EA041600B1 - MICROENCAPSULATED COMPOSITION OF NITRIFICATION INHIBITOR - Google Patents

Description

Field of invention

The present invention relates to improved compositions of nitrification inhibitors, methods for their preparation and their use in agriculture.

State of the art

Nitrogen fertilizers applied to the soil are easily transformed through a number of undesirable biological and chemical phenomena, including nitrification, leaching and evaporation. Many types of transformation reduce the amount of nitrogen available for uptake by the target plant. One such mechanism is nitrification. Some common soil bacteria metabolize the ammonium form of nitrogen in the soil through nitrification, which converts the nitrogen into nitrite and nitrate forms that are more susceptible to nitrogen loss due to leaching or volatilization during denitrification.

Due to the decrease in the amount of available nitrogen due to nitrification, it is necessary to add a large amount of nitrogen fertilizers to compensate for the loss of agriculturally active nitrogen available to plants. In this regard, there is a growing need to improve the efficiency of nitrogen application in order to reduce the costs associated with the use of additional nitrogen fertilizer.

Methods for reducing nitrification include treating the soil with agriculturally active compounds that inhibit or at least reduce the metabolic activity of at least some of the soil microorganisms involved in the nitrification reaction. These compounds include (trichloromethyl)pyridines such as nitrapyrine, which are used as nitrification inhibitors in combination with fertilizers as described in US Pat. No. 3,135,594, the disclosure of which is hereby incorporated by reference in its entirety. These compounds help to preserve the ammonium form of ammonium nitrogen used in agriculture (stabilized nitrogen), thereby improving plant growth and increasing their yield. These compounds are effective in several crops including corn, sorghum and wheat.

Compounds such as nitrapyrin are unstable in soil due to their high volatility. For example, nitrapyrine has a relatively high vapor pressure (2.8x10-3 mmHg at 23°C) and a tendency to volatilize. For this reason, it must be applied immediately, or after the treatment of the fertilizer with nitrapyrine, some protection against the rapid loss of nitrapyrine should be carried out. One approach is to add nitrapyrine to a volatile fertilizer, namely anhydrous ammonia, which itself must be added to the soil in such a way as to reduce the amount of volatile active substance escaping into the atmosphere. This method is problematic, because in this case it is necessary to use anhydrous ammonia, which is an aggressive substance that must be incorporated into the soil. This method of applying nitrapyrin with incorporation deep from the soil surface is not preferred. This method is unsuitable for many other types of fertilizers and standard applications, such as dry fertilizer granules, which are most often spread on the soil surface.

Other approaches to stabilize nitrapyrine and reduce its atmospheric loss include application to the soil surface and subsequent mechanical incorporation into the soil, or application during irrigation of the soil, usually within 8 hours after its spread, to reduce the release of nitrapyrine to the atmosphere. Yet another approach is to encapsulate the nitrapyrine for rapid or immediate release. Such encapsulated forms of nitrapyrine are formulated with lignin sulfonates as described in US Pat. No. 4,746,513, the contents of which are incorporated herein by reference in their entirety. Such compositions are less volatile than nitrapyrin alone, but at the same time, these compositions are more suitable for use not with dry fertilizers, but with liquid urea ammonium nitrate (UAN) or liquid manure fertilizers. While encapsulation slows down the release of nitrapyrine, upon contact with moisture, all of the nitrapyrine is released from the capsule and the same stability and volatility problems arise as with existing applications.

Another approach to stabilize nitrapyrine involves polycondensation encapsulation. Additional information about this method can be found in US patent No. 5925464, the description of which is incorporated into the present invention by reference in its entirety. If polyurea, rather than polyurea, is used to form at least part of the capsule shell, some of these compositions are safer to handle and the storage stability of nitrapyrine is improved.

In some cases, polyurea microencapsulation has been used to provide improved nitrification inhibitor formulations for delayed, sustained release of nitrification inhibitors for fertilizer applications. Such encapsulated forms of nitrapyrine are described in US Pat.

- 1 041600

There remains a need to develop nitrification inhibitors, such as (trichloromethyl)pyridines, in a more efficient manner and with compositions having improved storage stability, as measured by reduced crystal formation over a longer period of time, and retaining high efficacy compared to non-encapsulated nitrification inhibitors.

It is known that aqueous microcapsular suspensions (e.g. capsule suspensions or CS) of nitrapyrine (so-called microencapsulated nitrapyrine) as mentioned above are more stable than unencapsulated nitrapyrine in aqueous solution under certain conditions, but at the same time, it has been found that in crystals of nitrapyrine may form in the aqueous phase of the microencapsulated suspension of nitrapyrine. The percentage by weight of crystalline nitrapyrine in the volume of the aqueous phase of the microcapsule suspension may increase over time. Depending on the type of processing of the microcapsule suspension, the measurable content of crystalline nitrapyrine in the aqueous phase may be negligible or questionable. The presence of crystalline nitrapyrine in the aqueous phase of the microcapsule suspension in an amount of even about 0.1 wt.% or more can cause serious problems if the suspension is applied by spraying through a pointed nozzle with an atomizer equipped with built-in filters.

Additionally, in some commercial embodiments, polyurea microencapsulated nitrification inhibitors such as, for example, Instinct® and Entrench® (commercial embodiments sold by Dow AgroSciences LLC) are limited in the amount of active ingredient (nitrification inhibitor) that can be microencapsulated and suspended in aqueous phase without crystallization of the active ingredient in the aqueous phase. For example, in some embodiments, the Instinct® and Entrench® formulations comprise from about 17% to about 19% by weight of the active ingredient (nitrapyrine).

Crystallization of the active ingredient in the aqueous phase is limited by the increased content of the active ingredient in such aqueous capsule suspensions. The active load in some commercial formulations of nitrapyrine capsule suspension is 200 g/l, with the upper load limit being limited by the solubility of the nitrapyrine in the solvent that is used inside the microcapsules.

In some embodiments, implementation of the present invention does not require a solvent to dissolve the nitrapyrine (and/or other active ingredient) in the lipophilic phase. In some embodiments, stable aqueous suspensions of capsule suspensions without unwanted crystal formation are described, containing up to about 300 g/l of nitrapyrine. In some embodiments of the present invention, highly loaded compositions of aqueous capsule suspensions containing nitrapyrine may include compositions that contain microencapsulated nitrapyrin in an amount of at least about 150 g/l, at least about 200 g/l, at least about 220 g/l l, at least about 240 g/l, at least about 260 g/l, at least about 280 g/l, or at least about 300 g/l.

In some aspects, the present invention relates to compositions containing up to about 300 g/l of nitrapyrine, which prevent and/or reduce the undesirable crystal formation observed in aqueous capsule suspension compositions, for example, compositions containing microencapsulated nitrapyrine in an amount of at least about 150 g /l, at least about 200 g/l, at least about 220 g/l, at least about 240 g/l, at least about 260 g/l, or at least about 280 g/l. Crystal formation in nitrification inhibitor compositions can cause problems including filter clogging during field application of the compositions. In some cases, the crystals formed in the liquid phase of the capsule suspension are high purity crystals containing substantially pure organic nitrification inhibitor, such as nitrapyrine. In some cases, the formation of crystals of high purity nitrapyrine (99 wt.%) can be observed in modern commercial compositions. The formation of crystals in some cases depends on the temperature of the composition during its processing, storage and/or transportation.

In some embodiments, the microcapsule suspension compositions of the invention are stable, high loading, agricultural liquid compositions comprising aqueous microcapsule suspensions with active ingredients having a low melting point. In some embodiments, microcapsule suspension compositions are prepared without the use of an organic solvent to dissolve the low melting point active, such as, for example, a nitrification inhibitor, such as nitrapyrine. Also, a small amount of polymeric superhydrophobic material can optionally be used to form microcapsules. In some embodiments, the nitrapyrine-containing suspension composition may include a microencapsulated hydrophobic crystal inhibitor additive to prevent or inhibit the formation or growth of nitrapyrine crystals in

- 2 041600 water phase. In some embodiments, compositions containing nitrapyrin microencapsulated suspensions that include a microencapsulated hydrophobic crystal inhibitor additive have excellent physical and chemical and/or crystal stability during storage and acceptable volatility and nitrification inhibiting properties for soil application. In some embodiments, a nitrapyrine-containing microcapsule suspension composition containing a microencapsulated hydrophobic crystal inhibitor additive has superior physical and chemical stability and/or crystal formation stability during storage compared to compositions containing only a non-microencapsulated hydrophobic crystal inhibitor additive.

In some embodiments, in the microcapsule suspension compositions described herein, upon addition to the aqueous phase (i.e., after the formation of micromicrocapsules) of a microencapsulated hydrophobic crystal inhibitor additive, the rate of formation and/or growth of crystals in the aqueous phase during storage is reduced. In one embodiment, the addition of one or more microencapsulated hydrophobic crystal inhibitor additives provides significant inhibition or reduction of crystal growth during storage. In one embodiment, by way of example, after the addition of a microencapsulated hydrophobic crystal inhibitor additive that is an aromatic solvent, there is a significant inhibition or reduction of crystal growth in the aqueous phase of the microcapsule suspension composition containing nitrapyrine.

Thus, the present invention relates to compositions and methods for preventing crystal formation and/or reducing crystal formation in highly loaded agricultural compositions containing organic nitrification inhibitors such as nitrapyrine. In some embodiments, the addition of microencapsulated hydrophobic crystal inhibitor additives is more effective in preventing crystal formation and/or reducing crystal formation in microencapsulated nitrapyrine capsule suspensions than adding non-microencapsulated hydrophobic crystal inhibitors alone. In some embodiments, the microencapsulated hydrophobic crystal inhibitor additives provide excellent physical storage stability for highly loaded microencapsulated nitrapyrin compositions at conditions from about 15 to about 55°C.

In some embodiments, one or more microencapsulated hydrophobic crystal inhibitor additives are not added to the aqueous phase, in which case, even when using a non-microencapsulated hydrophobic crystal inhibitor additive in highly loaded nitrapyrine microcapsule suspension formulations, undesirable nitrapyrine crystals may form in the aqueous phase at a temperature in the range from about 15 to about 55°C. Over time, the content of such crystals can become up to 0.5 wt.% or more of the total weight of the microcapsule suspension composition. The formation of these crystals can occur, for example, at temperatures of 15, 20, 25, 30, 35, 40, 45, 50 and 55°C. Microencapsulated hydrophobic solvent-based crystal inhibitor additives such as aromatic solvents and ester compounds can increase the physical stability of highly loaded nitrapyrine microcapsule suspension compositions by preventing or at least reducing crystal formation in the aqueous phase of the microcapsule suspension composition.

For example, added microencapsulated aromatic solvents used as hydrophobic crystal inhibitor additives may include substances such as Aromatic 100 aromatic fluid, also called solvent naphtha, or light aromatics; Aromatic 150 aromatic fluid, also called solvent naphtha, heavy aromatics, type II high boiling aromatic naphtha, heavy aromatic solvent naphtha, hydrocarbons, C10 aromatics, >1% naphthalene, A150, S150 (Solvesso 150) and Aromatic 200 fluid , also called solvent naphtha, heavy aromatics, type II high boiling aromatic naphtha, heavy aromatic solvent naphtha, hydrocarbons, C10-13 aromatics, >1% naphthalene, A200 and S200 (Solvesso 200).

The microencapsulated aromatic solvents used in some embodiments are naphthalene-lean (ND) products, or contain less than about 1% naphthalene. These microencapsulated solvents can be added to the microcapsule suspension composition before crystal formation as a prophylactic or added to the microcapsule suspension composition after crystal formation as a corrective agent to remove or reduce crystals.

In some embodiments, ester compounds comprising 2,2,4

- 3 041600 trimethyl-1,3-pentanediol monoisobutyrate.

Additionally, the microcapsule suspension compositions of the present invention can be combined or used in combination with pesticides, including arthropodicides, bactericides, fungicides, herbicides, insecticides, nematicides, nitrification inhibitors such as dicyandiamide, urease inhibitors such as N-(n-butyl)thiophosphoric triamide acids and the like, or pesticidal mixtures of these substances. The microcapsule suspension composition of the present invention used for this purpose may be tank-mixed with the desired pesticide(s) or may be applied sequentially.

The present invention relates to a microcapsule suspension composition comprising: (a) a first suspended phase of a plurality of microcapsules with particles having a median volume size of about 1 to about 10 µm, wherein the microcapsules comprise: (1) a microcapsule wall formed by an interfacial polycondensation reaction between polymeric isocyanate and polyamine to form a polyurea shell; (2) at least one nitrification-inhibiting organic compound encapsulated in a polyurea shell; (b) a second suspended phase of a plurality of microcapsules with particles having a median volume size of about 1 to about 10 µm, the microcapsules comprising: (1) a microcapsule wall formed by an interfacial polycondensation reaction between a polymeric isocyanate and a polyamine to form a polyurea shell; and (2) at least one hydrophobic crystal inhibitor additive encapsulated in a polyurea shell; and (c) an aqueous phase. In some embodiments, the aqueous phase of the microcapsule suspension composition may further comprise at least one additional ingredient selected from the group consisting of non-encapsulated hydrophobic crystal inhibitor additives, dispersants, emulsifiers, rheological agents, antifoam agents, biocides, antifreeze agents, and mixtures thereof. .

In some embodiments, the first suspended phase of the plurality of microcapsules in the composition comprises 2-chloro-6-(trichloromethyl)pyridine. In other embodiments, the implementation of the composition includes 2-chloro-6-(trichloromethyl)pyridine in an amount of from about 15 to about 40 wt.%. In other embodiments, the composition comprises at least one polymeric superhydrophobic compound contained in the first suspended phase of the plurality of microcapsules in an amount of from about 0.1 to about 2.00% by weight. In some embodiments, at least one polymeric superhydrophobic compound includes polybutene.

In some embodiments, the aqueous phase of the microcapsule suspension composition comprises a hydrophobic crystal inhibitor additive encapsulated in a second suspended phase of a plurality of microcapsules in an amount of from about 1.0 to about 10.0 wt.%, from about 2.0 to about 8, 0 wt.%, or from about 3.0 to about 7.0 wt.%. In other exemplary embodiments, the hydrophobic crystal inhibitor additive is at least one compound selected from the group consisting of aromatic solvents, e.g., naphthalene-depleted heavy aromatics and esters, such as, e.g., 2,2,4-trimethyl -1,3-pentanediol monoisobutyrate and mixtures thereof.

In some embodiments, the aqueous phase of the microcapsule suspension composition includes an emulsifier, which is a non-ionic polymeric surfactant, in an amount of from about 1.0 to about 10 wt.%. In some embodiments, the non-ionic polymeric surfactant is selected from the group consisting of polyvinyl alcohols.

In some embodiments, the aqueous phase of the microcapsule suspension composition comprises at least one additive selected from the group consisting of the following: modified styrene acrylic polymeric surfactants (i.e., dispersants), polyvinyl alcohols (i.e., emulsifiers), aqueous emulsion of polydimethylsiloxanes (i.e. antifoam agents), xanthan gums (i.e. rheological additives)), microcrystalline celluloses (i.e. rheological additives), sodium carboxymethyl cellulose (i.e. rheological additives), propylene glycol (i.e. e. antifreeze agents), biocide and mixtures thereof. In other embodiments, the implementation of the aqueous phase of the composition is from about 40 to about 70 wt.%.

In some aspects, the invention relates to methods for preparing a microcapsule suspension composition comprising the following steps: (a) obtaining a lipophilic phase containing at least one lipophilic isocyanate and at least one polymeric superhydrophobic compound by mixing at least one lipophilic isocyanate and at least at least one polymeric superhydrophobic compound with at least one molten, low melting organic nitrification inhibitor compound; (b) obtaining an aqueous phase by dissolving and mixing in water at least one additive selected from the group consisting of dispersants, emulsifiers, antifoam agents, biocides and mixtures thereof; (c) combining the lipophilic phase and the aqueous phase to form an oil-in-water emulsion; and (d) combining the emulsion

- 4 041600 oil-in-water with a solution of at least one polyamine in water to obtain microcapsules.

In some embodiments of this method, the lipophilic phase comprises 2-chloro-6(trichloromethyl)pyridine. In other embodiments of this method, the lipophilic phase comprises 2-chloro-6-(trichloromethyl)pyridine in an amount of from about 75 to about 90% by weight. In other embodiments of this method, the lipophilic phase comprises at least one polymeric superhydrophobic compound in an amount of from about 0.1 to about 3.00% by weight. In other embodiments of this method, the lipophilic phase comprises polybutene (ie, a polymeric superhydrophobic compound).

In some embodiments, said method further comprises the step of adding at least one additive selected from the group consisting of the following: dispersants, biocides, an aqueous emulsion of polydimethylsiloxane concentrate, xanthan gum, microcrystalline cellulose, sodium carboxymethylcellulose, an antifreeze additive selected at least of one of ethylene glycol, propylene glycol or glycerin, a non-encapsulated hydrophobic crystal inhibitor additive, an aqueous microcapsule suspension containing a microencapsulated hydrophobic crystal inhibitor additive, and mixtures thereof, after the step of combining the oil-in-water emulsion with a solution of at least one polyamine in water to obtain microcapsules. In other embodiments of this method, the final composition of the microcapsule suspension includes at least one microencapsulated hydrophobic crystal inhibitor additive in an amount of from about 1.0 to about 10.0 wt.% (based on the weight percent of the hydrophobic crystal inhibitor additive). In some embodiments of said method, the exemplary hydrophobic crystal inhibitor additive is at least one compound selected from the group consisting of aromatic solvents, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, and mixtures thereof. In some exemplary embodiments of said method, a hydrophobic crystal inhibitor additive is added to the microcapsule suspension composition as a second microcapsule suspension, wherein the microcapsules of said second microcapsule suspension contain the hydrophobic crystal inhibitor additive. In some exemplary embodiments of this method, both a microencapsulated and a non-microencapsulated hydrophobic crystal inhibitor additive can be added to the microencapsulated suspension composition to prevent or inhibit crystal growth.

In other embodiments of this method, the aqueous phase includes a non-ionic polymeric surfactant in an amount of from about 1.0 to about 10 wt.%. In some embodiments, the non-ionic polymeric surfactant is selected from the group consisting of polyvinyl alcohols.

In other embodiments of the exemplary method, the final microcapsule suspension comprises at least one additive selected from the group consisting of a styrene acrylic polymeric surfactant, an aqueous emulsion of a polydimethylsiloxane concentrate, xanthan gum, microcrystalline cellulose, sodium carboxymethylcellulose, a biocide, propylene glycol, and their mixtures. In some embodiments, the implementation of the aqueous phase of the composition is from about 40 to about 70 wt.%. In other embodiments, the method further includes the step of controlling the temperature of the oil-in-water emulsion while mixing the lipophilic and aqueous phases to obtain oil globules of the desired size.

A detailed description of the (trichloromethyl)pyridine compounds used in the composition of the present invention includes compounds having a pyridine ring substituted with at least one trichloromethyl group and inorganic acid salts thereof. Suitable compounds include those containing, in addition to the trichloromethyl group, chlorine or methyl substituents on the pyridine ring and include methylpyridine chlorination products such as lutidine, collidine and picoline. Suitable salts of the chlorination products of methylpyridines include hydrochlorides, nitrates, sulfates and phosphates. The (trichloromethyl)pyridine compounds used to carry out the present invention are usually oily liquids or crystalline solids. Other suitable compounds are described in US Pat. No. 3,3135,594. A preferred (trichloromethyl)pyridine compound is 2-chloro-6-(trichloromethyl)pyridine, also known as nitrapyrine, and the active ingredient in N-SERVE™ (trademark of Dow AgroSciences LLC).

The usefulness of compounds such as nitrapyrine is greatly enhanced when these compounds are encapsulated in microcapsules together with suitable solvents. Particularly useful microcapsules include a nitrapyrine/hydrophobic solvent core surrounded by a polyurea shell. Microcapsules of suitable volume, shell thickness and composition can be suspended, stored and used in the aqueous phase. Such useful compositions are disclosed in U.S. Patent Application 12/393661, filed Feb. 26, 2009, Published Sept. 10, 2009, 2009-0227458 A1, later issued as U.S. Patent No. 8,7418,805 issued June 3, 2014; V

- 5,041,600 U.S. Patent Application No. 12/009432, filed January 18, 2008, in U.S. Published July 24, 2008 No. 2008-0176745 A1, later issued as U.S. Patent No. 8,377,849, issued February 19, 2013; and US Provisional Application No. 60/881,680, filed January 22, 2007, and all of these documents are expressly incorporated herein in their entirety as if they were individually incorporated herein by reference.

The aforementioned aqueous microcapsule suspensions are known to be more stable under certain conditions than unencapsulated nitrapyrine in aqueous solution, but it has also been found that nitrapyrine crystals can form in the aqueous phase of the nitrapyrine microcapsule suspension.

The mass percentage of crystalline nitrapyrine in the total volume of the aqueous phase of the microcapsule suspension may increase over time. Depending on the type of processing of the microcapsule suspension, the measurable content of crystalline nitrapyrine in the aqueous phase may be negligible or questionable. The presence of crystalline nitrapyrine in the aqueous phase of the microcapsule suspension, even in an amount of about 0.1 wt.% or more, can cause serious problems if the suspension is applied by spraying through a pointed nozzle using an atomizer equipped with built-in filters.

Additionally, some commercial capsule suspensions of polyurea microencapsulated nitrification inhibitors, such as Instinct® or Entrench® (commercial products from Dow AgroSciences LLC), have a limited amount of active ingredient (nitrification inhibitor) that can be microencapsulated and suspended in the aqueous phase without crystallization. active ingredient in the aqueous phase. For example, in some embodiments, the implementation of suspensions Instinct® and Entrench® include from about 17 to about 19% of the active ingredient (nitrapyrine) by weight. Crystallization of the active ingredient in the aqueous phase limits the use of an increased amount of the active ingredient in capsule suspensions. The active load of nitrapyrine in some commercial capsule suspension formulations is 200 g/L, with the upper load limit being limited by the solubility of the nitrapyrine in the hydrophobic solvent. In some embodiments, the present invention does not require an oily/hydrophobic solvent to dissolve the nitrapyrine (and/or other active ingredient) in the lipophilic phase, and aqueous capsule suspension compositions are described that are stable up to 300 g/L of nitrapyrine and without unwanted crystal formation, as shown in a long-term storage stability test.

In some embodiments, microcapsule suspension compositions of the invention are described which are stable, high loading agricultural liquid compositions comprising aqueous microcapsule suspensions with low melting point active ingredients. In some embodiments, microcapsule suspension compositions are prepared without the use of an organic solvent to dissolve the agricultural agent, such as nitrification inhibitors, such as nitrapyrine, with a small amount of polymeric superhydrophobic substance that is added prior to microcapsule formation and ultimately enters the interior of the microcapsule. In some embodiments, the microencapsulated hydrophobic crystal inhibitor additive is added to the highly loaded microcapsule slurry at a later date to provide compositions having significant physical and chemical stability and crystal formation stability upon storage and acceptable volatility and nitrification capacity when applied to soil.

Examples of polymeric superhydrophobic materials include polybutene, such as commercially available polybutene called Indopol® Grade H-15 from INEOS Oligomers. Examples of non-ionic polymers include, without limitation, polyvinyl alcohols (PVA).

Examples of microencapsulated hydrophobic crystal inhibitor additives (used during manufacture and/or after manufacture, crystal inhibitor additives after addition) include ester compounds such as 2,2,4-trimethyl-1,3pentanediol monoisobutyrate, commercially available under the name UCAR ® Filmer IBT (Dow Chemical; Midland, MI) and aromatic solvents such as light aromatics, naphthalene-depleted light aromatics, heavy aromatics and/or naphthalene-depleted heavy aromatics such as, for example, Aromatic 200ND. Encapsulated hydrophobic crystal inhibitor additives can be prepared using standard polyurea microencapsulation techniques well known in the art and described herein. In some embodiments, the second suspended phase of the plurality of microcapsules in microcapsule suspension compositions includes a hydrophobic crystal inhibitor additive placed within the microcapsules. In other embodiments, the composition comprises a hydrophobic crystal inhibitor additive in an amount of from about 0.01 to about 10.0 wt%. In another embodiment, the microcapsule suspension composition may further comprise a non-microencapsulated hydrophobic

- 6 041600 additive-crystallization inhibitor in an amount of from about 0.01 to about 5 wt.% in addition to microencapsulated hydrophobic additive-crystallization inhibitor.

Examples of microencapsulated hydrophobic crystal inhibitor additives include aromatic solvents and ester compounds. The microencapsulated hydrophobic crystal inhibitor additives of the present invention can be added to capsule suspensions of nitrapyrine microencapsulated using polyurea in any percentage by weight (based on liquid weight) in the range between any smallest amount, including from about 0.01, 0, 05, 0.10, 0.25, 0.50, 0.75 wt.% and about 1.00 wt.%, and any greater amount, including about 10.00, 7.50, 5.00, 3, 00, 2.50, 2.00 wt.% and about 1.50 wt.%.

In some embodiments, the microencapsulated aromatic solvents or ester compounds of the present invention may be added to aqueous capsule suspensions of polyurea microencapsulated nitrapyrine at any percentage by weight (based on liquid weight), in a range selected from the group consisting of the following ranges: from about 2.00 to about 3.00 wt.%, from about 1.00 to about 5.00 wt.%, from about 0.50 to about 7.50 wt.% and from about 0.01 to about up to 10.00 wt.%.

A wide range of common solvents and liquid compounds that can be used to dissolve crystalline (trichloromethyl)pyridine compounds, and as such used as microencapsulated hydrophobic crystal inhibitor additives, include aromatic solvents, in particular alkyl-substituted benzenes such as xylene or propylbenzene fractions, and mixed fractions of naphthalene and alkylnaphthalene; mineral oils; kerosene; fatty acid dialkylamides, in particular fatty acid dimethylamides such as caprylic acid dimethylamide; chlorinated aliphatic and aromatic hydrocarbons such as 1,1,1 trichloroethane and chlorobenzene; esters of glycol derivatives such as diethylene glycol n-butyl, ethyl or methyl ether acetate and dipropylene glycol methyl ether acetate; esters such as 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate; ketones such as isophorone and trimethylcyclohexanone (dihydroisophorone); and acetate products such as hexyl or heptyl acetate. Preferred microencapsulated solvents and compounds that can be used to prevent or inhibit the formation of crystalline (trichloromethyl)pyridine compounds are xylene, alkyl-substituted benzenes such as propylbenzene fractions, alkylnaphthane fractions, and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate .

The nitrapyrin-containing microcapsules used in the present invention can be obtained by a polycondensation reaction of a polymeric isocyanate and a polyamine to form a polyurea shell. Microencapsulation methods are well known in the art, and any such method can be used in the present invention to obtain a capsule suspension composition. In general, a capsule suspension composition can be prepared by first mixing a polymeric isocyanate with (trichloromethyl)pyridine and/or other low melting point agricultural actives, and optionally with a superhydrophobic compound such as a polymeric superhydrophobic compound. This mixture is then combined with an aqueous phase, which optionally includes an emulsifier, to form a two-phase system. The organic phase is emulsified into the aqueous phase by applying shear until the desired particle size is achieved. Then, an aqueous crosslinking polyamine solution is added dropwise with stirring to obtain encapsulated particles of (trichloromethyl)pyridine in an aqueous suspension. Alternatively, an oil-in-water emulsion may be added to an aqueous solution of polyamine under shear to form microcapsules. In some embodiments, the microcapsules of the invention may be produced by a batch process, a continuous process, or a combination of batch processing and continuous processing.

The desired particle size and the thickness of the capsule shell will depend on the actual application. Typically, the median volumetric particle size in nitrapyrin microcapsules is from about 1 to about 10 microns, and the thickness of the capsule shell is from about 50 to about 125 nm. In another embodiment in which stability of the soil surface is required, the desired particle size may be from about 1 to about 5 microns and the thickness of the capsule shell from about 75 to about 125 nm. Microcapsules containing a hydrophobic crystal inhibitor additive typically have a median volumetric particle size of about 1 to about 10 microns and a capsule shell thickness of about 10 to about 40 nm or about 20 to about 30 nm.

By way of example, other conventional additives such as emulsifiers, dispersants, thickeners, biocides, antifreeze agents, pesticides, salts, and film-forming polymers may also be included in the compositions.

Dispersing and emulsifying agents, known as surfactants or

- 7 041600 surfactants include condensation products of alkylene oxides with phenols and organic acids, alkylarylsulfonates, modified styrene acrylic polymeric surfactants, polyoxyalkylene derivatives of sorbitan esters, alcohol esters, soap soaps, lignin sulfonates, polyvinyl alcohols, and the like. Surfactants are typically used in an amount of from about 1 to about 20% by weight, based on the weight of the microcapsule suspension composition.

The weight ratio of the suspended phases to the aqueous phase in the microcapsule suspension composition of the present invention depends on the desired concentration of (trichloromethyl)pyridine compound in the final composition. Typically, the weight ratio is from about 1:0.75 to about 1:20. Generally, the desired ratio is from about 1:1 to about 1:7, and is preferably in the range from about 1:1 to about 1:4. The ratio may also be in the range of about 1:1 to about 1:2.

The presence of the (trichloromethyl)pyridine compound inhibits the nitrification of ammonium nitrogen in the soil or growth medium by inhibiting the activity of certain soil microorganisms, which prevents the rapid loss of ammonium nitrogen from its sources such as nitrogen fertilizers, organic nitrogen components and/or organic fertilizers, and the like.

Typically, the microcapsule suspension compositions of the present invention are applied such that the amount of (trichloromethyl)pyridine compound applied to the soil or growing medium is from about 0.5 to about 1.5 kg/ha, preferably in an amount of from about 0.58 up to approximately 1.2 kg/ha. The preferred amount may be determined by the desired application, taking into account factors such as soil pH and temperature, soil type and application regimen.

The microcapsule suspension compositions of the present invention may be used in any manner that is beneficial to the culture in question. In one embodiment, the microcapsule suspension composition is applied to the growth medium by tape or row application. In another embodiment, the composition is applied to or mixed with the growth medium prior to seeding or transplanting the desired plant culture. In yet another embodiment, the composition can be applied to the root zone of grown plants.

Additionally, microcapsule suspension compositions can be used in conjunction with nitrogen fertilization. The composition can be applied before, after or simultaneously with the application of fertilizers.

The microcapsule suspension compositions of the present invention have the additional advantage of being stable enough to be applied to the soil surface without the addition of additional water or mechanical incorporation to mix the composition with the soil; in some embodiments, the implementation of the composition may be on the surface of the soil for several days or even weeks. Alternatively, the compositions of the present invention may be incorporated into the soil directly upon application, if desired.

Microcapsule suspension compositions of the present invention typically have a concentration of (trichloromethyl)pyridine compound in an amount of from about 5, preferably from about 10 and more preferably from about 15 to about 40, usually up to about 35, preferably up to about 30, and more preferably from about 25 to 27 wt.% of the total weight of the microcapsule suspension composition. The microcapsule suspension compositions are optionally mixed with one or more solvents and/or water to obtain the desired concentration for use.

Soil treatment compositions can be prepared by dispersing, coating, or soaking the composition into a microencapsulated suspension of a fertilizer, such as an ammonium or organic nitrogen fertilizer. The resulting fertilizer composition may be used as such or may be modified by dilution with additional nitrogen fertilizer or an inert solid carrier to provide a composition containing any desired amount of soil treatment active.

Soil preparation using the microcapsule suspension compositions of the present invention can be carried out by any method, including mechanical mixing with the soil; application to the surface of the soil and subsequent incorporation into the soil or plowing to the desired depth; or by direct application to the soil by means such as injection, spraying, dusting or irrigation. For irrigation application, the compositions may be introduced into the irrigation water in a suitable amount to penetrate the (trichloromethyl)pyridine compound to the desired depth of up to 6 inches (15.24 cm).

It has surprisingly been found that soil-applied microcapsule suspension compositions of the present invention have advantages over other nitrapyrine preparations, especially non-encapsulated variants. The release of nitrapyrine from the encapsulated formulation was expected to be insufficient to achieve the same efficacy as the non-encapsulated variants because diffusion from the capsule is too slow to produce a biological effect, but in fact the opposite effect was shown.

- 8 041600

The controlled release of nitrapyrine in the microcapsule suspension compositions of the present invention has certain advantages over the use of unencapsulated nitrapyrine. First, the amount of nitrapyrine can be reduced since it is more efficiently released into the soil over a longer period of time. Second, the microcapsule suspension compositions of the present invention can be applied and left on surfaces to naturally penetrate the soil without the need for mechanical embedding, if desired.

In some embodiments, microencapsulated hydrophobic crystal inhibitor additives are added to the aqueous phase of microcapsule suspension compositions that include nitrapyrine to reduce the rate of formation and/or growth of crystals in the aqueous phase under certain temperature and/or storage conditions. In some embodiments, microencapsulated hydrophobic crystal inhibitor additives added after nitrapyrine crystal formation can provide both crystal reduction and crystal growth retardation at a temperature and/or storage conditions that significantly promote crystal growth. In some exemplary embodiments, the microencapsulated hydrophobic crystal growth inhibitor additives comprise at least one oil and are added to the aqueous phase of the compositions after formation of the nitrapyrine-containing microcapsules.

In some instances, microcapsule suspension compositions may have nitrapyrin crystals prior to the addition of any hydrophobic crystal-inhibiting additives to the aqueous phase. These suspensions can be treated with one or more encapsulated and/or non-encapsulated hydrophobic crystal inhibitor additives by adding them to the aqueous phase of the suspension to reduce or remove crystals over a period of time.

The compositions of the present invention comprise microcapsule suspension concentrates suspended in an aqueous solution, wherein the microcapsules comprise at least one low melting agricultural active ingredient and at least one superhydrophobic compound. The aqueous phase may include at least one non-ionic polymer and at least one or more microencapsulated hydrophobic crystal inhibitor additives, which are subsequently added to the compositions to stabilize the active ingredients against crystal growth in a homogeneous aqueous phase. In suspensions of highly loaded nitrapyrine capsules containing the active ingredient in an amount of more than about 150 g/l, more than about 200 g/l, more than about 220 g/l, more than about 220 g/l, more than about 240 g/l , more than about 260 g/l, more than about 280 g/l, or more than about 300 g/l, nitrapyrine crystals can form in the aqueous phase at a temperature of from about 15 to about 55°C. Under certain conditions, over time, the content of such crystals can be up to 0.5 wt.% or more of the total mass of microcapsule suspensions. Crystals may form at temperatures including, for example, 15, 20, 25, 30, 35, 40, 45, 50 and 55°C. The microencapsulated hydrophobic crystal inhibitor additives described herein provide significant physical stability by preventing or reducing crystal formation in the aqueous phase of highly nitrapyrine loaded microcapsule suspension formulations for a longer period of time compared to non-microencapsulated hydrophobic crystal inhibitor additives.

For example, added microencapsulated hydrophobic crystal inhibitor additives that are aromatic solvents include substances such as Aromatic 100 aromatic fluid, also called solvent naphtha, or light aromatics; Aromatic 150 aromatic fluid, also called solvent naphtha, heavy aromatics, type II high boiling aromatic naphtha, heavy aromatic solvent naphtha, hydrocarbons, C10 aromatics, >1% naphthalene, A150, S150 (Solvesso 150) and Aromatic 200 fluid , also called solvent naphtha, heavy aromatics, type II high boiling aromatic naphtha, heavy aromatic solvent naphtha, hydrocarbons, C10-13 aromatics, >1% naphthalene, A200 and S200 (Solvesso 200).

The microencapsulated aromatic solvents used in some embodiments are naphthalene-lean (ND) or contain less than 1% naphthalene. These microencapsulated solvents can be added to the microcapsule suspension composition before crystal formation as a prophylactic or added to the microcapsule suspension composition after crystal formation as a corrective agent to remove or reduce crystals.

Exemplary embodiments of the microcapsule suspension compositions of the present invention may further include any combination of stabilizers, thickeners, dispersants, biocides, surfactants, plasticizers, and/or solvents known in the art.

- 9 041600 specialists in this field, to adapt the viscosity, fluidity, density, thickness and/or stability of the compositions.

Additionally, the microcapsule suspension compositions of the present invention can be combined or used in conjunction with pesticides, including arthropodicides, bactericides, fungicides, herbicides, insecticides, miticides, nematicides, nitrification inhibitors such as dicyandiamide, urease inhibitors such as N-(n-butyl)triamide thiophosphoric acid and the like, or pesticide mixtures and mixtures of these substances. The microcapsule suspension composition of the present invention used for this purpose may be tank-mixed with the desired pesticide(s) or may be applied sequentially.

Examples of herbicides include, without limitation, acetochlor, alachlor, aminopyralid, atrazine, benoxacil or bromoxynil, carfentrazone, chlorsulfuron, clodinafop, clopyralid, dicamba, diclofop-methyl, dimethenamide, fenoxaprop, flucarbazone, flufenacet, flumetsulam, flumiclopic, fluroxypyr, glufosinate ammonium , halosulfuron-methyl, imazametabenz, imazamox, imazapine, imazakhin, imazetapyr, isoxaflutosol, quinomac, MCPA, MCP-amine, MCP-ester, mefenoxam, mesotrione, metolachlor, s-metolachlor, metribuzin, metsulfuron methyl, nicosulfuron, paraquat, pendimethalin , picloram, primisulfuron, propoxycarbazone, prosulfuron, pyraflufen ethyl, rimsulfuron, silmazine, sulfosulfuron, tralkoxydim, triallate, triasulfuron, tribenuron, triclopyr, trifluralin, 2,4-D, 2,4-O-amine, 2,4-D- ester and the like.

Examples of insecticides include, without limitation, 1,2-dichloropropane, 1,3-dichloropropene, abamectin, acephate, acequinocyl, acetamiprid, acetion, acetoprol, acrinathrine, acrylonitrile, alanicarb, aldicarb, aldoxycarb, aldrin, allethrin, allosamidin, allylxycarb, alpha-cypermethrin , α-ecdysone, amidithione, amidoflumet, aminocarb, amiton, amitraz, anabasine, arsenic oxide, atidathione, azadirachtin, azamethifos, azinphos-ethyl, azinphos-methyl, azobenzene, azocyclotin, azotoate, barium hexafluorosilicate, bartrin, benclothiaz, bendiocarb , benoxafos, bensultap, benzoximate, benzyl benzoate, beta-cyfluthrin, beta-cypermethrin, biphenazate, bifenthrin, binapacryl, bioalletrin, bioethanometrin, biopermethrin, bistrifluron, borax, boric acid, bromfenvinphos, bromo-DDT, bromocyclene, bromophos, ethyl bromophos, bromopropylate, bufencarb, buprofezin, butacarb, butadithiophos, butocarboxime, butanate, butoxycarboxym, cadusafos, calcium arsenate, calcium polysulfide, camphechlor, carbanolate, carbaryl, carbofuran, carb disulfide eroda, carbon tetrachloride, carbophenothione, carbosulfan, cartap, quinomethionate, chloranthranilprole, chlorbenzide, chlorbicyclene, chlordane, chlordecone, chlordimeform, chlorethoxyphos, chlorfenapyr, chlorphenetol, chlorfenetol, chlorphenzone, chlorphen sulfide, chlorphenvinphos, chlorfluazuron, chlormephos, chlorbenzilate, chlormethybuformin, , chlorpropylate, chlorfoxim, chlorprazifos, chlorpyrifos, chlorpyrifos methyl, chlorthiophos, chromafenoside, cynerin I, cynerin II, cismetrin, cloetocarb, clofentezin, closantel, clothianidin, copper acetoarsenite, copper arsenate, copper naphthenate, copper oleate, coumaphos, kumitoate, crotoate, crotoxyphos, cruentarene A and B, crufomat, cryolite, cyanofenphos, cyanophos, cyanatoate, cyclethrin, cyflumethophen, cyfluthrin, cyhalothrin, cyhextine, cypermethrin, cyfentrin, cyromazine, cythioate, d-limonene, dazomet, DBCP, DCIP, DDT, decarbofurafuran, deltamethrin , demefion, demafion O, demefion S, demeton, demeton-methyl, demeton O, demeton O-methyl, demeton S, demeton S-methyl, demeton S-methylsul background, diafenthiuron, dialyphos, diamidafos, diazinon, dikaton, dichlokfenthione, dichlofluanid, dichlorphos, dicofol, dicrezyl, dicrotophos, dicyclanil, dieldrin, dienochlor, difluvidazine, diflubenzuron, dilor, difluthrin, dimefluthrin, dimefox, dimethane, dimethomethylvinphos, dimethrin, dimethrin, dimethrin dimethylan, dinex, dinobuton, dinocap, dinocap 4, dinocap 6, dinoctone, dinopentone, dinoprop, dinozam, dinosulfone, dinotefuran, dinoterbone, diofenolan, dioxabenzophos, dioxacarb, dioxathion, diphenylsulfone, disulfiram, disulfotone, diticrophos, DNOC, dofenapine, doramectin, ecdysterone, emamectin, EMPC, empentrin, endosulfan, endothion, endrin, EPN, epofenonan, erinomectin, esfenvalerate, etafos, ethiofencarb, ethion, ethiprol, methyl ethioate, ethoprofos, ethyl DDD, ethyl formate, ethylene dibromide, ethylene dichloride, ethylene oxide, etofenprox, etoxazole, etrymphos, EXD, famfur, fenamiphos, fenazaflor, fenazakhin, fenbutatin oxide, fenchlorphos, fenetacarb, fenfluthrin, fenitrothion, fenobucarb, fenothiocarb, fenoxacrim, fenoxycarb, fe npyritrin, fenpropatrin, fenpyroximate, fenson, fensulfothion, fenthion, fenthion ethyl, fentrifanil, fenvalerate, fipronil, flonicamid, fluacripyrim, fluazuron, flubendiamide, flubenzimine, flucofuron, flubendiamide, flucycloxuron, flucitrinate, fluenetil, flufenoxibenerim, flufenoxubenerim, flufeneximine , fluvalinate, fonofos, formetanate, formotion, formaparanate, fosmethylian, fospirate, fostiazate, fostietan, fostietane, furatiocarb, furethrin, furfural, gamma-cyhalothrin, gamma-HCH, galfenprox, halofenoside, HCH, HEOD, heptachlor, heptenofos, heterophos, hexaflumuron , Hexothiazox, HHDN, Hydramethidnon, Hydrogen Cyanide, Hydroprene, Giquanarb, Imitiaphos, Imidacloprid, Imiprotrin, Indoxacarb, Iodomethane, IPSP, Isamidophos, Isazophos, Isobenzane, Isocarbophos, Isodrine, Isofenphos, Isoprocarb, Isoprothiolane, Isothioate, Isoxathion, Ivermectin I, Jasmoline I, Jasmolin II, Iodfenpros, Juvenile Hormone I, Juvenile Hormone II, Juvenile Hormone III, Kelevan, Kinoprene, Lambda Cyhalothrin, Lead Arsenate, L epimectin, leptophos, leptophos, lindane, lyrimphos, lufenuron, litidathione, malathion, malonobien, mazidox, mezacarbam, mearfon, menazone, mephospholane, mercury chloride, mesulfen, mesulfenfos, metaflumizone, metam,

- 10 041600 methacryphos, methamidophos, methydathione, methiocarb, methocrotophos, methomyl, methoprene, methoxychlor, methoxyphenoside, methyl bromide, methylisothiocyanate, methyl chloroform, methylene chloride, metofluthrin, metolcarb, methoxadiazon, mevinphos, mexacarbate, milbemictin, Moxypamiktin monocrotophos, morphothion, moxidectin, naphtalophos, naled, naphthalene, nicotine, nifluridide, niccomycins, nitenpyram, nithiazine, nitrilacarb, novaluron, noviflumuron, omethoate, oxamyl, oxydemeton methyl, oxideprofos, oxydisulfotone, paradichlorobenzene, parathion, parathion, methyl, peneflu permethrin, phencaptone, phenothrin, phentoate, phorate, phosalon, phospholane, phosmet, fosnichlor, folsfamidon, phosphine, phosphocarb, phoxim, methyl phoxim, pyrimetaphos, pyrimicarb, pyrimiphos ethyl, pyrimiphos methyl, potassium arsenite, potassium thiocyanate, pp' DDT, pralletrin , precocene I, precocene II, precocene III, primidophos, proclonol, profenofos, profluthrin, promacil, promecarb, propafos, propargit, propetamphos, propoc sur, protidathione, prothiophos, protoate, protrifenbut, pyraclophos, pyrafluprol, pyrazophos, pyresmethrin, pyrethrin I, pyrethrin II, pyridaben, pyridalil, pyridafenthione, pyrifluquinazone, pyrimidifen, pyritomate, pyriprole, pyriproxyfen, quassia, quinalphos, quinalphos, quinalfos methylion, quinalphos methylion , Quantify, Rafoxanide, Resmetrin, Rotenone, Riania, Sabadilla, Shradan, Selamectin, Silafluofen, Sodium Arsenite, Sodium Fluoride, Sodium Hexafluorosilicate, Sodium Thiocyanate, Spinetoram, Spinosad, Spirodiclofen, Spiromesifen, Spirotetramate, Sulcofuron, Sulfiram, Sulfluramide, Sulfur, Sulfotep , sulfuryl fluoride, sulprofos, tau fluvalinate, tazimcarb, TDE, tebufenoside, tebufenpyrad, tebupyrimphos, teflubenzuron, tefluthrin, temefos, TERP, teralletrin, terbufos, tetrachloroethane, tetrachlorvinphos, tetradifon, tetramethrin, tetranactin, tetrasul, theta-cypermethrin, thiacloprid, thiamethoxam tycrophos, thiocarboxym, thiocyclam, thiodicarb, thiophanox, thiometon, thionazine, thioquinox, thiosultap, thuringienzine, tolfenpyrad, trawl etrin, transfluthrin, transpermethrin, triartene, triazamate, triazophos, trichlorfon, trichlormetaphos 3, triclonate, triphenophos, triflumuron, trimetacarb, triprene, vamidothione, vamidothione, vaniliprole, vaniliprole, CMS, xylylcarb, zetacipermethrin and zolaprofos.

Additionally, you can use any combination of one or more of the above pesticides.

Additionally, for the implementation of the invention, you can use the plant protection chemical Rinaksipyr (Rynaxypyr ™, DuPont trademark), which is anthranilic diamide (chlorantraniliprole).

Used in the text of the invention, the concept of approximately should be understood as plus or minus 10% of the specified value, for example, the expression approximately 1.0 includes values from 0.9 to 1.1.

The following examples are presented to illustrate the present invention. The examples are not intended to limit the scope of the present invention and should not be interpreted as such. Quantitative indicators are given in mass parts or percent by mass, unless otherwise indicated.

Examples

Highly nitrapyrine-loaded capsule formulations containing hydrophobic crystal inhibitor additives (microencapsulated and/or non-microencapsulated) were prepared by microencapsulating oil-in-water emulsions. Were prepared as described in the invention, the following samples: 1) non-microencapsulated Aromatic 200 ND from 2.4 to 5.3 wt.%; 2) microencapsulated Aromatic 200 ND from 5.0 to 6.7 wt.% (liquid base) in the presence of non-microencapsulated Aromatic 200 ND in an amount from 0 to 2.4 wt.%; 3) non-microencapsulated Aromatic 150 ND at 4.8% by weight; and 4) microencapsulated Aromatic 100 ND in an amount of 5.0 to 7.0 wt.% (liquid base).

Aromatic 200 ND (or Aromatic 100 ND) microcapsule suspension (CS) preparation procedure: Aromatic 200 ND (or Aromatic 100 ND) microcapsule suspension compositions are shown in Table 1. The oil phase was prepared by mixing solvent Aromatic 200 ND (or Aromatic 100 ND) and PAPI 27 at ambient temperature. The aqueous phase was prepared by mixing PVA, Metasperse 500L, Proxel GXL and antifoam at ambient temperature. The oil phase was then combined with the aqueous phase and passed through a high shear emulsifier to achieve an average particle diameter (D ₅₀ ) of 3 µm. An aqueous solution of ethylenediamine was then added to the emulsion under the proper mixing conditions to form an Aromatic 200 ND (or Aromatic 100 ND) microcapsule suspension.

- 11 041600

Table 1

Composition of capsule suspension Aromatic 200 ND (or Aromatic 100 ND)

Component Source Weight, % Aromatic 200ND (or Aromatic 100ND) Exxon Mobile 50.0 Polymeric methylene diphenyl diisocyanate (MDI) PAPI-27 Dow Chemical 1.68 Ethylenediamine (30%) Huntsman 1.23 PVA (Selvol 205 p-p 21%) Brenntag 10.4 Metasperse 500L Croda 0.9 Antifoam agent Harcros 0.14 Proxel Arch Chemicals 0.11 Water for balance local source 35.54 Total 100

Preparation of the capsule suspension concentrate (CSC): the composition of the CSC nitrapyrine is given in table. 2. The oil phase was obtained by mixing technical nitrapyrin, polymer Indopol H and PAPI 27 at a temperature of from 75 to 100°C. The aqueous phase was obtained by mixing PVA, Metasperse 500L, Proxel GXL, water and antifoam at 60-90°C. The oil phase was then combined with the aqueous phase and passed through a high shear emulsifier to obtain the desired average particle size (D ₅₀ ) of approximately 3 μm. An aqueous solution of ethylenediamine was then added to the emulsion under low shear stirring to form a nitrapyrine capsule suspension concentrate (CSC).

table 2

Nitrapyrine Capsule Suspension Concentrate (CSC) Composition

Ingredient Source Weight, % Nitrapyrine Dow AgroScience 38.2 Polymeric methylene diphenyl diisocyanate (MDI) PAPI-27 Dow Chemical 8.0 Ethylenediamine (30%) Huntsman 6.3 PVA (Selvol 205 solution 21%) Brenntag 9.8 Metasperse 500L Croda 2.9 Indopol Η-15 Ineos Olefins and Polymers 1.0 Antifoam agent Harcros ο,ι Proxel Arch Chemicals ο,ι Water for balance local source 33.6 Total 100

Preparation of a capsule suspension sample with a high load of nitrapyrine.

Nitrapyrine Capsule Suspension Concentrate (CSC) was mixed with Kelzan S xanthan gum (as an aqueous solution of 1.5 or 2.0 wt%), propylene glycol, Aromatic 200 ND solvent (or Aromatic 150 ND solvent), and /or with pre-prepared capsule suspension A-200 ND, or with pre-prepared capsule suspension A-100 ND and with the required amount of water. Thus obtained samples are described in table. 3. Samples 1, 2, Control A, and Control B used the same batch of CSC. Samples 3, 4, Control C and Control D used a different batch of CSC. Samples 5 and 6 used a third batch of CSC.

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Table 3

Composition of capsular suspensions with a high load of nitrapyrine

Sample CSC ¹ nitrapyrine Non-micro encapsulated solvent A-200 ND Capsular suspension IYa A-200 ND Nemic Rockcaps Recovered Thinner A-150 ND Cape Ulna I Suspe Nzia A100 ND I drank engliko l Kelzan S (solution P 1.5%) Kelzan S (solution 2%) Water FOR balance 1 66.90% 0% 10.00% 0% 0% 10.3% 10.0% 0% 2.8% 2 67.20% 2.40% 10.00% 0% 0% 10.0% 10.0% 0% 0.4% 3 68.00% 0% 10.20% 0% 0% 10.0% 10.3% 0% 1.5% 4 67.90% 0% 13.40% 0% 0% 8.2% 10.4% 0% 0% 5 68.60% 0% 0% 0% 10% 10.0% 0% 7.4% 4.0% 6 68.60% 0% 0% 0% 14% 10.0% 0% 7.4% 0% Control A 67.90% 2.80% 0% 0% 0% 10.0% 10.1% 0% 9.2% Control B 69.40% 5.20% 0% 0% 0% 10.4% 0% 7.1% 7.9% Control C 68.10% 5.30% 0% 0% 0% 10.6% 0% 3.6% 12.2% Control D 69.40% 0% 0% 4.80% 0% 10.1% 10.5% 0% 5.3%

¹ The amount of nitrapyrine contained in the listed samples is in the range from 25.55 to 26.51 wt.%.

Samples 1, 2, 3, 4, 5 and 6 from the table. 3 contain microencapsulated hydrophobic additives, crystal formation inhibitors. These samples were tested for resistance to crystal formation at different time intervals and at different temperatures and compared with control samples A, B, C and D, which contained only liquid hydrophobic crystal inhibitor additive and did not contain microencapsulated crystal inhibitor additive. In some of the tests performed, small amounts of washed sea sand particles (from Fisher Scientific) were added to the samples to stimulate crystal formation. The test results for wet screening of these samples are given in table. 4. Samples containing encapsulated hydrophobic crystal inhibitor additives showed a minimal amount (<0.1 wt.%) of non-crystalline residue, while 4 control samples (A, B, C and D) containing only liquid hydrophobic additives α-crystallization inhibitors (i.e., non-encapsulated hydrophobic crystal inhibitor additives), crystal residue formation at an undesirable level (>0.1 wt.%) was detected. The presence of crystalline solids in the test samples after storage can be easily determined by microscopic examination in polarized light.

As shown in Table. 4, the following wet sieving technique was used to determine the crystal content of samples during storage: Approximately 20 g of sample was added to a glass beaker containing 100 to 200 g of tap water. The solution was stirred with a glass rod and then passed through a 100 mesh sieve (149 µm). The beaker was washed with additional water and the washing solution was also passed through a sieve. To wash and remove loose agglomerates, the sample on the sieve was poured with tap water for approximately 30 seconds. The precipitate remaining on the sieve was washed on a tared paper filter and subjected to vacuum filtration. This filter paper with the sample was left to dry in a laboratory cabinet for at least 4 hours and then reweighed. The percentage of residue was calculated using the following equation (1):

(1) percent residue = (filter paper and weight of residue after drying (g) - weight of filter paper (g)/(total weight of sieved sample (g))

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Claims (15)

Table 4 Accelerated Storage Stability Test Sample Wet Screen Residue, 100 mesh (wt.%): <0.1 wt.% and no crystals=Pass Presence of crystallization Test results (1) a microcapsule shell obtained by an interfacial polycondensation reaction between a polymeric isocyanate and a polyamine to form a second polyurea shell; (1) a microcapsule shell obtained by an interfacial polycondensation reaction between a polymeric isocyanate and a polyamine to form a polyurea shell; 1. Composition of a nitrification inhibitor in the form of a microcapsule suspension, comprising: (a) a first suspended phase of a plurality of microcapsules with particles having a median volume size of about 1 to about 10 microns, wherein said microcapsules include: 1 0.07% ¹ 0.09% ¹ 0.07% 1 0.09% ¹ 0.06% 1 0.07% 1 No Pass 2. The nitrification inhibitor composition of claim 1, wherein the aqueous phase further comprises at least one additional ingredient selected from the group consisting of dispersants, emulsifiers, rheological agents, antifoam agents, biocides, anti- (2) at least one hydrophobic additive, which is a crystal formation inhibitor, encapsulated in a second polyurea shell; and (c) an aqueous phase. (2) at least one (trichloromethyl)pyridine compound as a nitrification inhibitor encapsulated in a polyurea shell; (b) a second suspended phase of a plurality of microcapsules with particles having a median volume size of about 1 to about 10 microns, said microcapsules including: ² formed crystalline solids; 2 0.07% ¹ 0.08% ¹ 0.07% 1 0.09% ¹ 0.07% 1 0.07% 1 No Pass 2 weeks From ambient (no sand) 2 weeks From environment (with sand) 2 weeks 54°C (without sand) 2 weeks 54°C (with sand) 4 weeks 40°C (without sand) 8 weeks 40°C (without sand) 3. The nitrification inhibitor composition of claim 1, wherein the (trichloromethyl)pyridine compound comprises 2-chloro-6-(trichloromethyl)pyridine. ³ n/t - testing was not carried out. Notwithstanding the examples given and the detailed presentation of the new technology in the description section, the present description is to be considered illustrative and not restrictive in nature. It should be understood that only preferred embodiments have been shown and described, and that all changes and modifications that fall within the spirit of the new art are to be protected. The new technique has been illustrated using specific examples, theoretical arguments, calculations and illustrations, and these illustrations and the following discussion should in no way be interpreted as limiting the scope of the invention. All patents, patent applications and references to texts, scientific references, publications, etc. mentioned in the present invention are incorporated herein by reference in their entirety. CLAIM 3 0.06% ¹ n/t 0.05% 1 0.03% ¹ 0.03% 1 0% ¹ No Pass 4. The nitrification inhibitor composition of claim 1, wherein said composition further comprises an agriculturally active ingredient selected from the group consisting of arthropodicides, bactericides, fungicides, herbicides, insecticides, miticides, nematicides, fertilizers, dicyandiamide, urease inhibitors, and pesticide mixtures of these substances. . 4 0.05% ¹ n/t 0.06% 1 n/t 0.03% 1 0% ¹ No Pass 5. The composition of the nitrification inhibitor according to claim 3, the specified composition includes 2-chloro-6(trichloromethyl)pyridine in an amount of from about 15 to about 40 wt.%. 5 n/t 0% n/t 0.06% ¹ n/t n/t No Passed 6. The nitrification inhibitor composition of claim 1 further comprising at least one polymeric superhydrophobic compound. 6 n/t 0% n/t 0.06% ¹ n/t n/t No Passed Control A 0.05% ¹ n/t ³ 0.06% 1 n/t 0.24% 2 n/t Yes Failed Control B 0.07% ¹ 0.09% ¹ 0.08% 1 0.14% ² 0.07% 1 0.08% 1 Yes Failed Control C 0.06% ¹ n/t 0.06% 1 0.1% ² 0.05% 1 0.14 ² Yes Failed Control D 0.06% ¹ n/t 0.12% 2 n/t 0.03% 1 0% ¹ Yes Fail ¹ non-crystalline solids formed; 7. The nitrification inhibitor composition of claim 6 wherein the polymeric superhydrophobic compound comprises polybutene. 8. The nitrification inhibitor composition of claim 1, wherein said composition comprises a hydrophobic crystallization inhibitor additive in an amount of from about 1.0 to about 10.0 wt%. 9. A nitrification inhibitor composition according to any one of claims 1 and 8, wherein the hydrophobic crystal inhibitor additive is at least one compound selected from the group consisting of aromatic solvents and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate. 10. The nitrification inhibitor composition of claim 9, wherein the aromatic solvents comprise light aromatics, naphthalene-depleted light aromatics, heavy aromatics, and/or naphthalene-depleted heavy aromatics. 11. The nitrification inhibitor composition of claim 2, wherein the aqueous phase comprises an emulsifier in an amount of from about 1.0 to about 10% by weight. 12. The nitrification inhibitor composition of claim 11 wherein the emulsifier is a non-ionic polymeric surfactant selected from the group consisting of polyvinyl alcohols. 13. The nitrification inhibitor composition of claim 2, wherein the dispersing agent is a modified styrene-acrylic polymeric surfactant. 14. The nitrification inhibitor composition of claim 1, further comprising a non-microencapsulated hydrophobic crystal inhibitor additive in an amount of from about 0 to about 5 wt%. - 14 041600 frieze additives and mixtures thereof. 15. The nitrification inhibitor composition of claim 1, wherein said composition comprises an aqueous phase of from about 40% to about 70% by weight. Eurasian Patent Organization, EAPO Russia, 109012, Moscow, Maly Cherkassky per., 2