:1, or 30:1 to 1:1, or 100:1 to 30:1, or 100:1 to 40:1, or 100:1 to 50:1, or 100:1 to 50:1. 1, or 80:1 to 60:1, or 80:1 to 70:1, or 85:1 to 80:1, or 70:1 to 30:1, or 70:1 to 40:1, or 70:1 to 50:1, or 70:1 to 60:1, or 75:1 to 70:1, or 85:1 to 80:1, or 80:1 to 30:1, or 80:1 to 40:1, or 80:1 to 50:1, or 80:1 to 60:1, or 80 ...

[0370] In another embodiment of the present invention, the stability at high loadings of the agrochemical active on the sulfopolymer can also be quite good. For example, after standing at room temperature for at least 4 days, the stability of the formulation as determined upon oil-water phase separation and measured as the height of the clear water layer relative to the total formulation height can be less than 90%, or less than 80%, or less than 70%, or less than 60%, or less than 50%, or less than 40%, or less than 30%, or less than 25%, or less than 10%, or less than 9%, or less than 8%, or less than 7%, or less than 6%, or less than 5%, or less than 4%, or less than 3%, or less than 2%, or less than 1% or no clear water layer. In another embodiment of the present invention, the stability of the formulation after standing at room temperature for at least 6 days as determined above may be less than 90%, or less than 80%, or less than 70%, or less than 60%, or less than 50%, or less than 40%, or less than 30%, or less than 25%, or less than 10%, or less than 9%, or less than 8%, or less than 7%, or less than 6%, or less than 5%, or less than 4%, or less than 3%, or less than 2%, or less than 1% or no clear aqueous layer. In another embodiment of the present invention, the stability after standing at room temperature for at least 8 days as determined above may be less than 90%, or less than 80%, or less than 70%, or less than 60%, or less than 50%, or less than 40%, or less than 30%, or less than 25%, or less than 10%, or less than 9%, or less than 8%, or less than 7%, or less than 6%, or less than 5%, or less than 4%, or less than 3%, or less than 2%, or less than 1% or no clear aqueous layer. In another embodiment of the present invention, the stability after standing at room temperature for at least 10 days as determined above may be less than 90%, or less than 80%, or less than 70%, or less than 60%, or less than 50%, or less than 40%, or less than 30%, or less than 25%, or less than 10%, or less than 9%, or less than 8%, or less than 7%, or less than 6%, or less than 5%, or less than 4%, or less than 3%, or less than 2%, or less than 1% or no clear aqueous layer. In another embodiment of the present invention, the stability after standing at room temperature for at least 14 days as determined above may be less than 90%, or less than 80%, or less than 70%, or less than 60%, or less than 50%, or less than 40%, or less than 30%, or less than 25%, or less than 10%, or less than 9%, or less than 8%, or less than 7%, or less than 6%, or less than 5%, or less than 4%, or less than 3%, or less than 2%, or less than 1% or no clear aqueous layer. The measurement of separation can be further determined as described in the working examples. Rosin may be included in or combined with any of the other ingredients in any formulation described herein (eg, a concentrate, or as used in a formulation, composition, suspension, emulsion, dispersion, or adjuvant kit).Rosin can be added to the formulations of the present invention, either to the concentrate formulation ("in the tank"), to the RTU, or when diluting the concentrate ("in the drum"). Rosin can increase the viscosity of the formulation and act to physically or mechanically assist in suspending the particles, and also resist changes in particle size (whether solid or liquid, as described throughout the text) over time, making it more difficult for the particles to come into contact with each other and coalesce or agglomerate, thereby assisting in further stabilizing suspensions and emulsions.

[0371] In one embodiment or in combination with any of the aforementioned embodiments, the formulation, composition, combination of compositions, emulsion, dispersion, or mixture further comprises rosin, such as rosin resin and / or rosin ester. The rosin can include methyl esters of rosin, glycerol esters of rosin, triethylene glycol esters of rosin, pentaerythritol esters of rosin, and optionally, any rosin is hydrogenated before or after derivatization (e.g., esterification).

[0372] Optionally, the formulation, composition, combination of compositions, emulsion or mixture comprises at least 0.001% rosin, or at least 0.1 wt.%, or at least 0.5 wt.%, or at least 1.0 wt.%, or at least 1.5 wt.% rosin, and additionally or alternatively, at most 15 wt.%, or at most 12 wt.%, or at most 10 wt.%, or at most 8 wt.%, or at most 7 wt.%, or at most 5 wt.%, or at most 4.5 wt.%, or at most 4 wt.%, or at most 3 wt.%, or at most 2.5 wt.%, or at most 2 wt.% of any type of rosin. Exemplary ranges include 0.1 wt.% to 3 wt.%, 0.1 wt.% to 7 wt.%, 0.5 wt.% to 6.5 wt.%, 0.5 wt.% to 2.5 wt.%, 1.0 wt.% to 5.5 wt.%, 1.5 wt.% to 5.0 wt.%, 2.0 wt.% to 4.5 wt.%, 2.5 wt.% to 4.0 wt.%, 3.0 wt.% to 4.0 wt.%, or 1.0 to 2.0 wt.% of any type of rosin, relative to the total weight of the formulation, composition, combination of compositions, emulsion, dispersion, or mixture.

[0373] In one embodiment or combination with any of the mentioned embodiments, the formulation, composition, combination of compositions, emulsion, dispersion, or mixture is diluted with water at a volume ratio of 1:1, 1:5, 1:10, 1:25, 1:50, 1:75, 1:100, 1:250, 1:500, 1:750, or 1:1000.

[0374] In one embodiment or combination with any of the mentioned embodiments, the water used to prepare and / or dilute the composition, combination of compositions, concentrate, formulation, suspension, dispersion or emulsion has a total water hardness of 0 to 1500 ppm, 0 to 60 ppm, 61 to 120 ppm, 121 to 180 ppm or 181 to 1500 ppm.

[0375] In one embodiment or in combination with any of the embodiments, there is provided a composition, combination of compositions, concentrate, formulation, suspension, dispersion, or emulsion comprising water, wherein the composition, combination of compositions, concentrate, formulation, suspension, dispersion, or emulsion has a total water hardness of 0 to 1500 ppm, 0 to 60 ppm, 61 to 120 ppm, 121 to 180 ppm, or 181 to 1500 ppm. The amount of water in the composition, combination of compositions, concentrate, formulation, suspension, dispersion, or emulsion can be any amount recited in this disclosure.

[0376] In one embodiment or combination with any of the recited embodiments, the composition, combination of compositions, concentrate, formulation, suspension, dispersion or emulsion exhibits a percent spontaneity of dispersion of at least 80%, at least 90% or at least 95% as measured according to CIPAC method MT 160 using water having a total water hardness of 0 to 1500 ppm or any range therefor.

[0377] In one embodiment or in combination with any of the mentioned embodiments, the composition, combination of compositions, concentrate, formulation, suspension, dispersion or emulsion provides a diluted emulsion in which there is at most 40%, at most 30%, at most 20% or at most 10% free oil, or at most 5%, or at most 2% foam or cream formed on the top or bottom of the emulsion, or at most 40%, at most 30%, at most 20% or at most 10% free oil, or at most 5%, or at most 2% foam or cream, re-emulsified with at most ten (10) inversions of the test cylinder according to CIPAC method MT36.1.1 using CIPAC standard water having a total water hardness in the range of 0 to 1500 ppm or in any of the above ranges.

[0378] Another embodiment, or in combination with any of the aforementioned embodiments, is an agrochemical concentrate formulation comprising: 5 wt% to 90 wt% of an agrochemical active ingredient, or a mixture of two or more agrochemical active ingredients, optionally 0.1 wt% to 10 wt% of rosin, and up to 15 wt% of an unlyophilized sulfopolymer. In one embodiment, or in combination with any of the aforementioned embodiments, the formulation may further comprise 0.1 wt% to 10 wt% of rosin.

[0379] Another provided embodiment, or in combination with any of the aforementioned embodiments, is an agrochemical concentrate formulation comprising: at least one agrochemical active ingredient; and no more than 15 wt% of an unlyophilized sulfopolymer; the formulation being characterized by one or more of: dispersibility and / or reliable redispersibility of the active ingredient; high active ingredient loading; and / or increased stability of the formulation. For example, the concentrate formulation can be characterized as compared to a control agrochemical concentrate formulation that does not contain the sulfopolymer. In examples of agrochemical concentrate formulation embodiments, the control agrochemical concentrate formulation is one of the following: a formulation containing the same ingredients but omitting the sulfopolymer, or a formulation containing the same ingredients but replacing the sulfopolymer with an industry standard emulsifier. In one embodiment, or in combination with any of the aforementioned embodiments, the formulation or composition further comprises rosin.

[0380] In any of the provided formulations, the sulfopolymer can include a salt of a sulfoisophthalic acid moiety, such as 5-sodiumsulfoisophthalic acid (5-SSIPA). For example, the sulfopolymer includes a sulfopolyester, a sulfopolyamide, or a sulfopolyesteramide.

[0381] In certain exemplary formulations, the sulfopolymer comprises a sulfopolyester. The sulfopolyester may have an average molecular weight (MW) of at least 2 kDa. As a specific example, the sulfopolyester may, in some cases, comprise one or both of SPE1 or SPE2.

[0382] In any provided formulation, the agrochemical active agent may include one or more of an herbicide, insecticide, fungicide, nematicide, molluscicide, acaricide, larvicide, fertilizer, and / or hormone or other growth regulator. Any provided formulation may include: not more than 14 wt% of sulfopolyester; not more than 13 wt% of sulfopolyester; not more than 12 wt% of sulfopolyester; not more than 11 wt% of sulfopolyester; not more than 10 wt% of sulfopolyester; not more than 8 wt% of sulfopolyester; not more than 5 wt% of sulfopolyester; not more than 3 wt% of sulfopolyester; not more than 2 wt% of sulfopolyester; not more than 1 wt% of sulfopolyester; at least 0.05 wt% of sulfopolyester; at least 0.075 wt% of sulfopolyester; % sulfopolyester; at least 0.1 wt % sulfopolyester; at least 0.2 wt % sulfopolyester; at least 0.3 wt % sulfopolyester; at least 0.4 wt % sulfopolyester; at least 0.5 wt % sulfopolyester; at least 0.75 wt % sulfopolyester; at least 1 wt % sulfopolyester; at least 2 wt % sulfopolyester; at least 3 wt % sulfopolyester; at least 3.5 wt % sulfopolyester; at least 4 wt % sulfopolyester, or at least 4.5 wt % sulfopolyester.

[0383] Also provided is a formulation of any of the previous embodiments, or in combination with any of the mentioned embodiments, comprising: at least 0.005 wt% active ingredient; at least 0.01 wt% active ingredient; 0.1 wt% to 5 wt% active ingredient; a minimum of 0.05 wt% active ingredient; 0.05 wt% to 75 wt% active ingredient; 15 wt% to 70 wt% active ingredient; 30 wt% to 70 wt% active ingredient; 30 wt% to 60 wt% active ingredient; or no more than 50 wt% active ingredient.

[0384] Another example is any of the previous embodiments, or a combination of any of the aforementioned embodiments, further comprising at least one additional agriculturally acceptable ingredient. In representative examples of such formulations, the at least one additional agriculturally acceptable ingredient comprises one or more of the following: a defoamer, a dispersant, a solubilizer, a viscosity reducer, an antifreeze agent, a sticker, a spreader, a drift control adjuvant, a stabilizer, a preservative, a flavor enhancer, a colorant, a masking agent, a chelating agent, an antioxidant, a buffer or other pH adjuster, a solvent, an oil, or a polymer other than a sulfopolymer.

[0385] In any of the formulation embodiments provided, or in combination with any of the referenced embodiments, the stability of the formulation can include one or more of the following: stability at above 30°C for at least two weeks; stability at above 40°C for at least two weeks; stability at above 50°C for at least two weeks; stability at 54°C for at least two weeks; stability at ambient temperature for at least two months; stability at ambient temperature for at least four months; stability at ambient temperature for at least six months; stability at ambient temperature for at least eight months; stability at ambient temperature for at least one year; stability at 10°C or below for at least two weeks; stability at 8°C or below for at least two weeks; stability at 5°C or below for at least two weeks; or stability at 5°C for at least two weeks.

[0386] In one embodiment or in combination with any of the aforementioned embodiments, the formulation, composition, combination of compositions, adjuvant, emulsion, or mixture further comprises rosin, such as rosin resin and / or rosin ester. The rosin can include methyl esters of rosin, glycerol esters of rosin, triethylene glycol esters of rosin, pentaerythritol esters of rosin, and optionally, any rosin is hydrogenated before or after derivatization (e.g., esterification).

[0387] Optionally, the formulation, composition, combination of compositions, emulsion, adjuvant or mixture comprises at least 0.001% rosin, or at least 0.1 wt.%, or at least 0.5 wt.%, or at least 1.0 wt.%, or at least 1.5 wt.% rosin, and additionally or alternatively, at most 15 wt.%, or at most 12 wt.%, or at most 10 wt.%, or at most 8 wt.%, or at most 7 wt.%, or at most 5 wt.%, or at most 4.5 wt.%, or at most 4 wt.%, or at most 3 wt.%, or at most 2.5 wt.%, or at most 2 wt.% of any type of rosin. Exemplary ranges include 0.1 wt.% to 3 wt.%, 0.1 wt.% to 7 wt.%, 0.5 wt.% to 6.5 wt.%, 0.5 wt.% to 2.5 wt.%, 1.0 wt.% to 5.5 wt.%, 1.5 wt.% to 5.0 wt.%, 2.0 wt.% to 4.5 wt.%, 2.5 wt.% to 4.0 wt.%, 3.0 wt.% to 4.0 wt.%, or 1.0 to 2.0 wt.% of any type of rosin, relative to the total weight of the formulation, composition, combination of compositions, emulsion, or mixture.

[0388] It is understood that any formulation provided herein can include recovered sulfopolyester as the sulfopolymer.

[0389] Also provided are agricultural chemical compositions in an applied state comprising any formulation provided herein diluted in water. For example, such applied state compositions would comprise: at least 0.001 wt% of the concentrate formulation; at least 0.01 wt% of the concentrate formulation; at least 0.05 wt% of the concentrate formulation; no more than 1 wt% of the concentrate formulation; no more than 5 wt% of the concentrate formulation; no more than 8 wt% of the concentrate formulation; no more than 10 wt% of the concentrate formulation; no more than 20 wt% of the concentrate formulation; no more than 25 wt% of the concentrate formulation; no more than 50 wt% of the concentrate formulation; or no more than 75 wt% of the concentrate formulation.

[0390] The agrochemical formulations and agrochemical compositions can be provided in any application state for application to the surface of plant leaves, stems, petioles, branches, flowers, fruits or roots, or to a culture medium.

[0391] Additional embodiments, or in combination with any of the embodiments mentioned, include the use of unfreeze-dried sulfopolyesters for stabilizing agricultural active agents in formulations; the use of unfreeze-dried sulfopolyesters for uniformly dispersing agricultural active agents in formulations; and the use of unfreeze-dried sulfopolyesters as surfactant adjuvants in agrochemical formulations containing agriculturally active ingredients. In any such uses, the sulfopolymer may optionally include a salt of a sulfoisophthalic acid moiety, such as 5-sodiumsulfoisophthalic acid (5-SSIPA). In other examples of such uses, the sulfopolymer includes a sulfopolyester, a sulfopolyamide, or a sulfopolyesteramide. It is also contemplated that in such uses, the sulfopolymer may include a sulfopolyester. In examples of such embodiments, the sulfopolyester has an average molecular weight (MW) of at least 2 kDa. As specific examples, the sulfopolyester may include one or both of SPE1 or SPE2. In one embodiment, or in combination with any of the embodiments mentioned, the formulation may further include rosin.

[0392] In an example of a use embodiment, or in combination with any of the mentioned embodiments, the agrochemical active agent comprises one or more of an herbicide, insecticide, fungicide, nematicide, molluscicide, acaricide, larvicide, fertilizer, and / or hormone or other growth regulator.

[0393] In an example of a use embodiment, or in combination with any of the mentioned embodiments, the use is with a composition or formulation containing: not more than 14 wt% of a sulfopolyester; not more than 13 wt% of a sulfopolyester; not more than 12 wt% of a sulfopolyester; not more than 11 wt% of a sulfopolyester; not more than 10 wt% of a sulfopolyester; not more than 8 wt% of a sulfopolyester; not more than 5 wt% of a sulfopolyester; not more than 3 wt% of a sulfopolyester; not more than 2 wt% of a sulfopolyester; not more than 1 wt% of a sulfopolyester; at least 0.0 5 wt% sulfopolyester; at least 0.075 wt% sulfopolyester; at least 0.1 wt% sulfopolyester; at least 0.2 wt% sulfopolyester; at least 0.3 wt% sulfopolyester; at least 0.4 wt% sulfopolyester; at least 0.5 wt% sulfopolyester; at least 0.75 wt% sulfopolyester; at least 1 wt% sulfopolyester; at least 2 wt% sulfopolyester; at least 3 wt% sulfopolyester; at least 3.5 wt% sulfopolyester; at least 4 wt% sulfopolyester, or at least 4.5 wt% sulfopolyester.

[0394] In other example uses, the composition or formulation contains: at least 0.005 wt% of the active ingredient; at least 0.01 wt% of the active ingredient; 0.1 wt% to 5 wt% of the active ingredient; at least 0.5 wt% of the active ingredient; 5 wt% to 75 wt% of the active ingredient; 15 wt% to 70 wt% of the active ingredient; 30 wt% to 70 wt% of the active ingredient; 30 wt% to 60 wt% of the active ingredient; or no more than 50 wt% of the active ingredient. Optionally, in the examples of the uses provided, the composition or formulation further includes at least one additional agriculturally acceptable ingredient. For example, the at least one additional agriculturally acceptable ingredient may include one or more of the following: defoamers, dispersants, solubilizers, viscosity reducers, antifreeze agents, adhesives, spreaders, drift control adjuvants, stabilizers, preservatives, flavor enhancers, colorants, masking agents, chelating agents, antioxidants, buffers or other pH adjusters, solvents, oils, or polymers other than sulfopolymers.

[0395] It is contemplated that in any provided use embodiment, or in combination with any of the mentioned embodiments, there are instances where the sulfopolymer comprises a recycled sulfopolyester.

[0396] Also provided are the purposes of the preparations as herein described in the application state agrochemical compositions for application to plants, plant parts or culture media. For example, such purposes can include diluting a certain volume of the preparation in at least isopykalemic water. For example, the preparation is diluted into water with the following volume ratio: 1:1, 2:3, 1:2, 2:4, 1:3, 2:7, 1:4, 2:9, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:50, 1:100, 1:150, 1:200, 1:250, 1:500, 1:750, 1:1000, or a ratio more dilute than 1:1000.

[0397] Also provided is an agrochemical formulation in a ready-to-use state, comprising: at least one agrochemical active ingredient and an unlyophilized sulfopolyester. For example, such an aqueous formulation in a ready-to-use state is readily redispersible after settling. In one embodiment, or in combination with any of the aforementioned embodiments, the formulation or composition further comprises rosin.

[0398] Another embodiment, or in combination with any of the aforementioned embodiments, is an agrochemical formulation in an applied state comprising: at least one agrochemical active ingredient, and a sulfopolymer that has not been lyophilized. In one embodiment, or in combination with any of the aforementioned embodiments, the formulation or composition further comprises rosin.

[0399] Another embodiment, or in combination with any of the aforementioned embodiments, is an agrochemical formulation in an applied state comprising: 0.05 wt% to 20 wt% of an agrochemical active ingredient, or a mixture of two or more agrochemical active ingredients, and up to 5 wt% of an unlyophilized sulfopolymer. In one embodiment, or in combination with any of the aforementioned embodiments, the formulation or composition further comprises rosin.

[0400] Also provided are agrochemical formulations for use comprising: at least one insoluble or partially soluble agrochemical active ingredient; no more than 15 wt% of an unlyophilized sulfopolymer; the formulation being characterized by one or more of: dispersibility and / or reliable redispersibility of the active ingredient; high active ingredient loading; and / or increased stability of the formulation. For example, such a formulation may be characterized by comparison to a control agrochemical formulation for use that does not contain the sulfopolymer. For example, the control agrochemical formulation for use may be one of the following: a formulation containing the same components but omitting the sulfopolymer, or a formulation containing the same components but replacing the sulfopolymer with an industry standard emulsifier. In one embodiment, or in combination with any of the aforementioned embodiments, the formulation or composition further comprises rosin.

[0401] In the examples of the administered formulations and concentrate formulations described herein, the sulfopolymer includes a salt of a sulfoisophthalic acid moiety, such as 5-sodiumsulfoisophthalic acid (5-SSIPA). For example, the sulfopolymer may include a sulfopolyester, a sulfopolyamide, or a sulfopolyesteramide.

[0402] In specific examples of administered formulations and concentrated formulations, the sulfopolymer comprises a sulfopolyester. Exemplary sulfopolyesters have an average molecular weight (MW) of at least 2 kDa. As specific examples, the sulfopolyester can comprise one or both of SPE1 or SPE2.

[0403] In the above examples of application formulations, the agrochemical active agent may include one or more of herbicides, insecticides, fungicides, nematicides, molluscicides, acaricides, larvicides, fertilizers, and / or hormones or other growth regulators.

[0404] Examples of the above-mentioned application-state preparations include: not more than 9 wt% of sulfopolyester; not more than 8 wt% of sulfopolyester; not more than 7 wt% of sulfopolyester; not more than 6 wt% of sulfopolyester; not more than 5 wt% of sulfopolyester; not more than 3 wt% of sulfopolyester; not more than 2 wt% of sulfopolyester; not more than 1 wt% of sulfopolyester; not more than 0.5 wt% of sulfopolyester; not more than 0.3 wt% of sulfopolyester; not more than 0.25 wt% of sulfopolyester; or not more than 0.1 wt% of sulfopolyester.

[0405] Examples of the above-described application formulations include: a minimum of 0.5 wt% active ingredient; 5 to 75 wt% active ingredient; 15 to 70 wt% active ingredient; 30 to 70 wt% active ingredient; 30 to 60 wt% active ingredient; or no more than 50 wt% active ingredient.

[0406] Any application formulation may further include at least one additional agriculturally acceptable ingredient. For example, the at least one additional agriculturally acceptable ingredient includes one or more of the following: a defoamer, a dispersant, a solubilizer, a viscosity reducer, an antifreeze agent, a tackifier, a spreader, a drift control adjuvant, a stabilizer, a preservative, a flavor enhancer, a colorant, a masking agent, a chelating agent, an antioxidant, a buffer or other pH adjuster, a solvent, an oil, or a polymer other than a sulfopolymer.

[0407] Also provided are applied state agrochemical compositions and preparations as herein described for the purposes of processing plants or culture medium for agricultural purposes.For example, the agricultural purposes may include one or more of the following: increasing the availability of nutrients, increasing the absorption of nutrients, increasing plant growth, reducing plant growth, increasing the formation or maturation of seeds or fruits, inhibiting insect growth or reproduction, inhibiting nematode cell growth or reproduction, inhibiting fungal growth or reproduction, inhibiting mollusk growth or reproduction, killing or repelling insects, killing or repelling nematodes, or killing or repelling mollusks.In any such purposes, active ingredient may include one or more of fertilizers, hormones or other plant growth regulators, insecticides, larvicides, acaricides, herbicides, fungicides, nematicides, rodenticides or molluscicides.

[0408] Yet another embodiment, or in combination with any of the embodiments mentioned, is a method comprising: combining unlyophilized sulfopolymer and at least one agrochemical active ingredient with water to produce a mixture. In an example of this method, the sulfopolymer is added to the mixture as a homogenous aqueous dispersion. For example, the homogenous sulfopolymer dispersion can include: a 5 wt%-40 wt% sulfopolyester solution in water; a 10 wt%-40 wt% sulfopolyester solution in water; a 20 wt%-40 wt% sulfopolyester solution in water; a 25 wt%-40 wt% sulfopolyester solution in water; a 20 wt%-35 wt% sulfopolyester solution in water; a 15 wt%-30 wt% sulfopolyester solution in water; a 10 wt%-30 wt% sulfopolyester solution in water; a 15 wt% sulfopolyester solution in water; a 20 wt% sulfopolyester solution in water; a 25 wt% sulfopolyester solution in water; a 30 wt% sulfopolyester solution in water; a 35 wt% sulfopolyester solution in water; or a 40 wt% sulfopolyester solution in water. In further examples of these methods, the sulfopolymer comprises a salt of a sulfoisophthalic acid moiety, such as 5-sodiumsulfoisophthalic acid (5-SSIPA). In further examples, the sulfopolymer comprises a sulfopolyester, a sulfopolyamide, or a sulfopolyesteramide. In one embodiment, or in combination with any of the aforementioned embodiments, rosin is further combined to produce the mixture.

[0409] In yet further examples of methods of preparing a mixture, the sulfopolymer is added to the mixture as a solid. In such examples, the method can further include heating the mixture to at least 50°C while stirring for a time sufficient to produce a substantially homogeneous composition. Alternatively, the mixture is heated to at least 60°C, at least 65°C, at least 70°C, at least 80°C, or not more than 85°C. In these examples of methods, stirring comprises high shear mixing. For example, high shear mixing comprises mixing using a propeller stirrer rotating at 10,000 rpm, or equivalent.

[0410] In examples of methods for preparing a mixture, the insoluble or partially soluble agrochemical active ingredient is added before, during, or after the heating and stirring steps. For example, the mixture can be heated and stirred before the at least one insoluble or partially soluble agrochemical active ingredient is added to the mixture. In other examples, heating the mixture includes providing water to the mixture at a temperature above ambient temperature; for example, the water can be provided to the mixture at a temperature of at least 50°C; at least 60°C; at least 70°C; at least 80°C; or above 80°C.

[0411] In any method of preparing a mixture, there are embodiments that further include adding at least one additional agriculturally acceptable ingredient. For example, the at least one additional agriculturally acceptable ingredient may include one or more of the following: a defoamer, a dispersant, a solubilizer, a viscosity reducer, an antifreeze agent, a sticker, a spreader, a drift control adjuvant, a stabilizer, a preservative, a flavor enhancer, a colorant, a masking agent, a chelating agent, an antioxidant, a buffer or other pH adjuster, a solvent, an oil, or a polymer other than a sulfopolymer.

[0412] Examples of methods for preparing the mixture are provided, wherein the resulting mixture is formulated as a suspension, solvent dispersion, or emulsion. For example, such a formulation as an emulsion can be a solvent-in-water emulsion, a water-in-solvent emulsion, an oil-in-water emulsion, or a water-in-oil emulsion.

[0413] The solid particles of agricultural active ingredients have a tendency to agglomerate when suspended in water, and when the agglomerates are large enough, the dispersion loses its stability, resulting in, for example, compacted deposition of the active ingredient on the bottom of the container. Usually, this precipitate is difficult to redisperse. However, this agglomeration and / or sedimentation phenomenon is prevented by the presence of sulfopolymers. The optimal size of any given active ingredient particle in the suspension depends on the active ingredient, indication, mode of action, target pest, expected application rate, etc. Therefore, the optimal size of the particles in the suspension concentrate or preparation is determined based on a single product. However, it is crucial that the particle size does not change significantly during storage.

[0414] Similarly, in emulsion concentrates or ready-to-use agricultural formulations, the agriculturally active ingredient is dissolved in a non-water-soluble solvent or is itself a non-water-soluble liquid. The non-water-soluble liquid can be dispersed in the aqueous phase as evenly distributed droplets. These droplets tend to aggregate into larger droplets, which can cause complete phase separation, foaming or creaming. However, these agglomeration and / or phase separation phenomena are resisted by the presence of sulfopolymers. The optimal size of the droplets in any given formulation depends on the active ingredient, indication, mode of action, target pest, expected application rate, etc. Therefore, the optimal size of particles in the emulsion or formulation is determined based on a single product. However, the key is that the particle size does not change significantly during storage.

[0415] In one embodiment or in combination with any of the mentioned embodiments, there is provided a stable formulation (e.g., a concentrate or RTU) comprising at least one water-insoluble or partially water-soluble agrochemical active ingredient and a sulfopolymer, wherein at least 50%, or at least 60%, at least 70%, or at least 80%, or at least 90%, or more than 90% of the particles in the formulation (regardless of the composition) have a particle size of less than 2 microns, or no more than 1.95 microns, or no more than 1.9 microns, or no more than 1.7 microns, or no more than 1.5 microns, or no more than 1.3 microns, or no more than 1.1 microns, or no more than 1 micron, or no more than 1 micron. More than 0.9 micron, or no more than 0.7 micron, or no more than 0.5 micron, or <0.5 micron, or no more than 450 nm, or no more than 400 nm, or no more than 350 nm, or no more than 300 nm, or no more than 250 nm, or no more than 200 nm, or no more than 150 nm, or no more than 100 nm, or no more than 90 nm, or no more than 80 nm, or no more than 70 nm, or no more than 60 nm, or no more than 50 nm, or no more than 40 nm, or no more than 30 nm, or no more than 25 nm, or no more than 20 nm, or no more than 15 nm. The formulation can contain a high load of agrochemical actives and a low amount of sulfopolymer, all as described in the present disclosure, while remaining stable.

[0416] In one embodiment or in combination with any of the mentioned embodiments, the particles in the sulfopolymer-containing formulation (regardless of the composition or what the particles contain) have an unusually small particle size. Representative polymers may have an average d90 (also known as Dv(90); the point in the size distribution up to and including 90% of the total volume of material in a sample) particle size of less than 2 microns, or no more than 1.95 microns, or no more than 1.9 microns, or no more than 1.7 microns, or no more than 1.5 microns, or no more than 1.3 microns, or no more than 1.1 microns, or no more than 1 micron, or no more than 0.9 microns, or no more than 0.7 microns, or no more than 0.5 microns, or <0.5 microns, or no more than 450 nm, or no more than 400 nm, or no more than 350 nm, or no more than 300 nm, or no more than 250 nm, or no more than 200 nm, or no more than 150 nm, or no more than 100 nm, or no more than 90 nm, or no more than 80 nm, or no more than 70 nm, or no more than 60 nm, or no more than 50 nm, or no more than 40 nm, or no more than 30 nm, or no more than 25 nm, or no more than 20 nm, or no more than 15 nm. In one embodiment or in any of the mentioned embodiments, the aforementioned particle size may be a d50 particle size.

[0417] In one embodiment or in combination with any of the aforementioned embodiments is an aqueous suspension formulation in an application state comprising: at least one water-insoluble or partially water-soluble agrochemical active ingredient, and a sulfopolymer, wherein 50%, 60%, 70%, 80%, 90% or more of the particles have a particle size of less than 2 microns, or no more than 1.95 microns, or no more than 1.9 microns, or no more than 1.7 microns, or no more than 1.5 microns, or no more than 1.3 microns, or no more than 1.1 microns, or no more than 1 micron, or no more than 0.9 microns, or no more than 0.7 microns, or not more than 0.5 micron, or <0.5 micron, or not more than 450nm, or not more than 400nm, or not more than 350nm, or not more than 300nm, or not more than 250nm, or not more than 200nm, or not more than 150nm, or not more than 100nm, or not more than 90nm, or not more than 80nm, or not more than 70nm, or not more than 60nm, or not more than 70nm, or not more than 50nm, or not more than 40nm, or not more than 30nm, or not more than 25nm, or not more than 20nm, or not more than 15nm.

[0418] In one embodiment or in combination with any of the aforementioned embodiments, a formulation (e.g., a concentrate or application-state formulation, or an emulsion, or a suspension, whether aqueous or water-in-oil) is provided in which particle or droplet size growth over time is minimal. This measurement is another indicator of stability because particles or droplets suspended in a dispersion resist agglomeration and separation from the formulation. In one embodiment or in combination with any of the embodiments mentioned, a formulation (e.g., a concentrate or application-ready formulation, or an emulsion or suspension, whether aqueous or water-in-oil) is provided, wherein the particle size of the particles contained therein does not increase by more than 100%, or by more than 80%, or by more than 75%, or by more than 70%, or by more than 60%, or by more than 55%, or by more than 50%, or by more than 45%, or by more than 40%, or by more than 35%, or by more than 30%, or by more than 25%, or by more than 20%, or by more than 15%, or by more than 10%, or by more than 5%, or by more than 4%, or by more than 3%, or by more than 2%, or by more than 1%. As indicated in the present disclosure, particles used throughout the present disclosure may be solid or liquid (e.g., droplets of a water-insoluble oil or solvent) unless explicitly stated as one or the other or the context implies one or the other. The particle size measurement increase can be any of d10 start versus d10 end, d50 start versus d50 end, or d90 start versus d90 end. The sulfopolymer may be present in the aqueous phase. The test method for determining particle size increase or growth is as follows: a well-mixed formulation is prepared and immediately deposited into a container having a height (or shoulder, if present) to diameter ratio (H / D) anywhere between 20 and 0.7, and a diameter of at least 0.5 inches; and the container is allowed to stand at 54°C and 1 atmosphere for 14 days. As a base case ("Base Case"), the particle size is measured according to the following procedure:

[0419] Particle size was measured using a Mastersizer 2000 laser diffraction particle size analyzer (Malvern Panalytical) equipped with a Hydro 2000G measuring cell before and after aging for 14 days at 54°C. One gram of concentrate was added to 10 ml of demineralized water, optionally containing 1 wt.% of Tamol DN solution according to the procedures AC used. The mixture was stirred with a pipette until homogeneous. The sample was then added to the mixing tank of the Hydro 2000G sampler. The amount of concentrate was automatically determined by the Mastersizer 2000 by measuring the obscuration while slowly adding the sample. Once the obscuration was within preset limits, a sufficient amount of sample had been added and the measurement could be performed (all performed automatically by the software). This procedure was performed at the beginning of the test and at the end of the 14-day aging test, and in the case of procedure C, at the end of the additional room temperature holding period. The particle size variation described in any example is met if obtained according to any of the following procedures AC:

[0420] A. Base case, no Tamol DN was added to the 10 ml water used to dilute 1 g of the test sample for particle size measurement at the beginning of the test, and no Tamol DN was added to the 10 ml water used to dilute 1 g of the test sample for particle size measurement at the end of the aging period.

[0421] B. Base case, at the beginning and end of the aging period, the 10 ml of water used to dilute 1 g of the test sample for particle size measurement had 1 wt.% Tamol DN. C. Base case, at the beginning of the aging test, the 10 ml of water used to dilute 1 g of the test sample for particle size measurement had 1 wt.% Tamol DN, after the end of the aging test, the sample was allowed to stand at room temperature for at least 15 additional days without stirring, and when the particle size was measured at the end of the test period, no Tamol DN was added to the 10 ml of water used to dilute 1 g of the test sample for particle size measurement.

[0422] The percent increase in particle size is determined as (final particle size - initial particle size) / initial particle size x 100. In one embodiment or in combination with any of the aforementioned embodiments, any of the particle sizes, minimums, maximums, and ranges mentioned may relate to d10, d50, and d90 particle sizes. In one embodiment or in combination with any of the aforementioned embodiments, a formulation (e.g., a concentrate or dispersion in an application-ready state, or an emulsion, suspension, or formulation, whether aqueous or water-in-oil) is provided that contains particles or water-insoluble droplets and further comprises at least one sulfopolymer having an increase in d10, d50, or d90 particle size under the same conditions in any of the aforementioned percentage amounts. In one embodiment or in any of the aforementioned embodiments, the change in particle size may be negative at the end of the test, indicating a decrease in particle size. In any of these embodiments, the formulation may also contain at least one water-insoluble or partially water-soluble agrochemical active ingredient, and the sulfopolymer type may be any of those mentioned in this disclosure, and the amount of sulfopolymer may be any of those mentioned throughout this disclosure, and the loading of the sulfopolymer and active ingredient may be any of those mentioned in this disclosure.

[0423] In one embodiment or in combination with any of the embodiments, a formulation (e.g., a concentrate or application-ready formulation, or an emulsion or suspension, whether aqueous or water-in-oil) containing a sulfopolymer is provided, wherein the formulation is viscosity stable. Viscosity stable means that the viscosity of the formulation does not change (increase or decrease) by more than 150% under the following test conditions: a thoroughly mixed formulation is prepared and immediately deposited into a container having a height (or shoulder, if present) to diameter ratio (H / D) between 20 and 0.7 and a diameter of at least 0.5 inches; and the container is allowed to stand at 54°C and 1 atmosphere for 14 days. The viscosity is measured at the start of the test and at 14 days. The percent viscosity increase is determined as the absolute value of (final viscosity - initial viscosity) / initial viscosity x 100. The viscosity is determined by measuring the viscosity of the formulation produced before and after aging at 54°C for 14 days using a Brookfield DVII+Pro viscometer at 20°C. Viscosity is measured after 1 minute using a ULA-DIN-86 spindle at a shear rate of 150 rpm. If the formulation is phase separated, the final viscosity of the formulation is measured after the formulation is flipped according to the method described in the present disclosure to determine redispersibility. If, according to the method, the formulation is no longer dispersed or still phase separated after flipping, it is considered that the formulation viscosity is unstable. Viscosity stability can also have a viscosity change of no more than 100%, or no more than 80%, or no more than 75%, or no more than 70%, or no more than 60%, or no more than 55%, or no more than 50%, or no more than 45%, or no more than 40%, or no more than 35%, or no more than 30%, or no more than 25%, or no more than 20%, or no more than 15%, or no more than 10%, or no more than 8%, or no more than 5%, or no more than 4%, or no more than 3%, or no more than 2%. In any of these embodiments, the formulation may further contain at least one water-insoluble or partially water-soluble agrochemical active ingredient, and the amount of sulfopolymer may be any of those mentioned in the present disclosure, and the loading of sulfopolymer and active ingredient may be any of those mentioned in the present disclosure, and the active ingredient may be any of those mentioned in the present disclosure.

[0424] The formulations disclosed herein may further comprise a safener. Safeners are compounds that selectively reduce the phytotoxic effects of crop protection agents, such as herbicides, on crops. Safeners can also improve the selectivity between crop plants and the weed species targeted by the herbicide. Safeners can be applied to crop seeds, or they can be applied to plants as a mixture with one or more herbicides.

[0425] In one embodiment or in combination with any of the embodiments mentioned herein, the compositions, concentrates, combinations, formulations, suspensions, emulsions, dispersions or mixtures disclosed herein further comprise a safener. Additionally or alternatively, the safener does not include quinoline-type safeners. The safener can be added to the formulation to prepare a concentrate or RTU formulation ("in a tank"), or can be a part of an adjuvant kit added to the formulation in the field with water (in a tank mix).

[0426] In one embodiment or in combination with any of the referenced embodiments provided herein, the composition, combination, concentrate, formulation, emulsion, dispersion or mixture disclosed herein does not comprise a safener.

[0427] The composition (e.g., concentrate, emulsion, formulation) exhibits a coverage per unit area of ​​at least 30% and a contact angle of at least 76°, wherein the coverage per unit area and the contact angle are measured at a dilution of 1:10 to 1:100 according to the contact angle procedure described in the specification. While not wishing to be bound by theory, those skilled in the art generally recognize that lower contact angle measurements correlate with higher coverage per unit area, provided that the measurements are made with the same formulation, concentration, and on the same or very similar substrates. More simply, one would not expect to achieve good coverage at a relatively high contact angle.

[0428] In one embodiment or combination with any of the mentioned embodiments, the composition exhibits a contact angle of at least 76°, at least 80°, at least 85°, at least 90°, at least 92°, at least 94°, at least 96°, at least 97°, at least 98°, at least 99°, at least 100°, at least 102°, at least 104°, at least 106°, at least 108°, or at least 110°, wherein the contact angle is measured according to the procedure disclosed in the specification at a dilution of 1:10 to 1:100. Additionally or alternatively, the composition exhibits a contact angle of no more than 82°, no more than 84°, no more than 86°, no more than 88°, no more than 90°, no more than 92°, no more than 94°, no more than 96°, no more than 98°, or no more than 100°, or no more than 102°, or no more than 104°, or no more than 106°, or no more than 108°, or no more than 110°, wherein the contact angle is measured according to the procedure disclosed herein at a dilution of 1:10 to 1:100.

[0429] In one embodiment or in combination with any of the embodiments mentioned, the composition exhibits a percent coverage per unit area of ​​at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 95%, wherein the percent coverage per unit area is measured according to the procedure disclosed in the specification at a dilution of 1:10 to 1:100. Additionally or alternatively, the composition exhibits a contact angle of at least 76°, at least 80°, at least 85°, at least 90°, at least 92°, at least 94°, at least 96°, at least 97°, at least 98°, at least 99°, at least 100°, at least 102°, at least 104°, at least 106°, at least 108°, or at least 110°, wherein the contact angle is measured according to the procedure disclosed in the specification at a dilution of 1:10 to 1:100.

[0430] In one embodiment or combination with any of the mentioned embodiments, the composition exhibits a percent coverage per unit area of ​​at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 95%, wherein the percent coverage per unit area is measured according to the procedure disclosed in the specification at a dilution of 1:10 to 1:100, and has a contact angle of at least 76°, at least 80°, at least 85°, at least 90°, at least 92°, at least 94°, at least 96°, at least 97°, at least 98°, at least 99°, at least 100°, at least 102°, at least 104°, at least 106°, at least 108°, or at least 110°, wherein the contact angle is measured according to the procedure disclosed in the specification at a dilution of 1:10 to 1:100. For example, the composition exhibits a coverage per unit area of ​​at least 30% and a contact angle of at least 76°, or at least 40% and a contact angle of at least 76° or at least 80°, or at least 50% coverage per unit area and a contact angle of at least 76° or at least 80° or at least 85°, or at least 60% coverage per unit area and a contact angle of at least 85° or at least 90°, or at least 70% coverage per unit area and a contact angle of at least 90° or at least 95°.

[0431] (XII) Examples

[0432] Examples 1-24: Preparation and characterization of representative SC formulations

[0433] General test procedures for SC preparations:

[0434] The water used in the following examples was tap water from the municipal water system of Ghent, BE, and was used without further purification or filtration. 23 and FLK is a product of Solvay and is obtained through distribution. BC Antifoam FDK is a product of Basildon Chemical Company and is obtained through distribution. TERGITOL TM is a product of Dow, obtained through distribution. Sulfopolyester 1 (SPE1) and Sulfopolyester 2 (SPE2), FORALYN TM , ZiramPhyto 97%, and Thiram Phyto 99% are products of and were obtained from Eastman Chemical.

[0435] For small volume formulations, a four-blade stirrer with a 5 cm or 10 cm diameter MINITAR 40 controls to achieve mixing. For high shear mixtures, use T25digital Agitation was accomplished with a disperser mixer stirring at 10,000 RPM.

[0436] Preparation of 30% dispersion of sulfopolymer 1 (SPE1):

[0437] A stock dispersion of SPE1 in water was prepared by suspending pellets of SPE1 (1500 g) in water (3500 ml). The resulting suspension was heated to 80° C. with stirring and held at 80° C. for 30 minutes, then cooled to room temperature to afford a light yellow stock dispersion that was used without further purification.

[0438] Preparation of 30% dispersion of sulfopolymer 2 (SPE2):

[0439] A stock dispersion of SPE2 in water was prepared by suspending pellets of SPE2 (1500 g) in water (3500 ml). The resulting suspension was heated to 80° C. with stirring and held at 80° C. for 30 minutes, then cooled to room temperature to provide a light yellow stock dispersion that was used without further purification.

[0440] Examples 1-6

[0441] At room temperature and mechanical stirring, water, diethylene glycol (DEG), emulsifier, BC Antifoam FDK and FORALYN TM (if used) into the beaker. Slowly add the active ingredient while stirring to obtain a uniform suspension. After the active ingredient is added, stir the mixture under high shear (e.g., using a rotor homogenizer) while adding 23 to provide the suspension concentrates described in Table 1.

[0442] Table 1: Suspension concentrate composition (w / w%)

[0443]

[0444]

[0445] 1 During the addition of Ziram or Thiram to the sulfopolymer-containing formulation, a paste is formed that requires high shear mixing to dissolve. After mixing, the formulation provides a stable, pourable mixture.

[0446] Stability testing of SC formulations

[0447] The suspension was poured into a 250 ml small-necked bottle (bottle diameter 6 cm, shoulder height 4.2 cm), capped and stored at room temperature for the time shown in Table 2. Stability was determined by visual inspection of each sample for sedimentation or layer formation. Sedimentation or layer formation was measured with a ruler and expressed as the height of the clear layer relative to the total height of the formulation. Each suspension was evaluated for caking and solidification by turning the bottle five times for 2 seconds each time and visually inspecting the hard cake layer formed at the bottom.

[0448] Table 2: Stability test of Examples 1-6 at room temperature

[0449]

[0450] Dispersion test

[0451] Water (100 ml) was added to a series of 100 ml graduated cylinders. Aliquots (1-5 ml) of the suspensions prepared in Examples 1-6 were added to the graduated cylinders. For each suspension concentrate prepared in Examples 1-6, an aliquot was allowed to settle to the bottom of the graduated cylinder. The cylinder was capped and inverted several times for 2 seconds to obtain a uniform dispersion of the concentrated formulation.

[0452] Examples 7-10

[0453] At room temperature and mechanical stirring, water, DEG, emulsifier, BC Antifoam FDK and FORALYN TM (if used) into the beaker. Slowly add the active ingredient while stirring to obtain a uniform suspension. After the active has been added, stir the mixture under high shear while slowly adding 23. Join Thereafter, the mixture was stirred at 10,000 rpm for an additional 10 minutes to provide the suspension concentrate described in Table 3.

[0454] Table 3: Suspension concentrate composition (w / w%)

[0455]

[0456] 1 During the addition of zinc ziram or thiram to the sulfopolymer-containing formulation, a paste is formed that requires high shear mixing to dissolve. After mixing, the formulation provides a stable, pourable mixture.

[0457] Stability testing of SC formulations

[0458] The suspension was poured into 250 ml small-necked bottles (bottle diameter 6 cm, shoulder height 4.2 cm), capped and stored at 54°C for the time indicated in Table 4. Stability was determined by visual inspection of each sample for sedimentation or layer formation. After 10 days, the sedimentation of each suspension was visually assessed by measuring the amount of clear liquid on top of the formulation relative to the total height of the formulation (data reported as percentages in Table 4, and agglomeration and solidification were assessed by inverting the bottle five times for 2 seconds each time and visually inspecting the hard cake layer formed at the bottom). After this inversion, the bottles were stored at 54°C for an additional 4 days to provide a total of 14 days of storage at 54°C. Images of the bottles after 10 days of storage at 54°C, as shown Figure 1 shown.

[0459] Table 4: Stability test of Examples 7-10 at 54°C

[0460] time Example 7 Example 8 Example 9 Example 10 T＝0 Stablize Stablize Stablize Stablize 10 days 9％ 12％ 12％ 14％ 10-day rollover No lumps No lumps No lumps No lumps

[0461] Dispersion test

[0462] Water (100 ml) was added to a series of 100 ml graduated cylinders. Aliquots (1-5 ml) of the suspension concentrates prepared in Examples 7-10 were added to the graduated cylinders. After the formulation concentrates prepared in Examples 7-10 were added, The graduated cylinder was capped and inverted 1-5 times for 2 seconds each time. After inversion and standing at room temperature for 2 hours, a visual inspection of the diluted formulation was performed immediately. Sedimentation of the diluted formulation was observed as a relatively opaque layer at the top of the graduated cylinder and measured using a scale. The diluted formulation samples were also stored at 54°C for 14 days, after which minimal sedimentation was observed. By inverting 1-5 times for 2 seconds each time, all samples were easily redispersed. The results are listed in Table 5. Figure 2 Images of the formulations of Examples 7-10 are shown after dilution and settling for 2 h at room temperature.

[0463] Table 5: Dilution results and stability of Examples 7-10

[0464] Concentrate Source Example 7 Example 8 Example 9 Example 10 Water (ml) 100 100 100 100 Preparation concentrate (ml) 10 10 10 10 t=0 transparent layer height (ml) 4 0 0 4 t=2h transparent layer height (ml) 20 0 0 4

[0465] Examples 11-14

[0466] At room temperature and mechanical stirring, water, DEG, emulsifier, BC Antifoam FDK and FORALYN TM (if used) into the beaker. Slowly add the active ingredient while stirring to obtain a uniform suspension. After the active ingredient is added, stir the mixture under high shear while adding 23 to provide the suspension concentrate described in Table 6.

[0467] Table 6: Suspension concentrate (w / w%)

[0468]

[0469]

[0470] 1 During the addition of zinc ziram or thiram to the sulfopolymer-containing formulation, a paste is formed that requires high shear mixing to dissolve. After mixing, the formulation provides a stable, pourable mixture.

[0471] Stability testing of SC formulations

[0472] The suspension concentrate was poured into 250 ml small-necked bottles (bottle diameter 6 cm, shoulder height 4.2 cm), capped and stored at 54 ° C for the time shown in Table 7. Stability was determined by visual inspection of the sedimentation or layer formation of each sample. The amount of sedimentation was quantified by measuring the height of the transparent layer on the top of the preparation, and the relative sedimentation was expressed as a percentage of the total height of the preparation. After 10 days, the caking and solidification of each suspension were assessed by turning the bottle over three times, each time for 2 seconds, and visually inspecting the hard cake layer formed at the bottom. After the overturn, the sample was poured out from the bottle to check for sediment formation. Examples 13 and 14 produced a small layer of sediment at the bottom of the bottle, which looked like a viscous paste. The paste was easily dissolved by adding a small amount of water and manually stirring.

[0473] Table 7: Stability test of Examples 11-14 at 54°C

[0474] time Example 11 Example 12 Example 13 Example 14 T＝0 Stablize Stablize Stablize Stablize 5 days 4％ 3％ Stablize 2％ 10 days 8％ 6％ 14％ 6％ 10 days after flipping No lumps No lumps No lumps No lumps

[0475] Dispersion test

[0476] Water (100 ml) was added to a series of 100 ml graduated cylinders. An aliquot (1 ml) of the suspension prepared in Examples 11-14 was added to the graduated cylinder. After adding the formulation concentrate prepared in Examples 7-10, the graduated cylinder was flipped 1-5 times and held for 2 seconds. A visual inspection of the diluted formulation was performed immediately after flipping and leaving it at room temperature for 1 hour. It was observed that the sedimentation of the diluted formulation was a relatively opaque layer at the top of the graduated cylinder and was measured using a scale. The diluted formulation samples were also stored at 54°C for 14 days after which minimal sedimentation was observed. By flipping 1-5 times for 2 seconds each time, all were easily redispersed. The results are listed in Table 8. The images of the diluted samples after standing for 1 hour are shown in Table 8. Figure 3 middle.

[0477] Table 8: Dilution results and stability of Examples 11-14

[0478] Concentrate Source Example 11 Example 12 Example 13 Example 14 Water (ml) 100 100 100 100 Preparation concentrate (ml) 1 1 1 1 t=0 transparent layer height (ml) 0 0 0 0 t=1h transparent layer height (ml) 0 0 0 0

[0479] Examples 15-18

[0480] At room temperature and mechanical stirring, water, DEG, emulsifier, BC Antifoam FDK and (if using) add to beaker. For example, include TERGITOL TM XD, the resulting suspension was heated under gentle stirring. The active ingredient was slowly added under stirring to obtain a uniform suspension. After the addition of the active ingredient, the mixture was stirred under high shear while adding 23 to provide the suspension concentrate described in Table 9.

[0481] Table 9: Suspension concentrate (w / w %)

[0482]

[0483] Stability testing of SC formulations

[0484] The suspension concentrate was poured into 250 ml small-necked bottles (bottle diameter 6 cm, shoulder height 4.2 cm), capped and stored at 54°C for the time shown in Table 10. Stability was determined by visual inspection of each sample for sedimentation or layer formation. The amount of sedimentation was quantified by measuring the height of the clear layer on top of the formulation, and the relative sedimentation was expressed as a percentage of the total height of the formulation. After 14 days, each suspension was evaluated for agglomeration and solidification by turning the bottle three times for 2 seconds each time and visually inspecting the hard cake layer formed at the bottom. After turning, the sample was poured out of the bottle to check for precipitate formation. Examples 13 and 14 produced a thin layer of precipitate at the bottom of the bottle, which appeared to be a viscous paste. The paste was easily dissolved by adding a small amount of water and stirring manually. Images of the formulations after 14 days at 54°C are shown in Figure 4 middle.

[0485] Table 10: Stability test at 54°C

[0486] time Example 15 Example 16 Example 17 Example 18 T＝0 Stablize Stablize Stablize Stablize 5 days Stablize Stablize Stablize Stablize 10 days 5％ 3％ 3％ 3％ 14 days 5％ 3％ 3％ 3％ 14 days + rollover No lumps No lumps No lumps No lumps

[0487] Dispersion test: visual assessment

[0488] Water (100ml) was added to a series of 100ml graduated cylinders. An aliquot (1-5ml) of the suspension prepared in Examples 15-18 was added to the graduated cylinder. After adding the formulation concentrate prepared in Examples 15-18, the graduated cylinder was flipped 1-5 times and held for 2 seconds. After flipping and placing at room temperature for 8h, a visual inspection of the diluted formulation was performed immediately. It was observed that the sedimentation of the diluted formulation was a relatively opaque layer at the top of the graduated cylinder and was measured using a scale. The results are listed in Table 11. After standing for 8h, the image of the diluted sample is shown in FIG. Figure 5 middle.

[0489] Diluted formulation samples were also stored at 54°C for 14 days after which minimal settling was observed, and they were all easily redispersed by inverting 1-5 times for 2 seconds each. All formulations prepared in Examples 15-18 were stable, with no settling observed during dilution testing.

[0490] Table 11: Dispersibility results of Examples 15-18 after 8 hours at room temperature

[0491] Concentrate Source Example 15 Example 16 Example 17 Example 18 Water (ml) 100 100 100 100 Preparation concentrate (ml) 1 1 1 1 t=0 transparent layer height (ml) 0 0 0 0 t=8h transparent layer height (ml) 3 2 2 2

[0492] Dispersion Testing: Residual Assessment

[0493] A total of 5.00 g of the suspension (equal to 2.5 g of dry matter) is added to a 100 ml beaker before adding 15 ml of standard water "type D" (342 ppm hardness, pH 6-7). The mixture is shaken by hand at 120 rpm for 2 minutes.

[0494] After shaking, the suspension was allowed to stand for 4 minutes. The suspension was then quantitatively transferred to a specially manufactured 250ml graduated cylinder with a glass lid; the distance between the 0ml and 250ml marks was 20 to 21.5cm, and the distance between the 250ml mark and the glass lid was 4 to 6cm. The graduated cylinder was graduated every 5ml. Once the suspension was transferred to the graduated cylinder, the mixture was diluted to the 250ml mark with type D standard water. The glass lid was then installed, and the mixture was then flipped 30 times (180° flips) within 1 minute. After flipping, the graduated cylinder was allowed to stand for 30 minutes. After standing for 1 minute, foam formation could also be assessed.

[0495] After standing for 30 minutes, a 40 cm long, 5 mm diameter glass pipette was used to remove the top of the liquid by suction, so that only the bottom 25 ml of suspension remained in the graduated cylinder. This 25 ml was then quantitatively transferred to a petri dish coated with tar and placed in a warm water bath (70-100° C.) to dry. Once most of the water had evaporated, the petri dish was left in a baking oven (70-90° C.) for approximately 2 hours to remove any remaining water. The petri dish was then cooled to room temperature and the amount of sediment was weighed. The amount of sediment relative to the amount of dry matter (introduced into the graduated cylinder) was then calculated to obtain the percentage of dispersibility.

[0496] The dispersibility of the formulations of Examples 15-18 was tested before and after storage (14 days at 54°C). The results are shown in Table 12.

[0497] Table 12: Dispersibility Results for Examples 15-18

[0498] Example 15 Example 16 Example 17 Example 18 Before storage 99.20％ 98.29％ 98.72％ 97.11％ After 14 days at 54°C 98.70％ 97.63％ 98.52％ 97.29％

[0499] Examples 19-24

[0500] At room temperature and mechanical stirring, water, DEG, emulsifier, BC Antifoam FDK and (if used) into the beaker. Slowly add Captan 95% fungicide / bactericide while stirring to obtain a uniform suspension. After the active ingredient is added, stir the mixture under high shear while adding 23 to provide the suspension concentrate described in Table 13.

[0501] Table 13: Suspension concentrate (w / w%)

[0502]

[0503]

[0504] Stability testing of SC formulations

[0505] The suspension was poured into 250 ml small-necked bottles (bottle diameter 6 cm, shoulder height 4.2 cm), capped and stored at room temperature for the time shown in Table 14. Stability was determined by visual inspection of each sample for sedimentation or layer formation. If layer formation was noted, it was quantified by measuring the height of the clear layer at the top and expressed as a percentage of the clear layer relative to the total height of the formulation. After 10 days, each suspension was assessed for caking and solidification by flipping the bottle three times for 2 seconds each time and visually inspecting the hard cake layer formed at the bottom. The results of the stability tests are shown in Table 14. Images of the formulations of Examples 19-24 are shown in Table 14. Figure 6 middle.

[0506] Table 14: Stability test at room temperature

[0507] time Example 19 Example 20 Example 21 Example 22 Example 23 Example 24 T＝0 Stablize Stablize Stablize Stablize Stablize Stablize 1 day Small top floor Small top floor gel Stablize Small top floor gel 10 days Small top floor Top floor gel Stablize Top floor gel 10-day rollover No lumps Block formation gel No lumps Block formation gel

[0508] Examples 25-47 and 49

[0509] Preparation and characterization of representative EW formulations

[0510] General test procedures for EW preparations:

[0511] The water used in the following examples was tap water from the municipal water system of Ghent, BE, and was used without further purification or filtration. 23 and FLK is a product of Solvay and is obtained through distribution. BC Antifoam FDK is a product of Basildon Chemical Company and is obtained through distribution. TERGITOL TM A product of Dow, obtained through distribution. Radia 7956 - Methylated Seed Oil (MSO) obtained from Oleon. Petronas White Oil (PWO) obtained from Petronas Lubricants. Banana Oil obtained from Petronas Lubricants. Rosin FORALYN TM and ABALYN TM Obtained from Eastman Chemical Company. Sulfopolyester 1 (SPE1) and sulfopolyester 2 (SPE2) were obtained from Eastman Chemical Company. SOLVESSO TM 150ND is a product of ExxonMobil and is available through distributors. For small volume formulations, a four-blade stirrer equipped with a 5 cm or 10 cm diameter MINITAR 40 controls to achieve mixing. For high shear mixtures, use T25digital Agitation was accomplished with the mixer stirring at 10,000 RPM.

[0512] Preparation of 30% SPE1 dispersion:

[0513] A stock dispersion of SPE1 in water was prepared by suspending pellets of SPE1 (1500 g) in water (3500 ml). The resulting suspension was heated to 80° C. with stirring and held at 80° C. for 30 minutes, then cooled to room temperature to provide a light yellow 30% stock dispersion that was used without further purification.

[0514] Preparation of 30 wt% dispersion of SPE2:

[0515] A stock dispersion of SPE2 in water was prepared by suspending pellets of SPE2 (1500 g) in water (3500 ml). The resulting suspension was heated to 80° C. with stirring and held at 80° C. for 30 minutes, then cooled to room temperature to provide a light yellow 30% stock dispersion that was used without further purification.

[0516] The emulsions characterized in these examples were prepared according to one of the following two general methods. Details of the formulation preparation are shown in Table 15.

[0517] Emulsion preparation method 1:

[0518] Water is placed in a beaker and heated to 80°C with stirring. Solid particles of sulfopolyester (SPE1) are added (the desired amount to achieve the desired wt% in the final formulation) and the suspension is stirred at 80°C until the particles are completely dispersed. In a separate beaker, the oil phase is heated to 80°C with stirring. After the sulfopolyester is completely dispersed, BC Antifoam FDK is added to the beaker containing the sulfopolyester under high shear. After the defoamer is added, the oil phase is added to the water layer at 80°C over approximately 1 minute. The resulting mixture is stirred under high shear for 10 minutes. Rosin (if used) is added at 80°C while stirring under high shear. After the addition of the rosin (if used), the mixture is cooled to room temperature over 25 minutes while continuing to stir under high shear to provide a milky white emulsion.

[0519] Emulsion preparation method 2:

[0520] Water is placed in a beaker and heated to 80°C with stirring. Solid particles of sulfopolyester (SPE1) are added (the desired amount to achieve the desired wt% in the final formulation) and the suspension is stirred at 80°C until the particles are completely dispersed. After the sulfopolyester is completely dispersed, BC Antifoam FDK is added to the beaker containing the sulfopolyester under high shear. After the addition of the defoamer, the oil phase (at room temperature) is added to the water layer at 80°C over approximately 1 minute. The resulting mixture is stirred under high shear for 10 minutes. Rosin (if used) is added at 80°C while stirring under high shear. After the addition of the rosin (if used), the mixture is cooled to room temperature over 25 minutes while continuing to stir under high shear to provide a milky white emulsion.

[0521] Table 15: Emulsion Formulations

[0522]

[0523] EW stability test:

[0524] The EW at room temperature was poured into a 250 ml small neck bottle (bottle diameter 6 cm, shoulder height 4.2 cm), covered and stored at room temperature for the time shown in Table 16-Table 19. By visual inspection, the separation layer of each sample was checked for stability. The degree of formation of the separation layer was measured using a ruler and expressed as a percentage of the total emulsion height. Each EW was assessed as easily re-emulsified by flipping the bottle up to five times, each flipping for 2 seconds. Figure 7 The measurement of the separation layer and the calculation of the separation percentage are shown in FIG.

[0525] EW stability test at 54°C:

[0526] The formulations prepared in Examples 23, 24, and 26 were poured into 250 ml small-necked bottles (bottle diameter 6 cm, shoulder height 4.2 cm), capped, and stored at 54°C for 14 days. Stability was determined by visual inspection of the formation of a separate layer for each sample. The degree of separation layer formation was measured using a ruler and expressed as a percentage of the total emulsion height. The results of the high temperature test are shown in Table 19. After storage at 54°C for 14 days, the images of Examples 47-49 are shown in Table 19. Figure 8 middle.

[0527] Table 16: Stability of Examples 25-32

[0528] Example 25 Example 26 Example 28 Example 29 Example 30 Example 31 Example 32 1h 69％ 69％ 76％ 63％ 63％ 88％ 93％

[0529] Table 17: Stability of Examples 33-39

[0530] Example 33 Example 34 Example 36 Example 37 Example 38 Example 39 5 days 14％ 18％ 27％ 4 days 8％ 12％ 6％

[0531] Table 18: Stability of Examples 40-45

[0532] Example 40 Example 41 Example 43 Example 44 Example 45 4 days 7％ 9％ 5％ Unseparated Unseparated

[0533] Table 19: Stability of Examples 47, 48 and 49

[0534] Example 47 Example 48 Example 49 14 days (RT) 9％ 3％ 19％ 14 days (54°C) 4％ 7％ 18％

[0535] Dispersion test:

[0536] Water (100 ml) was added to a series of 100 ml graduated cylinders. Aliquots (1-5 ml) of the suspensions prepared in Examples 47-49 were added to the graduated cylinders. The degree of spontaneous dispersion was determined by measuring the turbid layer formed using a scale on the graduated cylinder after addition of the formulation concentrates prepared in Examples 47, 48, and 49, and calculated by the following formula: Dispersion % = (Height of turbid layer / Total height of liquid) x 100. Images of the samples after dilution but before inversion are shown in Figure 9The cylinder was covered with parafilm and inverted up to 5 times for 2 seconds each. The diluted formulation was visually inspected immediately after inversion and after standing at room temperature for 4 hours, looking for a more transparent layer in the milky emulsion. The results are listed in Table 20. The image of the top of the column 4 hours after inversion is shown in Figure 10 For any diluted formulation that showed separation characteristics, a single two-second inversion redispersed the emulsion evenly throughout the cylinder (data not shown). Figure 10 Available in.

[0537] Table 20: Dispersion results of representative emulsions

[0538] Example 47 Example 48 Example 49 t=0, spontaneous dispersion 50％ 45％ 43％ t=0h, separation after flipping 0％ 0％ 0％ t=4h, separate after flipping 0％ 7％ 8％

[0539] Example 50: Preparation of neem oil emulsion

[0540] Water (26.8 ml) was placed in a beaker and heated to 80° C. with stirring. Solid particles (1 g) of sulfopolyester (SPE1 or SP) were added and the suspension was stirred at 80° C. until the particles were completely dispersed. After the sulfopolyester was completely dispersed, BC Antifoam FDK (0.2 g) was added to the beaker containing the sulfopolyester with stirring at 10,000 rpm. After the Antifoam was added, neem oil (70 g) (room temperature) was added to the aqueous layer at 80° C. with stirring at 10,000 rpm for about 1 minute. After the addition of the oil was complete, the resulting mixture was stirred under high shear for 10 minutes. The mixture was cooled to room temperature over 25 minutes while continuing to stir under high shear to provide a milky white emulsion.

[0541] Example 51: Preparation of Neem Oil Emulsion with Rosin

[0542] Water (26.8 ml) was placed in a beaker and heated to 80°C with stirring. Solid particles (1 g) of sulfopolyester (SPE1 or another SP) were added and the suspension was stirred at 80°C until the particles were completely dispersed. After the sulfopolyester was completely dispersed, BC Antifoam FDK (0.2 g) was added to the beaker containing the sulfopolyester with stirring at 10,000 rpm. After the addition of Antifoam, neem oil (70 g) (room temperature) was added to the aqueous layer at 80°C with stirring at 10,000 rpm for about 1 minute. After the addition of the oil was complete, the resulting mixture was stirred under high shear for 10 minutes. While stirring under high shear, FORALYN TM (2g) (or another rosin). TM Thereafter, the mixture was cooled to room temperature over 25 minutes while continuing to stir under high shear to provide a milky white emulsion.

[0543] Example 52: Preparation of pyraclostrobin (21 wt% formulation)

[0544] Pyraclostrobin (35 g) was added to SOLVESSO at room temperature. TM 150ND (73.4ml) and stirred until completely dissolved to provide a 35wt% solution. Water (38.8ml) is placed in a beaker and heated to 80°C under stirring. Solid particles (1g) of sulfopolyester (SPE1 or another SP) are added and the suspension is stirred at 80°C until the particles are completely dispersed. After the sulfopolyester is completely dispersed, the solution is cooled to room temperature and BC Antifoam FDK (0.2g) is added while stirring at 10,000rpm. After adding Antifoam, at room temperature, under stirring at 10,000rpm, pyraclostrobin solution (60g) (at room temperature) is added to the water layer in about 1 minute. The resulting mixture is stirred under high shear for 25 minutes to provide a milky white emulsion.

[0545] Example 53: Preparation of pyraclostrobin with rosin (21 wt% formulation)

[0546] Pyraclostrobin (35 g) was added to SOLVESSO at room temperature. TM 150ND (73.4ml) and stirred until completely dissolved to provide a 35wt% solution. Water (36.8ml) was placed in a beaker and heated to 80°C with stirring. Solid particles (1g) of sulfopolyester (SPE1 or another SP) were added and the suspension was stirred at 80°C until the particles were completely dispersed. After the sulfopolyester was completely dispersed, the solution was cooled to room temperature and BC Antifoam FDK (0.2g) was added while stirring at 10,000rpm. After the addition of Antifoam, pyraclostrobin solution (60g) (at room temperature) was added to the aqueous layer within about 1 minute at room temperature while stirring at 10,000rpm (high shear). After the addition of the organic solvent was completed, the resulting mixture was stirred under high shear for 10 minutes. While stirring under high shear, FORALYN TM (2g) (or another rosin). TM The mixture was then stirred under high shear for 25 minutes to provide a milky white emulsion.

[0547] Examples 54-59: Rainfastness Characterization of Representative Formulations

[0548] General test procedures for SC preparations:

[0549] The water used in the following examples was tap water from the municipal water system of Ghent, BE, and was used without further purification or filtration. 23 and FLK is a product of Solvay and is obtained through distribution. BC Antifoam FDK is a product of Basildon Chemical Company and is obtained through distribution. TERGITOL TM is a product of Dow, obtained through distribution. Sulfopolyester 1 (SPE1) and Sulfopolyester 2 (SPE2), FORALYN TM , Ziram Phyto 97% and Thiram Phyto 99% are products of Eastman Chemical and were obtained from Eastman Chemical. For small volume formulations, the mixture was stirred by using a four-blade stirrer equipped with a 5 cm or 10 cm diameter stirrer. Minister 40 controls the mixing. For high shear mixtures, use T25 digital The mixer was stirred at 10,000 rpm to achieve stirring.

[0550] Example 54: Preparation of 30% dispersion of SPE2:

[0551] A stock dispersion of SPE2 sulfopolyester in water was prepared by suspending pellets of SPE2 (1500 g) in water (3500 ml). The resulting suspension was heated to 80° C. with stirring and held at 80° C. for 30 minutes, then cooled to room temperature to provide a light yellow stock dispersion that was used without further purification. A similar preparation can be performed using SPE1 instead of SPE 2.

[0552] Example 55: Preparation of concentrated formulations containing SPE2

[0553] Ziram Phyto (44.44 g) was slowly added to a mixture of water (35.88 g), fluorescein (1 g), DEG (2.5 g), SPE 2 (16.65 g, a 30% dispersion prepared in Example 54), and BC Antifoam FDK (0.43 g) at room temperature with mechanical stirring. The resulting suspension was stirred at 10,000 rpm while RHODOPOL 23 (0.10 g) was added. The resulting suspension was stirred at 10,000 rpm for an additional 10 minutes to provide a milky white suspension.

[0554] Example 56: Preparation of concentrated formulation without SPE2

[0555] At room temperature, under mechanical stirring, Ziram Phyto (44.44 g) was slowly added to water (35.88 g), fluorescein (1 g) DEG (2.5 g), FLK (3.26 g) and BC Antifoam FDK (0.43 g) were added to the mixture. The resulting suspension was stirred at 10,000 rpm while adding 23 (0.10 g). The resulting suspension was stirred at 10,000 rpm for another 10 minutes to provide a milky white suspension.

[0556] Example 57: Preparation of spray mixture using the concentrate from Example 54

[0557] The suspension from Example 54 (1 g) was added to water (99 ml) at room temperature with stirring. The resulting mixture was stirred at 5000 rpm for an additional 10 minutes to provide a milky white suspension. The suspension was transferred to a handheld spray bottle.

[0558] Example 58: Preparation of spray mixture using the concentrate from Example 56

[0559] The suspension from Example 56 (1 g) was added to water (99 ml) at room temperature with stirring. The resulting mixture was stirred at 5000 rpm for an additional 10 minutes to provide a milky white suspension. The suspension was transferred to a handheld spray bottle.

[0560] Example 59: Rain resistance test

[0561] The diluted formulations prepared in Examples 57 and 58 (1 ml) were sprayed onto a set of three 3-inch square parafilm sheets stretched across a pre-weighed stainless steel plate. After spray deposition, the parafilm sheets and backing were allowed to dry overnight and weighed. Initial counts of fluorescence intensity were taken using UV light and a digital camera.

[0562] After the initial image, the samples were exposed to simulated rain at a rate of 1 inch / h in an environmental chamber at room temperature. Samples were removed at 15, 30, and 60 minutes. After removal from the chamber, the samples were dried and weighed. Residual fluorescence was measured using UV light and a digital camera and visually assessed, expressed as a comparative value.

[0563] Formulations containing SPE1 and SPE2 are expected to exhibit higher residual fluorescence (and therefore better rain resistance) in terms of both absolute fluorescence and percentage of initial fluorescence for all rain exposure durations.

[0564] Examples 60-63: Drift Reduction Characterization of Representative Formulations

[0565] General test procedures for SC preparations:

[0566] The water used in the following examples was tap water from the municipal water system of Ghent, BE, and was used without further purification or filtration. 23 and and FLK is a product of Solvay and is obtained through distribution. BC Antifoam FDK is a product of Basildon Chemical Company and is obtained through distribution. TERGITOL TM is a product of Dow, obtained through distribution. Sulfopolyester 1 (SPE1) and Sulfopolyester 2 (SPE2), FORALYN TM Ziram Phyto 97% and Thiram Phyto 99% are products of Eastman Chemical and were obtained from Eastman Chemical. Dicamba 48% SL is a 48% aqueous solution of dicamba dimethylamine salt and is a product of AgLogic Chemical and was obtained through distribution. For small volume formulations, the mixture was prepared by using a four-blade stirrer equipped with a 5 cm or 10 cm diameter stirrer. Minister 40 controls the mixing. For high shear mixtures, use T25digital The mixer was stirred at 10,000 rpm to achieve stirring.

[0567] Example 60: Preparation of 30 wt% dispersion of SPE2:

[0568] A stock dispersion of SPE2 sulfopolyester in water was prepared by suspending pellets of SPE2 (1500 g) in water (3500 ml). The resulting suspension was heated to 80° C. with stirring and held at 80° C. for 30 minutes, then cooled to room temperature to provide a light yellow stock dispersion that was used without further purification. A similar preparation can be performed using SPE1 instead of SPE 2.

[0569] Example 61: Preparation of 4.8 wt% Dicamba Solution

[0570] Dicamba 48 wt% SL (10 ml) was added to water (90 ml) under stirring at room temperature. The resulting solution was stirred at room temperature for 10 minutes, transferred to a glass bottle and sealed with a screw cap to obtain a clear liquid EP1.

[0571] Example 62: Preparation of a 4.8 wt% Dicamba Solution with 1.5% SPE2

[0572] The SPE2 dispersion prepared in Example 60 (5 ml) was added to water (85 ml) under stirring at room temperature. Dicamba 48 wt% SL (10 ml) was added to the mixture under stirring. The resulting solution was stirred at room temperature for 10 minutes, transferred to a glass bottle and capped with a screw cap to obtain a clear liquid EP2.

[0573] Example 63: Volatility Assessment

[0574] While there are many methods available for determining the impact of spray drift on agricultural products such as herbicides, volatility is often difficult to measure. This exemplary method is derived from the method described in US 2016 / 0015033 A1.

[0575] Non-dicamba tolerant soybeans were grown to the 2-4 leaf stage in 10 cm square peat pots in a growth room.

[0576] The aliquot (1 ml) of the solution prepared in Example 61 is transferred to a culture dish. The aliquot (0.5 ml) of the solution prepared in Example 61 is transferred to a second culture dish. This process is repeated for two other culture dishes, using the aliquots of the solution prepared in Example 62, obtaining a total of four culture dishes, two using the solution (EP1) of Example 61, and two using the solution (EP2) of Example 62. The culture dishes are allowed to dry completely at room temperature and are then placed at the ends of four flat plates designed to keep small potted plants (one culture dish for each flat plate). Four pots containing non-dicamba tolerant soybean plants are placed at the opposite ends of the flat plate. The plate was covered with a clear plastic growth dome with multiple 1 / 2" holes at each end. A fan was used to draw air end-to-end through the dome, with the air flow going from the end with the Petri dishes to the end with the soybean seedlings. After 24 hours, the seedlings were removed and grown in the greenhouse for an additional 7 days. After the 7-day growth period, the plants were assessed for damage due to exposure to dicamba vapor. It was anticipated that visual inspection would show that the plants in the growth chamber with solution EP2 from Example 62 (containing SPE 2) were less damaged than the plants in the growth chamber with solution EP1 from Example 61 (without sulfopolymer).

[0577] Examples 64-67: Adhesion Characterization of Representative Formulations

[0578] General test procedures for SC preparations:

[0579] The water used in the following examples was tap water from the municipal water system of Ghent, BE, and was used without further purification or filtration. 23 and FLK is a product of Solvay and is obtained through distribution. BC Antifoam FDK is a product of Basildon Chemical Company and is obtained through distribution. TERGITOL TM is a product of Dow, obtained through distribution. Sulfopolyester 1 (SPE1) and Sulfopolyester 2 (SPE2), FORALYN TM , Ziram Phyto 97% and Thiram Phyto 99% are products of Eastman Chemical and were obtained from Eastman Chemical. For small volume formulations, the mixture was stirred by using a four-blade stirrer equipped with a 5 cm or 10 cm diameter stirrer. Minister 40 controls the mixing. For high shear mixtures, use T25digital The mixer was stirred at 10,000 rpm to achieve stirring.

[0580] Example 64: Preparation of a 30 wt% dispersion of SPE2:

[0581] A stock dispersion of SPE2 sulfopolyester in water was prepared by suspending pellets of SPE2 (1500 g) in water (3500 ml). The resulting suspension was heated to 80° C. with stirring and held at 80° C. for 30 minutes, then cooled to room temperature to provide a light yellow stock dispersion that was used without further purification.

[0582] Example 65: Preparation of SPE2 (2% w / w%) SC formulation

[0583] Water (45.87 ml), DEG (2.5 g), SPE2 (6.66 g, 30 wt% dispersion) and BC Antifoam FDK (0.43 g) were added to a beaker at room temperature with mechanical stirring. Ziram Phyto (44.44 g) was slowly added with stirring. During the addition of ziram to the formulation, a paste was formed which required high shear mixing to dissolve. After the active substance was added, the mixture was stirred under high shear while slowly adding 23 (0.1 g). Thereafter, the mixture was stirred at 10,000 rpm for 10 minutes to provide a suspension concentrate E1 as a milky white suspension.

[0584] Example 66: Preparation of FLK SC formulation

[0585] At room temperature, water (50.53 ml), DEG (2.5 g), FLK (2.00) and BC Antifoam FDK (0.43g) were added to the beaker. Ziram Phyto (44.44g) was slowly added under stirring. During the addition of Ziram to the formulation, a paste was formed which required high shear mixing to dissolve. After the active substance was added, the mixture was stirred under high shear while slowly adding 23 (0.1 g). Thereafter, the mixture was stirred at 10,000 rpm for 10 minutes to provide a suspension concentrate CE1 as a milky white suspension.

[0586] Example 67: Adhesive Characterization of Formulations

[0587] Parafilm was used to simulate the waxy surface of leaves. The SC preparations of Examples 65 and 66 were diluted in water at a ratio of 10:1 and mixed to obtain a milky white dispersion. 0.5 ml of each dispersion was applied to a separate film of 2 cm square parafilm and allowed to dry overnight. The film was then immersed in a water bath at room temperature 100 times, each immersion for 2 seconds. The film was allowed to dry again. The mass of the coated film was measured and compared with the mass of the film before immersion. The results were expressed as the mass ratio after immersion to that before immersion to evaluate SPE 2 as an adhesive adjuvant. The residual mass of the SPE2 coating was higher than that of the comparative example. This method was modified from the method taught in U.S. Patent No. 9,668,472.

[0588] Examples 68-72: Spreader Characterization of Representative Formulations

[0589] It is understood in the art that contact angle measurement is a method for determining the ability of an adjuvant to achieve spreading on a waxy substrate such as a leaf. For example, WO 97 / 23281 describes the use of contact angle measurement in agricultural adjuvants.

[0590] General test procedures for SC preparations:

[0591] The water used in the following examples was tap water from the municipal water system of Ghent, BE, and was used without further purification or filtration. 23 and FLK is a product of Solvay and is obtained through distribution. BC Antifoam FDK is a product of Basildon Chemical Company and is obtained through distribution. TERGITOL TM is a product of Dow, obtained through distribution. Sulfopolyester 1 (SPE1) and Sulfopolyester 2 (SPE2), FORALYN TM, Ziram Phyto 97% and Thiram Phyto 99% are products of Eastman Chemical and were obtained from Eastman Chemical. For small volume formulations, the mixture was stirred by using a four-blade stirrer equipped with a 5 cm or 10 cm diameter stirrer. Minister 40 controls the mixing. For high shear mixtures, use T25digital The mixer was stirred at 10,000 rpm to complete the stirring. The results were performed on a DSA100 Drop Shape Analyzer using a 200 μl sample size and Parafilm as the substrate. The measurements were performed at 10 s and 5.0 fps.

[0592] Examples 68-72

[0593] At room temperature and mechanical stirring, water, DEG, emulsifier, BC Antifoam FDK and FORALYN TM (if using) add to beaker. For example, include TERGITOL TM XD, the resulting suspension was heated under gentle stirring. The active ingredient was slowly added under stirring. During the addition of ziram to the formulation containing the SPE polymer, a paste was formed which required high shear mixing to dissolve. After the active substance was added, the mixture was stirred under high shear while slowly adding 23. Join Thereafter, the resulting mixture was stirred at 10,000 rpm for an additional 10 minutes to provide the suspension concentrate described in Table 21.

[0594] Table 21: Suspension concentrate (w / w %)

[0595]

[0596] Contact angle measurement

[0597] The suspension concentrates prepared in Examples 68-72 were diluted with water (1:10). Contact angles were measured on a Parafilm substrate by depositing 200 μl onto the surface. As can be seen, the contact angles of the suspensions containing SPE were lower than those of the blank water sample, indicating that the droplets spread on the surface compared to water alone. All examples were measured four times, and the results are shown as the calculated average. The results are shown in Table 22.

[0598] Table 22: Contact angle measurements of suspension concentrates 1-4

[0599] Example# Dilution rate Average contact angle (°) 68 1:10 73.57 69 1:10 75.66 70 1:10 99.03 71 1:10 95.51 72 --- 112.2

[0600] Examples 73-74: Phytotoxicity Characterization of Representative Formulations

[0601] General experimental procedures for phytotoxicity studies:

[0602] Corn and soybean seedlings were grown in 10 cm square peat pots to the 2-4 leaf stage. Once the seedlings reached the 2-4 leaf stage, they were divided into three different test groups, each containing a minimum of five pots of each plant species. Plants were housed in a growth chamber and maintained at constant temperature and humidity levels throughout the study, with a light cycle corresponding to 14 hours on and 10 hours off. Phytotoxicity results were visually assessed. Test solutions were applied using a hand sprayer until the leaves were visually covered with solution. Tap water was used without purification.

[0603] Examples 73-74: Dilution of SPE2 Masterbatch

[0604] Add water to the beaker. At room temperature, add aliquots of the 30 wt.% SPE2 dispersion to the water with stirring to produce 10% and 1% SPE dispersions. Pour the resulting dispersions into glass bottles and cap them for use throughout the phytotoxicity studies.

[0605] Dilution of SPE2 masterbatch

[0606] Example# Water (ml) SPE2 30wt% (ml) Final concentrate 73 200 100 10％ 74 290 10 1％

[0607] Each seedling was watered at soil level every other day. At the start of the test (day 0) and every five days thereafter, the seedlings in the test group (non-control group) were treated with SPE2 (from Example 73 or Example 74) solution using a hand sprayer. Results were measured on the 14th and 30th days. The seedlings were grown for a total of 30 days, continuing to be watered every other day as described, and the test solution was applied to the leaves every 5 days. During the test period, no measured differences were expected between the control (water only) and the test plants.

[0608] Spraying of formulations onto inert surfaces and contact angle measurements

[0609] The spray behavior of suspension concentrates and emulsions containing sulfopolyesters was evaluated in the test. The amounts of sulfopolyester (SPE2), Tergitol XD, and Foralyn 5020-F used in the exemplary suspension concentrates tested are shown in Table 23 (wt %, as a percentage of the total formulation concentrate weight). In addition to the ingredients listed in Table 23, all formulations contained 40 wt.% ziram, 6 wt.% diethylene glycol, 0.5 wt.% BC Antifoam FDK (Basildon Chemical Co., Ltd.), and 0.18 wt.% Rhodopol 23 xanthan gum (Solvay SA), with the remainder being demineralized water (wt %, as a percentage of the total formulation concentrate weight).

[0610] Table 23: Surfactant Kit Compositions for SC1-SC4

[0611] Examples Tergitol XD,% SPE2,% Foralyn 5020-F,% SC1 5 0 0 SC2 5 0 2 SC3 0 5 0 SC4 0 5 2

[0612] Determination of coverage percentage

[0613] SC1-SC4 were diluted to 1% and 10% with demineralized water and sprayed onto Petri dishes using a spray cabinet. The formulations were applied using a Teejet XR 11003 nozzle at 3 bar air pressure. After spraying, the treated Petri dishes were photographed, and the percentage of surface coverage and the number of droplets were counted. Data were statistically analyzed using Revolution Analytics R software, version 3.5.2. Table 24 lists the means and standard deviations for the percentage of coverage and the number of droplets.

[0614] Table 24: Percentage coverage and number of droplets from suspension concentrate spray trials

[0615]

[0616] Analysis of variance and post hoc Tukey's test showed that the higher coverage with sulfopolyester formulations SC3 and SC4 compared to control formulations SC1 and SC2 was statistically significant at both the 1% and 10% dilutions. At the 10% dilution, sulfopolyester formulations SC3 and SC4 essentially covered the entire dish.

[0617] Figure 11 A photograph of 1% dilution of SC1, SC2, SC3 and SC4 formulations is shown. Figure 12 A photograph of the same preparation at a 10% dilution is shown.

[0618] The higher coverage achieved with the sulfopolyester formulations was not predicted by contact angle measurements. These measurements were performed using a Kruss DSA 100 Drop Shape Analyzer using 10% dilutions of SC1, SC2, SC3, and SC4. A 2 μl drop size was used with Parafilm as the substrate. Each sample was measured four times. The average values ​​of the contact angle measurements are reported in Table 25.

[0619] Table 25: Contact angle measurements of suspension concentrates, 10% dilution

[0620] Examples Average contact angle, ° SC1 73.57 SC2 75.66 SC3 99.03 SC4 95.51

[0621] The use of SPE2 resulted in higher contact angles, but coverage of the surface after spraying was significantly better. The wetting results in the spray behavior tests were clearly unexpected in view of the contact angle measurements.

[0622] Hard water tolerance of emulsion and suspension concentrates

[0623] The tolerance of water-in-water emulsions and suspension concentrates to hard water was evaluated using a standard test method published in collaboration with the International Pesticide Analysis Cooperation Committee (CIPAC). The water used for the test contained calcium and magnesium ions and was prepared according to CIPAC Method MT 18. CIPAC Standard Waters D (342 ppm hardness, MT 18.1.4) and C (500 ppm hardness, MT 18.1.3) were prepared. Custom waters with a hardness of 1000 ppm and 2000 ppm were also prepared according to CIPAC Method MT 18.4.3. The tests on these waters were compared with softened water, 0 ppm hardness. Although there are no strict standards for hard water tolerance, it is generally considered that maintaining performance up to 342 ppm is a requirement for agrochemicals in hard water areas, and it is considered that maintaining performance up to 500 ppm is desirable.

[0624] Water-in-water emulsions were prepared using the aforementioned 0, 342, 500, 1000, and 2000 ppm water. The emulsions were formulated with 65% oil, either methylated seed oil or Petronas white oil, commonly used in agrochemicals. The formulation contained 1 wt% sulfopolyester SPE2, added as a 30 wt% aqueous dispersion, 2 wt% Foralyn 5020-F, and 0.2 wt% BC Antifoam FDK (Basildon Chemical Co., Ltd.). Standard water was placed in a beaker and heated to 80°C with stirring. Solid pellets of sulfopolyester SPE2 were added, and the suspension was stirred at 80°C until the pellets were completely dispersed. After the sulfopolyester was completely dispersed, BC Antifoam FDK was added to the beaker containing the sulfopolyester under high shear. After the defoamer was added, the oil phase (at room temperature) was added to the aqueous layer at 80°C over approximately 1 minute, and the resulting mixture was stirred under high shear for 10 minutes. The resulting mixture was stirred under high shear for 10 minutes. Foralyn 5020-F was added at 80°C while stirring under high shear. After the addition of Foralyn, the mixture was cooled to room temperature over 25 minutes while continuing to stir under high shear to provide a milky white emulsion.

[0625] When prepared, all emulsions containing 65% methylated seed oil were homogeneous. Emulsions prepared with 2000 ppm hard water and 65 wt% methylated seed oil began to separate after 30 minutes and were completely separated after 2 hours. Attempts to produce a homogeneous emulsion using 65% PETRONAS white oil containing 2000 ppm water failed. All other emulsions prepared using both oils with water hardness as low as 1000 ppm were homogeneous.

[0626] The first test was a visual comparison of concentrated emulsions prepared as described in CIPAC Method 46.1.3 "Accelerated Storage Procedure Emulsion Concentrates" after aging for up to 14 days at room temperature and 54°C. The emulsions prepared as described above were transferred to glass jars and capped for aging testing. The samples were observed for any free oil that separated at the top of the bottle and for a less concentrated, more transparent layer that separated at the bottom of the bottle.

[0627] The room temperature aging results are shown in Table 26.

[0628] Table 26: Room temperature aging of concentrated oil emulsions

[0629]

[0630] No oil separation was observed upon room temperature aging. All aged samples could be easily re-emulsified with minimal agitation, no more than five inversions without vortexing or shaking.

[0631] The aging results at 54°C are shown in Table 27.

[0632] Table 27: Aging of Concentrated Oil Emulsions at 54°C

[0633]

[0634] All aged samples could be easily re-emulsified with minimal agitation, no more than five inversions without vortexing or shaking.

[0635] In addition to visual assessment, the quality of the emulsions was assessed using CIPAC Method MT 36, "Emulsion Characteristics of Emulsifiable Concentrates", Section 36.1, "Five percent v / v oil phase". Each of the above emulsions, maintained at 30°C, was diluted to a 5% concentration in a 100 ml stoppered graduated cylinder containing the corresponding standard water used to prepare the emulsion, also at 30°C. The cylinder was stoppered and inverted once, and after 30 seconds, allowed to stand to assess whether the mixture spontaneously emulsified into a uniform diluted emulsion. The initial emulsion quality results are shown in Table 28. The cylinder was then inverted ten times, and the diluted emulsion was maintained at 30°C for 24 hours. The volume of free oil and cream was recorded 30 minutes, 2 hours, and 24 hours after the series of inversions. The results of the evaluation of the emulsion stability at 30°C for different times up to 24 hours after inversion are shown in Table 29. No free oil was observed during the 24-hour test period, with the exception of the methylated seed oil at 2000 ppm water hardness. The bottom of each emulsion became less turbid during the test period, but no clear separation between the oil and water phases was observed. At 1000 ppm or less, the emulsions demonstrated relative insensitivity to water hardness.

[0636] At the end of the 24h period, the graduated cylinder was inverted ten times. The graduated cylinder was allowed to stand for 30 seconds before assessing whether the mixture had re-emulsified into a uniform diluted emulsion. The volume of free oil and emulsifiable paste was recorded 30 min after this time and the second series of inversions. After aging for 24h, the results of the re-emulsification of the emulsions after the sample inversion are shown in Table 30. All emulsions were uniform after 30 seconds of re-emulsification. The methylated seed oil emulsion prepared and tested with softened and 1000ppm water remained uniform after 30 minutes. After 30 minutes, the bottom of the other emulsions became less turbid, but there was no obvious separation between the oil phase and the aqueous phase.

[0637] Table 28: Emulsion quality 30 seconds after initial tumbling according to CIPAC MT 36.1

[0638]

[0639] Table 29: Emulsion Quality of Aged Emulsions, CIPAC MT 36.1

[0640]

[0641]

[0642] Table 30: Re-emulsification of Aged Emulsions, CIPAC Method 36.1

[0643]

[0644] Two suspension concentrates were prepared containing 40 wt.% ziram, 5 wt.% sulfopolyester SPE2, 0 or 2 wt.% Foralyn 5020-F, 6 wt.% diethylene glycol, 0.5 wt.% BC Antifoam FDK (Basildon Chemical Co., Ltd.), 0.18 wt.% Rhodopol 23 xanthan gum (Solvay SA), and the balance demineralized water. First, water, diethylene glycol, SPE2 (as a 30 wt.% dispersion in water), and BC Antifoam FDK were added to a beaker at room temperature under mechanical stirring. Rhodopol 23 was slowly added under strong mechanical stirring. After the addition of Rhodopol 23, high shear mixing was applied. Ziram Phyto was slowly added while mechanically stirring. During the addition of ziram to the formulation, a paste was formed that required high shear mixing to dissolve. After the addition of ziram, the mixture was stirred at 10,000 rpm for 10 minutes to provide a suspension concentrate as a milky white suspension.A second suspension concentrate was prepared in a similar manner except that Foralyn 5020-F was added after Rhodopol 23 and before high shear mixing.

[0645] The tolerance of these suspension concentrates to hard water was measured according to CIPAC Method MT 160 "Spontaneity of Dispersion of Suspension Concentrates". The water used for the test was 0, 342, 500, 1000 and 2000 ppm hardness prepared according to CIPAC Method MT 18, as described under the emulsions. The standard water and the suspension concentrate were equilibrated at room temperature. The density of the suspension concentrate was determined and the mass equal to a volume of 12.5 ml was calculated. A stoppered graduated cylinder was placed on a top-loading balance and 237.5 ml of standard water was added. The suspension concentrate was added, the stopper was closed and the graduated cylinder containing the diluted suspension was inverted once. The graduated cylinder was allowed to stand for 5 minutes and the top 225 ml of the diluted suspension was removed using a pipette connected to a pump. The solids content was measured for the remaining 25 ml and the suspension concentrate. The spontaneity of dispersion was calculated using the following formula:

[0646] Spontaneity of dispersion (%) = 111 (cQ) / c

[0647] Where Q = the mass of the 25 ml sample remaining in the graduated cylinder, c = (wa) / 100, a = the mass percentage of the formulation, and w = the mass of the formulation added to the graduated cylinder. Each measurement was performed in duplicate. The average values ​​of the replicates are shown in Table 31.

[0648] Table 31: Spontaneity of dispersion of suspension concentrates, CIPAC Method MT 160

[0649]

[0650] Likewise, sulfopolyester SPE2 renders the suspension concentrate relatively insensitive to hard water levels of 1000 ppm or less.

[0651] Concentrated terpene phenol emulsion

[0652] Concentrated emulsions of the terpene phenols carvacrol (CAS Reg. #499-75-2) and thymol (CAS Reg. #89-83-8) in water were prepared. The emulsions were formulated with 30 wt.%, 47.5 wt.%, and 65 wt.% of each oil, respectively. All formulations contained 1 wt.% emulsifier, either SPE2, Soprophor FL / 60, or Tergitol XD. Each emulsion contained 0.2 wt.% BC Antifoam FDK. Both carvacrol emulsions also contained 2 wt.% Foralyn 5020-F. The remainder of the emulsions was CIPAC standard water C with a hardness of 500 ppm to achieve a 100 wt.% emulsion. The carvacrol emulsions are described in Table 32 and the thymol emulsions are described in Table 33.

[0653] Table 32: Carvacrol emulsion, 1 wt% emulsifier

[0654] sample# emulsifiers Carvacrol (wt%) Foralyn 5020-F (wt%) CE1 SPE2 30 0 CE2 SPE2 47.5 0 CE3 SPE2 65 0 CE4 SPE2 65 2 CE5 Soprophor FL / 60 30 0 CE6 Soprophor FL / 60 47.5 0 CE7 Soprophor FL / 60 65 0 CE8 Soprophor FL / 60 65 2

[0655] Table 33: Thymol Emulsion, 1 wt% Emulsifier

[0656]

[0657] All emulsions were visually assessed immediately after formation. The samples were separated and two samples of the resulting mixture were stored at room temperature and 54° C. for 14 days, respectively, and evaluated as described in CIPAC Method 46.1.3, "Accelerated Storage Procedure Emulsion Concentrates." Each emulsion was transferred to a glass jar and capped for aging testing. The samples were observed for any free oil that separated at the top of the bottle and for a lower concentration, more transparent layer that separated at the bottom of the bottle. After the aging period, the re-emulsification of each emulsion under minimal agitation was assessed by flipping the emulsion no more than five times without vortexing or shaking and evaluating the separation after 30 minutes.

[0658] The room temperature aging results for the carvacrol emulsions are described in Table 34, and the results for the thymol emulsions are described in Table 35. The 54°C aging results for the carvacrol emulsions are described in Table 36, and the results for the thymol emulsions are described in Table 37.

[0659] Table 34: Room temperature aging of concentrated carvacrol emulsions

[0660] sample initial 14 days Re-emulsification CE1 Uniform Separated Uneven CE2 Uniform Separated Uniform CE3 Uniform 5% bottom layer Uniform CE4 Uniform 3% bottom layer, visible oil droplets Uniform CE5 Uniform Separated Uniform CE6 Uniform Separated Uneven CE7 Uniform Separated Uneven CE8 Uniform Separated Uneven

[0661] Table 35: Room temperature aging of concentrated thymol emulsions

[0662]

[0663]

[0664] Table 36: Aging of concentrated carvacrol emulsions at 54°C

[0665]

[0666] Table 37: Aging of concentrated thymol emulsions at 54°C

[0667] sample initial 14 days Re-emulsification TE1 Uneven Separated Uneven TE2 Uniform Separated Uniform TE3 Uniform Separated Uneven TE4 Uniform Separated Uniform TE5 Uniform Separated Uneven TE6 Uneven Separated Uneven

[0668] Two suspension concentrates were prepared containing 40 wt% ziram, 2.5 wt% sulfopolyester SPE2, 0 or 2 wt% Foralyn 5020-F, 6 wt% diethylene glycol, 0.5 wt% BC Antifoam FDK (Basildon Chemical Co., Ltd.), 0.2 wt% Rhodopol 23 xanthan gum (Solvay SA), and the remainder CIPAC Standard Water C (500 ppm hardness, prepared according to CIPAC MT 18.1.3). First, water, diethylene glycol, SPE2 (as a 30% dispersion in CIPAC Standard Water C), and BC Antifoam FDK were added to a beaker at room temperature under mechanical stirring. Rhodopol 23 was slowly added under vigorous mechanical stirring. After the addition of Rhodopol 23, high shear mixing was applied (approximately 4 minutes at 3500 rpm using a universal disintegrator). Ziram Phyto was slowly added while mechanically stirring. During the addition of ziram to the formulation, a paste formed that required high shear mixing to resuspend (approximately 4 minutes at 3500 rpm using a universal disintegrator head) to provide a milky white suspension concentrate. A second suspension concentrate was prepared in a similar manner, except that Foralyn 5020-F was added after Rhodopol 23 and before high shear mixing. A third control suspension concentrate was prepared using the same method and ingredients as the first, except that 2.5% Tergitol XD (Dow Chemical Company) was added instead of sulfopolyester SPE2.

[0669] A visual comparison was made between the prepared suspension concentrate and the suspension concentrate after aging for 14 days at 54°C as described in CIPAC Method 46.1.3, "Accelerated Storage Procedure Emulsion Concentrates." The suspension concentrate prepared as described above was transferred to a glass jar and capped for aging. After 14 days, the sample was inverted once; no lumps or sedimentation were observed. The sample was inverted a total of ten times and observed for any free oil separating at the top of the jar, compaction and sedimentation, and the formation of any small lumps or clots. The results are shown in Table 3...

Claims

1. An agricultural chemical formulation comprising: at least one agrochemical active ingredient, and An unlyophilized sulfopolymer having a T of at least 25°C g And includes: (i) residues of one or more dicarboxylic acids; (ii) 4 to 40 mole % of the residues of at least one sulfomonomer, based on the total repeating units, said sulfomonomer residues comprising a salt of a sulfoisophthalate moiety derived from sodium sulfoisophthalic acid or an ester thereof; (iii) one or more diol residues, of which at least 20 mol % based on the total diol residues are polyethylene glycol having the following structure: H-(OCH2-CH2)n-OH wherein n is an integer in the range of 2 to 500; (iv) 0 to 25 mol% of the residue of a branching monomer having 3 or more functional groups, based on the total repeating units, wherein the functional groups are hydroxyl groups, carboxyl groups, or a combination thereof.

2. The agrochemical formulation according to claim 1, which is an agrochemical concentrate formulation comprising at least one agrochemical active ingredient in an amount at least twice that in an applied form.

3. The agrochemical formulation according to claim 2, wherein the agrochemical formulation comprises: Relative to the total weight of the preparation, 5 wt% to 90 wt% of an agrochemical active ingredient or a mixture of two or more agrochemical active ingredients, and Up to 15 wt% of sulfopolymer was not lyophilized.

4. An agricultural chemical composition in an applied state, comprising the formulation according to any one of claims 2 to 3 diluted in water. The agricultural chemical composition in an applied state according to claim 4 , wherein the water has a total water hardness of 0 to 1500 ppm.

6. The agricultural chemical composition in an applied state according to any one of claims 4 to 5, comprising: at least 0.001 wt% of the concentrate formulation relative to the total weight of the composition.

7. Use of the non-lyophilized sulfopolymer according to claim 1 for stabilizing agricultural active agents in formulations.

8. Use of the formulation or composition according to any one of claims 1 to 6 for the preparation of an applied agrochemical composition for application to whole plants, plant parts or culture media.

9. The agricultural chemical composition in an applied state according to claim 4, comprising: Relative to the total weight of the preparation, 0.05 wt% to 20 wt% of an agrochemical active ingredient or a mixture of two or more agrochemical active ingredients, and Up to 5 wt% of sulfopolymer that was not lyophilized.

10. The formulation of any one of claims 1 to 3, wherein the active ingredient comprises one or more of an insecticide, herbicide, fungicide, nematicide, molluscicide, acaricide, fertilizer and / or hormone or other growth regulator.

11. The formulation of any one of claims 1-3, wherein the formulation further comprises rosin.

12. The formulation of claim 11, wherein the rosin comprises a rosin ester.

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