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    abstract “Improved liquid formulations of urease inhibitors for fertilizers” an improved solvent system for the formulation and application of n-alkyl thiophosphoric triamide urease inhibitors. these formulations offer safety and performance benefits over existing alternatives and allow for storage, transport, and subsequent coating or mixing with urea-based or organic-based fertilizers. these formulations are mainly composed of ecologically correct aprotic and protic solvents (particularly dimethyl sulfoxide and alcohols/polyols) to stabilize the urease inhibitor. 1/1
    公开号:BR112015007327B1
    申请号:R112015007327
    申请日:2013-05-08
    公开日:2020-05-19
    发明作者:bruce parker David；david mcknight Gary；P Perkins Raymond；Wei Xu；Zehni Yang
    申请人:bruce parker David；david mcknight Gary；P Perkins Raymond；Wei Xu；Zehni Yang；
    IPC主号:
    专利说明:

    COMPOSITIONS UNDERSTANDING NITROGEN FERTILIZER, UREASE INHIBITOR AND DIMETHYL SULFOXIDE
    [001] This application claims priority, under 35 §USC 119 (e) for Provisional Application US 61 / 708,105 filed on October 1, 2012, all content of which is incorporated herein by reference.
    FIELD OF THE INVENTION
    [002] In embodiments, the present invention relates to improved solvent formulations for the N- (n-buty1) thiophosphoric triamide urease inhibitor, hereinafter referred to by its acronym NBPT. NBPT is a solid chemical substance, which is dissolved in a suitable solvent, to allow application at low levels in the field. In addition, NBPT solutions are desirable when it is to be incorporated as a component of a mixed granulated fertilizer, such that it can be deposited as a coating in a homogeneous and controlled layer. In one embodiment, the present invention proposes formulations of mixtures containing aprotic and protic solvents, which are more environmentally friendly and are safer for workers to handle than known NBPT solutions. In addition, the performance advantages over NBPT solution stability, solution handling, and load levels are disclosed for these new formulations.
    BACKGROUND OF THE INVENTION
    Description of the Prior Art
    [003] Nitrogen is an essential plant nutrient and is thought to be important for adequate and strong foliage. Urea provides a high nitrogen content and is one of the best of all nitrogen fertilizer materials, which consequently makes it an efficient fertilizer compound. In the presence of soil moisture, natural or synthetic ureas are
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    2/29 converted to ammonium ion, which is then available for uptake by plants. When applied as a fertilizing material, soil native bacteria enzymatically convert urea to two molar equivalents of ammonium ion for each mole of urea as demonstrated by the following two reactions:
    CO (NH2) 2 + 2 H2O (NH4) 2CO3 (NH4) 2CO3 + 2H + 2 NH4 + + CO2 + H2O
    [004] In the presence of water, the ammonium thus produced is in balance with ammonia. The balance between NH4 + and NH3 is dependent on pH, according to the following balance:
    [005] NH4 + + OH- NH3 (solution) + H2O
    [006] As such, ammonia gas losses are higher at higher pH values. The flow of NH3 in the soil is essentially dependent on the concentration of NH3, pH and temperature. In the presence of oxygen, ammonium can also be converted to nitrate (NO3 - ). Nitrogen in both its forms of ammonium and nitrates can then be captured as nutrient substances by growing plants.
    [007] The ammonium ion can also finally be converted to ammonia gas, which escapes into the air. The concentrations of NH3 in air and in solution are governed by the constant of Henry's law (H), which is a function of temperature:
    [NH3 (air)] = [NH3 (solution)]
    [008] Urea fertilizer is often applied only once at the beginning of the growing season. The weakness in this nitrogen dispensing system involves the different rates at which nitrate and ammonium are produced in the soil, and the rate at which nitrate and ammonium are required by the plant during its growth cycle. The generation of nitrate and ammonium is fast in relation to their uptake by plants, allowing a considerable amount of nitrogen fertilizer to become unusable or to be lost to
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    3/29 the atmosphere as ammonia gas, where it is no longer available to the plant So there is a desire to control urea hydrolysis to ammonium and ammonia gas, thus making urea fertilizer more effective for plant growth .
    [009] Numerous methods have been developed for the preparation of more effective urea fertilizers, and for controlling the volatilization of ammonia from urea. Weston et al. (US 5352,265) details a method for controlling losses of urea fertilizers, including: (1) various fertilizer treatments in the field, staged throughout the growing season, (2) the development of “controlled-release granulated fertilizer products ”, Using protective coatings that corrode slowly to introduce urea into the soil in a controlled manner, and (3) the discovery of simple chemical compounds (urease inhibitors) that inhibit the rate at which urea is metabolized by soil bacteria and converted for the ammonium ion.
    [010] The use of various urea coatings, to provide urea in a controlled manner to the plant, has been widely demonstrated. Urea phosphate coatings have been described by Barry et al, (US 3,425.81) in which the coating is applied to urea as an aqueous phosphate mixture. Miller (US 3,961,932) describes the use of chelated micronutrients to coat fertilizer materials. Polymer coatings have also been disclosed, which control the supply of fertilizer materials (see, for example, US 6,262,183 and 5,435,821).
    [011] Whitehurst et al, (6,830,603) teaches the use of borate salts for the production of coated urea fertilizers, as a means of controlling ammonia losses during the growth cycle. Whitehurst summarizes numerous examples of this coating strategy to inhibit ammoniacal nitrogen loss in the soil. Therefore, the prior art considers the
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    4/29 merits of coated fertilizer products as a means of inhibiting ammoniacal nitrogen loss in the soil. Urease inhibiting materials other than NBPT have been disclosed. Some examples include the use of polysulfide and thiosulfate salts as taught by Hojjatie et al (US 2006/0185411 A1) and the use of dicyandiamide (DCD) and nitrapirin.
    [012] Kolc et al (US 4,530,714) teaches the use of urease phosphoric aliphatic triamide inhibitors, including the use of NBPT for this purpose. Kolc mentions the use of aqueous and organic vehicle media, but specifies volatile (and flammable) solvents from the group including acetone, diisobutyl ketone, methanol, ethanol, diethyl ether, toluene, methylene chloride, chlorobenzene, and petroleum distillates. The main reason for using these solvents was to ensure that insignificant amounts of solvent residue are retained on the culture.
    [013] Improved vehicle systems for NBPT have been described subsequent to Kolc. NBPT is a substance that is both thermally and hydrolytically unstable and several solvent systems have been developed to overcome these and other deficiencies. Unfortunately, existing formulations are problematic in themselves, due to concerns about thermal stability and the toxicity of the main components of the formulation.
    [014] Generally, it is desirable that the solvents being used in conjunction with fertilizers, are soluble in water in all proportions, which allows easy dispersion, a point of use, as well as a relatively high instantaneous vaporization point (so that it has a reduced likelihood of explosions and / or fires at elevated temperatures). Many of the formulation solvents described in US 4,530,714 do not have these desirable properties. Examples of such problematic solvents in this patent include the use of toluene, a solvent
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    5/29 immiscible with water and flammable.
    [015] Weston et al. (US 5352265) describes the use of pyrrolidone solvents, such as N-methyl pyrrolidone (NMP), as does Narayanan et al. (US 5,160,528 and 5,071,463). It is shown that solvents of this type can dissolve high levels of NBPT to produce product concentrates and that the resulting concentrates have good temperature stability. These features are useful in that they allow commercial products to be stored, pumped, and transported in a conventional manner.
    [016] In US 5,698,003, Omilinsky and colleagues also disclose the use of “liquid amides, such as NMP in NBPT formulations. Omilinsky additionally talks about the importance of the stability of the solution and develops solvents of the glycol type, as desirable base solvents for the NBPT dispensing mixtures. The dominant role played by a liquid amide co-solvent is to depress the pour point of the mixture, which is not high enough, as a consequence of the natural viscosity of glycols at reduced temperatures. NMP plays several roles in NBPT based agrochemical formulations. As taught in '265,' 528 and '463, NMP is a useful solvent capable of producing formulations of concentrated NBPT products that have good temperature stability. In addition, it can be used as an additive to depress the pour point of viscous base solvents, such as propylene glycol. Omilinsky reveals the use of NMP as a co-solvent to depress the propylene glycol pour point in '003.
    [017] In mixtures, such as those described in US 5,698,003, the requirement for an additive to depress the pour point of glycol-type NBPT solvent formulations is described. Solvents like propylene glycol have the characteristic
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    6/29 attractive to be essentially non-toxic and are thus an attractive mixing component in agrochemical and pharmaceutical products. A disadvantage of some glycols is a relatively high viscosity level, which can make these materials resistant to flow and difficult to leak. In fact, the dynamic viscosity at 25 ° C of propylene glycol is 48.8 centipoise, almost 50 times that of water at the same temperature. Viscosity data for propylene glycol can be found in Glycols (Curime and Johnston, Reinhold Publishing Corp., New York, 1552). Omilinsky '003 describes the use of NMP as an additive capable of depressing the pour point of NBPT mixtures.
    [018] Although NMP and other liquid amide solvents perform useful functions in the described NBPT formulations, concerns about the safety of these solvents have increased considerably in recent years. In particular, European Directives 67/548 / EEC and / or 99/45 / EC, recently classified N-methyl pyrrolidone (NMP) as a reproductive toxin (R61) in amounts greater than 5% of the product formulation. It is planned to be listed on the “European Union Solvent List of great concern, which prevents its use in industrial and agrochemical formulations. In the USA, NMP is subject to the requirements of California Proposition 65 (The Safe Drinking Water and Toxic Enforcement Act of 1986), which regulate substances known to the US State of California to cause cancer or reproductive harm.
    [019] Nothing in the state of the art addresses the suitability of PWN in these formulations from the point of view of safety, or proposes suitable alternatives from the perspective of safety and performance.
    [020] Indeed, the guidelines for the use of reaction solvents in the pharmaceutical industry also address the relatively poor safety profile of PWN. As reaction solvents can be present at levels
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    7/29 residuals in finished drugs such considerations are warranted. The International Conference on Harmonization of Technical Requirements for the Registration of Pharmaceutical Products for Human Use (ICH) classifies NMP as a “solvent to be limited (class 2) in its document: Impurities: Guideline for Residual Solvents Q3C (R3).
    [021] PWN is potentially toxic if it is administered directly to humans and / or animals. In addition, it is possible that PWN can be toxic when it is ingested by animals of a higher order after passing through the food chain. For example, fertilizers are often not completely absorbed / used by fields / crops / plants in which they are used and fertilizers end up in watercourses (such as freshwater, brackish or salt water). In situations where at least part of the fertilizer ends up in these bodies of water, they can be absorbed, ingested or otherwise captured by organisms that are directly or indirectly consumed by higher animals (such as humans). In these cases, it is possible that the fertilizer and / or the compounds that are associated with said fertilizer can be directly and / or indirectly ingested by humans or animals and lead to toxicity to said humans. It is also possible that fertilizers that end up in watercourses can be directly ingested by higher / human animals that drink the water.
    [022] In addition, when the toxic compounds that are associated with various fertilizers are used. not only can they be toxic to higher animals, but they can also be toxic to lower animals in the food chain. At higher doses, this can mean death of lower animals in the food chain, which consequently means that there may be economic consequences, such as extinction, culture and / or
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    8/29 animal which means lower profit margins and less food available.
    [023] In view of the above, it is desirable to develop formulations / fertilizers that are less toxic to the environment and to animals and humans.
    [024] An important feature of the NBPT agrochemical formulation is its chemical stability in the solution. Although such products are diluted with water, at the point of use, NBPT undergoes hydrolysis in the presence of water. Aqueous solutions or NBPT emulsions are therefore not commercially practical and organic solvents are preferred as vehicles for dispensing concentrated NBPT products. But NBPT is not chemically inert to all solvents, and its stability must be evaluated in order to develop a product suitable for the needs of agrochemical users.
    [025] The stability of the NBPT to NMP was previously established in US 5,352,265 (Weston et al.) And by Narayanan et al. (US 5,160,528 and 5,071,463).
    [026] In addition, the consideration of the chemical stability of NBPT in the presence of formulation solvents is the inherent stability of the solvents themselves for hydrolysis. As NBPT products are often ultimately dispersed in water, the hydrolytic stability of NMP-type liquid amide solvents is a consideration.
    [027] At temperatures and high pH levels, hydrolysis of NMP can be significant (M-pyrrol ”product bulletin, International Specialty Products, p. 48).
    SUMMARY OF THE INVENTION
    [028] In one embodiment, the present invention relates to liquid formulations containing N- (n-butyl) thiophosphoric triamide (NBPT). In
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    9/29 an embodiment, the formulations can be prepared by dissolving the NBPT in an aprotic solvent consisting of a) dimethyl sulfoxide, b) dialkyl, diaryl, or alkylaryl sulfoxide having the formula R1-SO-R2, in that Ri represents a methyl, ethyl, n-propyl, phenyl or benzyl group and R2 is ethyl, npropyl, phenyl or benzyl, c) sulfolane, d), ethylene carbonate, propylene carbonate, or mixtures thereof. In one embodiment, these formulations can be mixed with a protic component consisting of 1) an alcohol or polyol from the alkylene and poly (alkylene) glycols (PG) family, 2) an alkylene glycol from the group consisting of ethylene, propylene, or butylene glycol, 3) glycerin, 4) an alkanolamine among the group comprising ethanolamine, diethanolamine, dipropanolamine, methyl diethanolamine, monoisopropanolamine and triethanolamine, and / or 5) ethyl, propyl, or butyl lactate. In one embodiment, it has been proposed to use dimethyl sulfoxide (DMSO) as a replacement for NBPT-based agrochemicals for more toxic solvents, such as, for N-methyl pyrrolidone.
    BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
    [029] Figure 1 shows the accelerated chemical stability of NBPT solutions, comparing the test product (50% PG, 25% DMSO, 25% NBPT) versus the commercial product containing N-methyl pyrrolidone. The stability test was carried out at 50 ° C, and the concentrations were tested by HPLC.
    [030] Figure 2 shows the accelerated chemical stability of NBPT solutions by comparing the test product (35% PG, 40% DMSO, 25% NBPT) versus the commercial product containing N-methyl pyrrolidone. The stability test was conducted at 50 ° C, and the concentrations were tested by HPLC.
    [031] Figure 3 shows accelerated chemical stability of NBPT solutions, comparing the test product (20% PG, 40% DMSO, 40% NBPT) versus the commercial product containing N-methyl pyrrolidone. The test of
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    10/29 stability was performed at 50 ° C, and concentrations were tested by HPLC.
    [032] Figure 4 shows accelerated chemical stability of NBPT solutions, comparing the test product (48.5% glycerin, 1.5% methanol, 25% DMSO, 25% NBPT) versus the commercial product containing N -methyl pyrrolidone. The stability test was carried out at 50 ° C, and the concentrations were tested by HPLC.
    [033] Figure 5 shows accelerated chemical stability of NBPT solutions, comparing the test product (48.5% glycerin, 1.5% methanol, 25% DMSO, 25% NBPT) versus the commercial product containing N-methyl pyrrolidone. The stability test was carried out at 50 ° C, and the concentrations were tested by HPLC.
    [034] Figure 6 shows accelerated chemical stability of four NBPT solutions: Mixture A; 75.0% N-methyl pyrrolidone, 25% NBPT. Mixture B; 75% PG, 25% NBPT. Mixture C; 75.0% buffered mixture, 25.0% NBPT. Mixture D; 75% DMSO, 25.0% NBPT. The stability test was carried out at 50 ° C, and the concentrations were tested by HPLC.
    [035] Figure 7 shows the results of the viscosity tests comparing propylene glycol mixtures with different percentages of DMSO versus NMP cosolvents. Viscosities were measured using a Brookfield digital LVDV-E rotational viscometer with the LVDVE shaft assembly. Also shown is the viscosity of the commercial NBPT product, which contains NMP and PG, from example 2.
    [036] Figure 8 shows the results of the viscosity tests comparing glycerol mixtures with different percentages of DM50 versus MP co-solvents. Viscosities were measured using a Brookfield LVDV-E digital rotational viscometer with the LVDV-E axis assembly. Also shown is the viscosity of the commercial NBPT product, which contains NMP and PG,
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    11/29 of example 2.
    [037] Figure 9 shows the results of the viscosity tests comparing mixtures of monoisopropanolamine (APL), with different percentages of DMSO versus NMP co-solvent. Viscosities were measured using a Brookfield digital rotational viscometer LVDV-E with LVDV-E axis assembly. Also shown is the viscosity of the commercial NBPT product, which contains NMP and PG, from example 2.
    [038] Figure 10 shows test results for ammonia emissions from soil, which had been applied commercial urea fertilizer versus commercial urea fertilizer coated with an NBPT solution containing 50.0% PG, 30.0% DMSO , and 20.0% NBPT by weight. The test was conducted for 7 days at 22 ° C using a commercially available soil-to-pot mixture, and was analyzed using a chemiluminescent ammonia analyzer.
    DETAILED DESCRIPTION OF THE INVENTION
    [039] In one embodiment, the present invention relates to formulations containing N- (n-butyl) thiophosphoric triamide (NBPT). In one embodiment, these formulations are prepared by dissolving NBPT in an aprotic solvent consisting of a) dimethyl sulfoxide, b) dialkyl, diaryl, or alkylaryl sulfoxide with the formula R1-SO-R2, where Ri is methyl , ethyl, n-propyl, phenyl or benzyl and R2 is ethyl, n-propyl, phenyl or benzyl, c) sulfolane, d), ethylene carbonate, propylene carbonate, or mixtures thereof. In one embodiment, these formulations can be mixed with a protic component consisting of 1) an alcohol or polyol from the alkylene and poly (alkylene) glycols (PG) family, 2) an alkylene glycol from the group consisting of ethylene , propylene, or butylene glycol, 3) glycerin, 4) an alkanolamine from the group comprising ethanolamine, diethanolamine,
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    12/29 dipropanolamine, methyl diethanolamine, monoisopropanolamine and triethanolamine, and / or 5) ethyl, propyl, or butyl lactate.
    [040] In one embodiment, dimethyl sulfoxide (DMSO) is used as a substitute in NBPT-based agrochemicals for more toxic solvents, such as, for N-methyl pyrrolidone (NMP).
    [041] In one embodiment, the solution is combined with dry or granulated urea fertilizer and applied to farmland to make the fertilizer more effective for plant growth, and / or applied directly to land, surfaces or products containing urea, to reduce ammonia emissions.
    [042] In one embodiment, coated granular urea products containing additional plant nutrients can be prepared from granulated urea, a source or sources of additional nutrients in powder form and the diluted mixture containing NBPT described below. Granular urea can be first moistened with the mixture containing diluted NBPT followed by mixing to distribute the liquid mixture containing NBPT over the granulated urea surface using any equipment commonly used to mix a liquid with a granulated solid. After dispensing the mixture containing diluted NBPT over the granulated surface, additional powdered nutrients can be added to the moistened mixture and the resulting combined ingredients can be further mixed to distribute the powdered materials. In an alternative embodiment, the powdered materials can first be mixed with the granulated urea and then the mixture containing diluted NBPT can be sprayed onto a rotating bed of the dry ingredients to agglomerate the dry materials. This latter method may be particularly suitable for continuous processing.
    [043] The term urea fertilizer as used herein refers to
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    13/29 to both natural and synthetic urea, used alone or mixed with other macro- and / or micronutrients and / or organic matter. The dry granulated urea fertilizer contains about 46% nitrogen by weight.
    [044] In one embodiment, the compounds listed in the present invention, as aprotic and protic solvents, can generally be described as sulfoxides and alcohols, respectively.
    [045] In one embodiment, the present invention relates to the use of safer and more environmentally friendly solvents to overcome the limitations of specific existing forms of urease inhibitors. In one embodiment, the solvents used in the present invention are less toxic than the solvents that have been used in the prior art, for example, NMP.
    [046] In one embodiment, the formulations use combinations of polar aprotic solvents (sulfoxides, sulfones, dialkyl carbonates) with protic solvents (glycols, triols, and alkanolamines) to produce NBPT formulations with acceptable viscosity levels and high charge of NBPT, while it is also relatively non-toxic. In addition, in one embodiment, aprotic / protic solvent mixtures demonstrate excellent stability of NBPT, as demonstrated by accelerated stability tests.
    [047] One aspect of the invention involves the use of dimethyl sulfoxide as a substitute for the most dangerous liquid amide component in formulations that require such a co-solvent, to modify the flow properties of the formulation. In this respect, this is a considerable improvement due to the increased regulatory control of liquid amide solvents.
    [048] In one embodiment, the present invention relates to the use of MSO with NBPT instead of NMP. PWN has a toxicity
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    14/29 recognized reproductive health and an acute toxicity examination of the data shows that NMP is considerably more dangerous than dimethyl sulfoxide, by any route of exposure. A summary of the basic toxicological indicators is given in Table 1.
    Table 1. Comparative data on acute / reproductive toxicity for dimethyl sulfoxide and N-methyl pyrrolidone.
    Toxicological indicatorCAS Dimethyl sulfoxide[67-68-64] N-methyl pyrrolidone[872-50-4] Oral LD-50 14,500 - 28,300 3,914 LD-50 dermal 40,000 8,000 Inhalation toxicity(MADL) Not established 3200 pg / day Reproductive toxin No Yes
    MADL - Maximum permitted dosage level / day (California Proposition
    65)
    [049] As shown in the table above, it should be evident to people skilled in the art that DMSO is significantly less toxic than NMP. In addition, DMSO has been classified as a solvent with low toxic potential (Class 3) ”- the most favorable classification.
    [050] In one embodiment, the present invention addresses the deficiencies of prior art solvents by using specific mixtures of low-toxic aprotic polar solvents (most especially dimethyl sulfoxide) and various common protic solvents, which also tend to be relatively non-toxic.
    [051] In one embodiment, the present invention relates to formulations comprising mixtures of aprotic / protic solvents that are used to fluidize the specific urease inhibitor N- (n-butyl) thiophosphoric
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    15/29 triamide in such a way that it can be used for coating fertilizer products.
    [052] In one embodiment, urea phosphate coatings can be used in which the coating is applied to urea as an aqueous phosphate mixture prior to the addition of the fertilizer additive of the present invention.
    [053] In one embodiment, chelated micronutrients can be used for fertilizer coating materials. Alternatively and / or in addition, polymer coatings can be used which controls the dispensing of fertilizer materials.
    [054] In one embodiment, the formulations of the present invention use DMSO as a solvent. DMSO has an advantage over state of the art solvents, such as NMP, because DMSO does not undergo hydrolysis which can be significant with NMP (see (M-pyrrol ”product bulletin, International Specialty Products, p. 48). if DMSO is used, there is significantly more latitude in the development of the formulation.
    [055] Furthermore, the solvent properties of DMSO are useful in these formulations in which concentrations of NBPT containing more than 50% by weight of NBPT are attainable. Such a high charge of an active substance by a solvent allows the manufacture of product concentrates, which can be less expensive to store, transport and use. When the fertilizer additive product reaches the user, the user is able to dilute the concentrate with water and use the fertilizer additive (with fertilizer) for their crops / plants or similar.
    [056] In one embodiment, the NBPT is dissolved in an aprotic solvent, such as dimethyl sulfoxide. The NBPT aprotic solvent solution can be used alone, or additionally mixed with a protic solvent
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    16/29 to improve handling, stability, and / or spillability of the solution product.
    [057] The mixing of materials can be established in any method commonly used: for example; simply mix the materials in the tank before use, using a measuring system to inject materials simultaneously, or mix using a spray injection system.
    [058] In one embodiment, the aprotic solvent / protic solvent / NBPT mixture is mixed to produce an NBPT concentration of 5% to 75% by weight. Alternatively, an NBPT concentration of 5% to 60% by weight can be used. Alternatively, an NBPT concentration of 5% to 50% by weight can be used. Alternatively, an NBPT concentration of 5% to 40% by weight can be used. The initial solubilization step in dimethyl sulfoxide can be carried out between, at an ambient temperature of about 19 ° C to about 150 ° C (the boiling point of DMSO at atmospheric pressure is - 10 ° C).
    [059] Alternatively, the solubilization step in dimethyl sulfoxide can be carried out between about 22 ° C and up to 60 ° C,
    [060] The mixture can be mixed in any common mixing tank. Although the dosage of NBPT, aprotic solvent and protic solvent can be based on weight, it can also be based on volumetric basis.
    [061] A dye or dye can be added to the mixture to assist in the visual assessment of the uniform coating during the granular urea coating. Alternatively, a dye or dye can be added to the mixture to assist in the visual assessment of the uniform coating during the coating of urea in aqueous mixtures immediately before application. In one embodiment, the colorant can include any
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    17/29 common non-toxic food coloring.
    EXAMPLES
    [062] The following examples are provided to illustrate the practice of the invention. The examples are not intended to illustrate the range of possible uses. All compositions are based on mass percentages, unless expressly stated. The concentrations of individual components are shown before their name. For example, 20.0% NBPT refers to a mixture containing 20.0% by weight of NBPT.
    Example 1
    [063] An NBPT solution was prepared by carefully mixing NBPT, DMSO, and PG to obtain the following weight percentages: 50.0% PG, 30.0% DMSO, 20.0% NBPT.
    Example 2
    [064] To test the toxicity of DMSO and compare it with the relative toxicity of NMP, a test to determine the acute toxicity range of 96 h was performed on juvenile lobsters (Procambarus clarkii) to estimate the lethal concentration for half the population (LC50) for the solution as described in example 1. Simultaneously, the LC50 was determined in a commercially available NBPT solution that contained 26.7% NBPT by weight (per product label), and approximately 10% N -methyl pyrrolidone (MSDS ranging from 10 to 30%), and approximately 63% propylene glycol (MSDS ranging from 40 to 70%). The lobsters were placed in static chambers and exposed to equal NBPT concentrations of 0, 72, 145, 290, 580, and 1160 mg / L in clean water. The LC50 of the solution in Example 1 was 145 mg of NBPT (as an active ingredient) / L, while the LC50 of Agrotain® Ultra was 75 mg of NBPT (as an active ingredient) / L. Since a higher LC50 indicates less toxicity, the solution in example 1 was about half as toxic as the
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    18/29 commercial product that contained N-methyl pyrrolidone.
    [065] This test demonstrates that the formulations of the present invention are significantly less toxic than formulations of the prior art.
    Example 3
    [066] NBPT solutions were prepared in DMSO and equal amounts of DMSO / PG to determine maximum solubility at room temperature of 22: ° C. Following mixing and sonification, the samples were visually inspected, then filtered through a 0.45 pm filter and analyzed by near infrared reflectance spectrometry. At 22 ° C, the solubility of NBPT in DMSO was at least 58.9% by weight. The solubility of NBPT in equal amounts of DMSO / PG was at least 55.0% by weight.
    [067] One would expect that at elevated temperatures beyond that described above, it may be able to increase the solubility of NBPT above the values found in the present example by providing an avenue for concentrates. Even if the temperature is reduced during transport, instructions on the use of the fertilizer additive can instruct the user to raise the temperature of the formulation to ensure complete solubilization of the product before use.
    Example 4
    [068] An NBPT solution was prepared by carefully mixing NBPT, DMSO, and PG to obtain the following weight percentages: 50% PG, 25% DMSO, and 25% NBPT. The commercially available NBPT solution from example 2 was also used for comparison.
    Example 5
    [069] The NBPT solutions of example 4 were placed in individual flasks and incubated for 45 days at 50 ± 1 ° C in a laboratory oven.
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    19/29
    The samples were periodically removed for analysis of NBPT in solution using a Waters High Performance Liquid Chromatograph (HPLC) model 1525 equipped with a Waters 2489 visible / UV tunable detector. Appropriate analytical parameters (mobile phase composition, selection of the column, etc.), as would be the case for workers experienced in the art, and the raw data from HPLC analyzes were calibrated to authentic NBPT standards having a nominal purity of> 99%. Figure 1 shows the results of the accelerated stability test.
    [070] This test shows that NBPT has no significant deterioration at elevated temperatures, which means that the formulations of the present invention can be transported without worrying about significant product degradation.
    Example 6
    [071] An NBPT solution was prepared by carefully mixing NBPT, DMSO, and PG to obtain the following weight percentages: 35% PG, 40% DMSO, and 25% NBPT. The commercially available NBPT solution from example 2 was also used for comparison.
    Example 7
    [072] The NBPT solutions of example 6 were placed in individual flasks and incubated for 45 days at 50 ± 1 ° C in a laboratory oven. The samples were periodically removed and analyzed using the procedures of example 5. Figure 2 shows the results of the accelerated stability test.
    [073] This test shows that NBPT has no significant deterioration at elevated temperatures when the relative amounts of DMSO are varied. Therefore, the formulations of the present invention can be transported without worrying about the significant degradation of the product, in different
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    20/29 levels of DMSO.
    Example 8
    [074] An NBPT solution was prepared by carefully mixing NBPT, DMSO, and PG to obtain the following weight percentages: 20% PG, 40% DMSO, and 40% NBPT. The commercially available NBPT solution from example 2 was also used for comparison.
    Example 9
    [075] Example 8 NBPT solutions were placed in individual flasks and incubated for 45 days at 50 ± 1 ° C in a laboratory oven. The samples were periodically removed and analyzed using the procedures of example 5. Figure 3 shows the results of the accelerated stability test.
    [076] This test shows that NBPT has no significant deterioration at elevated temperatures when the relative amount of NBPT is increased. Accordingly, the formulations of the present invention can be transported without concern for significant product degradation, even at a relatively high concentration of NBPT.
    Example 10
    [077] An NBPT solution was prepared by carefully mixing NBPT, DMSO, glycerin and methanol to obtain the following weight percentages: 48.5% glycerin, 1.5% methanol, 25% DM80, and 25% NBPT. The commercially available NBPT solution from example 2 was also used for comparison
    Example 11.
    [078] The NBPT solutions of example 10 were placed in individual flasks and incubated for 45 days at 50 ± 1 ° C in a laboratory oven. The samples were periodically removed and analyzed using the
    Petition 870200005516, of 1/13/2020, p. 39/53
    21/29 procedures in example 5. Figure 4 shows the results of the accelerated stability test.
    [079] This test shows that NBPT has no significant deterioration at elevated temperatures with this formulation which means that this formulation can be transported without worrying about significant product degradation.
    Example 12
    [080] A NBPT solution was prepared by carefully mixing NBPT, DMSO, glycerin, and methanol to obtain the following weight percentages: 33.5% glycerin, 1.5% methanol, 25% DMSO, and 40% of NBPT. The commercially available NBPT solution from example 2 was also used for comparison.
    Example 13
    [081] The NBPT solutions of example 12 were placed in individual flasks and incubated for 45 days at 50 ± 1 ° C in a laboratory oven. The samples were periodically removed and analyzed using the procedure of Example 5. Figure 5 shows the results of the accelerated stability test.
    [082] This test shows that NBPT has no significant deterioration at elevated temperatures with this formulation which means that this formulation can be transported without worrying about significant product degradation.
    Example 14
    [083] The buffer solution was prepared by carefully mixing monoisopropanolamine (MIPA) with glacial acetic acid (GAA) to obtain the following weight percentages: 62.5% MIPA, 37.5% GAA. The mixing was conducted in such a way that the temperature of the mixture remained below 50
    Petition 870200005516, of 1/13/2020, p. 40/53
    22/29 ° C. Multiple solutions of NBPT were prepared to obtain the following percentages by weight; Mixture A: 75% N-methyl pyrrolidone, 25% NBPT; Mixture B: 75% PG, 25% NBPT; Mixture C: 75% buffer solution, 0.25% NBPT; Mixture D: 75% DMSO, 25% NBPT.
    Example 5
    [084] The four NBPT solutions in example 4 were placed in individual flasks and incubated for approximately 200 hours at 50 ± 1 ° C. The samples were periodically removed and analyzed using the HPLC procedures of example 5. Figure 6 shows the results of the accelerated stability test.
    [085] This test shows that Mixture C had more sample degradation at elevated temperatures than mixtures containing DMSO (Mixture D), NMP (Mixture A) or PG (Mixture B). It should be noted that PG does not have the spill capacity of DMSO and NMP is more toxic than DMSO.
    Example 16
    [086] Dynamic viscosity measurements were collected for propylene glycol, glycerin, and a representative alkanolamine (monoisopropanolamine, MIPA), with increasing levels of DMSO and NMP. A Brookfielel LVDV-E digital rotational viscometer with the LVDVE shaft assembly (Brookfield Engineering Labs, inc., Middleboro, Mass.) Was used for this work and was calibrated using a standard general purpose synthetic oil base viscosity calibration solution 14, (Cannon Instrument Company, State College. PA). Sampling was performed at 21 ° C. Figures 7, 8, 9 show the ability of DMSO to depress the viscosity of NBPT mixtures at 21 ° C as a function of concentration, compared to similar NMP measurements.
    [087] This test shows that there is virtually no
    Petition 870200005516, of 1/13/2020, p. 41/53
    23/29 difference between DMSO and NMP in reducing the viscosity of various viscous formulations.
    Example 17
    [088] A dye solution was added to the solution of example 1. 454 grams of granulated urea were added to two 2000 ml clean, dry glass vials. Using a pipette, 1.87 ml, to represent the application rate of 2 quarts of product / ton of urea of the solution dyed in example 1, they were added to the urea in one of the flasks. Using a 1.87 mL pipette, to represent the application rate of 2 quarts of product / ton of urea of the commercial solution of example 2, the urea in the other bottle was added. With the cap on, the medium flasks were rotated hand over hand (1 rotation = 360 degrees back from hand over hand) until the urea was consistently coated. More complete coverage was observed after four turns in the tinted solution of example 1. The number of rotations required to obtain 100% visual coverage was recorded. The tinted solution of example 1 required 30 rotations for full coverage, while the commercial product of example 2 required 35 rotations.
    [089] This test shows that formulations containing DMSO and dye can more easily cover urea than a corresponding solution containing NMP and a dye.
    Example 18
    [090] The NBPT solutions of examples 4, 6, 8, 10 and 12, together with the commercial NBPT solution of example 2 were placed in a freezer at -20 ° C for 48 hours. The NBPT solutions of examples 4, 6, 8, and the commercial NBPT solution of example 2, were all freely flowable at -20 ° C. The BPT solution of example 10 was very viscous but still fluid. The NBPT solution in Example 12 was a solid at -20 ° C.
    Petition 870200005516, of 1/13/2020, p. 42/53
    24/29
    Example 19
    [091] Commercial granulated urea was treated with the NBPT solution from example 1. Both untreated and treated urea were applied to a mixture of commercially available potting soil 22, and ammonia concentrations in the upper space were measured over a period of 7 days, using a chemiluminescence analyzer. Ammonia concentrations in treated urea were considerably lower than those in untreated urea. Figure 10 shows the results of the ammonia emissions test.
    [092] This test shows that NBPT formulations containing DMSO are effective in reducing the hydrolysis of urea to ammonium, thus reducing ammonia losses to the atmosphere and making the fertilizer more effective. In certain embodiments, the present invention relates to formulations, fertilizer additives, methods and processes for producing and using these formulations and / or fertilizer additives.
    [093] In one embodiment, the present invention relates to a formulation comprising N- (n-butyl) thiophosphoric triamide and one or more of a C1-6 alkylene carbonate and R1S (O) xR2 where R1 and R2 are each independently a C1-6 alkylene group, an aryl group, a C1-3 alkylene aryl group or R1 and R2 with the sulfur to which they are attached form a 4- to 8-membered ring, where R1 and R2 together are a C1-6 alkylene group that optionally contains one or more atoms selected from the group consisting of O, S, Se, Te, N and P in the ring ex is 1 or 2. In a variation, the ring atoms can optionally include O, S, N and P or, alternatively, O, S, and N.
    [094] In one embodiment, the formulation contains R1S (O) xR2, which is dimethyl sulfoxide. Alternatively, the formulation contains R1S (O) xR2,
    Petition 870200005516, of 1/13/2020, p. 43/53
    25/29 which is a dialkyl, diaryl, or alkylaryl sulfoxide. Alternatively, R1 and R2 may be the same or different and each of R1 and R2 may be a C1-6 alkylene group, an aryl group, or a C1-3 alkylene aryl group.
    [095] In one embodiment, Ri is methyl, ethyl, n-propyl, phenyl or benzyl and R2 is methyl, ethyl, n-propyl, phenyl or benzyl, or mixtures thereof. In another embodiment, RiS (O) xR2 is sulfolane.
    [096] In one embodiment, the formulation may contain alkylene carbonate, which is ethylene carbonate, propylene carbonate, butylene carbonate or mixtures thereof. In a variation, the formulation may contain alkylene carbonate, which is ethylene carbonate, propylene carbonate, or mixtures thereof.
    [097] In one embodiment, the formulation can further comprise an alcohol or polyol in which the polyol is alkylene or poly (alkylene) glycols or mixtures thereof. In one embodiment, the polyol is an alkylene glycol selected from the group consisting of ethylene, propylene, and butylene glycol or mixtures thereof In one embodiment, the polyol is glycerin.
    [098] In one embodiment, the formulation may further comprise an alkanolamine selected from the group consisting of ethanolamine, diethanolamine, dipropanolamine, methyl diethanolamine, monoisopropanolamine and triethanolamine.
    [099] The formulation (s) may contain aqueous ethanolamine borate such as ARBORITE Binder. In one embodiment, the concentration of the secondary or tertiary amino alcohol can be maintained above about 1.2% and, alternatively, above about 20%. When the concentration of aqueous ethanolamine borate is less than about 12% concentration, a suspension of NBP in the aqueous mixture can form that can be resolved by
    Petition 870200005516, of 1/13/2020, p. 44/53
    26/29 stirring medium to be used to prepare other products.
    [100] In one embodiment of the invention, NBPT can be dissolved by melting the compound with sufficient triethanolamine to provide a mixture of up to about 30% by weight of BPT. The resulting mixture of NBPT in triethanolamine can be used to treat urea as described herein.
    [101] In another embodiment of the invention, NBPT is dissolved in diethanolamine in an amount of up to 40% by weight by melting the solid in diethanolamine until a solution is obtained. The mixture of diethanolamine and NBPT can be used to treat urea, as described herein.
    [102] In another embodiment of the invention, a liquid mixture of diisopropanolamine can be prepared by gently heating the solid until it has liquefied and the mixture of NBPT with the solid to the limit of solubility. The liquid mixture containing NBPT in diisopropanolamine can be used to treat urea, as described herein.
    [103] In one variation, the formulation may further comprise ethyl, propyl, or butyl lactate.
    [104] In one embodiment, N- (n-butyl) thiophosphoric triamide (NBPT) can be present in an amount that is between about 5 to 75% by weight of the formulation. In a variation, the formulation may contain between about 10 and 75% by weight of NBPT, 10 and 50% by weight of DMSO, and 10 and 80% by weight of PG (polyglycol) or alkylene carbonate. In a variation, the formulation may contain between about 10 and 60% by weight of NBPT, 1.0 and 40% by weight of DMSO, and 10 and 60% by weight of PG or alkylene carbonate. In a variation, the formulation may contain between about 10 and 50% by weight of NBPT, 10 and 50% by weight of DMSO, and 10 and 50% by weight of PG or alkylene carbonate. In one variation, the formulation may contain between about 0.10 and 40
    Petition 870200005516, of 1/13/2020, p. 45/53
    27/29% by weight of NBPT, 10 and 40% by weight of DMSO, and 10 and 50% by weight of PG or alkylene carbonate. In a variation, the formulation may contain between about 20 and 50% by weight of NBPT, 20 and 50% by weight of DMSO and 10 and 50% by weight of PG or alkylene carbonate. In a variation, the formulation can be diluted with water.
    [105] In one embodiment, the present invention relates to a fertilizer additive comprising N- (n-butyl) thiophosphoric triamide and one or more of a C1-6 alkylene carbonate and R1S (O) xR2 where R1 and R2 are each independently a C1-6 alkylene group, an aryl group, a C1-3 alkylene aryl group or R1 and R2 with the sulfur to which they are attached form a 4- to 8-membered ring, wherein R1 and R2 together are a C1-6 alkylene group that optionally contains one or more atoms selected from the group consisting of O, S, Se, Te, N and P in ring ex is 1 or 2.
    [106] In one embodiment, the fertilizer additive can comprise N- (n-butyl) thiophosphoric triamide and dimethyl sulfoxide. In a variation, the fertilizer may further comprise polyalkylene glycols. In a variation, polyalkylene glycols are selected from the group consisting of polymethylene glycols, polyethylene glycols, polypropylene glycols, polybutylene glycols, and mixtures thereof.
    [107] In one embodiment, the fertilizer additive can be any of the embodiments discussed above with respect to the formulation.
    In one embodiment, the present invention relates to a method of reducing the volatility of urea fertilizers comprising the addition of a composition comprising N- (n-butyl) thiophosphoric triamide and one or more of a C1 alkylene carbonate -6 and R1S (O) xR2 where R1 and R2 are each independently a C1-6 alkylene group, an aryl group, a
    Petition 870200005516, of 1/13/2020, p. 46/53
    28/29 C1-3 alkylene aryl or R1 and R2 with the sulfur to which they are attached form a 4- to 8-membered ring, where R1 and R2 together are a C1-6 alkylene group that optionally contains one or more atoms selected from from the group consisting of O, S, Se, Te, N and P in ring ex is 1 or 2.
    [108] In one embodiment, the present invention relates to a method of manufacturing a fertilizer formulation or additive, wherein to the N- (n-butyl) thiophosphoric triamide is added one or more of a C1 alkylene carbonate -6 and R1S (O) xR2 where R1 and R2 are each independently a C1-6 alkylene group, an aryl group, a C1-3 alkylene aryl group or R1 and R2 with the sulfur to which they are attached form a ring of 4 to 8 members, where R1 and R2 together are a C1-6 alkylene group that optionally contains one or more atoms selected from the group consisting of O, S, Se, Te, N and P in the ring ex is 1 or 2 .
    [109] In one embodiment, the methods may comprise R1S (O) xR2 which is dimethyl sulfoxide.
    [110] In one embodiment, the methods may comprise C1-6 alkylene carbonate, which is ethylene carbonate, propylene carbonate, butylene carbonate or mixtures thereof.
    [111] In one embodiment, the methods can comprise any of the fertilizer formulations and / or additives discussed above.
    [112] Each patent mentioned herein is incorporated by reference in its entirety.
    [113] It should be understood that the present invention is not to be limited by the foregoing description. Modifications can be made to the above without departing from the spirit and scope of the invention. It is contemplated, therefore, within the scope of the present invention, that any characteristic
    Petition 870200005516, of 1/13/2020, p. 47/53
    29/29 that is described above can be combined with any other characteristic that is described above. In addition, it should be understood that the present invention contemplates that minor modifications can be made to the formulations, additive fertilizer compositions, and methods of the present invention. When ranges are discussed, any number that may not be explicitly disclosed, but falls within the range is considered an end point for the range. The scope of protection to be granted will be determined by the following claims and the breadth of interpretation that the law allows.
    权利要求:
    Claims (17)
    [1]
    1. Composition, characterized by the fact that it comprises: a. a nitrogen fertilizer composed of urea and one or more members selected from the group consisting of a) urea formaldehyde polymer and b) dicyandiamide, b. a liquid solution composed of a urease inhibitor that has been solubilized in an aprotic solvent, wherein said aprotic solvent comprises dimethyl sulfoxide, wherein the composition comprises 45 to 5% of said urease inhibitor and 55 to 95% of sulfur dioxide dimethyl, and wherein said urease inhibitor is N- (n-butyl) thiophosphoric triamide.
    [2]
    2/4 liquid urea.
    2. Composition according to claim 1, characterized in that the composition further comprises aprotic solvents and protic solvents, wherein said aprotic solvents are one or more members selected from the group consisting of a) one or more carbonates of alkylene selected from the group consisting of propylene carbonate, ethylene carbonate and butylene carbonate, b) 2-methoxyethyl ether, c) cyclohexylpyrrolidone, d) 1,3dimethyl-2-imidazolidinone, e) dimethyloxyethane and f) liquid hexamethyl phosphoramides organo-phosphorous, and in which said protic solvents are one or more members selected from the group consisting of a) glycerin, b) ethyl lactate and c) one or more alcohols selected from the group consisting of npropyl alcohol, isopropyl alcohol, -hexanol, isobutyl alcohol and tercamyl alcohol.
    [3]
    3/4 that the composition comprises the polar aprotic solvent dimethyl sulfoxide.
    3. Composition, according to claim 1, characterized by the fact that the composition further comprises one or more members selected from the group consisting of buffer, flow aids, silicas, surfactants and dyes / dyes.
    [4]
    4/4 dyes / dyes.
    4. Composition, according to claim 1, characterized by the fact that the composition also comprises water, resulting in a fertilizer of
    Petition 870200005516, of 1/13/2020, p. 49/53
    [5]
    5. Composition, according to claim 1, characterized by the fact that said nitrogen fertilizer is combined with said liquid solution to make the fertilizer more effective when applied to the soil for plant growth, in which the composition reduces the hydrolysis of urea to ammonia, thus reducing ammonia losses to an atmosphere, resulting in improved nitrogen retention in the soil.
    [6]
    6. Composition, characterized by the fact that it comprises: a. a nitrogen fertilizer composed of urea and one or more members selected from the group consisting of a) formaldehyde urea polymer and b) dicyandiamide, b. a liquid fertilizer additive composed of urease inhibitor (s) which have been solubilized in polar aprotic solvents and one or more solvents selected from the group consisting of aprotic and protic solvents, wherein said polar aprotic solvents comprise one or more members selected from from the group consisting of: i. dimethyl sulfoxide, and ii. one or more sulfoxide (s) selected from the group consisting of dialkyl, diaryl or alkylaryl sulfoxide selected from the structure of formula: R9S (O) xR 10 where 1. R9 and R 10 are each independently an alkylene group C1-6, an aryl group, a C1-3 alkylene aryl group, or 2. R9 and R 10 with the sulfur to which they are attached form a 4- to 8-membered ring, where R 9 and R 10 together are a group C1-6 alkylene which optionally contains one or more atoms selected from the group consisting of O, S, Se, Te, N and P in the ring, 3. x = 1 or 2, where the composition comprises 75 to 5% of the said urease inhibitors and 25 to 95% of said polar aprotic solvents, said aprotic solvents and said protic solvents, wherein the composition comprises the urease inhibitor N- (n-butyl) thiophosphoric triamide.
    [7]
    7. Composition, according to claim 6, characterized by the fact that
    Petition 870200005516, of 1/13/2020, p. 50/53
    [8]
    8. Composition according to claim 6, characterized in that the composition comprises one or more aprotic solvents selected from the group consisting of: a) one or more alkylene carbonates selected from the group consisting of propylene carbonate, carbonate of ethylene and butylene carbonate, b) 2-methoxyethyl ether, c) cyclohexylpyrrolidone, d) 1,3dimethyl-2-imidazolidinone and e) hexamethyl phosphoramides, liquid organophosphorous.
    [9]
    9. Composition according to claim 6, characterized in that the composition comprises one or more protic solvents selected from the group consisting of a) one or more C1-6 alcohols, b) one or more polyols selected from the group that consists of alkylene and poly (alkylene) glycols, glycerin, c) one or more alkanolamines selected from the group consisting of ethanolamine, diethanolamine, dipropanolamine, methyl diethanolamine, monoisopropanolamine and triethanolamine, and d) one or more alkyl lactates selected from the group consisting in ethyl, propyl and butyl lactate.
    [10]
    10. Composition according to claim 6, characterized in that the composition further comprises one or more polyalkylene glycols selected from the group consisting of: polymethylene glycol, polyethylene glycol, polypropylene glycol and polybutylene glycol.
    [11]
    11. Composition according to claim 6, characterized in that the composition further comprises one or more alkylene glycols selected from the group consisting of ethylene glycol, propylene glycol and butylene glycol.
    [12]
    12. Composition according to claim 6, characterized by the fact that the composition further comprises one or more members selected from the group consisting of buffers, flow aids, silicas, surfactants and
    Petition 870200005516, of 1/13/2020, p. 51/53
    [13]
    13. Composition, according to claim 6, characterized by the fact that the composition still comprises water, resulting in a liquid urea fertilizer.
    [14]
    14. Composition according to claim 6, characterized by the fact that said nitrogen fertilizer is combined with said fertilizer additive to make the fertilizer more effective when applied to the soil for plant growth, in which the additive of fertilizer reduces the hydrolysis of urea to ammonia, thereby reducing ammonia losses to an atmosphere improving nitrogen retention in the soil.
    [15]
    15. Composition according to claim 6, characterized by the fact that the composition comprises 2 quarters of the liquid fertilizer additive per ton of urea.
    [16]
    16. Composition, characterized by the fact that it comprises: a. a nitrogen fertilizer composed of urea and one or more members selected from the group consisting of a) urea formaldehyde polymer and b) dicyandiamide, b. a liquid solution composed of a urease inhibitor that has been solubilized in an aprotic solvent, wherein said aprotic solvent comprises dimethyl sulfoxide, wherein the composition comprises 58.9 to 5% of said urease inhibitor and wherein said inhibitor of urease is N- (nbutyl) thiophosphoric triamide.
    [17]
    17. Composition according to claim 18, characterized by the fact that the composition further comprises one or more members selected from the group consisting of buffer, flow aids, silicas, surfactants and dyes / dyes.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112015007327B1|2020-05-19|compositions comprising nitrogen fertilizer, urease inhibitor and dimethyl sulfoxide
    AU2018222967B2|2020-06-18|Nitrification inhibitors designed for urea and manure based fertilizers
    US20200165174A1|2020-05-28|Compositons and methods comprising nitrification inhibitors containing a mixture of protic and aprotic solvent systems
    US8888886B1|2014-11-18|NBPT solutions for preparing urease inhibited urea fertilizers prepared from N-substituted morpholines
    ES2461146T3|2014-05-16|Liquid composition containing phosphoric or thiophosphoric triamide derivative and use thereof
    US9822044B2|2017-11-21|Urease inhibitor formulations
    US20210380496A1|2021-12-09|Liquid Formulations of Urease Inhibitors for Fertilizers
    US20190367426A1|2019-12-05|Liquid urease inhibitor formulations
    同族专利:
    公开号 | 公开日
    US11001537B2|2021-05-11|
    WO2014055132A1|2014-04-10|
    US20140090432A1|2014-04-03|
    US10301231B2|2019-05-28|
    CA2884699A1|2014-04-10|
    US20200346990A1|2020-11-05|
    US20180044255A1|2018-02-15|
    CO7350649A2|2015-08-10|
    EP2903993A1|2015-08-12|
    MX368841B|2019-10-18|
    PH12015500714B1|2015-05-18|
    AU2013325242B2|2018-08-02|
    US20200277242A1|2020-09-03|
    US20170297970A1|2017-10-19|
    US11198653B2|2021-12-14|
    US10597338B2|2020-03-24|
    US20200308075A1|2020-10-01|
    CN104781265A|2015-07-15|
    US20200189990A1|2020-06-18|
    CN104781265B|2018-01-02|
    US10221108B2|2019-03-05|
    US11021414B2|2021-06-01|
    PE20150766A1|2015-06-04|
    AU2013325242A1|2015-04-09|
    CA2884699C|2019-03-19|
    US20190202754A1|2019-07-04|
    PH12015500714A1|2015-05-18|
    MX2015004020A|2016-08-18|
    US9732008B2|2017-08-15|
    JP6685257B2|2020-04-22|
    EP2903993A4|2016-06-15|
    JP2015533769A|2015-11-26|
    JP2017149642A|2017-08-31|
    JP6126227B2|2017-05-10|
    US10329208B2|2019-06-25|
    US20180044256A1|2018-02-15|
    CL2015000808A1|2015-07-31|
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    法律状态:
    2018-12-04| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-10-15| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-03-10| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-05-19| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 08/05/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    2020-12-08| B17A| Notification of administrative nullity (patentee has 60 days time to reply to this notification)|Free format text: REQUERENTE DA NULIDADE: RHODIA OPERATIONS - 870200118906 - 23/9/2020 |
    2021-04-20| B09W| Correction of the decision to grant [chapter 9.1.4 patent gazette]|Free format text: REFERENCIA: RPI 2566 DE 10.03.2020 - CODIGO 9.1 |
    优先权:
    申请号 | 申请日 | 专利标题
    US201261708105P| true| 2012-10-01|2012-10-01|
    PCT/US2013/040199|WO2014055132A1|2012-10-01|2013-05-08|Improved liquid formulations of urease inhibitors for fertilizers|
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