RU2811428C2 - Method of obtaining fertilizer composition based on urea containing urease inhibitor triamide (thio)phosphoric acid by providing liquid or solid premix with certain mass ratio - Google Patents

Abstract

FIELD: agriculture.

SUBSTANCE: invention relates to nitrogen-containing fertilizers. A method of producing a fertilizer composition includes: a) providing a solid and/or liquid premix (P), b) adding a premix (P) to a melt (Q) comprising a urea-containing fertilizer (1), by forming a mixture (M) comprising at least at least one urea-containing fertilizer (1) and at least one (thio)phosphoric acid triamide (2), and c) forming solid fertilizer granules by using a mixture (M) comprising at least one urea-containing fertilizer (1) and at least one (thio)phosphoric acid triamide (2), wherein the fertilizer composition contains (I) at least one urea-containing fertilizer (1); and (II) at least one (thio)phosphoric acid triamide (2), which is N-n-butylthiophosphoric acid triamide (NBPT), N-n-propylthiophosphoric acid triamide (NPPT), and a combination thereof. The premix (P) contains at least one urea-containing fertilizer (1) and at least one (thio)phosphoric acid triamide (2) in a mass ratio of 4:1-50:1, based on the total mass of all urea-containing fertilizers fertilizers (1) and all (thio)phosphoric acid triamides (2), and at least 85 wt.% of the premix (P) (a1) is not a melt; and (a2) is not obtained by melting any of at least one urea-containing fertilizer (1) or melting any of at least one (thio)phosphoric acid triamide (2); and (a3) is prepared by dissolving or mixing at least one (thio)phosphoric acid triamide (2) in a solvent (S) having a boiling point above 100°C, where the solvent (S) contains an amine. The time provided to the mixture (M) before granulation is adjusted so that at least one (thio)phosphoric acid triamide (2) is not decomposed or almost not decomposed in the mixture (M).

EFFECT: proposed method of producing a fertilizer composition ensures resistance to premature decomposition of fertilizers containing urea and increases their shelf life.

11 cl, 3 tbl, 3 ex

Description

The present invention relates to a method for producing at least one urea-based fertilizer composition by providing a liquid or solid premix comprising a urea-containing fertilizer and a urease inhibitor (thio)phosphoric acid triamide, in certain weight ratios, and by adding this premix to the melt fertilizers that contain urea.

Worldwide, the predominant and increasing amount of nitrogen used for fertilization is in the form of urea or urea-containing fertilizer. However, urea itself is a form of nitrogen that is absorbed very little, if at all, being hydrolyzed relatively quickly by the enzyme urease, which is ubiquitous in soil, to produce ammonia and carbon dioxide. In this process, under certain circumstances, ammonia gas is released into the atmosphere and is thus no longer available in the soil for plants, thereby reducing the effectiveness of fertilization.

It is known that the nitrogen utilization rate of urea-containing fertilizers can be improved by applying the urea-containing fertilizer together with substances that are capable of inhibiting or reducing the enzymatic breakdown of urea (for an overview, see Kiss, S. Simihaian, M. (2002) Improving Efficiency of Urea Fertilizers by Inhibition of Soil Urease Activity, ISBN 1-4020-0493-1, Kluwer Academic Publishers, Dordrecht, The Netherlands).

The most potent urease inhibitors known include N-alkylthiophosphoric acid triamides and N-alkylphosphoric acid triamides, which are, for example, described in EP 0119487.

In addition, mixtures of N-alkylthiophosphoric acid triamides such as N-(n-butyl)thiophosphoric acid triamide (NBPT) and N-(n-propyl)thiophosphoric acid triamide (NPPT) can be used. The mixtures and their preparation are described, for example, in US 2010/218575 A1.

These urease inhibitors are, for example, described in US Pat. No. 4,530,714. In order for this class of compounds to be able to act as a urease inhibitor, conversion to the appropriate oxo form must first occur. This form subsequently reacts with urease, causing its inhibition.

It is recommended that urease inhibitors be applied with urea to or into the soil as this ensures that the inhibitor, along with the fertilizer, comes into contact with the soil. The urease inhibitor may be included in the urea, for example by dissolving it in the urea melt before granulating or prilling the urea. A method of this type is described, for example, in US Pat. No. 5,352,265. An additional option is to apply the urease inhibitor to the urea granules or prills, for example in the form of a solution. Suitable application methods as well as suitable solvents are described, for example, in US 2010/218575 A1.

On the one hand, it is known from the prior art that the shelf life of a urease inhibitor during storage is limited in the presence of urea-containing fertilizer. The higher the temperature, the shorter the shelf life. If, for example, urea is stored in a tropical climate, the bulk of the urease inhibitor will degrade, usually after about four weeks of storage.

Degradation of (thio)phosphoric acid triamide inhibitor is a known phenomenon that occurs during fertilizer storage. Slowing down the rate of decomposition allows the active material to be retained without loss of effectiveness and thus provides an economic advantage. The potential use of certain urease inhibitors is defined in Europe by the European Fertilizer Regulation CE 2003/2003 in its latest version of 15 December 2014. This regulation defines approved inhibitors as the acceptable minimum and maximum concentrations of NBPT in a urea-containing fertilizer. Thus, the rate of decomposition determines the shelf life of the fertilizer until the presence of the urease inhibitor can no longer be required. Because decomposition occurs and there are regulatory limits, the exact amount of urease inhibitor added to the fertilizer is important. Also, the exact amount of addition allows the amount of inhibitor to be adjusted to the desired concentration, in order to obtain either a long shelf life (concentration close to the upper regulatory limit) or a more cost-effective product (concentration close to the lower regulatory limit), depending from the desired storage time.

To address this problem of degradation and stability, WO 2015/062667 discloses a composition containing a urease inhibitor (thio)phosphoric acid triamide in combination with a functionalized amine to increase the stability and shelf life of (thio)phosphoric acid triamide urease inhibitors in the presence of urea-containing fertilizers .

US 2011/0154874 A1 discloses amine additives selected from methyldiethanolamine, tetrahydroxypropylethylenediamine, trimethylaminoethylethanolamine, N,N,N',N'-tetramethyl-1,6-hexanediamine, N,N',N''-tris(dimethylaminopropyl) hexahydrotriazine, and 2,2'-dimorpholinyl diethyl ether

On the other hand, it is also known from the prior art that the use of urease inhibitors of (thio)phosphoric acid triamides, such as N-n-butylthiophosphoric acid triamide (NBPT), is associated with some difficulties and problems associated with processing and the exact amount of addition, because NBPT is a sticky, waxy compound, sensitive to water and heat, and has a solid flow parameter that is unfavorable for precise direct addition of NBPT to urea-based fertilizers.

To solve this problem, WO 2017/125383 discloses a method for producing a urea fertilizer composition containing at least one (thio)phosphoric acid triamide urease inhibitor, which includes the steps of: a) providing at least one first melt containing at least one urease inhibitor at a temperature T1 at which the degradation of at least one urease inhibitor is completely or almost completely inhibited; b) providing at least one second melt of temperature T2 containing urea and/or at least one urea derivative; c) adding at least one first melt of at least one urease inhibitor to at least one second urea melt and/or at least one urea derivative by forming a mixture, wherein the residence time of the mixture thus formed before granulation is adjusted so that at least one urease inhibitor was not degraded or almost not degraded in the mixture; and d) forming solid fertilizer granules by using a mixture of at least one urease inhibitor and urea and/or at least one urea derivative. However, according to the method disclosed in WO 2017/125383, the (thio)phosphoric acid triamide urease inhibitor will be exposed to high temperatures in the first melt described in step a), which will affect the stability of the (thio)phosphoric acid triamide urease inhibitor later stages of the said process and will also later affect its stability in the ultimately obtained granules.

Therefore, it was an object of the present invention to provide a method for preparing a urea fertilizer composition containing at least one (thio)phosphoric acid triamide urease inhibitor, by which the stability of the (thio)phosphoric acid triamide urease inhibitor during the steps of the said method can be improved. , as well as its stability in the ultimately obtained granules, compared to prior art methods. It was further an object of the present invention to provide a method for preparing a urea fertilizer composition containing at least one (thio)phosphoric acid triamide urease inhibitor which has at least one of the following characteristics:

(I) more precise (direct) addition of the urease inhibitor (thio)phosphoric acid triamide to the urea-based fertilizer melt,

(II) better miscibility of the urease inhibitor (thio)phosphoric acid triamide with urea-based fertilizer melt,

(III) avoiding the use of low-boiling (e.g., boiling point below 100°C) solvents intended to dissolve the urease inhibitor (thio)phosphoric acid triamide,

(IV) improved processing of the urease inhibitor (thio)phosphoric acid triamide,

(v) providing a ready-to-use premix that can be stored and transported and directly added to the urease inhibitor melt.

Taking into account the above objects, the present invention relates to a method for producing

fertilizer composition containing

(I) at least one urea-containing fertilizer (1); And

(II) at least one (thio)phosphoric acid triamide (2) according to general formula (I)

wherein

X ¹ represents O or S;

R ¹ represents C ₁ -C ₂₀ -alkyl, C ₃ -C ₂₀ -cycloalkyl, C ₆ -C ₂₀ -aryl, C ₆ -C ₂₀ -aryl-C ₁ -C ₄ -alkyl, or C ₁ -C ₆ -(di)alkylaminocarbonyl;

R ² represents H, C ₁ -C ₂₀ -alkyl, C ₃ -C ₂₀ -cycloalkyl, C ₆ -C ₂₀ -aryl, C ₆ -C ₂₀ -aryl-C ₁ -C ₄ -alkyl, or C ₁ - C ₆ -(di)alkylaminocarbonyl; or

R ¹ and R ² together with the nitrogen atom linking them define a 5- or 6-membered saturated or unsaturated heterocyclic radical which optionally contains 1 or 2 additional heteroatoms selected from the group consisting of N, O, and S; And

R ³ , R ⁴ , R ⁵ , and R ⁶ are independently selected from the group consisting of H and C ₁ -C ₄ alkyl;

which includes stages:

a) providing solid and/or liquid premix (P),

wherein the premix (P) includes at least one urea-containing fertilizer (1) and at least one (thio)phosphoric acid triamide (2) in a mass ratio of 1:6 - 400:1, based on the total weight of all urea-containing fertilizers fertilizers (1) and all (thio)phosphoric acid triamides (2),

with at least 85 wt. % premix (P)

(a1) is not a melt; And

(a2) is not obtained by melting any of at least one urea-containing fertilizer (1) or melting any of at least one (thio)phosphoric acid triamide (2); And

(a3) is not prepared by dissolving at least one (thio)phosphoric acid triamide (2) in a solvent having a boiling point of less than 100° C., and

b) adding a premix (P) to a melt (Q) that includes a urea-containing fertilizer (1), by forming a mixture (M) that includes at least one urea-containing fertilizer (1) and at least one triamide (thio) phosphoric acid (2), wherein the residence time of the mixture (M) thus formed before granulation is adjusted so that at least one (thio)phosphoric acid triamide (2) is not decomposed or almost not decomposed in the mixture (M); And

c) forming solid fertilizer granules by using a mixture (M) that includes at least one urea-containing fertilizer (1) and at least one (thio)phosphoric acid triamide (2).

In the present patent application, at least one urease inhibitor (thio)phosphoric acid triamide (2) according to general formula (I) is referred to as "TPT". In the present invention patent application, the melt (Q) which includes the urea-containing fertilizer (1) is referred to as “urea melt (Q)” or “melt (Q)”. In the present invention patent application, a premix (P) which includes at least one urea-containing fertilizer (1) and at least one (thio)phosphoric acid triamide (2) in a certain ratio as defined above is used in the present invention, is referred to as “TPT-containing premix (P)” or “premix (P)”. In this invention patent application, percentages by weight are referred to as “wt.%”.

In a preferred embodiment of the present invention, the premix (P) is liquid.

In another preferred embodiment of the present invention, the premix (P) is solid.

In another preferred embodiment of the present invention, the premix (P) is partly solid and partly liquid. The weight ratio between the solid portion of the premix (P) and the liquid portion of the premix (P) is preferably in the range of 1 wt. % - 99 wt. %, more preferably in the range of 10 wt. % - 90 wt. %, most preferably in the range of 20 wt. % - 80 wt. %, especially preferably in the range of 25 wt. % - 75 wt. %, in particular, more preferably in the range of 30 wt. % - 70 wt. %, in particular in the range of 35 wt. % - 65 wt. %, especially preferably in the range of 40 wt. % - 60 wt. %, in particular, most preferably in the range between 45 wt. % and 55 wt. %, based on the total mass of the premix (P).

In a preferred embodiment of the present invention, the premix (P)

(a1) is not essentially a melt; And

(a2) is not substantially prepared by melting any of at least one urea-containing fertilizer (1) or melting any of at least one (thio)phosphoric acid triamide (2); And

(a3) is not substantially prepared by dissolving or mixing at least one (thio)phosphoric acid triamide (2) in a solvent/solvent (S) having a boiling point of less than 100°C.

In another preferred embodiment of the present invention, the premix (P)

(a1) is not essentially a melt; And

(a2) is not substantially prepared by melting any of at least one urea-containing fertilizer (1) or melting any of at least one (thio)phosphoric acid triamide (2); And

(a3) is not substantially prepared by dissolving or mixing at least one (thio)phosphoric acid triamide (2) in a solvent/solvent (S) having a boiling point of less than 120° C., preferably less than 140° C, more preferably less than 160°C, most preferably less than 180°C, especially preferably less than 200°C, in particular more preferably less than 220°C, in particular less than 240°C.

In another preferred embodiment of the present invention, at least 85 wt. % premix (P), preferably at least 88 wt. % premix (P), more preferably at least 90 wt. % premix (P), most preferably at least 92 wt. % premix (P), especially preferably at least 94 wt. % premix (P), in particular, more preferably at least 95 wt. % premix (P), in particular, most preferably at least 96 wt. % premix (P), for example, preferably at least 97 wt. % premix (P), for example, more preferably at least 98 wt. % premix (P), for example, most preferably at least 99 wt. % premix (P), for example, most preferably at least 99.5 wt. % premix (P), for example at least 99.9 wt. % premix (P)

(a1) is not a melt; And

(a2) is not obtained by melting any of at least one urea-containing fertilizer (1) or melting any of at least one (thio)phosphoric acid triamide (2); And

(a3) is not prepared by dissolving or mixing at least one (thio)phosphoric acid triamide (2) in a solvent/solvent (S) having a boiling point of less than 100°C.

In another preferred embodiment of the present invention, at least 85 wt. % premix (P), preferably at least 88 wt. % premix (P), more preferably at least 90 wt. % premix (P), most preferably at least 92 wt. % premix (P), especially preferably at least 94 wt. % premix (P), in particular, more preferably at least 95 wt. % premix (P), in particular, most preferably at least 96 wt. % premix (P), for example, preferably at least 97 wt. % premix (P), for example, more preferably at least 98 wt. % premix (P), for example, most preferably at least 99 wt. % premix (P), for example, most preferably at least 99.5 wt. % premix (P), for example at least 99.9 wt. % premix (P)

(a1) is not a melt; And

(a2) is not obtained by melting any of at least one urea-containing fertilizer (1) or melting any of at least one (thio)phosphoric acid triamide (2); And

(a3) is not prepared by dissolving or mixing at least one (thio)phosphoric acid triamide (2) in a solvent/solvent (S) having a boiling point of less than 120°C, preferably less than 140°C, more preferably less than 160°C, most preferably less than 180°C, especially preferably less than 200°C, in particular more preferably less than 220°C, in particular less than 240°C.

"Melt" means changing the state of a substance from a solid to a liquid without the addition of additives such as solvents.

In another preferred embodiment of the present invention, the mass ratio between at least one urea-containing fertilizer (1) and at least one (thio)phosphoric acid triamide (2) in the premix, which is provided in step a) of the method in accordance with the method according to of the present invention - based on the total weight of all urea-containing fertilizers (1) and all (thio)phosphoric acid triamides (2) - preferably at least 1:5, more preferably at least 1:4, most preferably at least 1 :3, particularly preferably at least 1:2, in particular more preferably at least 1:1, in particular most preferably at least 2:1, in particular at least 3:1, for example preferably according to at least 4:1, for example, more preferably at least 5:1, for example, most preferably at least 6:1, for example, in particular at least 8:1, for example at least 10:1, for example , preferably at least 12:1, for example more preferably at least 14:1, for example most preferably at least 16:1, for example, in particular at least 18:1, for example, particularly preferably at least 20:1, for example at least 22:1.

In another preferred embodiment of the present invention, the mass ratio between at least one urea-containing fertilizer (1) and at least one (thio)phosphoric acid triamide (2) in the premix, which is provided in step a) of the method in accordance with the method according to of the present invention - based on the total weight of all urea-containing fertilizers (1) and all (thio)phosphoric acid triamides (2) - preferably not more than 300:1, more preferably not more than 200:1, most preferably not more than 150:1, particularly preferably not more than 100:1, in particular more preferably not more than 80:1, in particular most preferably not more than 70:1, in particular not more than 60:1, for example, preferably not more than 50:1, for example more preferably not more than 45:1, for example, most preferably not more than 40:1, for example, in particular, not more than 35:1, for example, not more than 30:1, for example, preferably not more than 27:1, for example, more preferably not more than 23:1, for example, most preferably not more than 19:1, for example, in particular not more than 15:1, for example, especially preferably not more than 11:1, for example not more than 7:1.

In another preferred embodiment of the present invention, the mass ratio between at least one urea-containing fertilizer (1) and at least one (thio)phosphoric acid triamide (2) in the premix, which is provided in step a) of the method in accordance with the method according to of the present invention - based on the total weight of all urea containing fertilizers (1) and all (thio)phosphoric acid triamides (2) is preferably in the range of 1:5 - 300:1, more preferably in the range of 1:4 - 200 :1, most preferably in the range of 1:3 - 150:1, especially preferably in the range of 1:2 - 100:1, in particular, more preferably in the range of 1:1 - 80:1, in particular , most preferably in the range of 2:1 - 70:1, in particular in the range of 3:1 - 60:1, for example, preferably in the range of 4:1 - 50:1, for example, more preferably in range of 5:1 - 45:1, for example, most preferably in the range of 8:1 - 40:1, for example in the range of 10:1 - 35:1, for example, preferably in the range of 14: 1 - 30:1, for example, more preferably in the range of 18:1 - 27:1, for example in the range of 23:1 - 27:1.

In yet another preferred embodiment of the present invention, the weight ratio between at least one urea-containing fertilizer (1) and at least one (thio)phosphoric acid triamide (2) in the premix which is provided in process step a) in accordance with the method according to the present invention - based on the total weight of all urea-containing fertilizers (1) and all (thio)phosphoric acid triamides (2) is preferably in the range of 1:2 - 19:1, more preferably in the range of 1:1 - 15:1, most preferably in the range of 2:1 - 11:1, especially preferably in the range of 3:1 - 7:1.

In yet another preferred embodiment of the present invention, the at least one urea-containing fertilizer (1) which is contained in the premix (P) has an average particle size in the range of 0.0001-60 mm, preferably in the range of 0. 0005-20 mm, more preferably in the range of 0.001 to 6 mm, most preferably in the range of 0.005 to 4 mm, especially preferably in the range of 0.01-2 mm. In yet another preferred embodiment of the present invention, the at least one urea-containing fertilizer (1) contained in the premix (P) is urea and has an average particle size in the range of 0.0001-60 mm, preferably in the range 0.0005-20 mm, more preferably in the range of 0.001 to 6 mm, most preferably in the range of 0.005 to 4 mm, especially preferably in the range of 0.01-2 mm. Particle size can be determined by sieve analysis, laser diffraction, dynamic light scattering, or image analysis.

As used in this application, the term "(thio)phosphoric acid triamide" in each case covers thiophosphoric acid triamides and phosphoric acid triamides. Thus, the prefix "(thio)" used in this application in each case indicates that a P=S group or a P=O group is included. However, if the prefix "thio" is used without parentheses, it indicates that the group P=S is present.

It should be noted that the terms "(thio)phosphoric acid triamide" and "(thio)phosphoric triamide" can be used interchangeably.

As used in this application, the term "(thio)phosphoric acid triamides" can be represented by the following general formula (I)

wherein

X ¹ represents O or S;

R ¹ represents C ₁ -C ₂₀ -alkyl, C ₃ -C ₂₀ -cycloalkyl, C ₆ -C ₂₀ -aryl, C ₆ -C ₂₀ -aryl-C ₁ -C ₄ -alkyl, or C ₁ -C _b -(di)alkylaminocarbonyl;

R ² represents H, C ₁ -C ₂₀ -alkyl, C ₃ -C ₂₀ -cycloalkyl, C ₆ -C ₂₀ -aryl, C ₆ -C ₂₀ -aryl-C ₁ -C ₄ -alkyl, or C ₁ - C ₆ -(di)alkylaminocarbonyl; or

R ¹ and R ² together with the nitrogen atom linking them define a 5- or 6-membered saturated or unsaturated heterocyclic radical which optionally contains 1 or 2 additional heteroatoms selected from the group consisting of N, O, and S; And

R ³ , R ⁴ , R ⁵ , and R ⁶ are independently selected from the group consisting of H and C ₁ -C ₄ alkyl.

The organic fragments mentioned in the variable definitions above are collective terms for individual lists of individual group members. The prefix C _n -C _m indicates in each case the possible number of carbon atoms in the group.

The term "alkyl" as used in this application in each case refers to a linear or branched alkyl group having typically 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, often 1 to 6 carbon atoms, more preferably 1- 4 carbon atoms, for example 3 or 4 carbon atoms. Examples of alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl- 1-methylpropyl, and 1-ethyl-2-methylpropyl. Preferred alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, hexyl, 2-methylpentyl, n-heptyl, n-octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, and isodecyl.

The term "cycloalkyl" as used in this application in each case denotes a monocyclic cycloaliphatic radical having generally from 3 to 20 carbon atoms, preferably from 3 to 10 carbon atoms, more preferably from 3 to 6 carbon atoms, such as cyclopropyl, cyclobutyl , cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl or cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

The term "aryl" includes mono-, bi- or tricyclic aromatic radicals typically having from 6 to 14, preferably 6, 10, or 14 carbon atoms. Exemplary aryl groups include phenyl, naphthyl and anthracenyl. As the aryl group, phenyl is preferred.

The term "arylalkyl" refers to aryl as defined above, which is linked via a C ₁ -C ₄ alkyl group, in particular a methyl group (=arylmethyl), to the rest of the molecule, examples include benzyl, 1-phenylethyl, 2-phenylethyl, etc.

The term "heterocycle" or "heterocyclyl" includes 5- or 6-membered monocyclic heterocyclic non-aromatic radicals. Heterocyclic non-aromatic radicals typically contain 1 or 2 heteroatoms selected from N, O and S as ring members, where the S ring member atoms may be present as S, SO or SO ₂ . Examples of 5- or 6-membered heterocyclic radicals contain saturated or unsaturated, non-aromatic heterocyclic rings such as oxiranyl, oxyethanyl, thiethanyl, thiethanyl-S-oxide (S-oxothiethanyl), thiethanyl-S-dioxide (S-dioxothiethanyl), pyrrolidinyl, pyrrolinyl, pyrazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1,3-dioxolanyl, thiolanyl, S-oxothiolanyl, S-dioxothiolanyl, dihydrothienyl, S-oxodihydrothienyl, S-dioxodihydrothienyl, oxazolidinyl, oxazolinyl, thiazolinyl, oxathiolanyl, piperidinyl, pi perazinil, pyranil, dihydropyranil, tetrahydropyranyl, 1,3- and 1,4-dioxanyl, thiopyranyl, S-oxothiopyranyl, S-dioxothiopyranyl, dihydrothiopyranyl, S-oxodihydrothiopyranyl, S-dioxodihydrothiopyranyl, tetrahydrothiopyranyl, S-oxotetrahydrothiopyranyl, S-dioxotetrahydrothiopyranyl, morpholinyl, thiomorpholinyl, S-oxothiomorpholinyl , S-dioxothiomorpholinyl, thiazinyl and the like. Preferred examples of heterocyclic radicals are piperazinyl, morpholinyl, pyrrolyl, pyrazolyl, triazolyl, oxazolyl, thiazolyl, and imidazolyl groups.

The term "(di)alkylaminocarbonyl" refers to a (di)alkylamino group, that is, an amino group containing 1 or 2 alkyl substituents, which is linked to the rest of the molecule through a carbonyl group carbon atom (C=O).

It should be understood that the term "(thio)phosphoric acid triamide" preferably also includes stereoisomers, tautomers, N-oxides, as well as salts of (thio)phosphoric acid triamides. Stereoisomers are present if compounds contain one or more chirality centers. In this case, the compounds will be present as different enantiomers or diastereomers if there is more than one center of chirality. The term "(thio)phosphoric acid triamide" preferably covers every possible stereoisomer, that is, individual enantiomers or diastereomers, as well as mixtures thereof. Tautomers, for example, include keto-enol tautomers. N-oxides can form under oxidative conditions if tertiary amine groups are present. Salts, for example, can be formed with the basic amino groups of (thio)phosphoric acid triamides. Anions derived from the acid with which the (thio)phosphoric acid amide can react are, for example, chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, as well as C ₁ -C ₄ -alkanoic acid anions, preferably format, acetate, propionate and butyrate.

In a preferred embodiment, (thio)phosphoric acid triamide (2) may be represented by the following general formula (I)

wherein

X ¹ represents O or S;

R ¹ represents C ₁ -C ₈ -alkyl, C ₅ -C ₆ -cycloalkyl, phenyl, or benzyl;

R ² represents H, or C ₁ -C ₄ -alkyl; And

^R3 , ^R4 , ^R5 , and ^R6 are each H.

Preferably, (thio)phosphoric acid triamide (2) may be represented by the above formula (I), in which

X ¹ represents S;

R ¹ represents C ₁ -C ₈ -alkyl, C ₅ -C ₆ -cycloalkyl, phenyl, or benzyl;

R ² represents H or C ₁ -C ₄ -alkyl; And

R ³ , R ⁴ , R ⁵ , and R ⁶ each represent H;

and in which it is even more preferable

X ¹ represents S;

R ¹ represents C ₁ -C ₈ -alkyl;

R ² represents H or C ₁ -C ₄ -alkyl; And

^R3 , ^R4 , ^R5 , and ^R6 are each H.

It should be understood that the term "(thio)phosphoric acid (2) triamide" may also cover combinations of (thio)phosphoric acid (2) triamides according to formula (I) as defined above.

In one embodiment of the invention, (thio)phosphoric acid triamide (2) is selected from the group consisting of

N-benzyl-N-methylthiophosphoric acid triamide, N,N-diethylthiophosphoric acid triamide, N-(n-butyl)thiophosphoric acid triamide, N-isopropylphosphoric acid triamide, N-(n-hexyl)thiophosphoric acid triamide, N-( sec-butyl)thiophosphoric acid, N,N-diethylphosphoric acid triamide, N-(n-propyl)thiophosphoric acid triamide, N,N-diisopropylthiophosphoric acid triamide, N,N-dimethyl-thiophosphoric acid triamide, N-(n- octyl)phosphoric acid, N-(n-butyl)phosphoric acid triamide, N-cyclohexylphosphoric acid triamide, N-benzyl-N-methylphosphoric acid triamide, N,N-dimethylphosphoric acid triamide, N-cyclohexylthiophosphoric acid triamide, and combinations thereof.

In one embodiment of the invention, the (thio)phosphoric acid triamide (2) is N-n-butylthiophosphoric acid triamide (NBPT), N-n-propylthiophosphoric acid triamide (NPPT), or a combination thereof.

In one preferred embodiment of the invention, (thio)phosphoric acid triamide (2) is N-n-propylthiophosphoric acid triamide (NPPT) having the following chemical formula:

In another preferred embodiment of the invention, (thio)phosphoric acid triamide (2) is N-n-butylthiophosphoric acid triamide (NBPT) having the following chemical formula:

In yet another preferred embodiment of the invention, (thio)phosphoric acid triamide (2) is a combination of N-n-butylthiophosphoric acid triamide (NBPT) and N-n-propylthiophosphoric acid triamide (NPPT). It is particularly preferred when the (thio)phosphoric acid triamide (2) is a combination of NBPT and NPPT, which contains NBPT in an amount ranging from 40 to 95 wt. %, more preferably from 60 to 85 wt. %, especially preferably from 72 to 80 wt. %, in each case, based on the total weight of the combination.

In connection with the above-defined process according to the invention, it is generally preferred when (thio)phosphoric acid triamide (2) is provided in combination with at least one amine having a boiling point of more than 100°C. In the present invention patent application, at least one amine having a boiling point of more than 100°C is referred to as "amine (4)". The amine (4) generally exhibits a stabilizing effect on (thio)phosphoric acid triamide (2) in terms of degradation caused by urea-containing fertilizer (1).

Thus, (thio)phosphoric acid triamide (2) is preferably provided in combination with (thio)phosphoric acid triamide (2) and amine (4).

In general, the amine(s) (4) can be any amine having a boiling point greater than 100°C, that is, any chemical compound having at least one amino group, including (but not limited to)

- primary, secondary, and tertiary amines,

- linear, branched, and cyclic amines,

- aliphatic and aromatic amines,

- monomeric, oligomeric and polymeric amines,

- biogenic and non-biogenic amines.

In a preferred embodiment of the invention, (thio)phosphoric acid triamide (2) is provided in combination with at least one amine (4) selected from the group consisting of

(4a) polymer polyamine; And

(4b) an amine containing no more than one amino group and at least three alkoxy- or hydroxy-substituted C ₂ -C ₁₂ alkyl groups R ²¹ , where at least one of the R ²¹ groups differs from the other R ²¹ groups; And

(4c) an amine containing no more than one amino group and at least two alkoxy- or hydroxy-substituted C ₂ -C ₁₂ alkyl groups R ²² , wherein at least one of the R ²² groups carries an alkoxy or hydroxy substituent at the secondary or a tertiary carbon atom, and where at least one of the R ²² groups is different from the other R ²² group(s); And

(4d) an amine containing at least one saturated or unsaturated C ₈ -C ₄₀ alkyl group R ²³ ; And

(4e) a saturated or unsaturated heterocyclic amine which contains at least one oxygen atom as a ring atom and which does not contain an additional alkoxy group; And

(4e) an amine having a boiling point of more than 100°C, preferably more than 150°C, more preferably more than 200°C at ambient pressure (1 bar), and

(4g) primary amine, and

(4h) secondary amine, and

(4i) tertiary amine,

(4k) an amine containing no more than one amino group and at least two alkoxy- or hydroxy-substituted C ₂ -C ₁₂ alkyl groups R ²² ,

(4l) an amine containing no more than one amino group and at least three alkoxy- or hydroxy-substituted C ₂ -C ₁₂ alkyl groups R ²² ,

(4m) an amine containing no more than one amino group and at least three alkoxy- or hydroxy-substituted C ₂ -C ₁₂ alkyl groups R ⁴¹ , all R ⁴¹ groups in said amine being identical, and

(4n) amine containing no more than one amino group and at least two alkoxy- or hydroxy-substituted C ₂ -C ₁₂ alkyl groups R ⁴² , and at least one of the R ⁴² groups carries an alkoxy or hydroxy substituent at the secondary or tertiary carbon atom and wherein all R ⁴² groups with said amine are identical, and

(4o) an amine selected from the group consisting of methyldiethanolamine, tetrahydroxypropylethylenediamine, trimethylaminoethylethanolamine, N,N,N',N' tetramethyl-1,6-hexanediamine, N,N',N''-tris(dimethylaminopropyl)hexahydrotriazine, and 2,2'-dimorpholinyl diethyl ether, and

(4p) amine selected from the group consisting of (L10), (L11), (L12), (L13), (L14), (L15), (L16), (L17), (L18), (L19) , (L20), (L21), (L22), (L23), (L24) and (L29), as disclosed in WO 2016/103168.

According to one embodiment, amine (4) is

(4a) polymer polyamine.

In general, (4a) can be any polymeric polyamine, and is preferably polyalkyleneimine or polyvinylamine, more preferably polyalkyleneimine, most preferably polyethylenimine, polypropylenimine, or polybutylenimine, in particular polyethylenimine.

According to one embodiment, (4a) is preferably any polymeric polyamine containing ethyleneimine (-CH ₂ CH ₂ NH-) as monomer units, including homopolymers and any copolymers of ethyleneimine, and is preferably a homopolymer of ethyleneimine. The copolymers can be alternating, periodic, random or block copolymers.

Generally, (4a) can have any polymer structure, for example, be a linear polymer, a ring polymer, a cross-linked polymer, a branched polymer, a star polymer, a comb polymer, a brush polymer, a tree polymer, or a dendrimer, etc. According to one embodiment, (4a) is a substantially linear polymer, and preferably is a linear polymer.

Polyethylenimines that can be used are homopolymers of polyethylenimine, which may be present in uncrosslinked or crosslinked form. Polyethylenimine homopolymers can be prepared by known methods, as described, for example, in Rompps (Chemie Lexikon, 8th edition, 1992, pages 3532-3533), or in Ullmanns Enzyklopadie der Technischen Chemie, 4th edition, 1974, t 8, pages 212-213, and in the literature cited there. They have a molecular weight ranging from about 200 to 1,000,000 g/mol. Corresponding commercial products are, for example, available under the name Lupasol ^® from BASF SE.

According to one embodiment of the invention, polyethylenimine (4a) is preferably a polyethylenimine having a degree of branching in the range of 0.1 to 0.95 (which is also called “highly branched polyethylenimine”), and more preferably a polyethylenimine having a degree of branching in the range of branching in the range of 0.25 to 0.90, more preferably polyethylenimine having a branching degree in the range of 0.30 to 0.80, and most preferably polyethylenimine having a branching degree in the range of 0.50-0.80 0.80

Highly branched polyethylenimines are characterized by their high degree of branching, which can be determined, for example, by ¹³ C-NMR spectroscopy, preferably in D ₂ O, and is defined as follows:

Degree of branching = D+T/D+T+L

D (dendritic) equals the percentage of tertiary amine groups, L (linear) equals the percentage of secondary amine groups, and T (terminal) equals the percentage of primary amine groups.

Typically, the polymer polyamine (4a) may have different weight average molecular weights. The weight average molecular weight (4a) is preferably at least 200, more preferably at least 400, most preferably at least 550, in particular at least 650, for example at least 750. The weight average molecular weight (4a) is preferably not greater than 10,000, more preferably not more than 4,000, most preferably not more than 1,900, in particular not more than 1,500, for example not more than 1,350. The weight average molecular weight can be determined by standard gel permeation chromatography (GPC) known to one skilled in the art.

In one embodiment, the amine (4) is polyethylenimine, preferably polyethylenimine, as defined above.

Another class of polyamines includes polymers that can be obtained by condensation of at least one compound selected from N-(hydroxyalkyl)amines of formula (I.a) and/or (I.b),

in which

And independently selected from C ₁ -C ₆ -alkylene;

^R1 , R1 ^* , ^R2 , R2 ^* , R3, ^{R3 *} , R4, ^{R4 *} , ^R5 , and ^R5* are independently selected from each other, which are selected from hydrogen, alkyl, cycloalkyl or aryl, wherein at least three of said radicals may be optionally substituted; And

R ⁶ is selected from hydrogen, alkyl, cycloalkyl or aryl, which may be optionally substituted.

Preferred are polyethanolamines. In this regard, polyethanolamines are preferred when in the condensation product of the compounds of formulas (I.a) and/or (Ib) as defined above, A is C ₁ -alkylene, and R ¹ , R ^{1 *} , R ² , R ^2* , R ³ , R ^{3 *} , R ⁴ R ^{4 *} , R ⁵ , and R ^{5 *} are each H, and R ⁶ is selected from hydrogen and C ₂ -hydroxyalkyl.

In one preferred embodiment, the polyamine is polyethanolamine, which is commercially available under the trade name ^Lupasol® EO.

According to another embodiment, amine (4) is

(4b) an amine containing no more than one amino group and at least three alkoxy- or hydroxy-substituted C ₂ -C ₁₂ alkyl groups R ²¹ , wherein at least one of the R ²¹ groups is different from the other R ²¹ groups.

The number of R ²¹ groups in (4b) is at least 3, preferably 3-5, more preferably 3-4, and most preferably 3.

The number of carbon atoms in each R ²¹ group in (4b) is 2-12, preferably 2-9, more preferably 2-7, most preferably 2-5, especially preferably 2-4, in particular 2-3, for example 3, wherein said number of carbon atoms does not include carbon atoms in any of the alkoxy groups or in any of the other R ²¹ substituents.

The R ²¹ groups in (4b) are alkoxy- or hydroxy-substituted, preferably hydroxy-substituted.

For one amine (4b), among at least three R ²¹ groups, at least one of the R ²¹ groups is different from the other R ²¹ groups, preferably one of the R ²¹ groups is different from the other R ²¹ groups.

Preferably at least one of the R ²¹ groups, more preferably at least two of the R ²¹ groups, most preferably at least three of the R ²¹ groups, in particular all of the R ²¹ groups are covalently linked or linked to the amino group of the amine (4b).

According to another preferred embodiment, (4b)

- is an amine containing no more than one amino group and at least three hydroxy-substituted C ₂ -C ₈ - or preferably C ₂ -C ₅ - alkyl groups R ²¹ , where at least one of the R ²¹ groups differs from other groups R ²¹ ,

- is preferably an amine containing no more than one amino group and at least three hydroxy-substituted C ₂ -C ₃ alkyl groups R ²¹ , where at least one of the R ²¹ groups differs from the other R ²¹ groups,

- more preferably is an amine containing no more than one amino group and three hydroxy-substituted C ₂ -C ₃ alkyl groups R ²¹ that are covalently linked to the amino group, where one of the R ²¹ groups is different from the other R ²¹ groups, and

for example, is an amine selected from the group consisting of bis(hydroxyethyl)-isopropanolamine (DEIPA), and 1,1'-((2-hydroxyethyl)imino)-dipropan-2-ol.

According to another preferred embodiment, (4b) is the amine N(R ²¹ ) ₃ where

R ²¹ represents an alkoxy- or hydroxy-substituted, preferably hydroxyl-substituted - C ₂ -C ₁₂ - preferably C ₂ -C ₇ , more preferably a C ₂ -C ₃ - alkyl group, and where one of the groups of R ²¹ is different from the other group ^R21 .

According to another preferred embodiment, (4b) is the amine N(R ²¹ ) ₃ where

R ²¹ represents an alkoxy- or hydroxy-substituted, preferably hydroxyl-substituted - C ₂ -C ₁₂ - preferably C ₂ -C ₇ , more preferably a C ₂ -C ₃ - alkyl group, and where one of the groups of R ²¹ is different from the other group R ²¹ and where at least one of the R ²¹ groups carries an alkoxy or hydroxy substituent at the secondary or tertiary carbon atom.

According to another embodiment, amine (4) is

(4c) an amine containing no more than one amino group and at least two alkoxy- or hydroxy-substituted C ₂ -C ₁₂ alkyl groups R ²² , where at least one of the R ²² groups carries an alkoxy or hydroxy substituent at the secondary or tertiary carbon atom, and where at least one of the R ²² groups is different from the other R ²² group(s).

The number of R ²² groups in (4c) is at least 2, preferably 2-5, more preferably 2-4, and most preferably 2-3, for example 2.

The number of carbon atoms in each R ²² group in (4c) is 2-12, preferably 2-9, more preferably 2-7, most preferably 2-5, especially preferably 2-4, especially 2-3, for example 3, wherein said number of carbon atoms does not include carbon atoms in any of the alkoxy groups or in any of the other R ²² substituents.

The R ²² groups in (4c) are alkoxy- or hydroxy-substituted, preferably hydroxy-substituted.

For one amine (4c), among at least two R ²² groups, at least one of the R ²² groups is different from the other R ²² group(s), preferably one of the R ²² groups is different from the other ) group(s) R ²² .

Preferably at least one of the R ²² groups, more preferably at least two of the R ²² groups, most preferably all of the R ²² groups are covalently linked or linked to the amino group of the amine (4b).

Preferably at least one of the R ²² groups, more preferably one of the R ²² groups carries an alkoxy or hydroxy substituent at the secondary or tertiary carbon atom, in particular at the secondary carbon atom.

According to another preferred embodiment, (4b)

- is an amine containing no more than one amino group and at least two hydroxy-substituted C ₂ -C ₇ alkyl groups R ²² , where at least one of the R ²² groups carries a hydroxy substituent at the secondary or tertiary carbon atom and where at least one of the R ²² groups is different from the other R ²² group(s),

- more preferably is an amine containing no more than one amino group and at least two hydroxy-substituted C ₂ -C ₄ alkyl groups R ²² , where at least one of the R ²² groups carries a hydroxy substituent at the secondary carbon atom and where at least one of the R ²² groups is different from the other R ²² group(s),

- is most preferably an amine containing no more than one amino group and two hydroxy-substituted C ₂ -C ₃ alkyl groups R ²² that are covalently linked to the amino group of the amine (4b), where at least one of the R ²² groups bears hydroxy substituent on the secondary carbon atom and where one of the R ²² groups is different from the other R ²² group,

- for example, is an amine selected from the group consisting of 1-((2-hydroxyethyl)amino)propan-2-ol, and N-methyl-N-hydroxyethyl-isopropanolamine.

According to another preferred embodiment, (4c) is the amine R ²⁴ N(R ²² ) ₂ where

R ²⁴ represents H or a C ₁ -C ₁₂ -, preferably a C ₁ -C ₇ -, more preferably a C ₁ -C ₃ - alkyl group and

R ²² represents an alkoxy- or hydroxy-substituted, preferably hydroxy-substituted - C ₂ -C ₁₂ , preferably C ₂ -C ₇ -, more preferably C ₂ -C ₃ - alkyl group, and where at least one of the groups R ²² carries a hydroxy substituent at the secondary carbon atom and where one of the R ²² groups is different from the other R ²² group.

According to another embodiment, amine (4) is

(4 g) an amine containing at least one saturated or unsaturated C ₈ -C ₄₀ alkyl group R ²³ .

The number of carbon atoms in each R ²³ group in (4 g) is 8-40, preferably 8-32, more preferably 8-24, most preferably 8-19, especially preferably 8-16.

The R ²³ group in (4 g) is saturated or unsaturated, preferably unsaturated.

According to another preferred embodiment, (4d) contains at least one alkoxy or hydroxy group, more preferably at least one alkoxy and at least one hydroxy group, most preferably at least two alkoxy and at least one hydroxyl group, in in particular, at least four alkoxy and at least one hydroxyl group.

For example, (4d) is an amine selected from the group consisting of: ethoxylated (2) cocoalkylamine, ethoxylated (5) cocoalkylamine, ethoxylated (15) cocoalkylamine, ethoxylated (2) oleylamine, lauryl-dimethylamine, oleyl-dimethylamine, and 2 -propylheptylamine ethoxylate (5 EO), 2-propylheptylamine ethoxylate (10 EO), and 2-propylheptylamine ethoxylate (20 EO).

In one preferred embodiment, the amine (4) is an ethoxylated (2) cocoalkylamine.

In one preferred embodiment, the amine (4) is an ethoxylated (5) cocoalkylamine.

In one preferred embodiment, the amine (4) is an ethoxylated (15) cocoalkylamine.

In one preferred embodiment, the amine (4) is an ethoxylated (2) oleylamine.

In one preferred embodiment, the amine (4) is lauryl-dimethylamine.

In one preferred embodiment, the amine (4) is oleyl-dimethylamine.

In one preferred embodiment, the amine (4) is 2-propylheptylamine ethoxylate (5EO).

In one preferred embodiment, the amine (4) is 2-propylheptylamine ethoxylate (10 EO)

In one preferred embodiment, the amine (4) is 2-propylheptylamine ethoxylate (20 EO).

According to another embodiment, amine (4) is

(4e) a saturated or unsaturated heterocyclic amine which contains at least one oxygen atom as a ring atom and which does not contain an additional alkoxy group.

The term "heterocyclic amine" means a heterocyclic compound in which at least one ring atom of the heterocyclic ring is a nitrogen atom.

The heterocyclic amine (4d) is saturated or unsaturated, preferably saturated.

The heterocyclic amine (4e) is preferably a 5-, 6-, or 7-membered heterocyclic ring, more preferably a 5- or 6-membered ring, most preferably a 6-membered ring.

The heterocyclic amine (4e) contains at least one, more preferably 1-3, most preferably 1-2, in particular one oxygen atom as ring atom(s) of the heterocyclic ring.

The heterocyclic amine (4e) is preferably morpholine or a morpholine derivative, more preferably N-alkylmorpholine, most preferably N-methyl, N-ethyl, N-propyl, or N-butylmorpholine, eg N-methylmorpholine.

In one preferred embodiment, amine (4) is N-methylmorpholine.

According to another embodiment, amine (4) is

(4e) an amine having a boiling point of more than 100°C, preferably more than 150°C, more preferably more than 200°C, at ambient pressure (1 bar).

Such amines are described in US 2011/0154874 A1. Accordingly, preferred amines (4e) are secondary and/or tertiary amines, for example methyldiethanolamine, tetrahydroxypropylethylenediamine, trimethylaminoethylethanolamine, N,N,N',N'-tetramethyl-1,6-hexanediamine, N,N',N''- tris(dimethylaminopropyl)hexahydrotriazine, and 2,2'-dimorpholinyl diethyl ether.

According to another embodiment, amine (4) is

(4g) primary amine.

According to another embodiment, amine (4) is

(4h) secondary amine.

According to another embodiment, amine (4) is

(4i) tertiary amine.

In connection with the above embodiments which relate to (4g), (4h) and (4i), the term “amine” is preferably understood as an organic compound in which at least one amino group is bonded to a carbon atom. In a primary amine, the NH ₂ group is bonded to a carbon atom, and the NR ^A H group in a secondary amine is bonded to a carbon atom, and in a tertiary amine, the NR ^A R ^B group is bonded to a carbon atom, where R ^A and R ^B can each be separately selected from C ₁ -C ₂₀ -alkyl, di(C ₁ -C ₄ -alkyl)amino-C ₁ -C ₂₀ -alkyl, and C ₁ -C ₄ -alkylene chain, which is bonded to the carbon atom to which the NR ^A group is bonded H or NR ^A R ^B so that a heterocyclic ring is formed, or R ^A and R ^B can, together with the nitrogen atom to which they are bonded, form a 5- to 10-membered, preferably a 5- to 6-membered heterocyclic ring, where the heterocycle may contain 1, 2, or 3 additional nitrogen atoms, and where the N atoms, if present, are each individually further substituted by H, C ₁ -C ₄ -alkyl, di(C ₁ -C ₄ -alkyl)amino -C ₁ -C ₄ -alkyl, or through a C ₁ -C ₄ -alkylene chain that is bonded to the carbon atom to which the NR ^A R ^B group is bonded so that an additional heterocyclic ring is formed. If the carbon atom to which the NH ₂ , NR ^A H, or NR ^A R ^B group is bonded is not part of a heterocyclic ring that is formed with ^RA or ^RB , it is preferably part of a C ₁ -C ₂₀ alkyl group or di(C ₁ -C ₄ -alkyl)amino-C ₁ -C ₂₀ -alkyl group, so that the amino group can be represented by the formula C ₁ -C ₂₀ -alkyl-NH ₂ , C ₁ -C ₂₀ -alkyl-NR ^A H, or C ₁ -C ₂₀ -alkyl-NR ^A R ^B or the formula di(C ₁ -C ₄ -alkyl)amino-C ₁ -C ₂₀ -alkyl-NH ₂ , di(C ₁ -C ₄ -alkyl) amino-C ₁ -C ₂₀ -alkyl-NR ^A H, or di(C ₁ -C ₄ -alkyl)amino-C ₁ -C ₂₀ -alkyl-NR ^A R ^B , where R ^A and R ^B each separately can be selected from C ₁ -C ₂₀ -alkyl, and di(C ₁ -C ₄ -alkyl)amino-C ₁ -C ₂₀ -alkyl, or R ^A and R ^B can, together with the nitrogen atom to which they are bonded, form 5 - - 10-membered, preferably 5- to 6-membered heterocyclic ring, where the heterocycle may contain 1, 2, or 3 additional nitrogen heteroatoms, and where the N atoms, if present, are each individually further substituted by H, C ₁ -C ₄ -alkyl, or di(C ₁ -C ₄ -alkyl)amino-C ₁ -C ₄ -alkyl.

In one preferred embodiment of the invention, the amine (4) is a tertiary amine where 2 tertiary amino groups are present, and which can be represented by the formula R ^a R ^b N-(C ₁ -C ₁₀ -alkylene)-NR ^c R ^d where R ^a , R ^b , R ^c , and R ^d are independently selected from C ₁ -C ₄ alkyl, or R ^a and R ^b and/or R ^c and R ^d may, together with the nitrogen atom to which they are bonded , to form a 5- to 10-membered, preferably 5- to 6-membered heterocyclic ring, where the heterocycle may contain 1, 2, or 3 additional heteroatoms selected from N, O, and S, where the N atom, if present, is additional substituted by C ₁ -C ₄ -alkyl. Preferably, R ^a , R ^b , R ^c , and R ^d are independently selected from C ₁ -C ₄ alkyl.

In one embodiment of the invention, the amine (4) is selected from N,N,N,N'-tetramethyl-1,6-hexanediamine, N,N,N',N'-tetramethyl-1,3-propanediamine, N,N ',N''-tris(dimethylaminopropyl)hexahydrotriazine, and triethylenediamine (DABCO).

In one preferred embodiment of the invention, the amine (4) is N,N,N',N'-tetramethyl-1,6-hexanediamine (CAS [111-18-2]).

In one preferred embodiment of the invention, the amine (4) is N,N,N',N'-tetramethyl-1,3-propanediamine (CAS [110-95-2]).

In one preferred embodiment of the invention, the amine (4) is N,N',N''-tris(dimethylaminopropyl)hexahydrotriazine.

In one preferred embodiment of the invention, the amine (4) is triethylenediamine (DABCO, available as ^Lupragen® N201 from BASF).

According to another embodiment, amine (4) is

(4k) an amine containing no more than one amino group and at least two alkoxy- or hydroxy-substituted C ₂ -C ₁₂ alkyl groups R ²² .

According to another embodiment, amine (4) is

(4l) an amine containing no more than one amino group and at least three alkoxy- or hydroxy-substituted C ₂ -C ₁₂ alkyl groups R ²² .

According to another embodiment, amine (4) is

(4m) an amine containing no more than one amino group and at least three alkoxy- or hydroxy-substituted C ₂ -C ₁₂ alkyl groups R ⁴¹ , where all R ⁴¹ groups in the specified amine are identical.

According to another embodiment, amine (4) is

(4n) amine containing no more than one amino group and at least two alkoxy- or hydroxy-substituted C ₂ -C ₁₂ alkyl groups R ⁴² , where at least one of the R ⁴² groups carries an alkoxy or hydroxy substituent at the secondary or tertiary carbon atom, and wherein all R ⁴² groups with said amine are identical.

In the context of the above embodiments (4k)-(4h), the amine (4) in one embodiment may be an amino alcohol.

Amino alcohols may also be called alkanolamines and are characterized in that they contain at least one hydroxyl group and at least one amino group.

In one embodiment, the amino alcohols may be represented by the formula (H) _a N(C ₁ -C ₁₀ -hydroxyalkyl)b, preferably the formula (H) _a N(C ₁ -C ₈ -hydroxyalkyl) _b , where a represents 0 or 1, and b is 2 when a is 1, and 3 when a is 0. In this regard, it is understood that the term "hydroxyalkyl" means an alkyl group that contains at least one, preferably 1, 2 or 3 hydroxyl groups, particularly preferably one hydroxyl group. Exemplary hydroxyalkyl groups include hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, and 3-hydroxypropyl.

In one embodiment, it is preferred that the amino alcohol contains no more than one amino group and at least three hydroxyl-substituted C ₂ -C ₈ -, preferably C ₂ -C ₅ -alkyl groups, where at least one of these hydroxyl -substituted alkyl groups are different from other hydroxyl-substituted alkyl groups.

It is even more preferred when the amino alcohol contains no more than one amino group and at least three hydroxyl-substituted C ₂ -C ₃ -alkyl groups, where at least one of these hydroxyl-substituted alkyl groups is different from other hydroxyl-substituted alkyl groups groups.

It is even more preferred when the amino alcohol contains no more than one amino group and at least three hydroxyl-substituted C ₂ -C ₃ -alkyl groups that are covalently bonded to the amino group, wherein at least one of said hydroxyl-substituted alkyl groups is different from other hydroxyl-substituted alkyl groups.

In other embodiments, amino alcohols may be represented by the general formula A(H) _x N((CH ₂ ) _m -OH) _n where m is 1, 2, or 3, x is 0 or 1, and n is is 2 when x is 1 and 3 when x is 0, or by the general formula B(H) _yN (( _CH2 )-CHOH- _CH3 ) _z , so that the length of the carbon chain where the secondary is located hydroxyl group, is 3 when y is 0 or 1, and z is 2 when y is 1, and 3 when y is 0.

In another embodiment of the invention, amino alcohols can be represented by the formula (C ₁ -C ₄ -alkyl) ₂ N-(C ₁ -C ₄ -alkylene)-N(C ₁ -C ₄ -alkyl)(C ₁ -C ₄ - hydroxyalkyl). In this regard, an exemplary amino alcohol is N,N,N'-trimethylaminoethylethanolamine.

Preferred amino alcohols according to the invention may be selected from the group consisting of ethanolamine, diethanolamine, methyldiethanolamine, butyldiethanolamine, monoisopropanolamine, diisopropanolamine, methyldiisopropanolamine, triethanolamine, tetrahydroxypropylethylenediamine, trimethylaminoethylethanolamine, N,N-bis(2-hydroxyethyl)isopropanolamine, N,N , N'-trimethylaminoethylethanolamine, and N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine.

Preferred amino alcohols according to the invention include ethanolamine, diethanolamine, methyldiethanolamine, butyldiethanolamine, monoisopropanolamine, diisopropanolamine, methyldiisopropanolamine, triethanolamine, tetrahydroxypropylethylenediamine, and trimethylaminoethylethanolamine.

A preferred amino alcohol is triethanolamine.

Another preferred amino alcohol is N,N-bis(2-hydroxyethyl)isopropanolamine, also known as diethanolisopropanolamine (DEIPA).

Another preferred amino alcohol is N,N,N'-trimethylaminoethylethanolamine (CAS [2212-32-0], available as ^Lupragen® N400 from BASF).

Another preferred amino alcohol is N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine (CAS [102-60-3]).

In the context of the above embodiments (4k)-(4h), the amine (4) in another embodiment may be an etheramine.

Ether amines are characterized in that they contain at least one ether group and at least one amino group.

In one embodiment of the invention, etheramines can be represented by the general formula NR ^a R ^b -(CH ₂ ) _n -[O-(CH ₂ ) _m ] _p -NR ^c R ^d where n is 1, 2, 3, 4 , or 5, m is 1, 2, 3, 4, or 5, p is 1, 2, 3, 4, or 5, and R ^a , R ^b , R ^c , and R ^d are independently selected from H and C ₁ -C ₄ -alkyl, or R ^a and R ^b and/or R ^c and R ^d can, together with the nitrogen atom to which they are bonded, form a 5- to 10-membered, preferably 5- to 6-membered membered heterocyclic ring, where the heterocycle may contain 1, 2, or 3 additional heteroatoms selected from N, O, and S, where the N atom, if present, is further substituted by H or C ₁ -C ₄ -alkyl.

Preferably n is 1 or 2, m is 1 or 2, p is 1 or 2, R ^a , R ^b , R ^c , and R ^d are each independently selected from C ₁ -C ₂ alkyl, or R ^a and R ^b and R ^c and R ^d each, together with the nitrogen atom to which they are bonded, may form a 5- or 6-membered heterocyclic ring, where the heterocycle may contain 1 additional heteroatom selected from N, O, and S, where N- the atom, if present, is additionally substituted by a C ₁ -C ₂ alkyl group.

In one embodiment of the invention, etheramines are heterocyclic 5- to 10-membered, preferably 5- or 6-membered rings containing an oxygen atom and a nitrogen atom to form the desired amino and ether groups, and wherein the nitrogen atom is further substituted by H, C ₁ -C ₁₀ -alkyl, C ₁ -C ₁₀ -haloalkyl, C(=O)H, or C(=O)C ₁ -C ₁₀ -alkyl. Particularly preferred are morpholine compounds where the nitrogen atom is replaced by a C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl, C(=O)H, or C(=O)C ₁ -C ₄ -alkyl, preferably by C ₁ -C ₄ -alkyl, C(=O)H, or C(=O)CH ₃ .

Preferred etheramines include dimorpholinodiethyl ether, bis(2-dimethylaminoethyl)ether, N-acetylmorpholine, and N-formylmorpholine.

In one preferred embodiment of the invention, amine (4) is dimorpholinodiethyl ether (available as ^Lupragen® N106 from BASF).

In one preferred embodiment of the invention, the amine (4) is a bis(2-dimethylaminoethyl)ether (CAS [3033-62-3], available as ^Lupragen® N205 from BASF).

In one preferred embodiment of the invention, the amine (4) is a morpholine compound selected from N-acetylmorpholine and N-formylmorpholine.

Amines (4M) or (4H) are preferably

(L217) triethanolamine,

(L218)tripropanolamine,

(L219) diisopropanolamine,

(L220) triisopropanolamine,

(L221) diethanolamine, or

(L222) methyldipropanolamine.

In one preferred embodiment, the amine (4) is (L217) triethanolamine.

In another preferred embodiment, the amine (4) is (L218) tripropanolamine.

In another preferred embodiment, the amine (4) is (L219) diisopropanolamine.

In another preferred embodiment, amine (4) is (L220) triisopropanolamine.

In another preferred embodiment, the amine (4) is (L221) diethanolamine.

In another preferred embodiment, the amine (4) is (L222) methyldipropanolamine.

According to another embodiment, amine (4) is

(4o) amine selected from the group consisting of methyldiethanolamine, tetrahydroxypropylethylenediamine, trimethylaminoethylethanolamine, N,N,N',N'-tetramethyl-1,6-hexanediamine, N,N',N''-tris(dimethylaminopropyl)hexahydrotriazine, and 2,2'-dimorpholinyl diethyl ether.

In one embodiment, amine (4) is methyldiethanolamine.

In one embodiment, amine (4) is tetrahydroxypropylethylenediamine.

In one embodiment, amine (4) is trimethylaminoethylethanolamine.

In one embodiment, amine (4) is N,N,N',N'-tetramethyl-1,6-hexanediamine.

In one embodiment, amine (4) is N,N',N''-tris(dimethylaminopropyl)hexahydrotriazine.

In one embodiment, amine (4) is 2,2'-dimorpholinyl diethyl ether.

According to another embodiment, amine (4) is

(4p) amine selected from the group consisting of (L10), (L11), (L12), (L13), (L14), (L15), (L16), (L17), (L18), (L19) , (L20), (L21), (L22), (L23), (L24) and (L29), as disclosed in PCT application WO 2016/103168.

In one preferred embodiment, amine (4) is

(L10) aliphatic alkylenediamine according to general formula (IA)

in which the radicals are defined as follows:

R1 and R2 simultaneously or each independently represent hydrogen, linear or branched C ₇ - -C ₁₂ -alkyl, C ₇ - -C ₁₂ -aralkyl, C ₆ - -C ₁₀ -aryl, C ₃ - -C ₈ -cycloalkyl or C ₃ - -C ₈ -cycloalkyl, in which optionally - preferably necessarily - one or more CH ₂ groups have been replaced by O, NH or NR10; or

alternatively, R1 and R2 together represent linear or branched C ₁ - -C ₁₂ -alkyl, C ₇ - -C ₁₂ -aralkyl, C ₆ - -C ₁₀ -aryl, C ₃ - -C ₈ -cycloalkyl or C ₃ - -C ₈ -cycloalkyl, in which optionally - preferably necessarily - one or more CH ₂ groups have been replaced by O, NH or NR10; And

R3 _x and R4 _x simultaneously or each independently represent hydrogen, linear or branched C ₁ - -C ₁₂ -alkyl, C ₇ - -C ₁₂ -aralkyl, C _g - -C ₁₀ -aryl, C ₃ - -C ₈ - cycloalkyl or C ₃ - -C ₈ -cycloalkyl, in which optionally - preferably necessarily - one or more CH ₂ groups have been replaced by O, NH or NR10; And

R10 represents linear or branched C ₁ - -C ₁₂ -alkyl, C ₇ - -C ₁₂ -aralkyl, C ₆ - -C ₁₀ -aryl or C ₃ - -C ₈ -cycloalkyl; And

z is a value from 2 to 20, preferably from 2 to 12; And

x is an index that can take any value from 1 to z.

In one preferred embodiment, amine (4) is

(L11) oligomeric polyalkyleneamine according to general formula (II)

in which each of the radicals is defined as follows:

R1, R2 and R5 simultaneously or each independently represent hydrogen, linear or branched C ₁ - -C ₁₂ -alkyl, C ₇ - -C ₁₂ -aralkyl, C ₆ - -C ₁₀ -aryl, C ₃ - -C ₈ - cycloalkyl or C ₃ - -C ₈ -cycloalkyl, in which optionally - preferably necessarily - one or more CH ₂ groups have been replaced by O, NH or NR10; or

two of the three radicals R1, R2 and R5 are covalently bonded to each other to form linear or branched C ₁ - -C ₁₂ -alkyl, C ₇ - -C ₁₂ -aralkyl, C ₆ - -C ₁₀ -aryl, C ₃ - - C ₈ -cycloalkyl or C ₃ - -C ₈ -cycloalkyl, in which optionally - preferably necessarily - one or more CH ₂ groups have been replaced by O, NH or NR10, and the remaining one of the three radicals R1, R2 and R5 is hydrogen , linear or branched C ₁ - -C ₁₂ -alkyl, C ₇ - -C ₁₂ -aralkyl, C ₆ - -C ₁₀ -aryl, C ₃ - -C ₈ -cycloalkyl or C ₃ - -C ₈ -cycloalkyl, in in which optionally - preferably necessarily - one or more CH ₂ groups have been replaced by O, NH or NR10; And

R3 _y and R4 _y simultaneously or each independently represent hydrogen, linear or branched C ₁ - -C ₁₂ -alkyl, C ₇ - -C ₁₂ -aralkyl, C ₆ - -C ₁₀ -aryl, C ₃ - -C ₈ - cycloalkyl or C ₃ - -C ₈ -cycloalkyl, in which optionally - preferably necessarily - one or more CH ₂ groups have been replaced by O, NH or NR10;

R10 represents linear or branched C ₁ - -C ₁₂ -alkyl, C ₇ - -C ₁₂ -aralkyl, C ₆ - -C ₁₀ -aryl or C ₃ - -C ₈ -cycloalkyl;

a represents a value of 2-5;

b represents a value of 2-12;

and y is an index that can take on all values between 1 and b.

In one preferred embodiment, amine (4) is

(L12) polyetheramine according to general formula (III):

in which each of the radicals is defined as follows:

R1 and R2 simultaneously or each independently represent hydrogen, linear or branched C ₁ - -C ₁₂ -alkyl, C ₇ - -C ₁₂ -aralkyl, C ₆ - -C ₁₀ -aryl, C ₃ - -C ₈ -cycloalkyl or C ₃ - -C ₈ -cycloalkyl, in which optionally - preferably necessarily - one or more CH ₂ groups have been replaced by O, NH or NR10;

alternatively, R1 and R2 together represent linear or branched C ₁ - -C ₁₂ -alkyl, C ₇ - -C ₁₂ -aralkyl, C ₆ - -C ₁₀ -aryl, C ₃ - -C ₈ -cycloalkyl or C ₃ - -C ₈ -cycloalkyl, in which optionally - preferably necessarily - one or more CH ₂ groups have been replaced by O, NH or NR10; And

R3, R4 and R5 simultaneously or each independently represent hydrogen, linear or branched C ₁ - -C ₁₂ -alkyl, C ₇ - -C ₁₂ -aralkyl, C ₆ - -C ₁₀ -aryl, C ₃ - -C ₈ - cycloalkyl or C ₃ - -C ₈ -cycloalkyl, in which optionally - preferably necessarily - one or more CH ₂ groups have been replaced by O, NH or NR10;

R10 represents linear or branched C ₁ - -C ₁₂ -alkyl, C ₇ - -C ₁₂ -aralkyl, C ₆ - -C ₁₀ -aryl or C ₃ - -C ₈ -cycloalkyl;

x, y and z are each independently a value from 0 to 100, and the sum of x, y and z is at least 2.

In one preferred embodiment, amine (4) is

(L13) a polyvinylamine-related polymer selected from the group consisting of

(L501) polyvinylamine,

(L502) polyvinylamine according to general formula (IV)

which has an average molar mass (Mw) of from 200 to 2,000,000 g/mol, and where R ⁷ -R ¹¹ are independently

hydrogen, linear or branched radicals C _i - -C ₂₀ -alkyl, -alkoxy, -polyoxyethylene, -hydroxyalkyl, -(alkyl)carboxy, -phosphonoalkyl, -alkylamino, formamidyl radicals, pyrrolidonyl, imidazolyl, C ₂ - -C ₂₀ radicals -alkenyl or C ₆ - -C ₂₀ -aryl, -aryloxy, radicals o-hydroxybenzoyl, phthalimidoyl, o-carboxamidobenzoyl, o-(C ₁ - -C ₈ -alkoxycarbonyl)benzoyl, o-aminobenzoyl, o-(mono-C ₁ - -C ₈ -alkylamino)benzoyl, o-(di-C ₁ - -C ₈ -alkylamino)benzoyl, 2-cyano-3,3-diphenylacryloyl, or m-benzimidazolyl-n-hydroxybenzoyl, which may optionally be additionally substituted, where s is an integer, t is 0 or an integer, where the sum of s and t must be chosen so that the average molar mass is within the specified range,

(L503) polyallylamine,

(L504) poly(diallyldimethylammonium chloride),

(L505) cationic polyvinylformamide,

(L506) cationic polyvinylpyrrolidone,

(L507) cationic polyvinylacetamide,

(L508) cationic polyvinylmethylformamide,

(L509) cationic polyvinylmethylacetamide,

(L510) poly(dimethylaminopropyl methacrylamide),

(L511) poly(dimethylaminoethyl acrylate),

(L512) poly(diethylaminoethyl acrylate),

(L513) poly(acryloylethyltrimethylammonium chloride),

(L514) poly(acrylamidopropyltrimethylammonium chloride),

(L515) poly(methacrylamidotripropyltrimethylammonium chloride),

(L516) cationic polyacrylamide,

(L517) poly(vinylpyridine),

(L518) hexadimethrine bromide,

(L519) poly(dimethylamine-co-epichlorohydrin),

(L520) poly(dimethylamine-co-epichlorohydrin-co-ethylenediamine),

(L521) poly(amidoamine-epichlorohydrin),

(L522) linear, branched or hyperbranched polyamidoamines, or

(L523) polyamidoamines having an average molar mass (MW) of from 1000 to 200,000 g/mol, and

(L524) cationic starch, or copolymers which include N-vinylformamide, allylamine, diallyldimethylammonium chloride, N-vinylacetamide, N-vinylpyrrolidone, N-methyl-N-vinylformamide, N-methyl-N-vinylacetamide, dimethylaminopropyl methacrylamide, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, acryloylethyl tri methyl ammonium chloride or methacrylamidopropyltrimethylammonium chloride as polymerized units and, if desired, in cleavable form, and salts thereof when the polymers are basic polymers.

In one preferred embodiment, amine (4) is

(L14) polyethylenimine according to general formula (V)

which has a mean molar mass (MW) ranging from 200 to 1,000,000 g/mol, and where

R ¹ -R ⁶ independently represent hydrogen, linear or branched radicals C ₁ - -C ₂₀ -alkyl, -alkoxy, -polyoxyalkylene, -polyoxyethylene, -hydroxyalkyl, -(alkyl)carboxy, -phosphonoalkyl, -alkylamino, C ₂ - -C ₂₀ -alkenyl or C ₆ - -C ₂₀ -aryl, -aryloxy, -hydroxyaryl, -arylcarboxy radicals or -arylamino radicals, which are optionally further substituted, and

R ² , R ³ and R ⁵ may - independently of each other - optionally each additionally represent additional polymer chains of polyethylenimine, and

R ¹ may optionally be an NR ³ R ⁴ or NH ₂ radical, and

x, y and z are - independently of each other - 0 or an integer, where the sum of x, y and z must be chosen such that the average molar mass is within the specified range.

In one preferred embodiment, amine (4) is

(L15) polyethylenimine according to the general formula (V), in which at least one of the radicals R ² -R ⁶ is a polyoxyalkylene radical.

In one preferred embodiment, amine (4) is

polymer which can be produced by a process (L16P) which includes step L16a)

L16a) condensation of at least one compound selected from N-(hydroxyalkyl)amines of formula (I.a) and/or (I.b),

Where

And independently selected from C ₁ -C ₆ -alkylene;

R ¹ , R ¹ *, R ² , R ² *, R ³ , R ³ *, R ⁴ , R ⁴ *, R ⁵ and R ⁵ * are independently selected from hydrogen, alkyl, cycloalkyl or aryl, where the latter the three radicals mentioned may optionally be substituted; And

R ⁶ is selected from hydrogen, alkyl, cycloalkyl or aryl, which may be optionally substituted.

In one preferred embodiment, amine (4) is

(L17) a polymer which can be produced by a process (L17P) which includes two steps L17a) and L17b)

L17a) condensation of at least one compound selected from N-(hydroxyalkyl)amines of formula (I.a) and/or (I.b),

Where

And independently selected from C ₁ -C ₆ -alkylene;

R ¹ , R ¹ *, R ² , R ² *, R ³ , R ³ *, R ⁴ , R ⁴ *, R ⁵ and R ⁵ * are independently selected from hydrogen, alkyl, cycloalkyl or aryl, where the latter the three radicals mentioned may optionally be substituted; And

R ⁶ is selected from hydrogen, alkyl, cycloalkyl or aryl, which may be optionally substituted; And

L17b) reacting at least a portion of the remaining hydroxy groups and/or, if present, at least a portion of the secondary amino groups of the polyether provided in step L17a) with at least one alkylene oxide.

In one preferred embodiment, amine (4) is

(L18) derivative, which can be obtained by quaternization, protonation, sulfation and/or phosphating of the polymer (L16) or (L17).

In one preferred embodiment, amine (4) is

(L19) dendritic polyamines or their precursors selected from

(L554) N,N,N',N'-tetraaminopropylalkylenediamine,

(L555) dendritic amines which can be prepared from N,N,N',N'-tetraaminopropylalkylenediamine by amino-n-propylation (e.g. known as N14-, N30-, N62- and N128-amine by the number of their nitrogen atoms) ,

(L556) N,N,N',N'-tetraaminopropylethylenediamine,

(L557) dendritic amines which can be prepared from N,N,N',N'-tetraaminopropylethylenediamine by amino-n-propylation (e.g. known as N14-, N30-, N62- and N128-amine based on the number of their nitrogen atoms) ,

(L558) N,N,N',N'-tetraaminopropylpropylenediamine,

(L559) dendritic amines which can be prepared from N,N,N',N'-tetraaminopropylpropylenediamine by amino-n-propylation (e.g. known as N14-, N30-, N62- and N128-amine by the number of their nitrogen atoms) ,

(L560) N,N,N',N'-tetraaminopropylbutylenediamine,

(L561) dendritic amines which can be prepared from N,N,N',N'-tetraaminopropylbutylenediamine by amino-n-propylation (e.g. known as N14-, N30-, N62- and N128-amine by the number of their nitrogen atoms) .

In one preferred embodiment, amine (4) is

(L20) bicyclic, tricyclic or higher polycyclic polyamine.

In one preferred embodiment, amine (4) is

(L21) an amine containing not more than one amino group and two alkoxy- or hydroxy-substituted C2-C12 alkyl groups R21a and one C1-C10 alkyl group R21b, where the group R21a carries an alkoxy or hydroxy substituent at the secondary or tertiary carbon atom, and where the two R21a groups are identical.

In one preferred embodiment, amine (4) is

(L22) an amine containing no more than one amino group and one alkoxy- or hydroxy-substituted C ₂ -C ₁₂ alkyl group R ^22a and two C ₁ -C ₁₀ alkyl groups R ^22b , where the two R ^22b groups are identical.

In one preferred embodiment, amine (4) is

(L23) imidazolidinone N-substituted at one or two of its nitrogen atoms with alkyl moieties ^R23 , wherein ^R23 may optionally be substituted with OH groups.

In one preferred embodiment, amine (4) is

(L24) morpholine N-substituted with alkyl groups of R ²⁴ , where R ²⁴ may optionally be substituted with OH groups.

In one preferred embodiment, amine (4) is

(L29) homopolymer of amino acids.

In a preferred embodiment, the content of TPT in the combination containing TPT and amine (4), which is used in the premix (P), or which is used to prepare the premix (P), is preferably in the range of 1 wt. % - 99 wt. %, more preferably in the range of 10 wt. % - 87 wt. %, most preferably in the range of 20 wt. % - 75 wt. %, especially preferably in the range of 25 wt. % - 65 wt. %, in particular, more preferably in the range of 30 wt. % - 55 wt. %, in particular in the range of 35 wt. % - 45 wt. %, based on the total weight of the combination containing TPT and amine (4).

In another preferred embodiment, the TPT content of the combination containing TPT and amine (4) that is used in the premix (P) or that is used to make the premix (P) is preferably in the range of 30 wt. % - 70 wt. %, more preferably in the range of 40 wt. % - 60 wt. %, most preferably in the range of 45 wt. % - 55 wt. %, based on the total weight of the combination containing TPT and amine (4).

In another preferred embodiment, the TPT content of the combination containing TPT and amine (4) that is used in the premix (P) or that is used to make the premix (P) is preferably in the range of 40 wt. % - 80 wt. %, more preferably in the range of 50 wt. % - 70 wt. %, most preferably in the range of 55 wt. % - May 65. based on the total weight of the combination containing TPT and amine (4).

In another preferred embodiment, the content of TPT in the combination containing TPT and amine (4), which is used in the premix (P) or which is used to prepare the premix (P), is preferably in the range of 10 wt. % - 40 wt. %, more preferably in the range of 15 wt. % - 35 wt. %, most preferably in the range of 20 wt. % - 30 wt. %, based on the total weight of the combination containing TPT and amine (4).

In another preferred embodiment of the invention, (thio)phosphoric acid triamide (2) is provided in combination with at least one organic solvent (5) having a boiling point of more than 100°C. In another preferred embodiment of the invention, the (thio)phosphoric acid triamide (2) is provided in combination with at least one amine (4) having a boiling point greater than 100° C. and at least one organic solvent (5) , having a boiling point of more than 100°C. Preferably, the organic solvent (5) is an alcohol, more preferably a diol, triol, tetraol, pentaol, hexaol, heptaol, octaol, nonaol, decaol, or polyol. Most preferably, the organic solvent (5) is a diol, triol, tetraol, pentaol, or hexaol. Particularly preferably, the organic solvent (5) is a diol. Particularly, more preferably, the organic solvent (5) is ethanediol (ethylene glycol), propanediol (propylene glycol), or butanediol (butylene glycol). In particular, most preferably, the organic solvent (5) is propanediol (propylene glycol). For example, the organic solvent (5) is propane-1,2-diol (alpha-propylene glycol; CAS 57-55-6). According to another preferred embodiment, the organic solvent (5) is diethylene glycol. According to another preferred embodiment, the organic solvent (5) is DMSO. According to another preferred embodiment, the organic solvent (5) is a mixture containing propane-1,2-diol and DMSO, preferably a mixture containing 20 wt. % - 80 wt. % propane-1,2-diol and 20 wt. % - 80 wt. % DMSO, more preferably a mixture containing 35 wt. % - 65 wt. % propane-1,2-diol and 35 wt. % - 65 wt. % DMSO, based on the total mass of organic solvent (5).

The organic solvent (5) is preferably an alcohol having 2-50 carbon atoms, more preferably an alcohol having 2-20 carbon atoms, most preferably an alcohol having 2-11 carbon atoms, especially preferably an alcohol having 2-7 carbon atoms, in particular, an alcohol having 2-4 carbon atoms, for example an alcohol having 3 carbon atoms.

In a preferred embodiment, the content of TPT in the combination containing TPT and organic solvent (5) that is used in the premix (P) or that is used to prepare the premix (P) is preferably in the range of 1 wt. % - 99 wt. %, more preferably in the range of 10 wt. % - 87 wt. %, most preferably in the range of 20 wt. % - 75 wt. %, especially preferably in the range of 25 wt. % - 65 wt. %, in particular, more preferably in the range of 30 wt. % -55 wt. %, in particular in the range of 35 wt. % - 45 wt. %, based on the total weight of the combination containing TPT and organic solvent (5).

In another preferred embodiment, the content of TPT in the combination containing TPT and organic solvent (5) that is used in the premix (P) or that is used to prepare the premix (P) is preferably in the range of 30 wt. % - 70 wt. %, more preferably in the range of 40 wt. % - 60 wt. %, most preferably in the range of 45 wt. % - 55 wt. %, based on the total weight of the combination containing TPT and organic solvent (5).

In another preferred embodiment, the content of TPT in the combination containing TPT and organic solvent (5) that is used in the premix (P) or that is used to prepare the premix (P) is preferably in the range of 40 wt. % - 80 wt. %, more preferably in the range of 50 wt. % - 70 wt. %, most preferably in the range of 55 wt. % - 65 wt. %, based on the total weight of the combination containing TPT and organic solvent (5).

In another preferred embodiment, the content of TPT in the combination containing TPT and organic solvent (5), which is used in the premix (P) or which is used to prepare the premix (P), is preferably in the range of 10 wt. % - 40 wt. %, more preferably in the range of 15 wt. % - 35 wt. %, most preferably in the range of 20 wt. % - 30 wt. %, based on the total weight of the combination containing TPT and organic solvent (5).

In a preferred embodiment, the content of TPT in the combination containing TPT and the amine (4) and the organic solvent (5) that is used in the premix (P) or that is used to prepare the premix (P) is preferably in the range of 1 wt. % - 99 wt. %, more preferably in the range of 10 wt. % - 87 wt. %, most preferably in the range of 20 wt. % - 75 wt. %, especially preferably in the range of 25 wt. % - 65 wt. %, in particular, more preferably in the range of 30 wt. % - 55 wt. %, in particular in the range of 35 wt. % - 45 wt. %, based on the total weight of the combination containing TPT and amine (4) and organic solvent (5).

In another preferred embodiment, the TPT content of the combination containing TPT and the amine (4) and the organic solvent (5) that is used in the premix (P) or that is used to make the premix (P) is preferably in the range of 30 wt. . % - 70 wt. %, more preferably in the range of 40 wt. % - 60 wt. %, most preferably in the range of 45 wt. % - 55 wt. %, based on the total weight of the combination containing TPT and amine (4) and organic solvent (5).

In another preferred embodiment, the TPT content of the combination containing TPT and the amine (4) and the organic solvent (5) that is used in the premix (P) or that is used to make the premix (P) is preferably in the range of 40 wt. . % - 80 wt. %, more preferably in the range of 50 wt. % - 70 wt. %, most preferably in the range of 55 wt. % - 65 wt. %, based on the total weight of the combination containing TPT and amine (4) and organic solvent (5).

In another preferred embodiment, the TPT content of the combination containing TPT and the amine (4) and the organic solvent (5) that is used in the premix (P) or that is used to make the premix (P) is preferably in the range of 10 wt. . % - 40 wt. %, more preferably in the range of 15 wt. % - 35 wt. %, most preferably in the range of 20 wt. % - 30 wt. %, based on the total weight of the combination containing TPT and amine (4) and organic solvent (5).

The fertilizer composition obtained by the method according to the present invention also includes a urea-containing fertilizer (1). Said urea-containing fertilizer (1) may also further include other fertilizers such as nitrogen fertilizer, potassium fertilizer, or additional phosphorus-containing fertilizer (3), which is preferably an NPK fertilizer (nitrogen-phosphorus-potassium fertilizer), NP fertilizer ( nitrogen-phosphorus fertilizer), RK-fertilizer (phosphorus-potassium fertilizer), or P-fertilizer (phosphorus fertilizer).

As used in this application, the term "fertilizer" covers any chemical compound that increases the levels of available plant nutrients and/or the chemical and physical properties of the soil, thereby directly or indirectly promoting plant growth, crop yield, and plant quality. Fertilizers are usually applied either through the soil (for absorption by plant roots) or through foliar feeding (for absorption through leaves). The term fertilizer can be divided into two main categories: a) organic fertilizers (consisting of decomposed plant/animal remains) and b) inorganic fertilizers (consisting of chemicals and minerals). Organic fertilizers include manure, slurry, vermicompost, peat, seaweed, sewage, and guano. Green manure crops are also constantly grown to add nutrients (especially nitrogen) to the soil. Industrial organic fertilizers include compost, blood meal, bone meal and seaweed extracts. Additional examples are enzymatically digested proteins, fish meal, and feather meal. Another source of soil fertility is the decomposing remains of plants from past years. Additionally, naturally occurring minerals such as rock phosphate, potassium sulfate and limestone are also considered inorganic fertilizers. Inorganic fertilizers are usually made through chemical processes (such as the Haber-Bosch process), also using natural deposits, along with their chemical transformation (for example, concentrated triple superphosphate). Natural inorganic fertilizers include Chilean sodium nitrate, rock phosphate, and limestone.

As used in this application, the term "urea-containing fertilizer (1)" is defined as a fertilizer containing at least one component selected from the group consisting of urea, urea ammonium ammonium nitrate (UAN), isobutylidene diurea (IBDU), crotonylidene diurea (CDU) and urea formaldehyde (UF), urea-acetaldehyde, urea-glyoxal condensates.

In a preferred embodiment of the invention, the urea-containing fertilizer (1) is urea.

In a preferred embodiment of the invention, the percentage by weight of at least one component selected from the group consisting of urea, urea ammonium ammonium nitrate (UAN), isobutylidene diurea (IBDU), crotonylidene diurea (CDU) and urea formaldehyde (UF), urea-acetaldehyde, urea-glyoxal condensates relative to the total weight of the urea-containing fertilizer (1) are at least 100 wt. %, preferably at least 99.9 wt. %, more preferably at least 99 wt. %, most preferably at least 95 wt. %, especially preferably at least 90 wt. %, in particular, more preferably at least 80 wt. %, in particular, most preferably at least 70 wt. %, in particular at least 60 wt. %, for example at least 50 wt. %, for example at least 40 wt. %.

In a preferred embodiment of the invention, the percentage by weight of urea relative to the total weight of the urea-containing fertilizer (1) is at least 100 wt. %, preferably at least 99.9 wt. %, more preferably at least 99 wt. %, most preferably at least 95 wt. %, especially preferably at least 90 wt. %, in particular, more preferably at least 80 wt. %, in particular, most preferably at least 70 wt. %, in particular at least 60 wt. %, for example at least 50 wt. %, for example at least 40 wt. %.

In a preferred embodiment of the invention, the percentage by weight of at least one component selected from the group consisting of urea, urea ammonium ammonium nitrate (UAN), isobutylidene diurea (IBDU), crotonylidene diurea (CDU) and urea formaldehyde (UF), urea-acetaldehyde, urea-glyoxal condensates in relation to the total mass of fertilizer containing urea (1) are more than 5 wt. %, preferably more than 10 wt. %, more preferably more than 20 wt. %, most preferably more than 30 wt. %, especially preferably more than 40 wt. %, in particular, more preferably more than 50 wt. %, in particular, most preferably more than 60 wt. %, in particular more than 70 wt. %, for example, more than 80 wt. %, for example, preferably more than 90 wt. %, for example more than 94 wt. %.

In a preferred embodiment of the invention, the percentage by weight of urea relative to the total weight of the urea-containing fertilizer (1) is more than 5 wt. %, preferably more than 10 wt. %, more preferably more than 20 wt. %, most preferably more than 30 wt. %, especially preferably more than 40 wt. %, in particular, more preferably more than 50 wt. %, in particular, most preferably more than 60 wt. %, in particular more than 70 wt. %, for example, more than 80 wt. %, for example, preferably more than 90 wt. %, for example more than 94 wt. %.

In the case of the usual quality of fertilizers on the market, the urea has a purity of at least 90% and, for example, can be presented in crystalline, granular, compressed, prilled or ground form.

As used in this application, "phosphorus fertilizer (3)" is any fertilizer that provides any form of the chemical element phosphorus (P), or containing any chemical compound that includes the chemical element phosphorus (P), including, but not limited to them, phosphate-containing fertilizers or fertilizers containing P ₂ O ₅ . Preferably, the phosphorus-containing fertilizer is selected from the group consisting of NPK fertilizer, NP fertilizer, PK fertilizer, or phosphorus fertilizers. Most preferably, the phosphorus fertilizer is an NPK fertilizer. Of course, combinations of these fertilizers can also be used as an additional phosphorus-containing fertilizer (3b).

Phosphorus fertilizers, potassium fertilizers, and nitrogen fertilizers are simple fertilizers, that is, fertilizers that contain only one of the nutrients P, K, and N. However, it must be understood that these fertilizers may additionally contain at least one additional nutrient , selected from C, H, O, S, Ca, Mg, Fe, Mn, Cu, Zn, Mo, and B.

Preferred phosphate fertilizers include basic phosphate slag (Thomas slag), superphosphate, triple superphosphate, partially dispersed phosphate rock, amorphous phosphate rock, dicalcium phosphate, thermal (fused) phosphate, aluminum orthophosphate, and combinations thereof.

NPK fertilizers, NP fertilizers, and PK fertilizers are multinutrient fertilizers, that is, fertilizers that contain combinations of nutrients P, K, and N, as indicated by the terms "NPK," "NP," and " PK". However, it must be understood that these fertilizers may additionally contain at least one additional nutrient element selected from C, H, O, S, Ca, Mg, Fe, Mn, Cu, Zn, Mo, and B.

NPK fertilizers, NP fertilizers, and PK fertilizers can be provided in the form of complex fertilizers or in the form of bulk or mixed fertilizers. The term compound fertilizer refers to a complex fertilizer formed by mixing ingredients that react chemically. In the case of bulk or blended fertilizers, two or more granular fertilizers of similar size are mixed to form a compound fertilizer.

The premix (P) and the urea melt (Q) are mixed so that the decomposition of the more heat-sensitive urease inhibitor in the hotter melt of the urea or urea derivative composition prior to granulation is slowed down or even prevented. Since the urea melt (Q) has a higher temperature than the premix, it is advantageous to keep the residence time of the mixture of premix (P) and urea melt (Q) before granulation as short as possible. This avoids significant losses of TPT due to thermal decomposition in the hotter melt of urea (Q) after addition to it. This can be achieved by feeding the mixture as close as possible to the granulation unit, that is, the premix (P) is introduced into the pipeline carrying the urea melt (Q), at a short distance from the outlet of said pipeline into the granulation unit. The maximum residence time of the mixture (M) before granulation depends on the effective stability of the TPT under the conditions, and especially the temperature, at which the urea melt (Q) is fed for granulation.

In one embodiment of the present method, the residence time of the TPT in the urea melt (Q) is less than 60 minutes, preferably less than 45 minutes, more preferably less than 30 minutes, most preferably less than 15 minutes, especially preferably less than 5 minutes, particularly more preferably less 2.5 minutes and in particular most preferably less than 1 minute. When using NBPT and/or NPPT as TPT and a urea melt (Q) consisting essentially of urea, the maximum residence time may be less than 30 minutes, preferably less than 15 minutes, most preferably less than 5 minutes. In the most preferred embodiment, the residence time between administration (or mixing) and granulation is approximately 0.2-1 minute. In one embodiment of the present method, the residence time of the at least one urease inhibitor in the urea melt (Q) is selected such that any degradation of the at least one urease inhibitor in the urea melt (Q) is less than 15 percent, preferably less than 12 percent, more preferably less than 10 percent, most preferably less than 8 percent, especially preferably less than 6 percent, especially preferably less than 5 percent, particularly more preferably less than 4 percent, particularly more preferably less than 3 percent, eg less than 2 percent, eg less than 1 percent, relative to the initial TPT concentration.

To improve the mixing of the liquid and solid TPT-containing premix (P) with the urea melt (Q), a mixer can be used. However, considering the above mentioned reasons, it is advantageous to use a static mixer and only a short residence time of the urea melt (Q) in the mixer. In another embodiment of the method, additional additives are added to the urea melt (Q), in particular an additive containing formaldehyde. The additive is preferably added before the granulation process, for example, in order to improve the physical properties of the granules, especially their caking properties. This can be carried out just before the granulation stage using a static mixer which ensures proper mixing of the additive and the urea melt (Q). In this case, it is advantageous to introduce the TPT-containing premix (P) either together with said additional additives, or to introduce the TPT-containing premix (P) at a place close to the point of introduction of said additional additives and before the mixer. This is an economical solution because no additional mixer is required.

In another embodiment, in order to prevent caking, an external coating may be applied after the granulation step.

The concentration of TPT in the mixture (M) depends on many factors, such as the effectiveness of the inhibitor in blocking urease, and as a consequence the concentration required to achieve the desired agronomic effect. Therefore, the concentration depends on the nature of the TPT. Moreover, the concentration also depends on the stability of the TPT during the granulation process and during storage of the fertilizer, as well as on established regulatory limits, if any.

In the case of using NBPT as a urease inhibitor, the concentration is determined using established regulatory limits (see European Fertilizer Regulation CE 2003/2003) and optimized within these limits, taking into account economic aspects and also depending on the expected shelf life of the fertilizer. Accordingly, the concentration of NBPT in urea ranges between 0.042 and 0.093 percent by weight.

In general, the amount of TPT depends on the total urea or urea derivative content of the fertilizer.

A solvent with a boiling point less than 100°C is not used or added to TPT. Preferably, a solvent with a boiling point of less than 120° C. is not used or added to the TPT. More preferably, a solvent with a boiling point of less than 140° C. is not used or added to the TPT. Most preferably, a solvent with a boiling point of less than 140° C. is not used or added to the TPT. In particular, a solvent with a boiling point of less than 160° C. is not used or added to the TPT. Particularly preferably, a solvent with a boiling point of less than 180° C. is not used or added to the TPT. In particular, more preferably, a solvent with a boiling point of less than 200° C. is not used or added to the TPT. In particular, most preferably, a solvent with a boiling point of less than 220° C. is not used or added to the TPT. For example, a solvent with a boiling point less than 240° C. is not used or added to TPT.

Premix (P) can be obtained by mixing urea-containing fertilizer (1) with TPT. Premix (P) can also be prepared by mixing urea-containing fertilizer (1) with TPT, where TPT is combined with the amine (4) before mixing. Premix (P) can also be prepared by mixing urea-containing fertilizer (1) with TPT, where TPT is dissolved in the amine (4) before mixing. Heat may be required to combine or dissolve TPT with/in amine (4).

Temperature T1 is defined as the temperature (at normal pressure) of the TPT-containing premix (P) when the premix (P) is provided in accordance with process step a) as described above.

Moreover, it is preferable if the temperature T1 of the TPT-containing premix (P) is controlled so that little or no release of R1R2-NH2 as a TPT decomposition product is detected. Thus, the temperature T1 of the TPT-containing premix (P) must be adjusted according to the chemical nature of the TPT. Local overheating must also be avoided in order to prevent any decomposition of the TPT.

In one embodiment, the temperature T1 of the TPT-containing premix (P) does not exceed the melting point of the TPT and, in the case of more than one TPT, does not exceed the melting temperature of the TPT with the highest boiling point. In another embodiment, the temperature T1 of the TPT-containing premix (P) does not exceed the melting point of TPT minus 3°C - and in the case of using more than one TPT does not exceed the melting temperature of the TPT with the highest boiling point minus 3°C. In yet another embodiment, the temperature T1 of the TPT-containing premix (P) does not exceed the melting point of TPT minus 6°C - and in the case of using more than one TPT does not exceed the melting temperature of the TPT with the highest boiling point minus 6°C. In yet another embodiment, the temperature T1 of the TPT-containing premix (P) does not exceed the melting point of TPT minus 10°C - and in the case of using more than one TPT - does not exceed the melting temperature of the TPT with the highest boiling point minus 10°C. In yet another embodiment, the temperature T1 of the TPT-containing premix (P) does not exceed the melting point of TPT minus 15°C - and in the case of using more than one TPT, does not exceed the melting temperature of the TPT with the highest boiling point minus 15°C. In yet another embodiment, the temperature T1 of the TPT-containing premix (P) does not exceed the melting point of the TPT minus 20°C and, in the case of using more than one TPT, does not exceed the melting temperature of the TPT with the highest boiling point minus 20°C. In yet another embodiment, the temperature T1 of the TPT-containing premix (P) does not exceed the melting point of TPT minus 25°C - and in the case of using more than one TPT does not exceed the melting temperature of the TPT with the highest boiling point minus 25°C. In yet another embodiment, the temperature T1 of the TPT-containing premix (P) does not exceed the melting point of TPT minus 30°C - and in the case of using more than one TPT - does not exceed the melting temperature of the TPT with the highest boiling point minus 30°C. In yet another embodiment, the temperature T1 of the TPT-containing premix (P) does not exceed the melting point of TPT minus 35°C - and in the case of using more than one TPT - does not exceed the melting temperature of the TPT with the highest boiling point minus 35°C.

In another embodiment, the temperature T1 of the TPT-containing premix (P) is preferably no more than 60°C, more preferably no more than 55°C, most preferably no more than 50°C, especially preferably no more than 45°C, particularly more preferably not more than 40°C, in particular most preferably not more than 35°C, for example not more than 30°C, for example preferably not more than 25°C, for example not more than 20°C.

Temperature T2 is defined as the temperature (at normal pressure) of the urea melt (Q) at the point in time when the TPT-containing premix (P) is added to said urea melt (U) in accordance with process step b) as described above.

Moreover, it is preferable that the temperature T2 of the urea melt (Q) is maintained at a value slightly above the melting temperature of the mixture (M) in order to avoid subsequent decomposition of TPT when urea (Q) is added to said melt. In this case, it is possible to introduce (M) compounds into this mixture in order to lower its melting point. In case this melt consists mainly of urea, it is preferable if the melt temperature T2 (Q) is in the range between 110°C and 160°C, preferably in the range between 120°C and 140°C, most preferably in range between 130°C and 135°C.

In one embodiment of the present method, the TPT-containing premix (P) and/or urea melt (Q) includes additional additives, in particular a formaldehyde-containing compound, in particular in the form of a urea-formaldehyde polymer or condensate.

The TPT-containing premix (P) can be added to the urea melt (Q) by means of a suitable pump and/or flow meter or solids dosing device. As mentioned earlier, a mixture of TPT-containing premix (P) and urea melt (Q) can be passed through a static mixer located in the pipeline to mix the premix (P) with the urea melt (Q) so as to achieve uniform distribution of all compounds in combined melt. In a preferred embodiment, no additional elements are located or placed in the pipeline that would significantly increase the residence time of the melt mixture in the pipeline prior to the granulation step.

In the next granulation step, the mixture of TPT-containing premix (P) and urea melt (Q) is converted into solid fertilizer granules, and granulation should not be considered as a limitation in terms of the method used. The granulation step can be carried out, for example, through one of the following processes:

- Prilling process

- Fluid bed granulation

- Drum granulation

- Spherodizer process

or any other process designed to form solid fertilizer granules.

This method is carried out in an installation containing:

- at least one unit for providing a TPT-containing premix (P);

- at least one unit for providing urea and/or at least one urea derivative in molten form (such as a plant for the production of urea or at least one melting unit for urea and/or at least one urea derivative);

- at least one pipeline for transporting the urea melt (Q);

- at least one inlet (for example, an injection nozzle) for supplying a TPT-containing premix (P) into the pipeline,

- optionally a mixer, preferably a static mixer, for mixing the TPT-containing premix (P) and the urea melt (Q), and

- at least one granulation unit,

wherein at least one urease inhibitor melt inlet and preferably a static mixer are located upstream and close to the at least one granulation unit.

The term "unit" means in particular a separable and identifiable part of an installation and may, for example, be a device, a tank system, or a piping system.

The term "close" in the context of the present invention means that the inlet for the TPT-containing premix (P) and the static mixer are in the vicinity of the outlet of the pipeline transporting the urea melt (Q) to the granulation unit. This means that the distance between the premix inlet (P) and the granulation unit is selected so that the residence time of the TPT in the urea melt (Q) is kept to a minimum, that is, so that the TPT in the urea melt (Q) does not decompose, or only a small amount decomposes. his percentage.

As mentioned above, the object of the present invention is also achieved by providing a fertilizer composition including TPT and urea-containing fertilizer (1), which can be obtained using the described method.

The present composition is characterized by a uniform distribution of TPT in a urea-containing fertilizer (1).

The amount of TPT in the present composition may preferably be in the range between 0.0001 and 5 wt. %, more preferably in the range between 0.001 and 3 wt. %, most preferably in the range between 0.005 and 1 wt. %; the amount of urea-containing fertilizer (1) in the present composition may be in the range between 5 and 99.95 percent by weight, more preferably in the range between 15 and 99 weight percent. %, most preferably in the range between 20 and 97 wt. %, in particular between 25 and 95 wt. %, for example in the range between 30 and 90 wt. %. Additional additives may be added, such as additives containing formaldehyde or ammonium salts.

This fertilizer composition is characterized by increased storage stability. In particular, in the case of the present method, the degradation of TPT occurs more slowly, for example, when compared with a formulation in which the urea is coated with a urease inhibitor (eg, NBPT), especially if no additional additive is added to stabilize the TPT.

The effectiveness of a true urea fertilizer can also be measured by ammonia volatilization (that is, nitrogen loss due to ammonia released into the atmosphere) when it is applied to the soil surface. The indicated ammonia release can be determined in laboratory studies or in field experiments, and compared with the same fertilizer and under similar conditions, but not containing a urease inhibitor.

This method and fertilizer composition provide a number of advantages compared to known methods:

Compared with the use of TPT or NBPT solution, the technical advantage of the present method is that there is no need to use any solvent with a boiling point of less than 100°C to produce the combined fertilizer.

solvent means cost savings, fewer safety and health risks, no solvent residues in the resulting fertilizer or in the off-gases of the granulation process, which would complicate the off-gas cleaning device.

Compared to adding TPT or NBPT in the form of a melt, as described, for example, in WO 2017/125383, adding TPT or NBPT in the form of a premix that is not a melt allows for simpler technology, since the premix can be manufactured in another production facility, and then transported to the installation in the form of a ready-to-use premix. In addition, an effective urea fertilizer containing NBPT can be produced without using Urea-Formaldehyde Polymers (UFP) as a base for NBPT. This means that the new method does not require the pre-production of such NBPT-coated MFPs, but simply uses a premix containing NBPT to add urea to the melt.

The storage of TPT-treated urea was studied at room temperature over several months to observe the degradation of TPT during storage. Fertilizer samples were stored in closed bags in a climate chamber at a temperature of 25°C. The TPT content could be analyzed at various time points by HPLC, using the DIN EN 16651 method. The relationship between the content thus analyzed and the initial TPT content is expressed as the percentage of TPT recovery.

The ammonia volatilization of fertilizer produced according to the present process, compared to standard urea and TPT or NBPT coated urea surfaces, was analyzed using flash chambers. In these evaporation chambers, similar soil samples were placed in different cells with controlled humidity, and one fertilizer sample could be tested in each cell. Fertilizer samples were applied to the soil surface in each cell. The chambers were purged with a constant flow of air, which after the chamber passes through a sulfuric acid-based trap. If volatilization occurs, ammonia is transferred to the trap and the amount of volatilization is determined by analyzing the ammonia content in the trap. This volatilization is expressed as nitrogen loss in kg per hectare, taking into account the soil surface in the cells and the amount of fertilizer applied. Ammonia volatilization measurements continue over a period of four weeks.

The present invention will be illustrated using the following examples.

Examples

Materials:

Urease inhibitors:

Urease inhibitor "U1" was obtained from BASF SE. Compound:

• 18.75 wt. % N-Butylphosphorothionic acid triamide (NBPT, CAS No.: 94317-64-3)

• 6.25 wt. % N-propylphosphorothionic acid triamide (NPPT, CAS No.: 916809-14-8)

LTM is a technical mixture (100% NxPT concentration) containing 25% NPPT and 75% NBPT.

LFG is a polyethylenimine with a weight average molecular weight of 800 g/mol as determined by GPC (dry matter, pH 4.5)

Limus was formulated by mixing LTM (25% pure NxPT) with 15% DMSO, 5% LFG, and up to 100% propylene glycol. The mixture was stirred until the solid dissolved and analyzed for NxPT content (by HPLC), viscosity at 20° C. with a shear rate of 100 sec-1, dissolution (2%) in water and pH.

Fertilizers:

Urea (Piagran 46) was obtained from SKW Piesteritz.

The urea granules were ground to <0.5 mm. Urea powder was mixed with NBPT and NPPT powder to form a premix.

Example 1

a) Premix 1: Urea granules were ground to <0.5 mm. The urea powder was mixed with the Limus composition in a urea powder to solution ratio of 1:1 to obtain a suspension.

b) Premix 2: Urea granules were ground to <0.5 mm. The urea powder was mixed with the Limus formulation in a urea powder to solution ratio of 2:1 to form a paste.

c) Premix 3: Urea granules were ground to <0.5 mm. The urea powder was mixed with the Limus formulation at a urea powder to solution ratio of 10:1 to obtain a free-flowing powder.

Example 2

d) Premix 4: Urea granules were ground to <0.5 mm. Urea powder was mixed with a solution of NBPT and NPPT in polyethyleneimine (40 wt%) in a ratio of urea powder to solution of 1:1 to obtain a viscous liquid.

e) Premix 5: Urea granules were ground to <0.5 mm. Urea powder was mixed with a solution of NBPT and NPPT in polyethyleneimine (40 wt.%) in a ratio of urea powder to solution of 2:1, to obtain a paste.

f) Premix 6: Urea granules were ground to <0.5 mm. Urea powder was mixed with a solution of NBPT and NPPT in polyethyleneimine (40 wt%) in a ratio of urea powder to solution of 10:1 to obtain a free-flowing powder.

Example 3

A stainless steel vessel was filled with 500 g of urea and heated to 135°C under continuous stirring. After all the urea has melted, the appropriate amount of premix is added and mixed for 30 seconds. After this, the molten urea was poured onto a stainless steel tray and allowed to cool for 30 minutes at room temperature. Then, the solidified urea was broken into pieces, and 2 samples of 15 g, each dissolved in 100 ml of water, were analyzed using HPLC in accordance with the method DIN EN 16651, and the specified concentration of a.v. averaged and reported in the rightmost column (d.v. extraction).

The above results show that the TPT contained in the premix is not decomposed during the melting process, and therefore remains stable or stabilized during the melting process.

Claims (29)

1. A method for producing a fertilizer composition that contains (I) at least one urea-containing fertilizer (1); And (II) at least one (thio)phosphoric acid triamide (2), which is N-n-butylthiophosphoric acid triamide (NBPT), N-n-propylthiophosphoric acid triamide (NPPT), and a combination thereof; which includes stages: a) providing solid and/or liquid premix (P), wherein the premix (P) contains at least one urea-containing fertilizer (1) and at least one (thio)phosphoric acid triamide (2) in a mass ratio of 4:1-50:1, based on the total weight of all urea-containing fertilizers fertilizers (1) and all (thio)phosphoric acid triamides (2), wherein at least 85 wt.% of the premix (P) (a1) is not a melt; And (a2) is not obtained by melting any of at least one urea-containing fertilizer (1) or melting any of at least one (thio)phosphoric acid triamide (2); And (a3) is prepared by dissolving or mixing at least one (thio)phosphoric acid triamide (2) in a solvent (S) having a boiling point above 100°C, where the solvent (S) contains an amine; And b) adding a premix (P) to a melt (Q) comprising a urea-containing fertilizer (1) by forming a mixture (M) comprising at least one urea-containing fertilizer (1) and at least one (thio)phosphoric acid triamide (2), wherein the residence time of the mixture (M) thus formed before granulation is adjusted so that at least one (thio)phosphoric acid triamide (2) does not decompose or is almost not decomposed in the mixture (M); And c) forming solid fertilizer granules by using a mixture (M) comprising at least one urea-containing fertilizer (1) and at least one (thio)phosphoric acid triamide (2). 2. The method according to claim 1, wherein the urea-containing fertilizer (1) contained in the premix (P) has an average particle size in the range of 0.0001-60 mm. 3. Method according to claim 1 or 2, wherein the urea-containing fertilizer (1) contained in the premix (P) has an average particle size in the range of 0.005-4 mm. 4. Method according to one of paragraphs. 1-3, wherein the premix (P) which is provided in step a) contains - at least one urea-containing fertilizer (1) and - at least one (thio)phosphoric acid triamide (2) combined with an amine having a boiling point of more than 100°C. 5. Method according to one of paragraphs. 1-3, wherein the premix (P) which is provided in step a) contains - at least one urea-containing fertilizer (1) and - at least one (thio)phosphoric acid triamide (2) combined with a polymeric polyamine. 6. Method according to one of paragraphs. 1-5, and the premix (P) is liquid. 7. Method according to one of paragraphs. 1-5, and the premix (P) is solid. 8. Method according to one of paragraphs. 1-7, wherein the premix (P) is provided at a temperature T1 that does not exceed the melting point of the (thio)phosphoric acid triamide (2) having the highest boiling point among the at least one (thio)phosphoric acid triamide (2). 9. Method according to one of paragraphs. 1-8, and the premix (P) is provided at a temperature T1, which is not more than 50°C. 10. Method according to one of paragraphs. 1-9, wherein the urea-containing fertilizer (1) is urea. 11. Method according to one of paragraphs. 1-10, with at least 98 wt.% of the premix (P) (a1) is not a melt; And (a2) is not obtained by melting any of at least one urea-containing fertilizer (1) or melting any of at least one (thio)phosphoric acid triamide (2); And (a3) is prepared by dissolving or mixing at least one (thio)phosphoric acid triamide (2) in a solvent (S) having a boiling point above 100°C.