WO2021013582A1 - Compositions liquides de dicyandiamide et/ou de triamide d'alkyle thiophosphorique et leur utilisation dans des applications agricoles - Google Patents

Compositions liquides de dicyandiamide et/ou de triamide d'alkyle thiophosphorique et leur utilisation dans des applications agricoles Download PDF

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WO2021013582A1
WO2021013582A1 PCT/EP2020/069557 EP2020069557W WO2021013582A1 WO 2021013582 A1 WO2021013582 A1 WO 2021013582A1 EP 2020069557 W EP2020069557 W EP 2020069557W WO 2021013582 A1 WO2021013582 A1 WO 2021013582A1
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composition
solvent
liquid
fertilizer
inhibitor
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PCT/EP2020/069557
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English (en)
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Krish SHANMUGA
Rawad TADMOURI
Samantha Armisen
Matthieu Guirardel
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Rhodia Operations
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Publication of WO2021013582A1 publication Critical patent/WO2021013582A1/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
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C1/00—Ammonium nitrate fertilisers
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C9/00—Fertilisers containing urea or urea compounds
    • 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

  • This invention relates to liquid compositions comprising dicyandiamide and/or an alkyl thiophosphoric triamide, methods for incorporating
  • dicyandiamide and/or an alkyl thiophosphoric triamide into agricultural fertilizer compositions, agricultural fertilizer compositions comprising dicyandiamide and/or an alkyl thiophosphoric triamide, and the use of such compositions.
  • Nitrogen, phosphorus, potassium, calcium, magnesium, and sulfur are macronutrients that must be supplied to the plants and soil manually by farmers. In many crops, the amount of nitrogen supplied is critical to the overall quality and growth of the crop. Nitrogen is typically supplied in the form of
  • nitrogenous i.e., nitrogen precursor-containing, fertilizer compounds, such as urea, ammonium nitrate, or ammonium phosphate fertilizer compounds. Due to the high water solubility of these salts, however, applied nitrogen may be lost due to run-off and leaching of the nitrogenous fertilizer compounds. Once applied, the nitrogenous fertilizer compounds are typically degraded, for example, by microorganisms present in the soil, to nitrogenous species such as NH4+, N02-, N03-, and ammonia gas, that may be even more readily lost through evaporation, run-off, and leaching than the fertilizer compounds themselves. If degradation of the fertilizer compounds occurs at a rate that is faster than the nitrogenous degradation products can be used by the plants, then the nitrogen values in the degradation products are at increased risk of being lost.
  • nitrogen precursor-containing, fertilizer compounds such as urea, ammonium nitrate, or ammonium phosphate fertilizer compounds. Due to the high water solubility of these salts, however, applied
  • Nitrification and/or urease inhibitors are of potential use in delaying degradation of fertilizer compounds and thereby reducing losses of nitrogenous degradation products that would otherwise occurred in the absence of the inhibitors.
  • the use of nitrification and/or urease inhibitors in combination with nitrogenous fertilizer compounds tends to increase the amount of time the nitrogen sources remain in the soil and available for absorption by the plants, which tends to increase the effectiveness of the fertilizers and positively impact crop yield and quality.
  • Aqueous end use fertilizer solutions are typically prepared in the field by diluting commercially available concentrated fertilizer compositions with water.
  • Commonly used concentrated fertilizer compositions include concentrated ammonium nitrate compositions, such as, for example, UAN 18, UAN 28, UAN 30 and UAN 32.
  • Dicyandiamide is useful as a nitrification inhibitor in such aqueous end use fertilizer compositions, but has very low solubility (about 41 grams per liter (“g/1”)) in water and so is difficult to be incorporated into the aqueous end use fertilizer compositions, particularly under field conditions.
  • DMSO dimethylsulfoxide
  • Urease inhibitors can be used with a fertilizer (i.e., incorporated into a urea-containing fertilizer, e.g., urea and urea ammonium nitrate (UAN)) to slow the conversion of urea to ammonia gas and thus slow the loss of ammonia to volatilization, thus making ammonium available to plants in the soil for longer periods of time.
  • a fertilizer i.e., incorporated into a urea-containing fertilizer, e.g., urea and urea ammonium nitrate (UAN)
  • UAN urea and urea ammonium nitrate
  • the hydrolysis of urea is facilitated by urease enzyme present in the soil.
  • the amount of nitrogen supplied is critical to the overall quality and growth of the crop. Nitrogen is supplied in either urea or ammonium forms. Due to the high water solubility of these salts, however, much of the nitrogen applied is lost to run-off and leaching.
  • ammonium-based products if the nitrogen is not lost due to leaching or run-off, then ammonium can bind to soil particles and made available for the plant. . Conversion occurring near the surface of the soil, however, does not allow for binding and this ammonia is lost to the atmosphere.
  • Urease inhibitors are used to protect a farmer’s investment in fertilizers by preventing the breakdown of urea by urease, the soil microbe responsible for converting urea to usable ammonia in the soil. This increases the amount of time the nitrogen remains in the soil and is available to the plant for absorption.
  • nitrification inhibitors can be used with a fertilizer (i.e., incorporated into a urea-containing fertilizer, e.g., urea and urea ammonium nitrate (UAN)) to slow the process of ammonium conversion to nitrate, and subsequently the loss of nitrate to leeching, thus making ammonium available to plants in the soil for longer periods of time.
  • a fertilizer i.e., incorporated into a urea-containing fertilizer, e.g., urea and urea ammonium nitrate (UAN)
  • UAN ammonium nitrate
  • Ammonium is one of the main forms of nitrogen that can be utilized by plants. Increasing the amount of time that the nitrogen is available to the plant increases the effectiveness of the fertilizer which positively impacts crop yield and quality.
  • Fertilizers are common water soluble inorganic fertilizers that provide nutrients such as phosphorus-based, nitrogen -based, potassium-based or sulphur-based fertilizers.
  • fertilizers include: for nitrogen as the nutrient: nitrates and or ammonium salts such as ammonium nitrate, including in combination with urea e.g.
  • Uram type materials calcium ammonium nitrate, ammonium sulphate nitrate, ammonium phosphates, particularly mono-ammonium phosphate, di -ammonium phosphate and ammonium polyphosphate, ammonium sulphate, and the less commonly used calcium nitrate, sodium nitrate, potassium nitrate and ammonium chloride.
  • a fertilizer composition can comprise one or a combination of the fertilizers described herein.
  • a typical urease inhibitor alkyl thiophosphoric triamide (for example, N-
  • NBPT (n-butyl)-thiophosphoric triamide or otherwise“NBPT”)
  • NBPT is a sticky, waxy, heat and water sensitive material, which cannot be used in its solid form, as it is used at low concentrations making it difficult to evenly distribute on urea prills (i.e., large granules) and in soil.
  • urea prills i.e., large granules
  • soil In order to evenly distribute the NBPT onto the urea, the NBPT should be dispersed into a carrier prior to being sprayed onto the urea.
  • the use of a solvent system containing the NBPT is desirable as, in its liquid form, the solvent system is capable of distributing the NBPT into granular urea (e.g., urea prills) and into liquid fertilizers containing urea.
  • the NBPT is capable of being better dispersed in the liquid fertilizer.
  • One of the advantage of high load NBPT formulation is the application at lower use rate than the standard low concentration formulation ( ⁇ 30wt% NBPT) which reduces the anticaking problem during coating on urea and eliminates the need for anti caking agent during the coating process.
  • Dicyandiamide is useful as a nitrification inhibitor in aqueous agricultural applications, e.g., end use fertilizer compositions, but similar to urease inhibitors face drawbacks.
  • Nitrification inhibitors such as dicyandiamide
  • dicyandiamide generally have very low solubility (about 41 grams per liter (“g/1”)) in water and so it is difficult to incorporate into the aqueous end use fertilizer compositions, particularly under field conditions.
  • nitrification inhibitors, such as dicyandiamide have a generally low solubility, they are used at low concentrations in water making it difficult to evenly distribute on urea-containing prills (i.e., large granules) and in soil.
  • dicyandiamide In order to evenly distribute the dicyandiamide onto the urea-containing prills or granules, dicyandiamide should be dispersed into a solvent carrier prior to being sprayed onto the urea.
  • a solvent system containing dicyandiamide herein, also termed“DCD” is desirable as, in its liquid form, the solvent system is capable of distributing the dicyandiamide onto urea granules or prills, urea ammonium nitrate granules or prills or, otherwise, urea-containing granules or prills, and into liquid fertilizers containing urea or urea ammonium nitrate.
  • the dicyandiamide By introducing the dicyandiamide to liquid fertilizers containing urea (for example, urea-ammonium nitrate solutions or UAN) in a solvent system, the dicyandiamide is capable of being better dispersed in the liquid fertilizer.
  • urea for example, urea-ammonium nitrate solutions or UAN
  • concentrated fertilizer compositions include concentrated ammonium nitrate compositions, such as, for example, UAN 18, UAN 28, UAN 30 and UAN 32.
  • a solvent system containing alkyl thiophosphoric triamide for example, (N-(n-butyl)- thiophosphoric triamide), that has a favorable toxicological and/or ecological profile and desirable characteristics in terms of low volatility, biodegradability or ready biodegradability (i.e., readily biodegradable), low toxicity or low hazard level.
  • a solvent system containing a nitrification inhibitor for example, dicyandiamide, that has a favorable toxicological and/or ecological profile and desirable characteristics in terms of low volatility, biodegradability or ready biodegradability (i.e., readily
  • a solvent system containing a combination of a nitrification inhibitor and urease inhibitor that has a favorable toxicological and/or ecological profile and desirable characteristics in terms of low volatility, biodegradability or ready biodegradability (i.e., readily biodegradable), low toxicity or low hazard level.
  • DMSO solubilize N-(n- butyl) thiophosphoric triamide (NBPT) and to reduce decomposition of NBPT into non-effective substances. This decomposition can be observed through common signs of degradation while undergoing long-term storage stability studies. Specifically other side-products suspected of reacting with DMSO in formulation leaving large amounts of sediment and/or malodor in the formulation generated while undergoing stability studies.
  • NBPT N-(n- butyl) thiophosphoric triamide
  • the present invention aims at finding an alternative solvent to DMSO that makes it possible to reduce NBPT degradation during a long-term storage resulting in unwanted sedimentation and/or odor masking agent to minimize any malodor in the formulation.
  • compositions for use in agricultural applications comprising at least one of a dicyandiamide or an alkyl thiophosphoric triamide, which is dissolved in a solvent comprising levoglucosenone or dihydrolevoglucosenone or a derivative thereof.
  • liquid agricultural compositions comprising at least one of a nitrification inhibitor, a urease inhibitor or a mixture thereof; and a solvent comprising levoglucosenone or dihydrolevoglucosenone or a derivative thereof.
  • liquid inhibitor compositions comprising treating (e.g., contacting or spray applying) one or more nitrogenous fertilizer compounds with a liquid inhibitor composition.
  • the liquid inhibitor composition comprises a nitrification inhibitor and/or a urease inhibitor, homogenously dissolved or dispersed in a solvent comprising levoglucosenone or dihydrolevoglucosenone or a derivative thereof.
  • the liquid inhibitor composition in one embodiment, may further comprise at least one co-solvent as described below.
  • treating includes spray applying the liquid inhibitor composition with the one or more nitrogenous fertilizer compounds.
  • treating includes but is not limited to contacting the inhibitor composition with the one or more nitrogenous fertilizer compounds.
  • the nitrification inhibitor is dicyandiamide (otherwise referred to herein as“DCD”).
  • the urease inhibitor is an alkyl thiophosphoric triamide, for instance N-(n- butyl)-thiophosphoric triamide.
  • concentrated liquid fertilizer compositions comprising, based on weight of the composition: (a) up to about 99 pbw, by weight of composition, of one or more nitrogenous fertilizer
  • thiophosphoric triamide in combination with dicyandiamide, (c) at least one solvent comprising levoglucosenone or dihydrolevoglucosenone or a derivative thereof.
  • concentrated liquid fertilizer compositions comprising, based on weight of the composition: (a) up to about 99 pbw, by weight of composition, of one or more nitrogenous fertilizer
  • the concentrated liquid fertilizer compositions can further comprise at least one co solvent.
  • the concentrated liquid fertilizer compositions can further comprise one or more stabilizers.
  • solid or substantially solid fertilizer compositions comprising: (a) solid particles of one or more nitrogenous fertilizer compounds, and (b) an inhibitor composition comprising at least one of a dicyandiamide or an alkyl thiophosphoric triamide supported on at least a portion of the solid particles.
  • the inhibitor composition covers substantially all of the solid particles. In one embodiment, evenly covers (or substantially evenly covers) all of the solid particles.
  • the carrier utilized to contact the dicyandiamide or an alkyl thiophosphoric triamide with the solid particles comprises at least one solvent as described herein.
  • an aqueous end use fertilizer composition comprising contacting one or more nitrogenous fertilizer compounds with an inhibitor composition that comprises at least one of a dicyandiamide or an alkyl thiophosphoric triamide, which is dissolved or dispersed in a liquid medium comprising at least one solvent comprising levoglucosenone or dihydrolevoglucosenone or a derivative thereof.
  • the liquid medium can further comprise at least one co-solvent.
  • aqueous end use fertilizer composition comprising, based on weight of the composition: (a) up to about 99 pbw, based on the weight of the composition, of one or more nitrogenous fertilizer compounds, (b) at least one of a dicyandiamide or an alkyl
  • composition can further comprise at least one co-solvent.
  • aqueous end use fertilizer composition that comprises:
  • the alkyl thiophosphoric triamide is N-(n-butyl)- thiophosphoric triamide.
  • the present application also relates, more generally, to the use of levoglucosenone or dihydrolevoglucosenone or a derivative thereof as solvent in any agricultural crop protection formulation.
  • alkyl means a saturated straight chain, branched chain, or cyclic hydrocarbon radical, including but not limited to, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, pentyl, n-hexyl, and cyclohexyl.
  • aryl means a monovalent unsaturated hydrocarbon radical containing one or more six-membered carbon rings in which the unsaturation may be represented by three conjugated double bonds, which may be substituted one or more of carbons of the ring with hydroxy, alkyl, alkenyl, halo, haloalkyl, or amino, including but not limited to, phenoxy, phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, chlorophenyl,
  • alkylene means a divalent saturated straight or branched chain hydrocarbon radical, such as for example, methylene, dimethylene, trimethylene.
  • alkoxyl means an oxy radical that is substituted with an alkyl group, such as for example, methoxyl, ethoxyl, propoxyl, isopropoxyl, or butoxyl, which may optionally be further substituted on one or more of the carbon atoms of the radical.
  • alkoxyalkyl means an alkyl radical that is substituted with one or more alkoxy substituents, more typically a (Cl- C22)alkyloxy-(Cl-C6)alkyl radical, such as methoxym ethyl, and ethoxybutyl.
  • alkenyl means an unsaturated straight or branched hydrocarbon radical, more typically an unsaturated straight, branched, (which, in one particular embodiment, is C1-C75) hydrocarbon radical, that contains one or more carbon-carbon double bonds, such as, for example, ethenyl, n-propenyl, iso-propenyl.
  • arylalkyl means an alkyl group substituted with one or more aryl groups, more typically a (Cl-C18)alkyl substituted with one or more (C6-C14)aryl substituents, such as, for example, phenylmethyl,
  • aryloxy means an oxy radical substituted with an aryl group, such as for example, phenyloxy, methylphenyl oxy,
  • (Cr-Cs) in reference to an organic group, wherein r and s are each integers, indicates that the group may contain from r carbon atoms to s carbon atoms per group.
  • non-limiting examples of nitrification inhibitors comprise any one or more of N-2,5-dichlorophenyl succinamic acid,
  • DCD dicyandiamide
  • ATS ammonium thiosulphate
  • DMPP 3,4- dimethypyrazole phosphate
  • non-limiting examples of urease inhibitors comprise any one or more of N-butyl thiophosphoric triamide (NBPT), N-(w- butyl)phosphoric triamide, miophosphoryl triamide, cyclohexyl phosphoric triamide, cyclohexyl thiophosphoric triamide, phosphoric triamide,
  • NBPT N-butyl thiophosphoric triamide
  • miophosphoryl triamide miophosphoryl triamide
  • cyclohexyl phosphoric triamide cyclohexyl thiophosphoric triamide
  • phosphoric triamide phosphoric triamide
  • ATS ammonium thiosulphate
  • CHPT N-cyclohexyl phosphoric triamide
  • PPT phenyl phosphorodiamidate
  • Dicyandiamide is a known compound according to formula (I.b):
  • Dicyandiamide also known as“2-cyanoguanidine”
  • compositions according to the present invention comprise a urease inhibitor, such as an alkyl thiophosphoric triamide or ammonium thiosulfate, a nitrification inhibitor, or a combination of both a urease inhibitor and a nitrification inhibitor.
  • a urease inhibitor such as an alkyl thiophosphoric triamide or ammonium thiosulfate
  • a nitrification inhibitor such as sodium thiosulfate
  • a combination of both a urease inhibitor and a nitrification inhibitor such as an alkyl thiophosphoric triamide or ammonium thiosulfate
  • alkyl thiophosphoric triamide is N-(n-butyl)- thiophosphoric triamide (“NBPT”).
  • the at least one of alkyl thiophosphoric triamide or dicyandiamide or combination thereof can be present in the liquid agricultural composition at a lower range of 2% by weight of the composition.
  • the at least one of alkyl thiophosphoric triamide or dicyandiamide or combination thereof can be present in the liquid agricultural composition at a lower range of 3% by weight of the composition.
  • the at least one of alkyl thiophosphoric triamide or dicyandiamide or combination thereof can be present in the liquid agricultural composition at a lower range of 5% by weight of the composition.
  • At least one of a nitrification inhibitor, a urease inhibitor or a mixture thereof can be present in the liquid agricultural
  • composition an amount less than about 75 pbw, by total weight of composition, for instance in an amount less than about 55 pbw, by total weight of
  • At least one of urease inhibitor and/or nitrification inhibitor can be present in the liquid agricultural composition at a lower range of 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.
  • at least one of alkyl thiophosphoric triamide and/or dicyandiamide can be present in the liquid agricultural composition at a lower range of 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 at least one urease inhibitor or nitrification inhibitor or combination thereof can be present in the liquid agricultural composition at an upper range of 75%, or 65%, or 60% by weight of the composition.
  • the at least one of alkyl thiophosphoric triamide or dicyandiamide or combination thereof can be present in the liquid agricultural composition at an upper range of 75%, or 65%, or 60% by weight of the composition.
  • the at least one of alkyl thiophosphoric triamide or dicyandiamide or combination thereof can be present in the liquid agricultural composition at an upper range of 60% by weight of the composition.
  • the at least one of alkyl thiophosphoric triamide or dicyandiamide or combination thereof can be present in the liquid agricultural composition at an upper range of 55% by weight of the composition.
  • the at least one urease inhibitor or nitrification inhibitor or combination thereof can be present in the liquid agricultural composition at an upper range of 59%, or 57%, or 55% or 53 % or 50%, by weight of the composition.
  • at least one of alkyl thiophosphoric triamide and/or dicyandiamide can be present in the liquid agricultural composition at an upper range of 59%, or 57%, or 55% or 53 % or 50%, by weight of the composition.
  • the at least one urease inhibitor or nitrification inhibitor or combination thereof can be present in the liquid agricultural composition at an upper range of 48%, or 46%, or 45% or 42 % or 40%, by weight of the composition.
  • at least one of alkyl thiophosphoric triamide and/or dicyandiamide can be present in the liquid agricultural composition at an upper range of 48%, or 46%, or 45% or 42 % or 40%, by weight of the composition.
  • the at least one of alkyl thiophosphoric triamide or dicyandiamide or combination thereof can be present in the liquid agricultural composition at an upper range of 35% by weight of the composition. In another embodiment, the at least one of alkyl thiophosphoric triamide or dicyandiamide or combination thereof can be present in the liquid agricultural composition at an upper range of 30% by weight of the composition. In another embodiment, the at least one of alkyl thiophosphoric triamide or dicyandiamide or combination thereof can be present in the liquid agricultural composition at an upper range of 25% by weight of the composition.
  • the at least one of alkyl thiophosphoric triamide or dicyandiamide can be present in the liquid agricultural composition in an amount between about 7% by weight of the composition to about 55% by weight of the composition. In another embodiment, the at least one of alkyl thiophosphoric triamide or dicyandiamide can be present in the composition in an amount between about 8% by weight of the composition to about 50% by weight of the composition. In another embodiment, the at least one of alkyl thiophosphoric triamide or dicyandiamide can be present in the liquid agricultural composition in an amount between about 7% by weight of the composition to about 45% by weight of the composition. In another embodiment, the at least one of alkyl thiophosphoric triamide or dicyandiamide can be present in the liquid
  • agricultural composition in an amount between about 7% by weight of the composition to about 40% by weight of the composition.
  • the at least one of alkyl thiophosphoric triamide or dicyandiamide can be present in the liquid agricultural composition in an amount between about 7% by weight of the composition to about 35% by weight of the composition.
  • the at least one of alkyl thiophosphoric triamide or dicyandiamide can be present in the composition in an amount between about 0.5 % by weight of the composition and about 60 % by weight of the composition or, in another embodiment, can be present in the composition in an amount between about 1 % by weight of the composition and about 40 % by weight of the composition, and, in another embodiment, can be present in the composition in an amount between about 0.5 % by weight of the composition and about 20 % by weight of the composition.
  • thiophosphoric triamide or dicyandiamide is present in the composition in an amount between about 1 % by weight of the composition and about 30 % by weight of the composition.
  • the at least one of alkyl thiophosphoric triamide or dicyandiamide means that alkyl thiophosphoric triamide can be solely present, dicyandiamide can be solely present, or a combination of alkyl thiophosphoric triamide and dicyandiamide is present.
  • Levoglucosenone, of Formula (I) is a bicyclic a, b-unsaturated ketone containing a protected aldehyde.
  • the highly dehydrated sugar is derived from cellulose and hence provides a bio-based solvent, which is attractive as a“green” solvent.
  • Levoglucosenone, of molecular formula C6H603, is ((1 S,5 R)-6,8- dioxabicyclo[3.2.1]oct-2-en-4-one).
  • Levoglucosenone and/or derivatives thereof have been investigated as replacements for solvents such as N,N- dimethylformamide, N,N- dimethylacetamide and N-methylpyrolidinone, which are widely used in organic synthesis and chemical manufacture but have undesirable toxicity and environmental profiles.
  • levoglucosenone and/or derivatives thereof are particularly suitable for use in liquid agricultural compositions comprising at least one of a nitrification inhibitor, a urease inhibitor or a mixture thereof.
  • liquid agricultural compositions comprising at least one of a nitrification inhibitor, a urease inhibitor or a mixture thereof yields unexpectedly to stable compositions, even when said liquid agricultural compositions contain relative high loads of at least one of a nitrification inhibitor, a urease inhibitor or a mixture thereof (for example N-(n- butyl) thiophosphoric triamide (NBPT)), such as for instance at least 20 pbw of at least one of a nitrification inhibitor, a urease inhibitor or a mixture thereof (for example N-(n-butyl) thiophosphoric triamide (NBPT)), for instance at least 30 pbw, for instance at least 40 pbw, for instance at least 50 pbw, relative to the total weight of said liquid agricultural compositions.
  • NBPT N-(n- butyl) thiophosphoric triamide
  • nitrification inhibitors and/or urease inhibitors degrade at varying temperatures and extreme conditions, e.g., high temperatures or low temperatures.
  • NBPT - a urease inhibitor degrades rapidly at higher temperature, typically, above 45°C.
  • temperatures in agricultural fields e.g., corn fields, wheat fields, etc.
  • at 45°C NBPT formulated in different solvents changes color in days from colorless to a darker green/brown, followed by sludge/precipitate formation after weeks had been exposed to high heat.
  • liquid agricultural compositions comprising at least one of a nitrification inhibitor, a urease inhibitor or a mixture thereof and levoglucosenone and/or derivatives thereof as solvent are stable at high temperatures, such as those utilized in hot climates or weather.
  • levoglucosenone and/or derivatives thereof as solvent may for instance reduce decomposition of N-(n-butyl) thiophosphoric triamide (NBPT) into non-effective substances. This decomposition can be observed through common signs of degradation while undergoing long-term storage stability studies.
  • NBPT N-(n-butyl) thiophosphoric triamide
  • a liquid fertilizer composition of the invention is stable, meaning the liquid fertilizer composition is or substantially is in one phase, i.e., no visible crystals, no visible precipitation, and/or no visible multiple liquid phases.
  • a liquid fertilizer composition of the invention is stable, meaning the liquid fertilizer composition is or substantially is in one phase and shows little or slight discoloration.
  • a liquid fertilizer composition of the invention is stable, meaning that the solvent, and optional co-solvent, does not degrade or chemically react to other components in the composition.
  • references herein to a derivative mean a derivative of levoglucosenone or a derivative of dihydrolevoglucosenone.
  • the derivative of levoglucosenone or a derivative of dihydrolevoglucosenone.
  • levoglucosenone for example dihydrolevoglucosenone
  • levoglucosenone may be derived from levoglucosenone. That is, the derivative of levoglucosenone may be synthesized from levoglucosenone, directly and/or indirectly. In other words,
  • levoglucosenone may be a starting material and/or an intermediary material in a synthesis of the derivative of levoglucosenone.
  • an intermediary material in a synthesis of the derivative of levoglucosenone.
  • dihydrolevoglucosenone is a derivative of levoglucosenone.
  • Dihydrolevoglucosenone is derived from levoglucosenone by hydrogenation of levoglucosenone, for example over supported palladium catalysts.
  • dihydrolevoglucosenone is available as Cyrene (RTM) from Circa Group Pty Ltd (Australia).
  • Dihydrolevoglucosenone, of Formula (II), is a chiral dipolar aprotic solvent.
  • Dihydrolevoglucosenone, of molecular formula C6H803, is ((1 S,5 R)- 6,8-Dioxabicyclo[3.2.1]octan-4-one).
  • dihydrolevoglucosenone is considered to be a substitute for N- Methyl-2-pyrrolidone (NMP), being also similar in terms of hydrogen bonding capacity.
  • NMP N- Methyl-2-pyrrolidone
  • the agricultural composition of the invention comprises levoglucosenone and/or dihydrolevoglucosenone and/or the derivative thereof in an amount of at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, relative to the total weight of the composition.
  • the agricultural composition of the invention comprises a mixture of levoglucosenone and/or dihydrolevoglucosenone and/or one or more derivatives thereof.
  • the composition comprises, by weight of composition, greater than 40 pbw of NBPT (or NBPT in combination with DCD), the remainder being solvent or a mixture of solvents.
  • the composition comprises, by weight of composition, greater than 50 pbw of NBPT (or NBPT in combination with DCD), the remainder being solvent or a mixture of solvents.
  • the agricultural composition of the invention comprises a co-solvent.
  • the liquid medium further comprises a co-solvent selected from the group consisting of: a) at least one dioxolane compound of formula (Il.b): wherein R6 and R7 individually comprises a hydrogen, an alkyl group, an alkenyl group, or a phenyl group, wherein n is an integer of from 1 to 10; b) at least one dibasic ester; c) at least one compound of formula (III):
  • R3 comprises a C1-C36 alkyl group; wherein R4 and R5 individually comprise a C1-C36 alkyl group, wherein R4 and R5 can optionally together form a ring; and wherein A is a linear or a branched divalent C2-C12 alkyl group; d) at least one alkanolamine or alkoxylated alkanolamine; e) at least one glycol or glycol derivative; f) at least one organophosphate compound and g) any combination thereof.
  • Suitable polar aprotic organic solvents useful as optional co-solvent also include, for example, dichloromethane, dimethyl acetamide, dimethyl formamide, dimethyl sulfoxide, ethyl acetate, hexamethylphosphoramide, dimethyl sulfone, sulfolane, l,3-dimethyl-2-imidazoidinone, 1,3-dimethyl- 3,4,5,6-tetrahydro-2(lH)-pyrimidone, methyl acetate, ethyl lactate, N- methylpyrrolidone, tetrahydrofuran, propylene carbonate, and dibasic ester solvents.
  • the co-solvent is N-methylpyrrolidone.
  • Suitable dibasic ester solvents useful as optional co-solvent include, for example, dialkyl esters of dicarboxylic acids, more typically, the di(Cl- C12)alkyl esters of saturated linear or branched (C2-C8)aliphatic carboxylic acids or a mixture thereof.
  • the dibasic ester component comprises one or more compounds according to structure (II):
  • 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.
  • compositions and methods of the present invention comprises one or more dimethyl esters of saturated linear or branched (C4-C6)aliphatic carboxylic acids, such the dimethyl ester of succinic acid, dimethyl ester of ethyl succinic acid, the dimethyl ester of glutaric acid, the dimethyl ester of methyl glutaric acid, and the dimethyl ester of adipic acid, and mixtures thereof.
  • dimethyl esters of saturated linear or branched (C4-C6)aliphatic carboxylic acids such the dimethyl ester of succinic acid, dimethyl ester of ethyl succinic acid, the dimethyl ester of glutaric acid, the dimethyl ester of methyl glutaric acid, and the dimethyl ester of adipic acid, and mixtures thereof.
  • the dibasic ester component comprises the dimethyl ester of succinic acid, the dimethyl ester of glutaric acid, and optionally, the dimethyl ester of adipic acid
  • the dibasic ester component comprises the dimethyl ester of ethyl succinic acid, the dimethyl ester of methyl glutaric acid, and optionally, the dimethyl ester of adipic acid.
  • compositions and methods of the present invention comprises one or more dialkyl esters of saturated linear or branched (C4-C6)aliphatic carboxylic acids, such the dialkyl ester of succinic acid, dialkyl ester of ethylsuccinic acid, the dialkyl ester of glutaric acid, the dialkyl ester of methyl glutaric acid, and the dialkyl ester of adipic acid, and mixtures thereof.
  • dialkyl esters of saturated linear or branched (C4-C6)aliphatic carboxylic acids such the dialkyl ester of succinic acid, dialkyl ester of ethylsuccinic acid, the dialkyl ester of glutaric acid, the dialkyl ester of methyl glutaric acid, and the dialkyl ester of adipic acid, and mixtures thereof.
  • the dibasic ester component comprises the dialkyl ester of succinic acid, the dialkyl ester of glutaric acid, and optionally, the dimethyl ester of adipic acid
  • the dibasic ester component comprises the dialkyl dimethyl ester of ethylsuccinic acid, the dialkyl ester of methylglutaric acid, and optionally, the dialkyl ester of adipic acid.
  • Each alkyl group in the dialkyl group one embodiment, individually comprise a C1-C8 alkyl.
  • each alkyl group in the dialkyl group one embodiment, individually comprise a C1-C6 alkyl.
  • amino alcohol solvent component of the compositions and methods of the present invention are those compounds that comprise at least one primary, secondary, or tertiary amino moiety per molecule and at least one hydroxyalkyl moiety per molecule, more typically
  • the amino alcohol is a linear, branched, or cyclic, saturated or unsaturated hydrocarbon that is substituted on at least one carbon atom with an amino group and on at least one other carbon atom with hydroxyalkyl or hydroxyl group, such as monoethanolamine, ethylaminoethanol,
  • dimethylaminoethanol isopropylaminoethanol, diethanolamine, triethanolamine, methylaminoethanol, aminopropanol, methylaminopropanol, dimethylaminopropanol, aminobutanol, dimethylaminobutanol,
  • aminobutanediol trihydroxymethylaminoethane, diethylaminopropanediol, 1- amino-cyclopentane methanol, and aminobenzyl alcohol, or a heterocyclic ring that comprises at least one nitrogen atom as a ring member and/or is substituted on at least one carbon atom with an amino group and that is substituted on at least one other carbon atom with a hydroxyalkyl or hydroxyl group, such as methylaminomethyl-l,3-dioxolane.
  • Suitable heterocyclic alcohol solvents include, for example, 5- or 6- membered heterocyclic rings that include 1 or 2 oxygen atoms as ring member, that are substituted on at least one carbon atom of the ring with a (Cl-
  • heterocyclic alcohol includes dioxolane compounds.
  • the heterocyclic alcohol component of the present invention comprises a one or more compounds selected from heterocyclic alcohols according to structures (III), (IV), (V), (VI), and (VII):
  • glycols and glycol derivatives include but are not limited to aliphatic dihydroxy (dihydric) alcohols.
  • glycol derivatives include but are not limited to polypropylene glycol, triethylene glycol, glycol alkyl ethers such as dipropylene glycol methyl ether, diethylene glycol.
  • glycol derivatives include but are not limited to polyglycols such as polyethylene glycols (PEG) and polypropylene glycols.
  • Glycols are represented by the general formula CnH2n(OH)2, where n is at least 2.
  • glycols include ethylene glycol (glycol), propylene glycol (1,2- propanediol), 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,9-nonanediol, 1,10-decanediol, 1,8-octanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2,4-pentanediol, 2,5-hexanediol, 4,5-octanediol and 3,4-hexanediol, neopenty glycol, pinacol, 2, 2-diethyl- 1,3 -propanediol, 2- ethyl-l,3-hexaned
  • glycol derivatives include but are not limited to glycol stearate, ethylene glycol monostearate, ethylene glycol distearate, ethylene glycol amido stearate, dilaurate glycol, propylene glycol monostearate, propylene glycol dicaprylate, propylene glycol dicaprate diacetate glycol, dipalmite glycol, diformate glycol, dibutyrate glycol, dibenzorate glycol, dipalmate glycol, dipropionate glycol, monoacetate glycol, monopalmitate glycol and monoformate glycol.
  • glycol derivatives also include polypropylene glycol, triethylene glycol, dipropylene glycol methyl ether, or di ethylene glycol.
  • Polyglycol derivatives include but are not limited to polyethylene glycol (PEG) 200-6000 mono and dilaurates, such as, PEG 600 dilaurate, PEG 600 monolaurate, PEG 1000 dilaurate, PEG 1000 monolaurate, PEG 1540 dilaurate and PEG 1540 monolaurate, polyethylene glycol 200-6000 mono and dioleates, such as, PEG 400 monoleate, PEG 600 dioleate, PEG 600 monooleate, PEG 1000 monoleate, PEG 1540 dioleate, PEG 1540 monooleate and polyethylene glycol 200-6000 mono and di stearates, such as, PEG 400 di stearate, PEG 400 monostearate, PEG 600 distearate, PEG 600 monostearate, PEG 1000 distearate, PEG 1000 monostearate, PEG 1500 monostearate, PEG 1540 distearate, PEG 1540 monostearate and PEG 3000 monostea
  • Suitable compounds useful as optional co-solvent include compounds of general formul a (II) : R3 OOC- A-CONR4R5 (II)
  • the expression “compound” denotes any compound corresponding to the general formula (II).
  • the term “compound” also refers to mixtures of several molecules corresponding to general formula (II). It may therefore be a molecule of formula (II) or a mixture of several molecules of formula (II), wherein both fall under the definition of the term“compound” when referring to formula (II).
  • the R3, R4 and R5 groups can be, in some embodiments, identical or, in other embodiment, different.
  • the R4 and R5 groups may optionally be substituted. In one particular embodiment, the groups are substituted with hydroxyl groups.
  • R3 group is chosen from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, isoamyl, n-hexyl, cyclohexyl, 2- ethylbutyl, n-octyl, isooctyl, 2-ethylhexyl, tridecyl groups.
  • R4 and R5 groups which are identical or different, in one embodiment, may especially be chosen from methyl, ethyl, propyl (n-propyl), isopropyl, n- butyl, isobutyl, n-pentyl, amyl, isoamyl, hexyl, cyclohexyl or hydroxyethyl groups.
  • the R4 and R5 groups may also be such that they form, together with the nitrogen atom, a morpholine, piperazine or piperidine group.
  • R4 and R5 are each methyl, or R4 and R5 are each ethyl, or R4 and R5 are each hydroxyethyl.
  • A comprises a linear group of formula— CH2— CH2— and/or of formula— CH2— CH2— CH2— CH2— and/or of formula — ( CH2)8— then it is a mixture of A groups.
  • A is linear, then it is a mixture of A groups, for example a mixture of two or three— CH2— CH2— (ethylene);— CH2— CH2— CH2— (n- propylene); and— CH2— CH2— CH2— CH2— CH2— (n-butylene) groups (or isomers thereof).
  • the A group is a divalent linear alkyl group chosen from the groups of the following formulae: - - CH2— CH2— (ethylene); - CH2- CH2- CH2- (n-propylene); - CH2- CH2-
  • the solvent system comprises the cosolvent in an amount of at most 50%, at most 45%, at most 40%, at most 35%, at most 30%, at most 25%, at most 20%, at most 15%, at most 10%, at most 5%, at most 2.5% or at most 1 %, wherein the amount of the cosolvent is a percentage by weight of the total amount of solvent in the formulation.
  • the solvent system comprises the cosolvent in an amount of at least 50%, at least 45%, at least 40%, at least 35%, at least 30%, at least 25%, at least 20%, at least 15%, at least 10%, at least 5%, at least 2.5% or at least 1 %, wherein the amount of the cosolvent is a percentage by weight of the total amount of solvent in the formulation.
  • the solvent system comprises a plurality of cosolvents.
  • the solvent comprises the plurality of cosolvents in an amount of at most 50%, at most 45%, at most 40%, at most 35%, at most 30%, at most 25%, at most 20%, at most 15%, at most 10%, at most 5%, at most 2.5% or at most 1 %, wherein the amount of the plurality of cosolvents is a percentage by weight of the total amount of solvent in the formulation.
  • the solvent system comprises the plurality of cosolvents in an amount of at least 50%, at least 45%, at least 40%, at least 35%, at least 30%, at least 25%, at least 20%, at least 15%, at least 10%, at least 5%, at least 2.5% or at least 1 %, wherein the amount of the plurality of cosolvents is a percentage by weight of the total amount of solvent in the formulation.
  • composition of the invention may further comprise at least one stabilizer, for instance an amine stabilizer.
  • a composition of the invention may further comprise at least one member selected from the group consisting of buffer, flow aide, silicas, surfactants and dyes/colorants.
  • the inhibitor composition of the present invention comprises, based on 100 parts by weight (“pbw”) of the composition:
  • the inhibitor composition of the present invention comprises one or more urease inhibitors, such as, for example, NBPT or ammonium thiosulfate.
  • the nitrogenous fertilizer compound is treated with the inhibitor composition by contacting the nitrogenous fertilizer composition with the inhibitor composition described herein (e.g., nitrification inhibitor or urease inhibitor or a combination of both).
  • the nitrogenous fertilizer composition may be in solid or liquid form.
  • Suitable nitrogenous fertilizers are those containing a nitrogenous compound such as urea, nitrate salts, ammonium salt, or a mixture thereof, such as ammonium nitrate, ammonium sulfate, ammonium thiosulfate, ammonium polysulfide, ammonium phosphates, ammonium chloride, ammonium bicarbonate, anhydrous ammonia, calcium nitrate, nitrate soda, calcium cyanamide.
  • the nitrogenous fertilizer comprises ammonium nitrate.
  • Suitable ammonium nitrate-containing fertilizers include, for example, UAN 18, UAN 28, and UAN 30.
  • the nitrogenous fertilizer composition is in solid particulate form, and the contacting of the nitrogenous fertilizer composition with the inhibitor composition is conducted by, for example, spraying the composition of the present invention on the particles of solid fertilizer composition.
  • the concentrated fertilizer composition of the present invention is a solid nitrification-inhibited fertilizer composition that comprises, based on 100 pbw of the composition:
  • the solid nitrification-inhibited fertilizer composition of the present invention further comprises one or more urease inhibitors, more typically NBPT.
  • the end use fertilizer composition of the present invention is made by combining the inhibitor composition of the present invention with a solid nitrogenous fertilizer to form a solid nitrification-inhibited fertilizer composition and subsequently dissolving the solid nitrification- inhibited fertilizer composition in an aqueous medium, typically water, in a ratio of up to about 500 pbw, more typically from 100 to 500 pbw and even more typically from about 100 to about 300 pbw, of the aqueous medium per 1 pbw of the solid nitrification-inhibited fertilizer composition.
  • an aqueous medium typically water
  • the fertilizer compound is in liquid form and the contacting of the fertilizer composition with the inhibitor composition is conducted by mixing the inhibitor composition with the liquid fertilizer composition.
  • the concentrated fertilizer composition of the present invention is a concentrated liquid nitrification-inhibited fertilizer composition that comprises, based on 100 pbw of the composition:
  • the concentrated liquid nitrification-inhibited fertilizer composition of the present invention further comprises one or more urease inhibitors, more typically NBPT.
  • the end use fertilizer composition of the present invention is made by combining the inhibitor composition of the present invention with a concentrated nitrogenous fertilizer to form a concentrated liquid nitrification-inhibited fertilizer composition and subsequently diluting the concentrated liquid nitrification-inhibited fertilizer composition with an aqueous medium, typically water in a ratio of up to about 500 pbw, more typically from about 10 to about 500 pbw and even more typically from about 100 to about 300 pbw, of the aqueous medium per 1 pbw concentrated liquid nitrogenous fertilizer composition.
  • an aqueous medium typically water in a ratio of up to about 500 pbw, more typically from about 10 to about 500 pbw and even more typically from about 100 to about 300 pbw, of the aqueous medium per 1 pbw concentrated liquid nitrogenous fertilizer composition.
  • the end use fertilizer composition of the present invention is made by combining the inhibitor composition of the present invention, a solid or concentrated liquid nitrogenous fertilizer, and an aqueous medium.
  • the end use fertilizer composition is applied to target plants or to an environment for the target plants, i.e., to ground on or within which the target plants are growing or to be grown, at a rate of from about 0.01 pounds to about 5 pounds of the fertilizer composition, more typically from about 0.05 pounds to about 2 pounds of the fertilizer composition, per 100 square feet of ground.
  • the end use fertilizer composition is applied to target plants or to an environment for the target plants at a rate effective to provide a dosage of nitrogenous fertilizer compound of from about 0.01 pounds to about 5 pounds of fertilizer compound, more typically from about 0.05 pounds to 2 pounds of fertilizer compound, per 100 square feet of ground.
  • composition of the present invention provides improved ease of handling of a dicyandiamide and/or an alkyl thiophosphoric triamide, improved solubility characteristics, low toxicity of the solvents; good storage
  • aqueous compositions such as aqueous nitrogenous fertilizer formulations.
  • Example 1 The compositon of Example 1 was made by dissolving 500 mg of N-(n- butyl)-thiophosphoric triamide (NBPT) in 500 pL of dihydrolevoglucosenone (Cyrene (RTM) available from Aldrich), under stirring on a rotary shaker, at room temperature during 28hrs.
  • NBPT N-(n- butyl)-thiophosphoric triamide
  • RTM dihydrolevoglucosenone
  • Example 1 The composition of Example 1 remained in one phase in each of the above detailed storage condition, and no sedimentation was observed in solution.
  • composition of Example 1 turned a slight yellow, transparent color), which further confirmed that NBPT did not undergo severe degradation in this solvent.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Soil Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Fertilizers (AREA)

Abstract

Une composition d'inhibiteur contient du dicyandiamide en tant qu'inhibiteur de nitrification, du triamide d'alkyle thiophosphorique en tant qu'inhibiteur d'uréase, ou une combinaison de ceux-ci, dissous dans un milieu liquide comprenant un solvant comprenant de la lévoglucosénone ou de la dihydrolévoglucosénone ou un dérivé de ceux-ci, et est utile dans la fabrication de compositions d'engrais et dans un procédé de fertilisation de plantes cibles.
PCT/EP2020/069557 2019-07-23 2020-07-10 Compositions liquides de dicyandiamide et/ou de triamide d'alkyle thiophosphorique et leur utilisation dans des applications agricoles WO2021013582A1 (fr)

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Publication number Priority date Publication date Assignee Title
WO2022236389A1 (fr) * 2021-05-12 2022-11-17 Oxiteno S.A. Indústria E Comércio Composition agrochimique, formulation agrochimique, utilisation d'un dérivé de dioxabicycloalcane, et procédé pour le traitement et/ou la prévention de maladies ou de nuisibles dans une plante ou une graine de plante

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