Solvent systems for dicyandiamide and alkyl thiophosphoric triamide and use in agricultural applications

Abstract

The present invention provides a composition comprising: i) from 10% to 60% by weight of at least one urease inhibitor comprising n-(n- butyl)-thiophosphoric triamide (NBPT), ii) from 1% to 20% by weight of at least one nitrification inhibitor comprising dicyandiamide (DCD), iii) from 60% to 89% by weight of at least one solvent selected from polyethylene glycol polymers with a weight-average molecular weight superior or equal to 160 g.mol-1, with respect to the total weight of the composition.

Description

[0001] SOLVENT SYSTEMS FOR DICYANDIAMIDE AND ALKYL THIOPHOSPHORIC TRIAMIDE AND USE IN AGRICULTURAL APPLICATIONS

[0002] FIELD OF THE INVENTION

[0003] The present invention relates to a composition comprising an urease inhibitor, in particular a alkylthiophosphoric triamide such as N-(n-butyl)thiophosphoric triamide (NBPT), and / or a nitrification inhibitor, such a dicyandiamide (DCD), useful for agricultural compositions, and more particularly fertilizer formulations and its manufacture. It also relates to the agricultural compositions which can be derived therefrom and their use.

[0004] BACKGROUND OF THE INVENTION

[0005] In the agrochemical industry, farmers use various fertilizers to impart macronutrients to plants either by application to the soil or application to plant leaves. 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+, NO2; NO3; 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.

[0006] 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 occur 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.

[0007] 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.

[0008] Urease inhibitors can be used with a fertilizer ( / .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. The hydrolysis of urea is facilitated by urease enzyme present in the soil. In many crops, 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. In ammonium-based products, if the nitrogen is not lost due to leaching or run-off, then ammonium can bind to soil particles and be 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.

[0009] A typical urease inhibitor, alkyl thiophosphoric triamide (for example, N-(n- butyl)-thiophosphoric triamide or otherwise “NBPT”), however, faces drawbacks in its use as NBPT is extremely difficult to handle. 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 ( / .e., large granules) and in 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. It is known (see for example US10173935) that the use of a solvent system containing the NBPT in a liquid solvent system is capable of distributing the NBPT into granular urea (e.g., urea prills) and into liquid fertilizers containing urea. By introducing the NBPT to liquid fertilizers containing urea (for example, ureaammonium nitrate solutions or UAN) in a solvent system, the NBPT is capable of being better dispersed in the liquid fertilizer.

[0010] There is a very limited number of solvents available that can solubilize high amounts of NBPT. It has been already reported to use dimethylsulfoxide (DMSO) in order to solubilize N-(n-butyl)-thiophosphoric triamide (NBPT), see for example US10597338.

[0011] DMSO however, has some drawbacks notably in terms of stability of the solutions obtained and the capability of carrying high loads of urease inhibitor over the whole applicable temperature range. In particular, the combination of NBPT and DMSO may be responsible of the emissions of unpleasant, harmful or even toxic volatile organic sulfur such as hydrogen sulfide (H2S), dimethyl sulfide (DMS) or dimethyl disulfide (DMDS). Further, these gas emissions are associated storage stability issues, degradation of NBPT, recrystallization or sedimentation, change in physical appearance (dark color for undyed product), and / or unwanted odor / smell.

[0012] US10487019 proposes phosphoric or thiophosphoric triamide compositions having a concentration range of 35 to 50 wt.% and comprising 5-30 wt% of specific glycol or glycol derivative and 20-50 wt. % of an amide solvent wherein the preferred solvent is n-methylpyrrolidone. However, n-methylpyrrolidone is highly toxic.

[0013] Another problem associated with the use of NBPT is its degradation at higher temperature, typically above 45°C. Often times temperature in agricultural fields (e.g. corn fields, wheat fields etc...) reach in excess of 35°C and sometimes up to 45°C or higher. For example, at 45°C, NBPT formulated in different solvents changes color in days from colorless to a darker green / brown, followed by sludge / precipitate formation. This it is also desirable to have solvent systems containing urease inhibitor that are stabilized at high temperatures.

[0014] WO2017 / 144698 discloses a method for the manufacture of a liquid composition essentially consisting of an organic solvent of the type glycol, such as propylene glycol, diethylene glycol monomethyl ether (DEGMME) or diethylene glycol monobutyl ether (DEGMBE), and a urease inhibitor of the type phosphoric triamide. The compositions are only able to maintain a low urease inhibitor load and they appear to crystallize at < -10°C and do not appear to present a storage stability at that temperature.

[0015] Therefore, the aim of the present invention is to provide a composition comprising high loadings of urease inhibitor and / or of nitrification inhibitor, while eliminating all or parts, preferably all, of the drawbacks observed in the presence of DMSO.

[0016] In particular, the aim of the invention is to provide a composition comprising high loadings of urease inhibitor and / or of nitrification inhibitor, which is stable over storage over a large range of temperature, while having a favorable and / or ecological profile and desirable characteristics in terms of low volatility, biodegradability.

[0017] Advantageously, the aim of the invention is to provide a composition comprising high loadings of urease inhibitor and / or of nitrification inhibitor, which is stable over storage over a large range of temperature, preferably at high temperature, while having a favorable and / or ecological profile and desirable characteristics in terms of low volatility, biodegradability.

[0018] SUMMARY OF THE INVENTION

[0019] The invention firstly relates to a composition comprising: i) at least one urease inhibitor and / or at least one nitrification inhibitor, provided that, when present, said at least one nitrification represents at most 20% by weight with respect to the total weight of the composition, ii) at least 60% by weight, with respect to the total weight of the composition, of at least one solvent selected from polyethylene glycol polymers with a weightaverage molecular weight superior or equal to 160 g.mol’1.

[0020] Preferably, said at least one urease inhibitor is chosen from alkylthiophosphoric triamides, preferably comprises n-(n-butyl)-thiophosphoric triamide (NBPT), more preferably consists in n-(n-butyl)-thiophosphoric triamide (NBPT).

[0021] Preferably, said at least one nitrification inhibitor comprises dicyandiamide (DCD), more preferably consists in n-(n-butyl)-thiophosphoric triamide (NBPT).

[0022] According to a preferred embodiment, the composition as defined above and described in more details below comprises n-(n-butyl)-thiophosphoric triamide (NBPT) and dicyandiamide (DCD). According to a preferred embodiment, the composition as defined above and described in more details below comprises, preferably consists essentially of, more preferably consists of, with respect to the total weight of the composition: i) from 10% to 37.5 % by weight of at least one urease inhibitor comprising n- (n-butyl)-thiophosphoric triamide (NBPT), ii) from 1% to 20% by weight of at least one nitrification inhibitor comprising dicyandiamide (DCD), iii) from 60% to 89% by weight of at least one solvent selected from polyethylene glycol polymers with a weight-average molecular weight superior or equal to 160 g.mol’1, and iv) optionally, from 0.1 % to 1 % by weight of at least one dye.

[0023] Advantageously, the polyethylene glycol polymer has a weight-average molecular weight ranging from 180 g.mol’1to 450 g.mol’1, preferably from 185 g.mol’1to 400 g.mol’1, more preferably from 190 g.mol’1to 300 g.mol’1, even more preferably from 190 g.mol’1to 210 g.mol’1.

[0024] Preferably, the polyethylene glycol is of formula (I): wherein n, representing the average number of ethylene oxide units, is superior to 3 and inferior to 10, preferably ranges from 3.5 to 9.5, more preferably from 4 to 7, even more preferably from 4 to 5.

[0025] Preferably, the content of urease inhibitor(s), notably of -(n-butyl)- thiophosphoric triamide (NBPT), in the composition as defined above and described in more details below ranges from 15% to 35% by weight, with respect to the total weight of the composition, preferably from 20% to 32.5% by weight.

[0026] Preferably, the content of nitrification inhibitors, notably of dicyandiamide (DCD), in the composition as defined above and described in more details below ranges from 5% to 17.5% by weight, with respect to the total weight of the composition, preferably from 7.5% to 15% by weight. Preferably, the content of solvent ii) in the composition as defined above and described in more details below ranges from 65% to 80% by weight, with respect to the total weight of the composition, preferably from 67.5% to 72.5% by weight.

[0027] According to a preferred embodiment, the composition as defined above and described in more details below is free of demethylsulfoxide (DMSO), preferably free of demethylsulfoxide (DMSO) and N-Methyl-2-pyrrolidone (NMP).

[0028] The invention also relates to an agricultural composition comprising: a. a nitrogenous fertilizer, and b. a composition as defined above and in more details below.

[0029] According to a first embodiment, the agricultural composition is a liquid enduse composition.

[0030] According to a second embodiment, the agricultural composition is a solid end-use comprising, preferably comprising a core comprising said nitrogenous fertilizer and a coating comprising said composition as defined above and in more details below.

[0031] The invention further concerns a method of making a solid or concentrated liquid fertilizer composition comprising contacting one or more nitrogenous fertilizer with a composition as defined above and in more details below.

[0032] The invention also relates to a method for fertilizing target plants, wherein the end-use composition as defined above and in more details below is applied to target plants or to an environment for the target plants.

[0033] The invention further concerns the use of a polyethylene glycol polymer with a weight-average molecular weight of greater than or equal to 160 g.mol'1for stabilizing a composition comprising n-(n-butyl)-thiophosphoric triamide (NBPT) and dicyandiamide (DCD).

[0034] The invention also relates to the use of a polyethylene glycol polymer with a weight-average molecular weight of greater than or equal to 160 g.mol'1as solvent in a fertilizer composition for decreasing and / or reducing greenhouse gas emissions, notably dimethyl sulfide (DMS) and / or dimethyl disulfide (DMDS) gas emissions, associated to said fertilizer composition, notably when compared to a same fertilizer composition comprising demethylsulfoxide (DMSO) as solvent. The invention finally relates to the use of a polyethylene glycol polymer with a weight-average molecular weight of greater than or equal to 160 g.mol’1as solvent in a fertilizer composition for decreasing and / or reducing soil and / or land pollution, notably when compared to a same fertilizer composition comprising demethylsulfoxide (DMSO) as solvent.

[0035] The inventors have surprisingly discovered that use as solvent of specific polyethylene glycol polymers allows the preparation of high loaded compositions of urease inhibitor(s) and / or of nitrification inhibitor(s). In particular, they have discovered that the obtained compositions are stable over storage over a large range of temperature, notably when stored 2 weeks at 54°C, 4°C, 0°C or even - 10°C. Further, the obtained compositions have a favorable and / or ecological profile and desirable characteristics in terms of low volatility.

[0036] DETAILED DESCRIPTION

[0037] Throughout the description, the expression “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, -hexyl and cyclohexyl.

[0038] As used herein, the term "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, trichloromethylphenyl, aminophenyl, and tristyryl phenyl.

[0039] As used herein, the term "alkylene" means a divalent saturated straight or branched chain hydrocarbon radical, such as for example, methylene, dimethylene, trimethylene.

[0040] As used herein, the term "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.

[0041] As used herein, the term "alkoxyalkyl" means an alkyl radical that is substituted with one or more alkoxy substituents, more typically a (C1- C22)alkyloxy-(C1-C6)alkyl radical, such as methoxymethyl, and ethoxybutyl.

[0042] As used herein, the term "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, isopropenyl.

[0043] As used herein, the term "arylalkyl" means an alkyl group substituted with one or more aryl groups, more typically a (C1-C18)alkyl substituted with one or more (C6-C14)aryl substituents, such as, for example, phenylmethyl, phenylethyl, and triphenylmethyl.

[0044] As used herein, the term "aryloxy" means an oxy radical substituted with an aryl group, such as, for example, phenyloxy, methylphenyloxy, isopropylmethylphenyloxy.

[0045] As used herein, the terminology "(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.

[0046] Throughout the description, references to standard method refers to the version of said standard method pending at the date of filing of this patent application.

[0047] Throughout the description, the expression “comprises” includes the meaning of “consists essentially of’ or even of “consists of”.

[0048] The invention firstly relates to a composition comprising: i) at least one urease inhibitor, and / or at least one nitrification inhibitor, provided that when present said at least one nitrification represents less than or equal to 20% by weight the total weight of the composition, ii) more than or equal to 60% by weight, with respect to the total weight of the composition, of at least one solvent selected from polyethylene glycol polymers with a weight-average molecular weight superior or equal to 160 g.mol’1.

[0049] Urease inhibitors

[0050] According to an embodiment, the composition according to the invention comprises at least one urease inhibitor.

[0051] Preferably, the at least one urease inhibitor is selected from the group consisting of alkylthiophosphoric triamides. Non-limiting examples of alkylthiophosphoric triamide urease inhibitors comprise any one of n-butyl thiophosphoric triamide (NBPT), n-propyl thiophosphoric triamide , cyclohexyl thiophosphoric triamide and mixtures thereof.

[0052] N-(n-butyl)-thiophosphoric triamide (“NBPT”) is particularly preferred as urease inhibitor.

[0053] The purity of the urease inhibitor, in particular of the alkylthiophosphoric triamide and more particularly of NBPT is generally at least of 90% by weight, preferably at least of 95% by weight, more preferably at least of 97% by weight, and still more preferably at least of 98% by weight.

[0054] Advantageously, when present, the urease inhibitor(s), in particular the alkylthiophosphoric triamide(s) and more particularly NBPT, represents from 10% to 40% by weight, with respect to the total weight of the composition, preferably from 15% to 35% by weight, more preferably from 20% to 32.5% by weight.

[0055] Nitrification inhibitors

[0056] According to an embodiment, the composition according to the invention comprises at least one nitrification inhibitor. According to this same embodiment, said at least one nitrification represents at most 20% by weight of the total weight of the composition.

[0057] Preferably, the at least one nitrification inhibitor is selected from the group consisting of: N-2,5-dichlorophenyl succinamic acid, dicyandiamide (DCD), zinc- ethylene-bis-dithiocarbamate, 2,4,6-triehloroaniline, pentachlorophenol, thiourea, ammonium thiosulphate (ATS), 3,4-dimethypyrazole phosphate (DMPP) and any mixtures thereof.

[0058] More preferably, the nitrification inhibitor is dicyandiamide (DCD).

[0059] Advantageously, when present, the nitrification inhibitor(s), in particular DCD, represents from 1% to 20% by weight, with respect to the total weight of the composition, preferably from 5% to 17.5% by weight, more preferably from 7.5% to 15% by weight.

[0060] According to a preferred embodiment, the composition according to the invention comprises at least one urease inhibitor and at least one nitrification inhibitor. According to more preferred embodiment, the composition according to the invention comprises both:

[0061] - at least one urease inhibitor selected from alkylthiophosphoric triamides, and

[0062] - at least one nitrification inhibitor selected from the group consisting of: N- 2,5-dichlorophenyl succinamic acid, dicyandiamide (DCD), zinc-ethylene-bis- dithiocarbamate, 2,4,6-triehloroaniline, pentachlorophenol, thio-urea, ammonium thiosulphate (ATS) 3,4-dimethypyrazole phosphate (DMPP) or mixtures thereof.

[0063] According to an even preferred embodiment, the composition according to the invention comprises both N-(n-butyl)-thiophosphoric triamide (NBPT) and dicyandiamide (DCD).

[0064] Preferably, when they are both present, the at least one urease inhibitor and the at least one nitrification inhibitor are present in the composition according to the invention according to a weight ratio urease inhibitornitrification inhibitor ranging from 1:1 to 39:1, more preferably from 1 :1 to 5:1 , even more preferably from 1 :1 to 5:2.

[0065] Solvent(s)

[0066] The composition according to the invention also comprises at least solvent selected from polyethylene glycol (PEG) polymers with a weight-average molecular weight superior or equal to 160 g.mol’1. Said at least one solvent represents at least 60% by weight, with respect to the total weight of the composition.

[0067] The polyethylene glycol polymer may be linear or branched. Preferably, the polyethylene glycol polymer of the invention is linear.

[0068] The polyethylene glycol polymer of the invention may be capped or not capped. Preferably, the polyethylene glycol of the invention is chosen from noncapped polyethylene glycol polymers, designated hereafter as PEG-OH.

[0069] By “capped polyethylene glycol polymer”, we refer in the context of the invention to PEG polymers whose two hydroxyl -OH terminal groups have been reacted to form -OR terminations with R being an alkyl group having from 1 to 5 carbon atoms, typically with R being a methyl group. Reversely, “non-capped polyethylene glycol polymers”, also designated hereafter as PEG-OH, are PEG polymers with two hydroxyl -OH termination groups. Preferably, the polyethylene glycol polymer has a weight-average molecular weight (Mw) ranging from 180 g.mol’1to 450 g.mol’1, preferably from 185 g.mol’1to 400 g.mol’1, more preferably from 190 g.mol’1to 300 g.mol’1, even more preferably from 190 g.mol’1to 210 g.mol’1.

[0070] Mw denotes the weight-average molecular weight and is determined by the size exclusion chromatography (or GPC) technique. The measurement conditions are known to a person skilled in the art. For the organic compounds of the invention, an aqueous mobile phase and a refractometric detector are generally used. Polyethylene glycol (PEG) standards are also generally used to obtain the calibration curve. A person skilled in the art may refer to the work Column Handbook for Size Exclusion Chromatography, Academic Press, ISBN 0-12- 76555-7, to determine the GPC measurement conditions.

[0071] In the case of PEG-OH, the weight-average molecular weight may also be calculated via the measurement of the hydroxyl number of the PEG. The hydroxyl number of a PEG polymer may for example be measured according to standard method ASTM E 1899 or even EN ISO 4629-2 (in replacement of DIN 53240-2).

[0072] Preferably, the PEG-OH polymer has a hydroxyl number, measured according to ASTM E 1899, inferior or equal to 650 mg KOH / g of PEG-OH, more preferably from 150 mg KOH / g to 650 mg KOH / g, even more preferably from 250 mg KOH / g to 650 mg KOH / g, typically from 500 mg KOH / g to 650 mg KOH / g.

[0073] The weight-average molecular weight of the PEG-OH polymer may then be calculated using the following formula:

[0074] 2000 Mw = - with:

[0075] Mw: the weight-average molecular weight of the PEG-OH (in g.mol’1), M(KOH): the molecular weight of potassium hydroxide KOH (in g.mol’1), and N(OH): the hydroxyl number of the PEG-OH (in mg KOH / g of PEG-OH).

[0076] Considering the molecular weight of potassium hydroxide KOH as equal to 56.1 g.mol’1, the preceding formula may be simplified as follows:

[0077] 112 200 with:

[0078] Mw: the weight-average molecular weight of the PEG-OH (in g.mol’1), and N(OH): the hydroxyl number of the PEG-OH (in mg KOH / g of PEG-OH). According to a preferred embodiment, the polyethylene glycol polymer is chosen polymers of formula (I): wherein n, representing the average number of ethylene oxide units, is superior to 3 and inferior to 10.

[0079] Preferably ranges from 3.5 to 9.5, more preferably from 4 to 7, even more preferably from 4 to 5.

[0080] Suitable polyethylene glycol polymer are typically PEG200, PEG300 or even PEG400 polymers. Such polymers are commercially available from The Dow Chemical Company (DOW) under the name of CARBOWAX™ polyethylene glycol (PEG) 200, 300 or 400, or from Syensqo under the name Rhodasurf® PEG 200, 300 or 400.

[0081] According to a particular embodiment, the solvent is in the form of a mixture of polyethylene glycols having different weight-average molecular weight.

[0082] Preferably, the composition according to the invention comprises from 60% to 99% by weight of polyethylene glycol polymer(s) as defined above, with respect to the total weight of the composition, more preferably from 65% to 95% by weight, even more preferably from 67.5% to 92.5% by weight.

[0083] According to a particular embodiment wherein the composition comprises both at least one urease inhibitor and at least one nitrification inhibitor, the composition according to the invention comprises from 60% to 89% by weight of polyethylene glycol polymer(s) as defined above, with respect to the total weight of the composition, more preferably from 65% to 80% by weight, even more preferably from 65% to 72.5% by weight.

[0084] Optional additives

[0085] The composition according to the invention may further comprise additive(s), notably chosen from dyes.

[0086] According to an embodiment, the composition according to the invention further comprises at least one dye.

[0087] Suitable dyes are commercially available. One example is Oracet ® Blue 780 F or Sensient Blue LF. It has been found that the compositions according to the invention are compatible with dyes used in agricultural compositions. If a dye is used, its content is generally equal to or lower than 1% wt., preferably equal to or lower than 0.5% wt. relative to the total weight of the composition. If a dye is used, its content is generally sufficient to impart the desired coloration, for example equal to or more than 0.1 % wt. relative to the total weight of the composition.

[0088] Composition

[0089] According to an embodiment, the composition according to the invention comprises, preferably consists essentially of, even more preferentially consists of, with respect to the total weight of the composition: i) at least one of: a1) from 10% to 40% by weight, preferably from 15 to 35% by weight, more preferably from 20% to 32.5% by weight, of at least one urease inhibitor, preferably chosen from alkylthiophosphoric triamides, more preferably of N-(n- butyl)-thiophosphoric triamide (NBPT), and a2) from 1 % to 20% by weight, preferably from 5% to 17.5% by weight, more preferably from 7.5% to 17.5% by weight, of at least one nitrification inhibitor, preferably chosen from the group consisting of: N-2,5-dichlorophenyl succinamic acid, dicyandiamide (DCD), zinc-ethylene-bis-dithiocarbamate, 2,4,6- triehloroaniline, pentachlorophenol, thio-urea, ammonium thiosulphate (ATS) 3,4- dimethypyrazole phosphate (DMPP) or mixtures thereof, more preferably of dicyandiamide (DCD); ii) from 60% to 99% by weight, preferably from 65% to 95% by weight, even more preferably from 67.5% to 92.5% by weight, of at least solvent selected from polyethylene glycol polymers with a weight-average molecular weight superior or equal to 160 g.mol'1, preferably ranging from 180 g.mol'1to 450 g.mol'1, more preferably from 185 g.mol'1to 400 g.mol'1, even more preferably from 190 g.mol'1to 300 g.mol'1, typically from 190 g.mol'1to 210 g.mol'1; and iii) Optionally, from 0.1 % to 1% by weight, preferably from 0.1% to 0.5% by weight, of at least one dye.

[0090] According to a particular embodiment, the composition according to the invention comprises, preferably consists essentially of, even more preferentially consists of, with respect to the total weight of the composition: i) from 10% to 40% by weight of at least one urease inhibitor; ii) from 1 % to 20% by weight of at least one nitrification inhibitor; iii) from 60% to 89% by weight of at least solvent selected from polyethylene glycol polymers with a weight-average molecular weight superior or equal to 160 g.mol’1; and iv) optionally, from 0.1 % to 1 % by weight, of at least one dye.

[0091] According to a preferred embodiment, the composition according to the invention comprises, preferably consists essentially of, even more preferentially consists of, with respect to the total weight of the composition: i) from 15 to 35% by weight, of at least one urease inhibitor chosen from alkylthiophosphoric triamides; ii) from 5% to 17.5% by weight of at least one nitrification inhibitor chosen from the group consisting of: N-2,5-dichlorophenyl succinamic acid, dicyandiamide (DCD), zinc-ethylene-bis-dithiocarbamate, 2,4,6-triehloroaniline, pentachlorophenol, thio-urea, ammonium thiosulphate (ATS) 3,4-dimethypyrazole phosphate (DMPP) or mixtures thereof; iii) from 65% to 80% by weight of at least solvent selected from polyethylene glycol polymers with a weight-average molecular weight ranging from 180 g.mol’1to 450 g.mol’1; and iv) optionally, from 0.1% to 0.5% by weight of at least one dye.

[0092] According to an even preferred embodiment, the composition according to the invention comprises, preferably consists essentially of, even more preferentially consists of, with respect to the total weight of the composition: i) from 20% to 32.5% by weight of N-(n-butyl)-thiophosphoric triamide (NBPT); ii) from 7.5% to 17.5% by weight of dicyandiamide (DCD); iii) from 65% to 72.5% by weight, of at least solvent selected from polyethylene glycol polymers with a weight-average molecular weight ranging from 185 g.mol’1to 400 g.mol’1, preferably from 190 g.mol’1to 300 g.mol’1, even more preferably from 190 g.mol’1to 210 g.mol’1; and iv) Optionally from 0.1% to 0.5% by weight of at least one dye.

[0093] According to a preferred embodiment, the composition of the invention is free of 3,4-dimethylpyrazole (DMP), preferably is free of triazole compounds. Preferably, the composition according to the invention has a flash point value superior or equal to 150°C, more preferably superior or equal to 160°C. The volatility of the composition may be measured according to according to any known method. The flash point value of the composition of the invention may for example be measured using a GRABNER INSTRUMENTS® Flashpoint Touch equipment.

[0094] Therefore, the composition according to the invention has a lower volatility, with respect to compositions of the prior art prepared from dimethylsulfoxide (DMSO) and / or N-Methyl-2-pyrrolidone (NMP). Indeed, such compositions (prepared from dimethylsulfoxide (DMSO) and / or N-Methyl-2-pyrrolidone (NMP)) typically have a flash point value inferior or equal to 90°C.

[0095] According to an embodiment, the composition according to the invention is free of demethylsulfoxide (DMSO).

[0096] According to an embodiment, the composition according to the invention is free of N-Methyl-2-pyrrolidone (NMP).

[0097] According to a preferred embodiment, the composition according to the invention is free of demethylsulfoxide (DMSO) and of N-Methyl-2-pyrrolidone (NMP).

[0098] In the context of the invention, the expression “free of compound X” means that the composition according to the invention comprises less than 1 % by weight of said compound X, preferably less than 0.1 % by weight, even more preferably less than 0.01% by weight, with respect to the total weight of the composition.

[0099] Advantageously, the compositions of the present invention remain flowable after at least 2 weeks of storage at a temperature equal to 0°C, 4°C or 54°C.

[0100] Advantageously, the compositions of the present invention are substantially not discolored upon heating at temperatures up to 54°C for 2 weeks.

[0101] Advantageously, the compositions of the present invention do not precipitate upon heating at temperatures up to 54°C for 2 weeks.

[0102] Applications

[0103] The invention also relates to an agricultural composition comprising a composition according to the invention and a nitrogenous fertilizer. Non-limiting examples of nitrogenous fertilizer include urea, ammonium nitrate or ammonium phosphate fertilizers. Particular nitrogenous fertilizer compositions which can be included in the agricultural composition according to the invention include concentrated ammonium nitrate compositions, such as UAN 18, UAN 28, UAN 30 or UAN 32.

[0104] A particular embodiment of the agricultural composition according to the invention concerns an end-use composition.

[0105] In one embodiment, the end use composition is a solid end use composition comprising a solid nitrogenous fertilizer and the composition of the present invention. The end-use composition may be in solid state, for example in particulate or granular form or as a pellet, which comprises the agricultural composition according to the invention. More particularly, the end-use composition may comprise a core of nitrogenous fertilizer, as described above and a coating comprising the composition according to the invention.

[0106] In another embodiment, the end use composition is a liquid end use composition comprising a solid nitrogenous fertilizer and the composition of the present invention. In that case, it generally comprises or consists of a mixture or blend of a composition of the invention and of a liquid fertilizer, which can be in particular a concentrated ammonium nitrate composition as cited above. In that aspect, the amount of composition according to the invention may generally be from 0.05 wt. % to 0.50 wt. % relative to the total weight of the end-use composition.

[0107] The invention further relates to a method of making a solid or liquid en use composition comprising contacting one or more nitrogenous fertilizer compounds with a composition of the present invention.

[0108] In another aspect, described herein are methods of making an aqueous enduse fertilizer composition comprising contacting one or more nitrogenous fertilizer compounds with an agricultural composition according to the invention and an aqueous medium, preferably water.

[0109] In another aspect, described herein are methods for fertilizing target plants, wherein the end-use composition according to the invention is applied to target plants or to an environment for the target plants. The end-use composition, in particular in its liquid state, can be used diluted with any appropriate solvent, such as water. The invention also concerns a process for manufacturing the composition according to the invention or the agricultural composition according to the invention which comprises mixing a urease inhibitor and / or a nitrification inhibitor with at least one polyethylene glycol polymer as defined above. If appropriate, the process according to the invention comprises adding further functional additives such as for example one or more stabilizers and / or a dye and / or an odor masking agent.

[0110] Preferably, in the process according to the invention the mixing forms a homogeneous liquid phase. This is advantageous in terms of processing and storage of the composition while maintaining an adequate physical and chemical stability of the composition.

[0111] The invention also relates to the use of a polyethylene glycol polymer as defined above for stabilizing a composition comprising an urease inhibitor, preferably n-(n-butyl)-thiophosphoric triamide (NBPT), and / or a nitrification inhibitor, preferably dicyandiamide (DCD).

[0112] The invention also relates to the use of a polyethylene glycol polymer as defined above as solvent in a fertilizer composition for decreasing and / or reducing greenhouse gas emissions, notably dimethyl sulfide (DMS) and / or dimethyl disulfide (DMDS) gas emissions, associated to said fertilizer composition, notably when compared to a same fertilizer composition comprising demethylsulfoxide (DMSO) as solvent.

[0113] In particular, the invention relates to the use of a composition according to the invention and / or of an end-use composition according to the invention for decreasing and / or reducing greenhouse gas emissions, notably dimethyl sulfide (DMS) and / or dimethyl disulfide (DMDS) gas emissions, notably when compared to a same composition comprising demethylsulfoxide (DMSO).

[0114] The invention finally relates to the use of a polyethylene glycol polymer as defined above as solvent in a fertilizer composition for decreasing and / or reducing soil and / or land pollution, notably when compared to a same fertilizer composition comprising demethylsulfoxide (DMSO) as solvent.

[0115] The invention finally relates to the use of a composition according to the invention and / or of an end-use composition according to the invention for decreasing and / or reducing soil and / or land pollution, notably when compared to a same composition comprising demethylsulfoxide (DMSO) as solvent. Should the disclosure of any patents, patent applications, and publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.

[0116] EXAMPLES

[0117] In the following examples, and unless otherwise explicitly stated, contents are in given in percentages by weight, with respect to the total weight of the composition.

[0118] 1. Materials & Methods

[0119] The following compositions are prepared from:

[0120] - Urease inhibitor: n-(n-butyl)-thiophosphoric triamide (NBPT), commercially available from Wuwei Jincang Bioscience Co., LTD;

[0121] - Nitrification inhibitor: dicyandiamide (DCD) commercially available from Su International Group, Inc. under the name of Cyanoguanidine and dicyanodiamide;

[0122] - PEG200: polyethylene glycol with a weight-average molecular weight equal to 200 g.mol'1, commercially available from The Dow Chemical Company (DOW) under the name of CARBOWAX™ polyethylene glycol (PEG) 200;

[0123] - PEG300: polyethylene glycol with a weight-average molecular weight equal to 300 g.mol'1, commercially available from The Dow Chemical Company (DOW) under the name of CARBOWAX™ polyethylene glycol (PEG) 300;

[0124] - PEG400: polyethylene glycol with a weight-average molecular weight equal to 400 g.mol'1, commercially available from Syensqo under the name of Rhodasurf® PEG 400;

[0125] - TEG: triethylene glycol, commercially available from DOW Chemical under the name of triethylene glycol;

[0126] - PG: propylene glycol, commercially available from Dow Chemical under the name of propylene glycol; and

[0127] - DMSO: dimethylsulfoxide, commercially available from Gaylord under the name of dimethyl sulfoxide. The properties of the compositions have been evaluated according to the following protocols:

[0128] - Initial appearance: visually assessed by the operator, and

[0129] - Storage stability: the appearance of the compositions after a prolonged period of storage in specific conditions is observed and then compared to their appearance before storage. The appearance of the compositions is observed after 2 weeks of storage at 54°C, 4°C and 0°C.

[0130] 2. Preparation and evaluation of compositions A to L

[0131] Compositions A to L have been prepared by charging a clean closed jar with the required amount of solvent. Then adding, the required amount of NBPT (and DCD) is charged under stirring and the mixture is mixed until a homogeneous clear liquid mixture is obtained.

[0132] The details of the compositions are given in table 1 below. The content are expressed in % by weight, with respect to the total weight of the compositions.

[0133] Compositions B, D, F, K and L are according to the invention.

[0134] Compositions A, C, E and G to J are comparative.

[0135] The initial appearance and the storage stability of compositions have then been evaluated according to the above-detailed protocols. The associated results are presented in table 2 below.

[0136] Table 1 > details of the compositions

[0137] Table 2 > evaluation of the compositions

[0138] We observe that freshly-prepared compositions B, D, F, K and L according to the invention are homogenous and clear. They are also all stable after 2 weeks of storage at a temperature equal to 54°C, 4°C and 0°C. Compositions B, D and L according to the invention also showed good stability after 2 weeks of storage at a temperature equal to -10°C.

[0139] Freshly prepared compositions A*, G*, H* and I* are also homogeneous and clear. However, these compositions are not storage stable: compositions A* and I* are frozen after 2 weeks of storage at a temperature equal to 0°C or even -10°C; compositions G*, H* and I* settle / sediment after 2 weeks of storage at 54°C.

[0140] Finally, compositions C*, E*, and J* are not homogenous: the inhibitors are not soluble in these solvent systems.

Claims

CLAIMS1. A composition comprising, with respect to the total weight of the composition: i) from 10% to 37.5 % by weight of at least one urease inhibitor comprising n- (n-butyl)-thiophosphoric triamide (NBPT), ii) from 1% to 20% by weight of at least one nitrification inhibitor comprising dicyandiamide (DCD), iii) from 60% to 89% by weight of at least one solvent selected from polyethylene glycol polymers with a weight-average molecular weight superior or equal to 160 g.mol’1, and iv) optionally, from 0.1 % to 1 % by weight of at least one dye.

2. The composition according to claim 1 , consisting essentially of, preferably consisting of: i) from 10% to 37.5 % by weight of n-(n-butyl)-thiophosphoric triamide (NBPT), ii) from 1 % to 20% by weight of dicyandiamide (DCD), iii) from 60% to 89% by weight of at least one solvent selected from polyethylene glycol polymers with a weight-average molecular weight superior or equal to 160 g.mol’1, And iv) optionally, from 0.1 % to 1 % by weight of at least one dye.

3. The composition according to claim 1 or 2, with a content of solvent ii) ranging from 65% to 80% by weight, with respect to the total weight of the composition, preferably from 67.5% to 72.5% by weight.

4. The composition according to any of the preceding claims, wherein the polyethylene glycol polymer has a weight-average molecular weight ranging from 180 g.mol’1to 450 g.mol’1, preferably from 185 g.mol’1to 400 g.mol’1, more preferably from 190 g.mol’1to 300 g.mol’1, even more preferably from 190 g.mol’1to 210 g.mol’1.

5. The composition according to any of the preceding claims, wherein the polyethylene glycol is of formula (I):wherein n, representing the average number of ethylene oxide units, is superior to 3 and inferior to 10, preferably ranges from 3.5 to 9.5, more preferably from 4 to 7, even more preferably from 4 to 5.

6. The composition according to any of the preceding claims, with a content of urease inhibitor(s), preferably of n-(n-butyl)-thiophosphoric triamide (NBPT), ranging from 15% to 35% by weight, with respect to the total weight of the composition, preferably from 20% to 32.5% by weight.

7. The composition according to any of the preceding claims, with a content of nitrification inhibitor(s), preferably of dicyandiamide (DCD), ranging from 5% to 17.5% by weight, preferably from 7.5% to 15% by weight.

8. The composition according to any of the preceding claims, which is free of demethylsulfoxide (DMSO), preferably free of demethylsulfoxide (DMSO) and N- Methyl-2-pyrrolidone (NMP).

9. An agricultural composition comprising: a. a nitrogenous fertilizer, and b. a composition as defined in any of the preceding claims.

10. The agricultural composition according to claim 9, which is a liquid end-use composition.

11. The agricultural composition according to claim 9, which is a solid end-use comprising, preferably comprising a core comprising said nitrogenous fertilizer and a coating comprising said composition as defined in any claims 1 to12. A method of making a solid or concentrated liquid fertilizer composition comprising contacting one or more nitrogenous fertilizer with a composition as defined in any of clams 1 to 8.

13. A method for fertilizing target plants, wherein the end-use composition according to claim 10 or 11 is applied to target plants or to an environment for the target plants.

14. Use of a polyethylene glycol polymer with a weight-average molecular weight of greater than or equal to 160 g.mol’1for stabilizing a composition comprising n-(n-butyl)-thiophosphoric triamide (NBPT), and dicyandiamide (DCD).

15. Use of a polyethylene glycol polymer with a weight-average molecular weight of greater than or equal to 160 g.mol’1as solvent in a fertilizer composition for decreasing and / or reducing greenhouse gas emissions, notably dimethyl sulfide (DMS) and / or dimethyl disulfide (DMDS) gas emissions, associated to said fertilizer composition, notably when compared to a same fertilizer composition comprising demethylsulfoxide (DMSO) as solvent.

16. Use of a polyethylene glycol polymer with a weight-average molecular weight of greater than or equal to 160 g.mol’1as solvent in a fertilizer composition for decreasing and / or reducing soil and / or land pollution, notably when compared to a same fertilizer composition comprising demethylsulfoxide (DMSO) as solvent.

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