WO2017069827A1 - Formulation à base de solvant polaire d'inhibiteur de nitrification non corrosif - Google Patents

Formulation à base de solvant polaire d'inhibiteur de nitrification non corrosif Download PDF

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Publication number
WO2017069827A1
WO2017069827A1 PCT/US2016/044461 US2016044461W WO2017069827A1 WO 2017069827 A1 WO2017069827 A1 WO 2017069827A1 US 2016044461 W US2016044461 W US 2016044461W WO 2017069827 A1 WO2017069827 A1 WO 2017069827A1
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Prior art keywords
weight percent
trichloromethyl
pyridine
formulation
formulation according
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PCT/US2016/044461
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English (en)
Inventor
Hiteshkumar Dave
Lei Liu
Alex Williams
Rajesh Goyal
Nicholas Fradette
Chloe Moreau
Samantha Armisen
Kevin Mayer
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Dow Agrosciences, Llc
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Priority claimed from US15/152,396 external-priority patent/US10173942B2/en
Application filed by Dow Agrosciences, Llc filed Critical Dow Agrosciences, Llc
Priority to CN201680074961.4A priority Critical patent/CN109641814B/zh
Priority to CA3002528A priority patent/CA3002528A1/fr
Priority to MX2018004945A priority patent/MX2018004945A/es
Publication of WO2017069827A1 publication Critical patent/WO2017069827A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/90—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting the nitrification of ammonium compounds or urea in the soil
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
    • Y02P60/20—Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2
    • Y02P60/21—Dinitrogen oxide [N2O], e.g. using aquaponics, hydroponics or efficiency measures

Definitions

  • the present invention relates to relatively non-corrosive, high load nitrapyrin liquid formulations, comprising polar solvents and novel metal corrosion inhibitors and method of preparing and using the same.
  • nitrapyrin also referred to herein as liquid inhibitor compositions
  • Some encapsulated formulations of nitrapyrin are suitable for rapid or dump release of nitrapyrin into the soil.
  • Some formulations of nitrapyrin encapsulated with lignin sulfonates, especially useful for quick release applications, are disclosed in U.S. 4,746,513, which is incorporated herein by reference.
  • Polycondensation encapsulation as disclosed in U.S. 5,925,464, has also been used to encapsulate agriculturally active ingredients such as nitrapyrin, particularly to enhance handling safety and storage stability of the active ingredient by using polyurethane rather than polyurea encapsulants.
  • Encapsulated nitrapyrin formulations exhibit certain advantages over liquid non-encapsulated formulations of nitrapyrin, such as improved stability. Despite the advantages of encapsulated nitrapyrin formulations, liquid non-encapsulated formulations of nitrapyrin are still used, at least in part, because they tend to be easier to formulate and may cost less than encapsulated nitrapyrin formulations. As with most any soil amendment there is an advantage to using formulations that include a high level of the agriculturally active component of the formulation. Formulations that have higher levels of an active ingredient generally mean that less material must be moved, stored, and applied to the field; the net result is that these formulations may exhibit lower material handling costs.
  • nitrapyrin i.e., a liquid inhibitor composition
  • nitrapyrin is present in polar solvents and is especially formulated to be non- corrosive or at least less corrosive than previous formulations of nitrapyrin that included significant levels of polar solvents.
  • Dibasic ester refers to a compound containing two ester groups. Examples of dibasic esters include, but are not limited to, dimethyl glutarate, dimethyl succinate, dimethyl adipate, dimethyl 2-methylglutarate, and mixtures thereof.
  • Some embodiments include a liquid formulation of nitrapyrin comprising of: nitrapyrin, at least one polar solvent selected from the group consisting of: (1) N,N-dialkyl fatty acid amides such as those found in products such as, but not limited to, di-substituted amides including for example N, N-dimethylocotanamide (N,N-dimethylcarprylamide) and dimethyldecanamide ( ⁇ , ⁇ -dimethylcapramide), compounds sold under the trade names, Hallcomid M810, Hallcomid M10, still other compounds that can be used in capacity include, for example, Rhodiasolv® ADMA 810, Rhodiasolv® ADMA 10, Genagen 4166 and Genagen 4296; (2) cyclohexanone; (3) dibasic esters such as, but not limited to, dimethyl 2-methylglutarate, which is available as Rhodiasolv® IRIS; and a dibasic ester mixture composed of dimethyl glutarate, dimethyl succinate,
  • the liquid formulations of the present invention may include high levels of nitrapyrin and exhibit relatively non-corrosive properties, making them suitable for use with metal objects such as metal storage tanks and metal application equipment.
  • the alkoxybenzene compound is methoxybenzene (anisole).
  • the organophosphate compound is triethyl phosphate.
  • the corrosion inhibitor is selected from the group consisting of: nicotinamide, a-picoline, 2,6 lutidine, expoxidized linseed oil (ELO) and DER 331 liquid epoxy resin.
  • the corrosion inhibitor is niacin, also known as nicotinic acid.
  • the corrosion inhibitor is a niacin-derivative.
  • the corrosion inhibitor is niacinamide (it is understood that the terms "niacinamide” and “nicotinamide” are synonymous), methyl isonicotinate, niacin esters, acipimox, aluminum nicotinate, niceritrol, nicoclonate, nicomol, inositol hexaniacinate, oxiniacic acid or combinations thereof.
  • Non-limiting examples of niacin derivatives include methyl isonicotinate, niacin esters, niacinamide salicylate, niacinamide ascorbate, niacinamide folate, niacinamide lipoate, niacinamide lactate, niacinamide glycolate, niacinamide mandalate, niacinamide malate, niacinamide hydroxycitrate, niacinamide hydroxytetronate, niacinamide aleurate, niacinamide petroselinate, niacinamide pantothenate, niacinamide adenosine monophosphate (AMP), niacinamide diphosphate (ADP), niacinamide adenosine triphosphate (ATP), niacinamide hydroquinone carboxylate, nicotinic acid, niacinamide, Acipimox (5-
  • the corrosion inhibitor is derivatized linseed oil, including but not limited to epoxidized linseed oil.
  • the corrosion inhibitor is a 1,2-epoxyalkane such as 1,2-epoxydecane.
  • the corrosion inhibitor is an amino alcohol, for example, 2-amino-2-methyl-l-propanol (i.e., AMP-95 or AMP-99).
  • the corrosion inhibitor is an imidazole compound, for example, 1-methylimidazole.
  • the polar solvent is diethylene glycol butyl ether (DGBE).
  • the corrosion inhibitor and/or co-solvent is an esteramide compound.
  • the corrosion inhibitor is selected from niacinamide, methyl isonicotinate, niacin esters, acipimox, aluminum nicotinate, niceritrol, nicoclonate, nicomol, inositol hexaniacinate, oxiniacic acid, derivatized linseed oil, including but not limited to epoxidized linseed oil, 1 ,2-epoxydecane, an amino alcohol, for example, 2- amino-2-methyl-l-propanol, 1-methylimidazole, a quinolone compound such as quinaldine, or any combination thereof.
  • liquid fertilizer compositions for use in agricultural applications comprising: one more nitrogenous fertilizer compounds; at least one nitrification inhibitor comprising a (trichloromethyl)pyridine compound; a polar solvent; and, optionally, a corrosion inhibitor.
  • the liquid inhibitor composition or liquid fertilizer composition further comprises at least one additional component including, but not limited to, a co-solvent, a pH adjustor, flow agents, preservatives, buffering agents, antifoam agents, compatibility agents, deposition agents, dispersants, drift control agents, penetrants, surfactants, spreaders, and wetting agents, and the like.
  • the nitrogenous fertilizer compound is anhydrous ammonia.
  • Polar solvents that can be used to practice some embodiment of the invention include, but are not limited to, cyclohexanone, propylene carbonate, ⁇ , ⁇ -dialkyl fatty acid amides: specifically the mixture of C8/C10 fatty acid ⁇ , ⁇ -dimethylamides (Hallcomid M810), other fatty acid amides also C8 & CIO ⁇ , ⁇ -dimethylamides individually, the dibasic ester mixture composed of dimethyl glutarate, dimethyl succinate, and dimethyl adipate (Rhodiasolv® RPDE), organophosphate compounds which are trialkyl phosphates, and alkoxybenzene compounds such as methoxybenzene (anisole) and ethoxybenzene.
  • cyclohexanone propylene carbonate
  • ⁇ , ⁇ -dialkyl fatty acid amides specifically the mixture of C8/C10 fatty acid ⁇ , ⁇ -dimethylamides (Hallcomid M810), other
  • the organophosphate compound may be selected from the group including triethyl phosphate, tri(isobutyl)phosphate, tributoxyethyl phosphate (TBEP) and tris(2- ethylhexyl) phosphate.
  • the polar solvent is comprised of the dibasic ester mixture composed of dimethyl glutarate, dimethyl succinate, and dimethyl adipate (Rhodiasolv® RPDE) and cyclohexanone.
  • the alkoxybenzene compound is methoxybenzene (anisole).
  • Polar solvents that have not worked in some of the exemplary formulations disclosed herein include; (1) dipropylene glycol monomethyl ether (Dowanol DPM), (2) methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate (Polarclean), and N-butylpyrrolidone (TamiSolve NxG).
  • Dowanol DPM dipropylene glycol monomethyl ether
  • Polyclean methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate
  • TamiSolve NxG N-butylpyrrolidone
  • Corrosion inhibitors that may not be well suited, or even efficacious, for the practice of the instant invention include, methyltrioctyl ammonium chloride, poly(12-hydroxyoctadecanoic acid-co-ethylenimine) (e.g., Atlox LP6).
  • Corrosion inhibitors that may be used to practice some embodiments of the invention include, for example, pyridinecarboxamides (i.e., nicotinamide or niacinamide), methylpyridines (i.e., a-picoline, 2,6-lutidine), epoxidized seed or vegetable oils (i.e., epoxidized linseed oil (ELO), epoxidized soybean oil, etc.) and epoxy resin (liquid reaction product of epichlorohydrin and bisphenol, such as, D.E.R.TM 331TM liquid epoxy resin (DER 331)).
  • pyridinecarboxamides i.e., nicotinamide or niacinamide
  • methylpyridines i.e., a-picoline, 2,6-lutidine
  • epoxidized seed or vegetable oils i.e., epoxidized linseed oil (ELO), epoxidized soybean oil, etc.
  • a first set of embodiments include a formulation, comprising: 2-chloro-6-
  • polar solvent selected from the group consisting of: a mixture of N, N-dimethyloctanamide (N, N- dimethylcaprylamide) and N, N-dimethyldecanamide (N, N-dimethylcapramide); a ketone, and a dibasic ester, wherein the polar solvent comprises between about 40 to about 70 weight percent of the solvent system of the formulation; at least one polar solvent miscible corrosion inhibitor, selected from the group consisting of: a liquid epoxy resin; 2, 6-dimethylpyridine; epoxidized linseed oil; and nicotinamide; wherein said polar solvent miscible corrosion inhibitor, comprises about 0.5 to about 2.5 weight percent; and at least one optional second solvent selected from the group consisting of: solvent naphtha, an aromatic solvent, a mineral oil,
  • a second set of embodiments includes a formulation comprising: about 240 to about 350 g/L of 2-chloro-6-(trichloromethyl)pyridine; about 40 to about 60 weight percent of a mixture of N, N-dimethyloctanamide (N, N-dimethylcaprylamide) and ⁇ , ⁇ -dimethyldecanamide (N, N-dimethylcapramide); about 0.5 to about 1.5 weight percent of liquid epoxy resin and about 0.5 to about 1.5 weight percent 2, 6-dimethylpyridine; and about 5 to about 20 weight percent solvent naphtha.
  • a third set of embodiments includes a formulation comprising: about 230 to about 300 g L of 2-chloro-6-(trichloromethyl)pyridine; about 45 to about 55 weight percent of a mixture of N, N-dimethyloctanamide (N, N-dimethylcaprylamide) and ⁇ , ⁇ -dimethyldecanamide (N, N-dimethylcapramide); about 0.75 to about 1.4 weight percent of liquid epoxy resin; about 0.5 to about 1.5 weight percent 2, 6-dimethylpyridine; and about 10 to about 15 weight percent solvent naphtha.
  • a fourth set of embodiments includes a formulation comprising: about 240 g/L of 2-chloro-6-(trichloromethyl)pyridine; about 50.0 to about 55 weight percent of a mixture of N,N-dimethyloctanamide ( ⁇ , ⁇ -dimethylcaprylamide) and N, N- dimethyldecanamide ( ⁇ , ⁇ -dimethylcapramide); about 1.0 to about 1.1 weight percent of liquid epoxy resin oil; about 0.5 to about 1.5 weight percent 2, 6-dimethylpyridine; and about 1 1.0 to about 14.0 weight percent solvent naphtha.
  • a fifth set of embodiments includes a formulation comprising: about 240 g/L of 2-chloro-6-(trichloromethyl)pyridine; about 50.55 weight percent of a mixture of N,N-dimethyloctanamide ( ⁇ , ⁇ -dimethylcaprylamide) and N,N-dimethyldecanamide (N,N-dimethylcapramide); about 1. 2 weight percent of liquid epoxy resin oil; about 0.5 to about 1.5 weight percent 2,6-dimethylpyridine; and about 12.64 weight percent solvent naphtha.
  • a sixth set of embodiments includes a formulation comprising: about 200 to about 400 g/L of 2-chloro-6-(trichloromethyl)pyridine; about 20 to about 50 weight percent of a dibasic ester; about 0.5 to about 2.5 weight percent of epoxidized linseed oil; about 0.5 to about 2.5 weight percent nicotinamide; and about 20.0 to about 50.0 weight percent cyclohexanone.
  • a seventh set of embodiments includes a formulation comprising: about 240 g/L to about 350 g/L of 2-chloro-6-(trichloromethyl)pyridine; about 45 to about 55 weight percent of a dibasic ester; about 1.0 to about 2.0 weight percent of epoxidized linseed oil; and about 0.8 weight percent nicotinamide; and about 11.0 to about 14.0 weight percent cyclohexanone.
  • An eighth set of embodiments includes a formulation comprising: about 240 g/L of 2-chloro-6-(trichloromethyl)pyridine; about 50.47 weight percent of a dibasic ester; about 1.5 weight percent of epoxidized linseed oil; about 0.8 weight percent nicotinamide; and about 12.62 weight percent cyclohexanone.
  • a ninth set of embodiments includes a formulation, comprising: about 200 to about 400 g/L of 2-chloro-6-(trichloromethyl)pyridine; about 40 to about 60 weight percent of a dibasic ester; about 0.5 to about 2.5 weight percent of epoxidized linseed oil; and about 0.4 to about 1.5 weight percent nicotinamide.
  • a tenth set of embodiments include the twelfth embodiment: about 240 g/L of
  • 2-chloro-6-(trichloromethyl)pyridine about 63.08 weight percent of a dibasic ester; about 1.5 weight percent of epoxidized linseed oil; and about 0.6 to about 1.0 weight percent nicotinamide.
  • An eleventh set of embodiments include a formulation, comprising: about 240 g/L of 2-chloro-6-(trichloromethyl)pyridine; about 63.08 weight percent of a dibasic ester; about 1.5 weight percent of epoxidized linseed oil; and about 0.8 weight percent nicotinamide.
  • a twelfth set of embodiments includes a formulation, comprising: about 200 to about 400 g/L of 2-chloro-6-(trichloromethyl)pyridine; about 40 to about 70 weight percent of triethyl phosphate; about 0.5 to about 2.5 weight percent of epoxidized linseed oil; and about 0.5 to about 2.5 weight percent of methyl nicotinate.
  • a thirteenth set of embodiments includes a formulation, comprising: about
  • a fourteenth set of embodiments including at least one of the formulations according to any of the first through the thirteenth set of embodiments and at least one additional agricultural ingredient selected from the group consisting of: herbicides, insecticides, miticides, fungicides, and fertilizers.
  • a fifteenth set of embodiments including any of the formulations according to the fourteenth set of embodiments, wherein the agricultural ingredient is a fertilizer.
  • a sixteenth set of embodiments including any of the formulations according to the formulation of the fifteenth set of embodiments, wherein the fertilizer includes nitrogen.
  • a seventeenth set of embodiments including methods for treating soil comprising the steps of: applying at least one of the formulations according to the first through sixteenth set embodiments to at least one area selected from the area consisting of: the surface of a portion of soil, beneath the surface of a portion of soil, a portion of a plant, and a portion of a surface adjacent to a plant.
  • the eighteenth set of embodiments including the any of the methods according to the seventeenth set of embodiments, wherein the applying step includes injecting at least one of the formulations into a portion of soil.
  • (Trichloromethyl)pyridine compounds useful in the composition of the present invention include compounds having a pyridine ring which is substituted with at least one trichloromethyl group and mineral acid salts of these compounds thereof.
  • the presence of a (trichloromethyl)pyridine compound suppresses the nitrification of ammonium nitrogen in the soil or growth medium, thereby preventing the rapid loss of ammonium nitrogen originating from nitrogen fertilizers, organic nitrogen constituents, or organic fertilizers and the like.
  • Suitable compounds include those containing chlorine or methyl substituents on the pyridine ring in addition to a trichloromethyl group, and are inclusive of chlorination products of methyl pyridines such as the lutidines, the collidines and the picolines.
  • Suitable salts of the (trichloromethyl)pyridine compounds include hydrochlorides, nitrates, sulfates and phosphates.
  • the (trichloromethyl)pyridine compounds useful in the practice of the present invention are typically oily liquids or crystalline solids dissolved in a solvent. Other suitable compounds are described in U.S. 3,135,594.
  • a preferred (trichloromethyl)pyridine is 2-chloro-6-(trichloromethyl)pyridine, also known as nitrapyrin, and the active ingredient of the product N-SERVETM (Trademark of Dow AgroSciences LLC).
  • N-SERVETM has an active nitrapyrin loading level of about 240 g/L.
  • the nitrapyrin loading level of N-SERVETM is set in part by the solubility of nitrapyrin in the solvents used in the formulation (e.g., Aromatic 100) and its corrosiveness at elevated temperature (i.e., 50°C).
  • solvents used in the formulation e.g., Aromatic 100
  • Still other non-polar hydrophobic solvents which can be used in relatively non-corrosive formulations of nitrapyrin include, but are not limited to, other naphthalene depleted solvents, i.e., aromatic solvent that includes less than about 1% naphthalene.
  • Aromatic 100 Fluid also known as solvent naphtha or light aromatic
  • Aromatic 150 Fluid also known as solvent naphtha, heavy aromatic, high flash aromatic naphtha type II, heavy aromatic solvent naphtha, hydrocarbons, CIO aromatics, >1% naphthalene, A150, SI 50
  • Aromatic 200 Fluid also known as solvent naphtha, heavy aromatic, high flash aromatic naphtha type II, heavy aromatic solvent naphtha, hydrocarbons, CI 0-13 aromatics, >1% naphthalene, A200, and S200.
  • Nitrapyrin tends to be more soluble in polar solvents than in non-polar solvents.
  • formulations of nitrapyrin in polar solvents tend to be corrosive, especially towards carbon steel storage containers. Due at least in part to their corrosive properties, formulations of nitrapyrin in polar solvents have proved to be difficult to commercialize.
  • Some aspects of the present invention include identifying and using especially useful corrosion inhibition additives which make practical liquid formulations of nitrapyrin in polar solvent that include on the order of about 200 to about 400 g/L of nitrapyrin. These inventive formulations are markedly less corrosive than are currently available nitrapyrin polar solvent formulations.
  • the (trichloromethyl)pyridine compound is nitrapyrin.
  • the (trichloromethyl)pyridine compound is present in the liquid inhibitor composition at a lower range of 2% by weight of the composition, or in other embodiments, at a lower range of 3% by weight of the composition, or in other embodiments, at a lower range of 5% by weight of the composition.
  • the (trichloromethyl)pyridine compound is present in the liquid inhibitor composition at a lower range 0.5%, or 1%, or 2%, or 3%, or 4%, or 5%, 6%, or 8%, or 10% or 12 % or 14%, by weight of the composition.
  • the (trichloromethyl)pyridine compound is present in the liquid inhibitor composition at an upper range of 75%, or 65%, or 60% by weight of the composition.
  • the (trichloromethyl)pyridine compound is present in the liquid inhibitor composition at an upper range of 60% by weight of the composition.
  • the (trichloromethyl)pyridine compound is present in the liquid inhibitor composition at an upper range of 55% by weight of the composition.
  • the (trichloromefhyl)pyridine compound is present in the liquid inhibitor composition at an upper range of 59%, or 57%, or 55% or 53 % or 50%, by weight of the composition. In another embodiment, the (trichloromethyl)pyridine compound is present in the liquid inhibitor composition at an upper range of 48%, or 46%, or 45% or 42 % or 40%, by weight of the composition.
  • compositions in one embodiment, a loading level of 360g/L
  • nitrapyrin which demonstrate stability in various extreme conditions, such as cold conditions.
  • the compositions as described herein are also capable of provide corrosion resistance to carbon steel tanks.
  • the (trichloromethyl)pyridine compound is dispersed in the liquid inhibitor composition at loading level of at least 200 g/L, or in another embodiment, at least 250 g/L, or in another embodiment, at least 300 g/L, or in another embodiment, at least 320 g/L, or in a further embodiment, at least 340 g/L, or in another embodiment, at least 360 g/L, or in yet another embodiment, at least 380 g/L, or in another embodiment, at least 400 g/L.
  • the (trichloromethyl)pyridine compound typically 2- chloro-6-(trichloromethyl)pyridine, has a solubility at 25 °C of at least 300 grams per liter (g/L), or in another embodiment, at least 320 g/L, or in a further embodiment, at least 340 g/L, or in another embodiment, at least 360 g/L, or in yet another embodiment, at least 380 g/L, or in another embodiment, at least 400 g/L.
  • the liquid inhibitor composition are made by contacting one or more nitrification inhibitors with a solvent comprising at least one organophosphate compound, whereby the nitrification inhibitor is dissolved or dispersed in the solvent.
  • the liquid inhibitor composition can further comprises at least one additional component, typically a corrosion inhibitor.
  • the liquid fertilizer compositions comprise: one more nitrogenous fertilizer compounds; at least one nitrification inhibitor comprising a (trichloromethyl)pyridine compound; a solvent comprising an organophosphate compound; and, optionally, a corrosion inhibitor.
  • the liquid inhibitor composition further comprises at least one additional component including, but not limited to, a co- solvent, a pH adjustor, flow agents, preservatives, buffering agents, antifoam agents, compatibility agents, deposition agents, dispersants, drift control agents, penetrants, surfactants, spreaders, and wetting agents, and the like.
  • the nitrogenous fertilizer compound is anhydrous ammonia.
  • liquid fertilizer compositions comprising, based on weight of the composition: (a) up to about 99 wt%, by weight of composition, of one or more nitrogenous fertilizer compounds, which in one embodiment is anhydrous ammonia (b) a (trichloromethyl)pyridine compound, which in one embodiment is 2-chloro-6-(trichloromethyl)pyridine, (c) a solvent comprising an organophosphate compound, and (d) a corrosion inhibitor.
  • the organophosphate compound is an alkyl phosphate.
  • the organophosphate compound is triethyl phosphate.
  • the organophosphate compound is triethyl phosphate, tri(isobutyl)phosphate, tributoxyethyl phosphate (TBEP) or tris(2-ethylhexyl) phosphate.
  • Methods of making a liquid fertilizer composition comprising contacting one or more nitrogenous fertilizer compounds with a liquid inhibitor composition, as described herein.
  • the nitrogenous fertilizer compound is anhydrous ammonia.
  • the liquid inhibitor composition comprises, in one embodiment, at least one of a nitrification inhibitor, which is dissolved or dispersed in a solvent comprising at least one organophosphate compound.
  • the nitrification inhibitor comprises a (trichloromethyl)pyridine compound.
  • the liquid inhibitor composition in one embodiment, further comprises at least one additional component, typically a corrosion inhibitor.
  • the liquid fertilizer compositions as described herein are utilized for treating soil.
  • the term “treating” in one embodiment means contacting the compositions as described herein with soil.
  • the term “treating”, in yet another embodiment, means concurrent mechanical mixing of the described compositions with soil.
  • the term “treating” means applying the described compositions to the surface of the soil and thereafter mechanically incorporating the compositions into soil (for example, at a certain depth).
  • the term “treating” means incorporating the described compositions into the soil at a certain depth, such as by injection and irrigation.
  • the term “treating” means injecting the liquid fertilizer composition as described herein into soil at a depth of less than or equal to 10 inches. In another embodiment, the term “treating” means injecting the liquid fertilizer composition as described herein into soil at a depth of less than or equal to 9 inches, or in some embodiments, less than or equal to 8 inches, or in some embodiments, less than or equal to 7 inches, or in some embodiments, less than or equal to 6 inches, or in some embodiments, less than or equal to 5 inches, or in some embodiments, less than or equal to 4 inches, or in some embodiments, less than or equal to 3 inches.
  • liquid fertilizer composition comprising: one more nitrogenous fertilizer compounds; at least one nitrification inhibitor comprising a (trichloromethyl)pyridine compound; a solvent comprising an organophosphate compound, and, optionally, a corrosion inhibitor.
  • the liquid inhibitor composition further comprises at least one additional component including, but not limited to, a co-solvent, a pH adjustor, flow agents, preservatives, buffering agents, antifoam agents, compatibility agents, deposition agents, dispersants, drift control agents, penetrants, surfactants, spreaders, and wetting agents, and the like.
  • the nitrogenous fertilizer compound is anhydrous ammonia.
  • the liquid inhibitor composition or liquid fertilizer composition forms a stable composition at temperatures less than or equal to 10 °C, or 7 °C, or 5 °C, or 3 °C. In another embodiment, the liquid inhibitor composition or liquid fertilizer composition, as described herein, forms a stable composition at temperatures less than or equal to 0 °C.
  • the liquid inhibitor composition or liquid fertilizer composition forms a stable composition at temperatures less than or equal to -1 °C, or -2 °C, or -3 °C, or -4 °C, or -5 °C, or -6 °C, or -7 °C, or -8 °C, or -9 °C, or -10 °C.
  • a stable composition means that no flocculation or crystallization is observed over a period of time.
  • the liquid inhibitor composition or liquid fertilizer composition forms a stable composition for a period of at least 24 hours. In one embodiment, the liquid inhibitor composition or liquid fertilizer composition, as described herein, forms a stable composition for a period of at least 48 hours. In one embodiment, the liquid inhibitor composition or liquid fertilizer composition, as described herein, forms a stable composition for a period of at least 1 week. In one embodiment, the liquid inhibitor composition or liquid fertilizer composition, as described herein, forms a stable composition for a period of at least 2 weeks.
  • compositions as described herein are stable for at least
  • compositions as described herein are stable for at least 2 months in metal containers at 25°C (or in some embodiments, 50°C). In one embodiment, the compositions as described herein are stable for at least 1 month in metal containers at 25°C (or in some embodiments, 50°C).
  • the metal containers can be, in one embodiment, carbon steel containers.
  • compounds suitable as the organic solvent component of the composition and methods of the present invention form liquid, or otherwise stable, compositions with the nitrification inhibitor at temperatures at or greater than -16 °C, in alternative embodiments, greater than -14 °C, in other embodiments, greater than -12 °C, in other embodiments, greater than -10 °C, in further embodiments, greater than -8 °C, in other embodiments, greater than -5 °C, in other embodiments, greater than -3 °C, in other embodiments, greater than -2 °C, in other embodiments, greater than 0 °C, in other embodiments, greater than 2 °C, in other embodiments, greater than 4 °C, in other embodiments, greater than 5°C.
  • the liquid fertilizer composition is stable, meaning the nitrification inhibitor(s) do not react with the solvent or solvent component under anticipated manufacturing, storage, and use conditions.
  • the liquid fertilizer composition is stable, meaning the liquid fertilizer composition or liquid inhibitor composition is or substantially is in one phase, i.e., no visible crystals, no visible precipitation, and/or no visible multiple liquid phases.
  • the organophosphate compound is according to formula
  • Rl, R2 and R3 are each independently chosen from H, a CI -CI 6 alkyl group, a Cl- C16 alkenyl, group, a CI -CI 6 alkoxyalkyl group, a C7-C30 alkylarylalkyl group, a C7-C30 arylalkyl group, or an aryl group; provided that at least one of Rl, R2 or R3 is not H.
  • Rl, R2 and R3 are each independently chosen from H, a CI -CI 2 alkyl group, a CI -CI 2 alkenyl, group, a CI -CI 2 alkoxyalkyl group, a C7-C30 alkylarylalkyl group, a C7-C30 arylalkyl group, or an aryl group; provided that at least one of Rl, R2 or R3 is not H.
  • Rl , R2 and R3, are each independently chosen from H, a Cl- C4 alkyl group, a C4-C8 alkyl group, a C1-C12 alkenyl, group, a C1-C4 alkoxyalkyl group, a C7-C30 alkylarylalkyl group, a C7-C30 arylalkyl group, or an aryl group; provided that at least one of Rl, R2 or R3 is not H.
  • Rl, R2 and R3, are each independently chosen from a linear or branched CI -CI 2 alkyl group, a linear or branched CI -CI 2 alkenyl, group, a linear or branched CI -CI 2 alkoxyalkyl group, a linear or branched C7-C30 alkylarylalkyl group, a linear or branched C7-C30 arylalkyl group, or an aryl group.
  • Rl, R2 and R3, are each independently chosen from a CI -CI 2 alkyl group, more typically, a C2-C8 alkyl group.
  • Rl, R2 and R3, are each independently a C1-C3 alkyl group, typically an ethyl group.
  • Rl, R2 and R3, are each independently a branched CI -CI 2 alkyl group, typically, a 2-ethylhexyl group.
  • Rl, R2 and R3, are each independently a CI -CI 2 alkoxyalkyl group, typically a butoxyethyl group.
  • liquid inhibitor composition for use in agricultural applications and/or liquid fertilizer compositions comprising: at least one nitrification inhibitor comprising a (trichloromethyl)pyridine compound; a polar solvent blend comprising at least two polar solvents: (i) a dibasic ester blend and (ii) a ketone such as cyclohexanone ; and, optionally, a corrosion inhibitor.
  • liquid inhibitor compositions comprising contacting one or more nitrification inhibitors with a polar solvent blend comprising at least two polar solvents: (i) a dibasic ester blend and (ii) a ketone such as cyclohexanone, whereby the nitrification inhibitor is dissolved or dispersed in the polar solvent blend.
  • the nitrification inhibitor comprises a (trichloromethyl)pyridine compound.
  • the liquid inhibitor composition in one embodiment, further comprises at least one additional component, typically a corrosion inhibitor.
  • liquid fertilizer compositions for use in agricultural applications comprising: one or more nitrogenous fertilizer compounds; at least one nitrification inhibitor comprising a (trichloromethyl)pyridine compound; a polar solvent blend comprising at least two polar solvents: (i) a dibasic ester blend and (ii) a ketone such as cyclohexanone; and, optionally, a corrosion inhibitor.
  • the dibasic ester blend comprises:
  • Ri and/or R 2 can individually comprise a hydrocarbon having from about 1 to about 8 carbon atoms, typically, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, n-butyl, isoamyl, hexyl, heptyl or octyl.
  • the dibasic ester blend comprises: a diester of the formula (Ilia):
  • R ⁇ and/or R 2 can individually comprise a hydrocarbon having from about 1 to about 8 carbon atoms, typically, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, n-butyl, isoamyl, hexyl, heptyl, or octyl.
  • the blend typically comprises (by weight of the blend) (i) from about 5% to about 30% of the diester of formula (Ilia), (ii) from about 70% to about 95% of the diester of formula (Illb), and (iii) from about 0% to about 10%) of the diester of formula (IIIc).
  • the blend typically comprises (by weight of the blend): (i) from about 6% to about 12% of the diester of formula (Ilia), (ii) from about 86% to about 92% of the diester of formula (Illb), and (iii) from about 0.5% to about 4% of the diester of formula (IIIc).
  • the blend comprises (by weight of the blend): (i) about 9% of the diester of formula (Ilia), (ii) about 89% of the diester of formula (Illb), and (iii) about 1% of the diester of formula (IIIc).
  • the blend is generally characterized by a flash point of of 98°C, a vapor pressure at 20 °C of less than about 10 Pa, and a distillation temperature range of about 200-275 °C.
  • the polar solvent blend comprises (by weight of the solvent blend) up to 100 wt% or 99.9 wt% of the ketone. In one embodiment, the polar solvent blend comprises (by total weight of the polar solvent blend) up to 80 wt% of the ketone. In one embodiment, the polar solvent blend comprises (by total weight of the polar solvent blend) up to 90 wt% of the ketone. In one embodiment, the polar solvent blend comprises (by total weight of the polar solvent blend) up to 70 wt% of the ketone. In one embodiment, the polar solvent blend comprises (by total weight of the polar solvent blend) up to 65 wt% of the ketone.
  • the polar solvent blend comprises (by total weight of the polar solvent blend) up to 60 wt% of the ketone. In one embodiment, the polar solvent blend comprises (by total weight of the polar solvent blend) up to 55 wt% of the ketone. In one embodiment, the polar solvent blend comprises (by total weight of the polar solvent blend) up to 50 wt% of the ketone. In one embodiment, the polar solvent blend comprises (by total weight of the polar solvent blend) up to 45 wt% of the ketone. In one embodiment, the polar solvent blend comprises (by total weight of the polar solvent blend) up to 40 wt% of the ketone. It is believe that the composition of the polar solvent blend allows for the loading levels as described herein.
  • ketones include but are not limited to any one or more of acetone, methyl ethyl ketone, methyl propyl ketone, cyanoacetone, ethoxy: acetone, acetonylacetone, diacetone alcohol, methyl isobutyl ketone, diethyl ketone, diisopropyl ketone, diisobutyl ketone, methyl-n-amyl ketone, methyl-n-hexyl ketone, cyclopentanone, methylcyclohexanone, methyl-cyclopentanone, cyclohexanone, methylallylcyclohexanone, phenylcyclohexanone, cyclohexylcyclohexanone, benzylcyclohexanone, phorone, isophorone, and , B-ionone, methyl vinyl ketone, methyl isopropenyl ketone, and cyanoacetone,
  • the dibasic ester blend comprises adducts of alcohol and linear diacids, each adduct having the formula (IV):
  • R is an alkyl group (e.g., methyl, ethyl, etc.) and A is a mixture of -
  • the blend comprises adducts of alcohol, typically ethanol, and linear diacids, the adducts having the formula Rl-OOC-A- COO-R2, wherein at least part of Rl and/or R2 are residues of at least one linear alcohol having 4 carbon atoms, and/or at least one linear or branched alcohol having at least 5 carbon atoms, and wherein A is a divalent linear hydrocarbon.
  • A is one or a mixture of -(CH2)4-, -(CH2)3, and -(CH2)2-.
  • the dibasic ester comprises adducts of an alcohol and linear or branched diacids, the adducts having the formula (IV): R-OOC-A-COO-R, wherein R is an alkyl group (e.g., methyl, ethyl, etc.) and A one of the following :-(CH2)4-, -(CH2)3, -(CH2)2-, -CH2-, or any mixture thereof.
  • R is an alkyl group (e.g., methyl, ethyl, etc.) and A one of the following :-(CH2)4-, -(CH2)3, -(CH2)2-, -CH2-, or any mixture thereof.
  • the dibasic ester blend may be derived from one or more by-products in the production of polyamide, for example, polyamide 6,6.
  • at least one dibasic ester comprises a blend of linear or branched, cyclic or noncyclic, CI C20 alkyl, aryl, alkylaryl or arylalkyl esters of adipic diacids, glutaric diacids, and succinic diacids.
  • the composition comprises a blend of linear or branched, cyclic or noncyclic, CI C20 alkyl, aryl, alkylaryl or arylalkyl esters of adipic diacids, methylglutaric diacids, and ethylsuccinic diacids
  • polyamide is a copolymer prepared by a condensation reaction formed by reacting a diamine and a dicarboxylic acid.
  • polyamide 6,6 is a copolymer prepared by a condensation reaction formed by reacting a diamine, typically hexamethylenediamine, with a dicarboxylic acid, typically adipic acid.
  • the blend of dibasic esters can be derived from one or more by-products in the reaction, synthesis and/or production of adipic acid utilized in the production of polyamide, the composition comprising a blend of dialkyl esters of adipic diacids, glutaric diacids, and succinic diacids (herein referred to sometimes as "AGS" or the “AGS blend”).
  • the dibasic ester blend comprises dimethyl adipate, dimethyl glutarate and dimethyl succinate.
  • the blend of esters is derived from by-products in the reaction, synthesis and/or production of hexamethylenediamine utilized in the production of polyamide, typically polyamide 6,6.
  • the composition comprises a blend of dialkyl esters of methylglutaric diacids, ethylsuccinic diacids, and optionally adipic diacids (herein referred to sometimes as "MGA”, “MGN”, “MGN blend” or “MGA blend”).
  • the dibasic ester blend comprises dimethyl adipate, dimethyl methylglutarate and dimethyl ethylsuccinate.
  • the liquid inhibitor composition or liquid fertilizer composition further comprises at least one additional component including, but not limited to, a co-solvent, a pH adjustor, flow agents, preservatives, buffering agents, antifoam agents, compatibility agents, deposition agents, dispersants, drift control agents, penetrants, surfactants, spreaders, and wetting agents, and the like.
  • the nitrogenous fertilizer compound is anhydrous ammonia.
  • a liquid fertilizer compositions comprising contacting one or more nitrogenous fertilizer compounds with liquid inhibitor composition.
  • the nitrogenous fertilizer compound is anhydrous ammonia.
  • the liquid inhibitor composition comprises, in one embodiment, at least one of a nitrification inhibitor, which is dissolved or dispersed in a solvent blend comprising at least two solvents: (i) a dibasic ester blend and (ii) a ketone such as cyclohexanone.
  • the nitrification inhibitor comprises a (trichloromethyl)pyridine compound.
  • the liquid inhibitor composition in one embodiment, further comprises at least one additional component, typically a corrosion inhibitor.
  • one or more second solvents can be used to dissolve or disperse (trichloromethyl)pyridine compounds at high loading levels and include, but are not limited to, solvent naphtha, aromatic solvents, mineral oils, kerosene, and chlorinated aliphatic and aromatic hydrocarbons.
  • the one or more second solvents used to dissolve or disperse (trichloromethyl)pyridine compounds at high loading levels include but are not limited to xylene and solvent naphtha.
  • the co-solvent is an esteramide compound according to formula
  • A is a divalent linear or branched (C2-C8)aliphatic group
  • Rl, R2, and R3 are each independently (Cl-C12)alkyl, (Cl-C12)aryl, (Cl- C12)alkaryl or (Cl-C12)arylalkyl, and R2 and R3 may each optionally be substituted with one or more hydroxyl groups.
  • the inventive formulations of (trichloromethyl)pyridine compound may be applied to the soil or a growth medium at a rate in the range of at least one lower limit selected from the group of lower limits consisting of about 0.1., about 0.25, about 0.5 and about 0.58 kg/hectare to at least one upper limit selected from the group consisting of about 1.0, about 1.2 and about 1.5 kg/hectare.
  • the preferred amount can be easily ascertained by the application preference, considering factors such as soil pH, temperature, soil type and mode of application.
  • the formulation of the present invention can be applied in any manner which will benefit the crop of interest.
  • the inventive formulation is applied to growth medium in a band or row application.
  • the formulation is applied to or throughout the growth medium prior to seeding or transplanting the desired crop plant.
  • the formulation can be applied to the root zone of growing plants.
  • the soil may be prepared in any convenient manner compatible with the use of the present invention, including mechanically mixing the formulation with the soil. Still other application may include applying the formulation to the surface of the soil and thereafter dragging, dicing or cutting the formulation into the soil to a desired depth. Still other methods of delivering the nitrification inhibitor into the soil, include methods such as injection, and spraying, or irrigation. In many applications the (trichloromethyl)pyridine compound is delivered into the soil to the desired depth of up to 6 inches (15.24 cm.).
  • inventive nitrapyrin formulation may be used along with other agriculturally active ingredients such as insecticides, fungicides, mitocides, herbicides, and the like.
  • Some exemplary herbicides which can be used along with the inventive nitrapyrin formulations include, but are not limited to acetochlor, alachlor, aminopyralid, atrazine, benoxacor, bromoxynil, carfentrazone, chlorsulfuron, clodinafop, clopyralid, dicamba, diclofop-methyl, dimethenamid, fenoxaprop, flucarbazone, flufenacet, flumetsulam, flumiclorac, fluroxypyr, glufosinate-ammonium, glyphosate, halosulfuron-methyl, imazamethabenz, imazamox, imazapyr, imazaquin, imazethapyr, isoxaflutole, quinclorac, MCPA, MCP amine, MCP ester, mefenoxam, mesotrione, metolachlor, s-metolachlor, metribuzin, met
  • Ar represents a phenyl group substituted with one to four substituents independently selected from halogen, C1-C6 alkyl, C1-C6 alkoxy, C2-C4 alkoxyalkyl, C2-C6 alkylcarbonyl, C1-C6 alkylthio, C1-C6 haloalkyl, C1-C6 haloalkoxy, C2-C4 haloalkoxyalkyl, C2-C6 haloalkylcarbonyl, C1-C6 haloalkylthio, -OCH2CH2-, -OCH2CH2CH2-, -OCH20- or -OCH2CH20-;
  • R represents H or F;
  • X represents CI or vinyl; and Y represents CI, vinyl or methoxy; and their salts and esters as disclosed, for example, in US7314849 B2, US7300907 B2, US7786044 B2 and US7642220 B2.
  • these compounds may be applied along with the inventive nitrapyrin formulation.
  • the compound may be applied by any suitable means either before or after the inventive formulation is applied to the soil.
  • herbicides useful with the compositions and methods described herein include 2,4-D, 2,4-DB, aminocyclopyrachlor, aminopyralid, clopyralid, dicamba, fluroxypyr, halauxifen, MCPA, MCPB, picloram, triclopyr, acetochlor, atrazine, benfluralin, cloransulam, cyhalofop, diclosulam, dithiopyr, ethalfluralin, florasulam, flumetsulam, glufosinate, glyphosate, haloxyfop, isoxaben, MSMA, oryzalin, oxyfluorfen, pendimethalin, penoxsulam, propanil, pyroxsulam, quizalofop, tebuthiuron, trifluralin, and the compound of the Formula.
  • Some exemplary insecticides which can be used along with the inventive nitrapyrin formulations include, but are not limited to abamectin, acephate, acetamiprid, acrinathrin, alpha-cypermethrin, alpha-endosulfan, azadirachtin, azinphos-ethyl, azinphos- methyl, bendiocarb, benfuracarb, bensultap, beta-cyfluthrin, beta-cypermethrin, bifenthrin, bufencarb, buprofezin, butacarb, cadusafos, carbaryl, carbofuran, carbosulfan, cartap, cartap hydrochloride, chlorantraniliprole, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chlo yrifos, chlorpyrifos-methyl
  • these compounds may be applied along with the inventive nitrapyrin formulation.
  • the compound may be applied by any suitable means either before or after the inventive formulation is applied to the soil.
  • Some exemplary fungicides which can be used along with the inventive nitrapyrin formulations include, but are not limited to tricyclazole, phthalide, carpropamide, pyroquilon, diclocymet, fenoxanil, probenazole, isoprothiolane, iprobenfos, isotianil, tiadinil, kasugamyein, flutolanil, mepronil, pencycuron, polyoxins, validamycin, toclophos-methyl, boscalid, penthiopyrad, thifluzamide, bixafen, fluopyram, isopyrazam, propiconazole, difenoconazole, fenbuconazole, ipconazole, triadimefon, hexaconazole, azoxystrobin, metaminostrobin, orysastrobin and acibenzolar-S-methyl.
  • Some of these fungicides may not be effective for disease control when applied at the timing of application of the inventive formulation because fungal disease propagation and growth cycles may not be optimal.
  • the effective use and application timing of these fungicides can be easily determined by one of normal skill in the art.
  • these compounds may be applied along with the inventive nitrapyrin formulation. In many instances the compound may be applied by any suitable means either before or after the inventive formulation is applied to the soil.
  • Some exemplary herbicide safeners which can be used along with the inventive nitrapyrin formulations include, but are not limited to benoxacor, benthiocarb, cloquintocet-mexyl, daimuron, dichlormid, dicyclonon, dimepiperate, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, Harpin proteins, isoxadifen-ethyl, mefenpyr- diethyl, mephenate, MG 191, MON 4660, naphthalic anhydride (NA), oxabetrinil, R29148 and 7V-phenyl-sulfonylbenzoic acid amides.
  • benoxacor benthiocarb
  • cloquintocet-mexyl daimuron
  • dichlormid dicyclonon, dimepiperate
  • fenchlorazole-ethyl fenclo
  • the herbicide safener compounds used in the presence of the component of the inventive formulation and the preferred mode of applying the compounds may be applied along with the inventive nitrapyrin formulation.
  • the compound may be applied by any suitable means either before or after the inventive formulation is applied to the soil.
  • Some exemplary plant growth regulators which can be used along with the inventive nitrapyrin formulations include, but are not limited to 2,4-D, 2,4-DB, IAA, IBA, naphthaleneacetamide, a-naphthaleneacetic acid, kinetin, zeatin, ethephon, aviglycine, 1-methylcyclopropene (1-MCP), ethephon, gibberellins, gibberellic acid, abscisic acid, ancymidol, flurprimidol, mefluidide, paclobutrazol, tetcyclacis, uniconazole, brassinolide, brassinolide-ethyl and ethylene.
  • these compounds may be applied along with the inventive nitrapyrin formulation.
  • the compound may be applied by any suitable means either before or after the inventive formulation is applied to the soil.
  • Example 1 The high load nitrapyrin SL formulations (360 g/L) comprising polar solvents were prepared by dissolving nitrapyrin technical in the solvent systems, which included polar solvents corrosion inhibitors. The solutions were mixed under IKA mixing until they were essentially homogeneous.
  • Table 1 Example compositions of stable high load nitrapyrin SL formulations (360 g/L Nitrapyrin technical) comprising polar solvents after corrosion testing with carbon steel coupons at 50°C.
  • the control (N-SERVE) sample (Sample 1) has a loading of 240 g/L.
  • Hallcomid M- 8-10 Mixture of N, N-dimethyloctanamide (N, N-dimethylcaprylamide) and ⁇ , ⁇ -dimethyldecanamide (N, N-dimethylcapramide); RhodiaSolv RPDE: Reaction mass of dimethyl adipate and dimethyl glutarate and dimethyl succinate; Aromatic 100: Solvent Naphtha (petroleum), light aromatic; TamiSolve NxG: N-butylpyrrolidone.
  • Example 2 A stock solution of 360g/L nitrapyrin technical grade in triethyl phosphate was prepared and additives in specific amounts to limit corrosion to carbon steel were added to this solution. A small quantity ( ⁇ 15mL) of the solution in glass jars were left for storage stability at room temperature ( ⁇ 20C) and -12 C. The -12C sample was seeded after it reached 24 hrs age by incorporating few small grains of nitrapyrin technical in the cold solution and was immediately stored back to the -12 C storage temperature. A carbon steel coupon was partially submerged into the solution stored at 54C. The coupon was periodically observed for any sign of corrosion in liquid and vapor phases. The solutions at room temperature and -12C were observed for any inhomogeneity, crystallization and flowability. Table 2 shows summary of the observations.
  • Example 3 Homogeneous compositions of nitrapyrin technical grade (360 g/L) were made in different ratios of mixture of cyclopentanone or cyclohexanone and Rhodiasolv RPDE (mixture of dimethyl glutarate, dimethyl adipate and dimethyl succinate). A small quantity ( ⁇ 15mL) of the solution in glass jars were left for storage stability at room temperature ( ⁇ 20C) and -IOC. The -IOC sample was seeded after it reached 24 hrs age by incorporating few small grains of Nitrapyrin technical in the cold solution and was immediately stored back to the -IOC temperature. The solutions at different temperatures were observed for any inhomogeneity, crystallization and flowability. No crystals or any other inhomogeneities were observed in the solution at any temperatures within 2 weeks of storage. Table 3 shows a summary of the compositions and their stability.
  • Corrosion tests A stock solution of 360g/L nitrapyrin technical grade in cyclohexanone/RPDE (60:40 weight ratio) was prepared and corrosion inhibitors in specific amounts were added to this solution. The resultant solutions were tested for corrosion issues with carbon steel tanks using following protocol. A carbon steel coupon was partially submerged into the solution stored at 54C. The coupon was periodically observed for any sign of corrosion in liquid and vapor phases. Table 4 shows a summary of the observations.
  • Example 4 Storage stability tests : Homogeneous composition of nitrapyrin technical grade (360 g/L) was dispersed in methoxybenzene solvent, and a quantity of about 15 mL of the solution in glass jars were left for storage stability at room temperature ( ⁇ 20 °C), 54°C and -7°C. The -7°C sample was seeded after it reached 24 hrs age by incorporating few small grains of nitrapyrin technical in the cold solution and was immediately stored back to the -7°C temperature. The solutions at different temperatures were observed for any inhomogeneity, crystallization and flowability. No crystals or any other inhomogeneities were observed in the solution at any temperatures within 2 weeks of storage.

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  • Life Sciences & Earth Sciences (AREA)
  • Soil Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Fertilizers (AREA)
  • Pyridine Compounds (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

La présente invention concerne des formulations liquides stables de l'inhibiteur de nitrification intitulé nitrapyrine comprenant des solvants polaires qui sont stabilisés par de petites quantités de composés qui aident à réduire la tendance des solutions polaires de nitrapyrine à corroder les surfaces métalliques. De nombreuses formulations selon la présente invention présentent des propriétés physiques, chimiques et bioactives utiles, notamment des niveaux réduits de corrosion lorsqu'elles sont en contact avec des métaux ferreux.
PCT/US2016/044461 2015-10-22 2016-07-28 Formulation à base de solvant polaire d'inhibiteur de nitrification non corrosif WO2017069827A1 (fr)

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