Compositions with improved urease-inhibiting effect comprising (thio)phosphoric acid triamide and further compounds such as amines and colorants

Abstract

A composition comprising: (A) a mixture comprising at least one (thio)phosphoric acid triamide according to the general formula (I) R.sup.1R.sup.2N—P(X)(NH.sub.2).sub.2, wherein X is oxygen or sulfur; R.sup.1 is a C.sub.1 to C.sub.20 alkyl, C.sub.3 to C.sub.20 cycloalkyl, C.sub.6 to C.sub.20 aryl, or dialkylaminocarbonyl group; R.sup.2 is H, or R.sup.1 and R.sup.2 together with the nitrogen atom linking them define a 5- or 6-membered saturated or unsaturated heterocyclic radical, which optionally comprises 1 or 2 further heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur, and (L1) at least one amine selected from the group consisting of (L10), (L11), (L12), (L13), (L14), (L15), (L16), (L17), (L18), (L19), (L20), (L21), (L22), (L23), (L24), and (L29).

Claims

1. A composition comprising: (A) a mixture comprising at least one (thio)phosphoric acid triamide according to the general formula (I)
R.sup.1R.sup.2N—P(X)(NH.sub.2).sub.2, wherein X is oxygen or sulfur; R.sup.1 is a C.sub.1 to C.sub.20 alkyl, C.sub.3 to C.sub.20 cycloalkyl, C.sub.6 to C.sub.20 aryl, or dialkylaminocarbonyl group; R.sup.2 is H, or R.sup.1 and R.sup.2 together with the nitrogen atom linking them define a 5- or 6-membered saturated or unsaturated heterocyclic radical, which optionally comprises 1 or 2 further heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur; (L1) at least one amine selected from: (L29) homopolymers of amino acids; and (C) at least one amine selected from: (C1) polymeric polyamines.

2. The composition according to claim 1, further comprising: at least one amine selected from the group consisting of: (C2) an amine containing not more than one amino group and at least three alkoxy- or hydroxy-substituted C.sub.2 to C.sub.12 alkyl groups R.sup.21, wherein at least one of the groups R.sup.21 is different to the other groups R.sup.21; (C3) an amine containing not more than one amino group and at least two alkoxy- or hydroxy-substituted C.sub.2 to C.sub.12 alkyl groups R.sup.22, wherein at least one of the groups R.sup.22 bears the alkoxy or hydroxy substituent at a secondary or tertiary carbon atom and wherein at least one of the groups R.sup.22 is different to the other group(s) R.sup.22; (C4) an amine containing at least one saturated or unsaturated C.sub.8 to C.sub.40 alkyl group R.sup.23; and (C5) a saturated or unsaturated heterocyclic amine which contains at least one oxygen atom as ring atom and which does not contain a further alkoxy group.

3. The composition according to claim 1, wherein (C1) is polyethylene imine.

4. The composition according to claim 2, wherein (C2) is an amine selected from the group consisting of Bis(hydroxyethyl)-isopropanolamine (DEIPA), and 1,1′-((2-Hydroxyethyl)imino)dipropan-2-ol.

5. The composition according to claim 1, further comprising: (E) an alcohol comprising at least two hydroxy groups which are not dissociable in an aqueous medium.

6. The composition according to claim 1, further comprising: (E) propane-1,2-diol (alpha-propylene glycol).

7. The composition according to claim 1, further comprising: (K1) an amine selected from the group consisting of: (L211) methyldiethanolamine; (L212) tetrahydroxypropylethylenediamine; (L213) trimethylaminoethylethanolamine; (L214) N,N,N′,N′-tetramethyl-1,6-hexanediamine; (L215) N,N′,N″-tris(dimethylaminopropyl)hexahydrotriazine; and (L216) 2,2′-dimorpholinyldiethyl ether.

8. The composition according to claim 1, further comprising an amine selected from the group consisting of: (L217) triethanolamine; (L218) tripropanolamine; (L219) diisopropanolamine; (L220) triisopropanolamine; (L221) diethanolamine; and (L222) methyldipropanolamine.

9. The composition according to claim 1, further comprising DMSO.

10. The composition according to claim 1, further comprising a mixture of propane-1,2-diol (alpha-propylene glycol) and DMSO.

11. The composition according to claim 1, wherein the mixture (A) comprises at least one N-n-butylthiophosphoric acid triamide (NBPT) and N-n-propylthiophosphoric acid triamide (NPPT).

12. The composition according to claim 1, further comprising (D) at least one amide according to the general formula (III)
R.sup.31CO—NR.sup.32R.sup.33 wherein R.sup.31CO is an acyl radical having 1 to 22 carbon atoms; R.sup.32 is H or alkyl; and R.sup.33 is H or alkyl; or R.sup.32 and R.sup.33 together with the nitrogen atom linking them define a 5- or 6-membered saturated or unsaturated heterocyclic radical, which optionally comprises 1 or 2 further heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur.

13. The composition according to claim 12, wherein (D) is a N,N-dialkyl amide based on lactic acid, citric acid, tartaric acid, ricinoleic acid, 12-hydroxy stearic acid, or their mixtures.

14. The composition according to claim 1, wherein the homopolymers of amino acids (L29) are selected from the group consisting of: (L573) homopolymers of an alpha-amino acid (α-amino acid), (L574) homopolymers of a naturally occurring alpha-amino acid, (L575) homopolymers of a proteinogenic alpha-amino acid, (L576) homopolymers of alanine, (L577) homopolymers of arginine, (L578) homopolymers of asparagine, (L579) homopolymers of aspartic acid, (L580) homopolymers of cysteine, (L581) homopolymers of glutamic acid, (L582) homopolymers of glutamine, (L583) homopolymers of glycine, (L584) homopolymers of histidine, (L585) homopolymers of isoleucine, (L586) homopolymers of leucine, (L587) homopolymers of lysine, (L588) homopolymers of methionine, (L589) homopolymers of phenylalanine, (L590) homopolymers of proline, (L591) homopolymers of serine, (L592) homopolymers of threonine, (L593) homopolymers of tryptophan, (L594) homopolymers of tyrosine, (L595) homopolymers of valine, (L596) homopolymers of selenocysteine, (L597) homopolymers of pyrrolysine, (L598) homopolymers of N-formylmethionine, and (L599) homopolymers of ornithine.

15. The composition according to claim 14, wherein the homopolymers of amino acids (L29) are selected from the group consisting of homopolymers of lysine (L587).

16. The composition according to claim 15, wherein the homopolymers of lysine (L587) are selected from the group consisting of: (L600a) homopolymers of L-lysine, (L601a) homopolymers of D-lysine, (L602) alpha-polylysine, and (L603) epsilon-polylysine.

17. A composition comprising: (A) a mixture comprising at least one (thio)phosphoric acid triamide according to the general formula (I)
R.sup.1R.sup.2N—P(X)(NH.sub.2).sub.2, wherein X is oxygen or sulfur; R.sup.1 is a C.sub.1 to C.sub.20 alkyl, C.sub.3 to C.sub.20 cycloalkyl, C.sub.6 to C.sub.20 aryl, or dialkylaminocarbonyl group; R.sup.2 is H, or R.sup.1 and R.sup.2 together with the nitrogen atom linking them define a 5- or 6-membered saturated or unsaturated heterocyclic radical, which optionally comprises 1 or 2 further heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur; (L1) at least one amine selected from: (L29) homopolymers of amino acids; and (C) at least one amine selected from: (C2) an amine containing not more than one amino group and at least three alkoxy- or hydroxy-substituted C.sub.2 to C.sub.12 alkyl groups R.sup.21, wherein at least one of the groups R.sup.21 is different to the other groups R.sup.21.

18. The composition according to claim 17, wherein (C2) is an amine selected from the group consisting of Bis(hydroxyethyl)-isopropanolamine (DEIPA), and 1,1′-((2-Hydroxyethyl)imino)dipropan-2-ol.

Description

EXAMPLE 1.1

(1) 500 g granulated urea was charged to a rotating drum (Type Hege 11) and 2 g of the formulation of each example (e.g. Example no. 8) was sprayed on the urea using a rotating disc. The homogeneous coated urea was discharged after 1 min and analyzed for the content of NBPT, NPPT, NxPT (by HPLC).

(2) Stability on Urea

(3) The coated urea sample of 300 g was stored in a petri dish for 4 weeks at 50% humidity at 40° C. in a climate chamber. For analysis the sample was homogenized and analyzed for the content of NBPT, NPPT, NxPT (by HPLC). The stability on urea in % was calculated as difference between the content before and after storage.

(4) The content of NxPT measured by HPLC measurement is always the sum of the both components NBPT and NBPT.

(5) Viscosity was measured at the undiluted formulation with a cone-plate rheometer AR 2000ex (TA Instruments) at shear rate of 100 s.sup.−1 and 20° C.

(6) The pH value was measured at 2% concentration in CIPAC water D.

(7) All examples of the inventions are liquid, clear compositions which are either colourless or yellow.

(8) TABLE-US-00002 TABLE 2 Examples of the compositions of the invention and of comparative compositions, and data on their viscosity, pH value, cold stability, formulation stability and stability on urea InvEx InvEx InvEx InvEx InvEx CpEx CpEx Formulation ExNo. 1 2 3 4 5 6 7 Active [%] 25% 25% 25% 25% 25% 30% 20% ingredient LTM LTM LTM LTM LTM NBPT NBPT Formulation Solvent PG PG PG PG PG 30%-60% PG (ad 100%) PG Formulation Cosolvent 20% 20% 20% 25% 25% 15%-40% 30% DMSO DMSO DMSO DML DML TGBE and DMSO 1%-5% DGBE Formulation Polymers 6.25% 6.25% 6.25% 6.25% 6.25% LFG LFG LFG LFG LFG Formulation Amine 10% 10% 10% TEOA DEIPA DEIPA Formulation Colorant 1% 1% 1% 1% 1% Viscosity [mPa*s] 53 70 69 77 103 15 21 pH 1% 10.7 10.7 10.7 10.7 10.7 7.5 9 Cold stability 1w/1w seeded 20° C. (+) (+) (+) (+) (+) (+) (+) 15° C. (+) (+) (+) (+) (+) (+) (+) 10° C. (+) (+) (+) (+) (+) (+) (+) 5° C. (+) (+) (+) (+) (+) (+) (+) 0° C. (+) (+) (+) (+) (+) (+) (+) −5° C. (+) (+) (+) (+) (+) (+) (+) −10° C. (+) (+) (+) (+) (+) (+) (+) Formulation 14d/54° C. 99.4 97.70 99.7 99.0 99.9 98.5 98.10 stability [%] Stability on 4w/40° C./ 78 86 76 80 74 46 54 urea [%] 50% rH InvEx InvEx InvEx InvEx InvEx InvEx InvEx Formulation ExNo. 8 9 10 11 12 13 14 Active [%] 25% 25% 25% 25% 25% 25% 25% ingredient LTM LTM LTM LTM LTM LTM LTM Formulation Solvent PG PG PG PG PG PG PG (ad 100%) Formulation Cosolvent 15% 15% 25% 15% 15% 15% 15% DMSO DMSO DML DMSO DMSO DMSO DMSO Formulation Polymers 5% 10% 5% 5% 15% 20% 10% LFG LFG LFG LEO LEO LEO LEO Viscosity [mPa*s] 52 81 62 42 61 78 49 pH 1% 10.5 10.7 10.4 9.2 9.5 9.6 9.4 Cold stability 20° C. (+) (+) (+) (+) (+) (+) (+) 1w/1w 15° C. (+) (+) (+) (+) (+) (+) (+) seeded 10° C. (+) (+) (+) (+) (+) (+) (+) 5° C. (+) (+) (+) (+) (+) (+) (+) 0° C. (+) (+) (+) (+) (+) (+) (+) −5° C. (+) (+) (+) (+) (+) (+) (+) −10° C. (−) (−) (−) (−) (−) (+) (−) Formulation 14d/54° C. 99.71 99.19 99.55 99.02 97.13 99.74 98.95 stability [%] Stability on 4w/40° C./ 72.29 77.9 74.36 60 70 78.05 76.74 urea [%] 50% rH InvEx InvEx InvEx InvEx InvEx InvEx InvEx CpEx Formulation ExNo. 15 16 17 18 19 20 21 30 Active [%] 25% 25% 25% 25% 25% 25% 25% 25% ingredient LTM LTM LTM LTM LTM LTM LTM LTM Formulation Solvent PG PG PG PG PG PG PG PG (ad 100%) Formulation Cosolvent 25% 15% 15% 25% 15% 25% 15% 15% DML DMSO DMSO DML DMSO DML DMSO DMSO Formulation Polymers 10% 5% 10% 5% 10% 10% 10% LEO LGA LGA LGA PEIE0 PEIEO PEIPO Viscosity [mPa*s] 62 53 85 62 66 77 61 34 pH 1% 9.3 10.4 10.6 10.3 10 10 9.9 7.6 Cold stability 20° C. (+) (+) (+) (+) (+) (+) (+) (+) 1w/1w 15° C. (+) (+) (+) (+) (+) (+) (+) (+) seeded 10° C. (+) (+) (+) (+) (+) (+) (+) (+) 5° C. (+) (+) (+) (+) (+) (+) (+) (+) 0° C. (+) (+) (+) (+) (+) (+) (+) (+) −5° C. (+) (+) (+) (+) (+) (+) (+) (+) −10° C. (−) (−) (−) (−) (−) (−) (−) (−) Formulation 14d/54° C. 98.7 99.95 100 99.79 99.33 97.96 99.41 99.05 stability [%] Stability on 4w/40° C./ 66.67 59.52 78.05 60 77.38 82.05 72.5 42.86 urea [%] 50% rH InvEx InvEx InvEx InvEx InvEx InvEx InvEx CpEx Formulation ExNo. 22 23 24 25 26 27 28 29 Active [%] 25% 25% 25% 25% 25% 25% 25% 25% ingredient LTM LTM LTM LTM LTM LTM LTM LTM Formulation Solvent PG PG PG PG PG PG PG PG (ad 100%) Formulation Cosolvent 25% 15% 25% 15% 25% 15% 25% 25% DML DMSO DML DMSO DML DMSO DML DML Formulation Polymers 10% 10% 10% 10% 10% 10% 10% PEIPO Poly- Poly- Poly- Poly- LPEI LPEI lysine lysine lysine lysine (L604) (L604) (L605) (L605) Viscosity [mPa*s] 72 103 127 94 117 116 145 40 pH 1% 9.9 10.2 10.2 10.2 10.1 9.8 9.8 7.2 Cold stability 20° C. (+) (+) (+) (+) (+) (+) (+) (+) 1w/1w 15° C. (+) (+) (+) (+) (+) (+) (+) (+) seeded 10° C. (+) (+) (+) (+) (+) (+) (+) (+) 5° C. (+) (+) (+) (+) (+) (+) (+) (+) 0° C. (+) (+) (+) (+) (+) (+) (+) (+) −5° C. (+) (+) (+) (+) (+) (+) (+) (+) −10° C. (−) (−) (−) (−) (−) (−) (−) (−) Formulation 14d/54° C. 99.28 99.55 98.78 97.5 98.91 100 100 99.3 stability [%] Stability on 4w/40° C./ 72.09 61.9 62.65 69.88 69.51 79.52 74.39 45 urea [%] 50% rH
Study on Ammonia Volatilization Losses
Material and Methods—Laboratory Studies

(9) The method used to measure NH3 volatilization losses from urea in the laboratory is described by Fenn & Kissel (1973) and Terman (1979). In brief, air passes for up to 21 days over 200 g soil Limburgerhof (loamy sand, pH(CaCl2)) 6.8), with a moisture content of about 55% water holding capacity, in a gas exchange vessel after surface application of 0.25 g nitrogen in form of differently formulated urea. To scrub NH3 from the air leaving the vessel at a rate of about 4 L/min, it is bubbled through a solution of 200 mL 0.15 N H2SO4. NH3-N is quantified at regular intervals in the solution as NH4-N by means of an autoanalyzer.

(10) Fenn, L. B. and D. E. Kissel (1973) Ammonia volatilization from surface applications of ammonium compounds on calcareous soils: I. General theory. Soil Sci. Am. Proc. 37, 855-859. Terman, G. L. (1979) Volatilization losses of nitrogen as ammonia from surface-applied fertilizers, organic amendments and crop residues.

(11) Advances in Agronomy 31, 189-223.

(12) The results of the study on ammonia volatilization losses is shown in FIG. 1. In FIG. 1, the axis “X” stands for “days after urea application”, the axis “Y” stands for “NH3-N losses, cumulated (% of applied urea nitrogen)”, the unfilled circles “(i)” stand for “urea”, the filled squares “(ii)” stand for “0.04% (A1) in propylene glycol formulation”, the filled circles “(iii)” stand for “0.04% (A1) in AD25 formulation”.