MX2008009664A - Preparations with improved urease-inhibiting effect and urea-containing fertilizers containing the latter - Google Patents

Abstract

The invention relates to preparations with improved urease-inhibiting effect which comprise at least two different (thio)phosphoric triamides, and urea-containing fertilizers which include these preparations. The invention further relates to a method for producing these preparations, the use of these preparations in the application of urea-containing fertilizers, and the use of urea-containing fertilizers which include these preparations in agriculture or in horticulture.

Description

PREPARATIONS WITH IMPROVED INHIBITOR OF UREASA IMPROVED AND FERTILIZERS CONTAINING UREA CONTAINING THEMSELVES.

Description The invention relates to preparations with improved urease inhibitory effect, which contain at least two different triods of (thio) phosphoric acid, as well as to urea-containing fertilizers, which comprise these preparations. Furthermore, the invention relates to a process for obtaining these preparations, to the use of these preparations in fertilization with urea-containing fertilizers, as well as to the use of urea-containing fertilizers, which comprise these preparations, in agriculture or in horticulture .

The higher amount of nitrogen used for fertilization predominantly in the form of urea or fertilizers containing urea is generally used throughout the world. But urea itself is a form of nitrogen that is not absorbed or hardly absorbed, since urea is rapidly hydrolyzed in the soil by the enzyme contained therein, urease, in ammonia and carbon dioxide (Mobley, HLT, Island, MD, Hausinger , RP (1995) Molecular biology of microbial ureases, Microbiol Rev. 59, 452-480). In this process, gaseous ammonia is released into the atmosphere under certain circumstances, which is no longer available in the soil for plants, a phenomenon that reduces the efficiency of fertilization.

It is known to improve the use of nitrogen when fertilizers containing urea are used, applying fertilizers containing urea together with substances, capable of reducing or inhibiting the enzymatic separation of urea (Kiss, S., Simhaiian, M. (2002) Improving Efficiency of Urea Fertilizers by Inhibition of Soil Ureaase, ISBN 1-4020-0493-1, Kluwer Academic Publishers , Dordrecht, The Netherlands). The most potent urease inhibitors known are N-alkylthiophosphoric acid triamides and N-alkylphosphoric acid triamides, which are described, for example, in EP 0 119. However, one application of these urease inhibitors on large surfaces was affected. because of the relatively high manufacturing prices or because the required application quantities were too high.

The invention aims to improve the utilization of nitrogen when urease inhibitors are used in urea fertilization or urea-containing fertilizers. Another task is to reduce the amounts of application required in urease inhibitors.

Surprisingly, it has been found, that when using preparations, which contain at least two different triamides of (thio) phosphoric acid, it is possible to reduce the losses of gaseous ammonia more strongly after having applied urea or fertilizers containing urea, that when applies the same amount of a triamide of acid (thio) phosphoric by itself. The object is thus reached by means of preparations with improved urease inhibiting effect, which contain at least two different triamide (thio) phosphoric acid.

Thus, the object of the invention is a preparation, which contains at least two triamides of different (thio) phosphoric acid with structures according to the general formula (I), wherein X is oxygen or sulfur, Ri represents a d-Cio-alkyl, C3-Cio-cycloalkyl, C6-Cio-aryl or dialkylaminocarbonyl group and R2 is hydrogen, or R1 and R2 form together with the nitrogen atom joins a saturated or unsaturated heterocyclic radical with five or six members, which may optionally still contain one or two additional heteroatoms, selected from the group, comprising nitrogen, oxygen and sulfur, which differ in at least one of the radicals R1 or R2.

Examples of alkyl groups are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tere-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl and isodecyl. Cycloalkyl groups are, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclooctyl, aryl groups are, for example, phenyl or naphthyl. Examples of heterocyclic radicals R 1 R 2 N- are piperazinyl, morpholinyl, pyrrolyl, pyrazolyl, triazolyl, oxazolyl, thiazolyl or midazolyl groups.

Such compounds are known, for example from EP 0 119 487, WO 00/58317 and EP 1 183 220 as urease inhibitors.

Especially preferred are the N-alkylthiophosphoric acid triamides (with X = S and R2 = H) and the N-alkylphosphoric acid triamides (with X = O and R2 = H).

Such urease inhibitors can be prepared, eg by known methods from thiophosphoryl chloride, primary or secondary amines and ammonia, as described, for example, in US 5,770,771. Here, the thiophosphoryl chloride is initially reacted with an equivalent of a primary or secondary amine, in the presence of a base, and then the product is transformed with an excess of ammonia in the final product.

The preparations according to the invention contain at least two different derivatives of the general formula (I), which must be differentiated in at least one of the radicals Ri or R2. For example, a preparation according to the invention contains the active ingredients triamide of N-n-butylthiophosphoric acid (NBTPT) and triamide of N-n-propylthiophosphoric acid (NPTPT). Each of the active ingredients is contained in the preparation in at least 0.01% by weight and, at most, 99.99% by weight, with respect to the total amount of the active ingredients in the preparation. Preferably, the different active ingredients are contained in an amount of 20 to 40% by weight or 60 to 80% by weight.

Preferred are preparations, which contain N-n-butylthiophosphoric acid triamide (NBTPT) as one of the active ingredients. The at least one other active ingredient is preferably a derivative selected from the group, which comprises: N-cyclohexyl acid triamide, N-pentyl- triamide, N-iso-butyl- and N-triamide acid triamide. -propylphosphoric and -thiophosphoric. Especially preferred are those preparations containing NBTPT in quantities of 40 to 95% by weight, in particular 60 to 80% by weight, in each case with respect to the total amount of active ingredient.

It is known that the thiophosphoric acid triamides can be hydrolyzed relatively easily in the corresponding phosphoric acid triamides. Since moisture generally can not be completely excluded, the thiophosphoric acid triamide and the corresponding phosphoric acid triamide are often present as mixtures with each other. Thus, the term "thiophosphoric acid triamide" refers to both the thiophosphoric acid triamides or pure phosphoric acid triamides and their mixtures.

The preparations according to the invention can consist either of the pure active compound mixtures or can also be present in the form of liquid or solid formulations. Liquid formulations may contain, in addition to the mixture of active principles, still solvents, such as water, alcohols, glycols or amines, as well as their mixtures, in an amount of approx. 1 to approx. 80% by weight. Examples of suitable liquid formulations of (thio) phosphoric acid triamides are found in WO 97/22568, to which reference is made in its entirety. Solid formulations may contain, in addition to the mixture of active ingredients, still additives, binders or granulation aids, for example, lime, gypsum, silicon dioxide or kaolinite, in an amount of ca. 1 to approx. 95% by weight. Preparations according to the invention can comprise, in addition to the mixture of active ingredients, also simultaneously solvents or mixtures of solvents and additives, as well as being present as a suspension.

The preparations according to the invention, which contain at least two different triods of (thio) phosphoric acid, can be prepared, for example, by mixing two or more individual active principles synthesized separately. Another possibility consists in using in the first stage of the synthesis described above a mixture of at least two primary and / or secondary amines, so that after the transformation with ammonia in the second stage, a mixture of at least two (thio) -phosphoric acid triamides is obtained directly as a product. Another object of the invention is, therefore, a process for obtaining preparations with improved urease inhibitory effect, or by mixing at least two triamides of (thio) -phosphoric acid synthesized separately, or by transforming thiophosphoryl chloride with a mixture of at least two different primary and / or secondary amines and then with ammonia, directly obtaining a product with the composition according to the invention. Thus, it can be obtained by reacting a mixture of, for example, two primary amines, such as n-butylamine and n-propylamine with thiophosphoryl chloride and subsequently reacting with ammonia directly a mixture of NBTPT and NPTPT. The resulting quantitative ratio of the two products corresponds here, as a rule, to that of the amines used, provided that the reaction rates of the two amines are comparable.

Another object of the invention is a urea-containing fertilizer, which comprises a preparation according to the invention, which contains at least two different triods of acid (thio) phosphoric with structure according to the general formula (I).

Under a fertilizer containing urea is understood, first, the urea itself. As the usual market for fertilizers, the urea has a purity of at least 90% and may be present, for example, in crystalline, granulated, compacted or milled form. Additionally, mixtures of urea with one or more other nitrogen fertilizers, such as ammonium sulfate, ammonium chloride, cyanamide, dicyanamide or calcium nitrate, as well as slow-acting fertilizers, for example, condensates of urea-formaldehyde, may be included. , urea-acetaldehyde or urea-glyoxal. In addition, fertilizers containing urea of multiple nutrients are also included, which in addition to nitrogen still contain at least one additional nutritive substance, such as, for example, phosphorus, potassium, magnesium, calcium or sulfur. Additionally, the trace elements boron, iron, copper, five, manganese or molybdenum may also be contained. Such fertilizers containing urea of multiple nutrients may also be present in granulated, compacted, milled or crystalline form. In addition, liquid fertilizers containing urea, such as ammonium-urea nitrate solution or semi-liquid fertilizers are also included. Urea-containing fertilizers may additionally contain one or more other active ingredients, such as nitrification inhibitors, herbicides, fungicides, insecticides, growth regulators, hormones, pheromones or other phytosanitary products or soil aids in an amount of 0.01 to 20% by weight.

The fertilizers according to the invention are prepared either by mixing at least two different triamides of (thio) phosphoric acid separately or by the preparations containing at least two different triamide (thio) phosphoric acid or in liquid or solid form with the fertilizers containing urea, or granulating or compacting them in them by adding them to a corresponding mixture of fertilizers or a macerated mixture or suspension. In addition, at least two different triamides of (thio) phosphoric acid or preparations containing at least two different triamides of (thio) phosphoric acid on the surface of granules or compacted ready-mixed fertilizers containing urea can be applied. example, by spraying, dusting or impregnation. This can also be done using other auxiliary substances, such as adherent agents or materials of. Suitable apparatuses for this application are, for example, plates, drums, mixers or fluidized bed apparatuses, but the application can also be carried out on conveyor belts or their unloading places or by means of pneumatic conveyors for solids.

The total amount of triamides of (thio) -phosphoric acid contained in the fertilizers according to the invention is, as a rule, between 0.001 and 0.5% by weight, preferably between 0.01 and 0.3% by weight, very preferably, between 0.02 and 0.2% by weight, each time with respect to the urea contained.

Another object of the invention is the use of these preparations, which contain at least two different triamides of acid (thio) phosphoric, in the fertilization with fertilizers containing urea. This use can be carried out by separately applying the urea-containing fertilizers described above, which contain minus two different triods of acid (thio) phosphoric, or by separately applying the preparations according to the invention on a surface for agricultural or horticultural use before or after the application of the corresponding fertilizers containing urea. In addition, the preparations according to the invention can also be applied in the form of additives to semi-liquid fertilizer or for the treatment of, for example, animal pens and fences to reduce odors.

Another object of the invention is the use of urea-containing fertilizers, which comprise a preparation, which contains at least two different triods of (thio) phosphoric acid with structures according to the general formula (I), in agriculture or in the horticulture.

The following examples illustrate the invention in more detail.

Examples The effectiveness of (thio) -phosphoric acid triamides alone or in combination was examined in analogy to the Fenn & Kissel ((1973) Ammonia volatilized from surface applications of ammonium compounds on calcareous soils, Soil Sci. Soc. Am. J. 37, 855-859) as to its influence to reduce the losses of volatile ammonia of urea or fertilizers containing urea . Three different soils were used, in which volatile ammonia losses after fertilization with urea are highly marked. These soils are notable for presenting relatively high pH values of > 6.5 and / or a reduced basic tamponing. Due to the reduced basic buffering the pH value of the soil around the urea granule is increased due to the ammonia that it is formed in equilibrium with an ammonium hydroxide formation, which in turn displaces the equilibrium between NH3 + H2O < ? NH4 + + OH- in favor of gaseous ammonia. 200 g of dry soil with 5.4 ml of completely desalted water were moistened by incubation vessel and 1.087 g of urea (equivalent to 500 mg of urea-N) were applied as granules. When solutions containing urea were examined, then the 200 g of the soil was moistened with an aqueous solution containing urea, containing 1,630 g of urea (equivalent to 750 mg of urea-N), without or with urease inhibitor or combinations thereof. same. The solution was applied by distributing it with a pipette in drops on the surface of the floor. The amount of triamides of (thio) -phosphoric acid as individual substances or in combination in different percentages always amounted uniformly to 0.125% (w / w), with respect to urea. Incubations were performed at 20 ° C (18-22 ° C) in a climatic chamber. The ammonia collected in the acid trap was quantified as ammonium by a Continuous Flow Analyzer (Cía Bran + Luebbe) according to the methods known to the expert.

Characteristic data of soils: Soils pH Distribution of grain size Organic substance. (CaC)% sand% silt% clay% carbon Limburgerhof 6,8 73 16 11 < 1 Hannover 7.5 32 47 20 1 France 7.6 31 23 36 10 Results: Tables 1 to 4 show the losses of NH3 after a ten-day incubation of granulated urea without and with the addition of (thio) -phosphoric acid triamides by themselves and in combination with each time NBTPT. It is observed that the effect of NBTPT is markedly improved when 20 to 40 parts by weight of NBTPT are replaced by NcHTPT, NPenTPT, NiBTPT or NPTPT.

Tables 4, 9 and 10 show the results for the analogous tests with the combination of the active ingredients NBTPT and NPTPT on three different soils. The improved effect of the combinations according to the invention is manifested in all three soils.

Tables 5 to 8 show the results of the analogous tests with urea solution. It is observed that the level of ammonia losses without urease inhibitor is lower than in the case of granulated urea and corresponds, depending on the test series, to only 11 to 28% of the amount of nitrogen fertilized in the form of urea, while in case of granulated urea it amounted to approx. 39% This is because the urea solution has penetrated into the soil and the negatively charged components of the soil have increasingly removed ammonium ions from the equilibrium of NH3"? · NhU *. Another factor that determines ammonia losses is the movement of air. This is also smaller in the soil than on the surface of the soil.

The effect design of acid (thio) -phosphoric triamides with each other and the special efficiency of reducing ammonia losses also from a solution, when and 40% by weight of the amount of NBTPT are replaced by NPenTPT, NiBTPT or NPTPT is also observed in this case.

Tables 11 and 12 show the results of the comparative tests with the active compound combinations that do not correspond to the invention from NBTPT and triamide of α, β-Di-n-butyl-thiophosphoric acid (Table 11) or NBTPT and?,? - Di-isobutyl-thiophosphoric acid triamide (Table 12). With these mixtures no improvement of the effect is achieved.

Table 1: Volatile nitrogen losses after a ten-day incubation of granulated urea without and with the addition of urease inhibitors NBTPT and N-cyclohexyl thiophosphoric acid triamide (NcHTPT) and their combination in Limburgerhof soil Table 2: Losses of volatile nitrogen after ten days of incubation of granulated urea without and with the addition of urease inhibitors NBTPT and N-pentyl-phosphoric acid triamide (NPenTPT) and their combination in Limburgerhof soil Table 3: Losses of volatile nitrogen after ten days of incubation of granulated urea without and with the addition of urease inhibitors NBTPT and N-isobutylthiophosphoric triamide (NiBTPT) and their combination in Limburgerhof soil Table 4: Losses of volatile nitrogen after ten days of incubation of granulated urea without and with the addition of urease inhibitors NBTPT and N-propylthiophosphoric acid triamide (NPTPT) and their combination in Limburgerhof soil Table 5: Losses of volatile nitrogen after 10 days of incubation of 30% urea solution without and with the addition of urease inhibitors NBTPT and NcHTPT and their combination in Limburgerhof soil Table 6: Losses of volatile nitrogen after ten days of incubation of 30% solution of urea without and with the addition of urease inhibitors NBTPT and NPenTPT and their combination in Limburgerhof soil Table 7: Losses of volatile nitrogen after ten days of incubation of 30% solution of urea without and with the addition of urease inhibitors NBTPT and NiBTPT and their combination in Limburgerhof soil Table 8: Losses of volatile nitrogen after ten days of incubation of 30% solution of urea without and with the addition of urease inhibitors NBTPT and NPTPT and their combination in Limburgerhof soil Table 9: Losses of volatile nitrogen after ten days of incubation of granulated urea without and with the addition of urease inhibitors NBTPT and NPTPT and their combination in Hannover soil Table 10: Losses of volatile nitrogen after ten days of incubation of granulated urea without and with the addition of urease inhibitors NBTPT and NPTPT and their combination in soil of France Table 11: Losses of volatile nitrogen after ten days of incubation of 30% solution of urea without and with the addition of urease inhibitors NBTPT and triamide of α, β-di-n-butyl-thiophosphoric acid (NNDBTPT) and its combination in soil of Limburgerhof Table 12: Losses of volatile nitrogen after ten days of incubation of 30% solution of urea without and with the addition of urease inhibitors NBTPT and N, N-di-isobutyl-thiophosphoric acid triamide (NNDiBTPT) and their combination in Limburgerhof soil

Claims (2)

Claims

1. Preparations containing at least two different trioxide (thio) phosphoric acid with structures according to the general formula (I), wherein X means oxygen or sulfur, Ri is a Ci-Cio-alkyl, C3-Ci0-cycloalkyl, C6-Ci0-aryl or dialkylaminocarbonyl group and R2 is hydrogen, or R1 and R2 form together with the nitrogen atom that joins a saturated or unsaturated heterocyclic radical with five or six members, which may optionally still contain one or two additional heteroatoms, selected from the group, comprising nitrogen, oxygen and sulfur, which differ in at least one of the radicals R1 or R2.

2. Preparation according to claim 1, characterized in that one of the (thio) -phosphoric acid triamides is an N-alkyltriamide of (thio) -phosphoric acid and / or N-alkylphosphoric acid triamide. Preparation according to one of claims 1 or 2, characterized in that one of the (thio) -phosphoric acid triamides is a triamide of N-n-butylthiophosphoric acid. Preparation according to claim 3, characterized in that in addition to N-butylthiophosphoric acid triamide still contains at least one derivative selected from the group comprising: N-cyclohexyl acid triamide, N-pentyl- triamide, N-triamide acid iso-butyl- and triamide of N-propylphosphoric acid and -thiophosphoric acid. Preparation according to claim 4, characterized in that the triamide content of N-n-butylthiophosphoric acid amounts to 40 to 95% by weight, based on the total weight of all the triodal acid (thio) -phosphonic acid contained in the preparation. Process for obtaining preparations according to claim 1, characterized in that thiophosphoryl chloride is transformed with a mixture of at least two different primary and / or secondary amines and then with ammonia. Use of preparations according to claim 1 in fertilization with fertilizers containing urea. Fertilizer containing urea, characterized in that it comprises a preparation according to claim 1. Fertilizer containing urea according to claim 8, characterized in that the total content of triamides of (thio) -phosphoric acid, with respect to the urea contained, ranges between 0.001 and 0.5% by weight. Use of fertilizers containing urea according to claim 8 in agriculture or horticulture.