CAPSULES COMPRISING BENZYLPROPARGYLETHERS FOR USE AS NITRIFICATION INHIBITORS

Abstract

Capsules comprising benzylpropargylethers for use as nitrification inhibitors. The capsules include a core and a shell and may further include a matrix. When including a core and a shell, the core includes benzylpropargylether compounds and the shell includes a shell material. When including a core, a shell, and a matrix, the matrix includes benzylpropargylether compounds and a matrix material. The disclosure further relates to methods of reducing nitrification using the capsules.

Claims

1. Capsules comprising: (1) a core (a) and a shell (b), wherein the core (a) is encapsulated by the shell (b); or (2) a matrix (c); wherein, if the capsules comprise a core (a) and a shell (b) according to option (1), the core (a) comprises compounds of formula I ##STR00022## or a stereoisomer, salt, tautomer, or N-oxide thereof wherein R.sup.1 and R.sup.2 are independently of each other selected from the group consisting of H, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.4-alkyl C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenyloxy, C.sub.2-C.sub.6-alkynyloxy, wherein the C-atoms may in each case be unsubstituted or may carry 1, 2 or 3 identical or different substituents R.sup.e; C.sub.3-C.sub.8-cycloalkyl, C.sub.3-C.sub.8-cycloalkenyl, heterocyclyl, aryl, hetaryl, C.sub.3-C.sub.8-cycloalkyl-C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.8-cycloalkenyl-C.sub.1-C.sub.6-alkyl, heterocyclyl-C.sub.1-C.sub.6-alkyl, aryl-C.sub.1-C.sub.6-alkyl, and hetaryl-C.sub.1-C.sub.6-alkyl, phenoxy and benzyloxy, wherein the cyclic moieties may in each case be unsubstituted or may carry 1, 2, 3, 4, or 5 identical or different substituents R.sup.a; A is phenyl, wherein said phenyl ring may be unsubstituted or may carry 1, 2, 3, 4, or 5 identical or different substituents R.sup.A; wherein R.sup.A is selected from the group consisting of CN, halogen, NO.sub.2, OR.sup.b, NR.sup.cR.sup.d, C(Y)R.sup.b, C(Y)OR.sup.b, C(Y)NR.sup.cR.sup.d, S(Y).sub.mR.sup.b, S(Y).sub.mOR.sup.b, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-alkylthio, wherein the C-atoms may in each case be unsubstituted or may carry 1, 2 or 3 identical or different substituents R.sup.e; C.sub.3-C.sub.8-cycloalkyl, C.sub.3-C.sub.8-cycloalkenyl, heterocyclyl, aryl, hetaryl, C.sub.3-C.sub.8-cycloalkyl-C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.8-cycloalkenyl-C.sub.1-C.sub.6-alkyl, heterocyclyl-C.sub.1-C.sub.6-alkyl, aryl-C.sub.1-C.sub.6-alkyl, and hetaryl-C.sub.1-C.sub.6-alkyl, phenoxy and benzyloxy, wherein the cyclic moieties may be unsubstituted or may carry 1, 2, 3, 4, or 5 identical or different substituents R.sup.a; and wherein R.sup.a is selected from CN, halogen, NO.sub.2, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl and C.sub.1-C.sub.4-alkoxy; or two substituents R.sup.a on adjacent C-atoms may be a bridge selected from CH.sub.2CH.sub.2CH.sub.2CH.sub.2, OCH.sub.2CH.sub.2CH.sub.2, CH.sub.2OCH.sub.2CH.sub.2, OCH.sub.2CH.sub.2O, OCH.sub.2OCH.sub.2, CH.sub.2CH.sub.2CH.sub.2, CH.sub.2CH.sub.2O, CH.sub.2OCH.sub.2, O(CH.sub.2)O, SCH.sub.2CH.sub.2CH.sub.2, CH.sub.2SCH.sub.2CH.sub.2, SCH.sub.2CH.sub.2S, SCH.sub.2SCH.sub.2, CH.sub.2CH.sub.2S, CH.sub.2SCH.sub.2, S(CH.sub.2)S, and form together with the C atoms, to which the two R.sup.a are bonded to, a 5-membered or 6-membered saturated carbocyclic or heterocyclic ring; R.sup.b is selected from H, C1-C6-alkyl, C2-C.sub.4-alkenyl, C2-C.sub.4-alkynyl, C1-C.sub.4-haloalkyl, phenyl and benzyl; R.sup.c and R.sup.d are independently of each other selected from the group consisting of H, C.sub.1-C.sub.4-alkyl, and C.sub.1-C.sub.4-haloalkyl; or R.sup.c and R.sup.d together with the N atom to which they are bonded form a 5- or 6-membered, saturated or unsaturated heterocycle, which may carry a further heteroatom being selected from O, S and N as a ring member atom and wherein the heterocycle may be unsubstituted or may carry 1, 2, 3, 4, or 5 substituents which are independently of each other selected from halogen; R.sup.e is selected from CN, halogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-alkoxy, and C.sub.1-C.sub.4-haloalkoxy; Y is O or S; and m is 0, 1 or 2; and the shell (b) comprises a shell material, which is selected from the group consisting of (b1) polyaddition products of isocyanates; (b2) poly(meth)acrylates; and (b3) aminoplasts; and wherein, if the capsules comprise a matrix (c) according to option (2), the matrix (c) comprises compounds of formula I ##STR00023## or a stereoisomer, salt, tautomer, or N-oxide thereof wherein R.sup.1 and R.sup.2 are independently of each other selected from the group consisting of H, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.4-alkyl C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenyloxy, C.sub.2-C.sub.6-alkynyloxy, wherein the C-atoms may in each case be unsubstituted or may carry 1, 2 or 3 identical or different substituents R.sup.e; C.sub.3-C.sub.8-cycloalkyl, C.sub.3-C.sub.8-cycloalkenyl, heterocyclyl, aryl, hetaryl, C.sub.3-C.sub.8-cycloalkyl-C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.8-cycloalkenyl-C.sub.1-C.sub.6-alkyl, heterocyclyl-C.sub.1-C.sub.6-alkyl, aryl-C.sub.1-C.sub.6-alkyl, and hetaryl-C.sub.1-C.sub.6-alkyl, phenoxy and benzyloxy, wherein the cyclic moieties may in each case be unsubstituted or may carry 1, 2, 3, 4, or 5 identical or different substituents R.sup.a; A is phenyl, wherein said phenyl ring may be unsubstituted or may carry 1, 2, 3, 4, or 5 identical or different substituents R.sup.A; wherein R.sup.A is selected from the group consisting of CN, halogen, NO.sub.2, OR.sup.b, NR.sup.cR.sup.d, C(Y)R.sup.b, C(Y)OR.sup.b, C(Y)NR.sup.cR.sup.d, S(Y).sub.mR.sup.b, S(Y).sub.mOR.sup.b, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-alkylthio, wherein the C-atoms may in each case be unsubstituted or may carry 1, 2 or 3 identical or different substituents R.sup.e; C.sub.3-C.sub.8-cycloalkyl, C.sub.3-C.sub.8-cycloalkenyl, heterocyclyl, aryl, hetaryl, C.sub.3-C.sub.8-cycloalkyl-C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.8-cycloalkenyl-C.sub.1-C.sub.6-alkyl, heterocyclyl-C.sub.1-C.sub.6-alkyl, aryl-C.sub.1-C.sub.6-alkyl, and hetaryl-C.sub.1-C.sub.6-alkyl, phenoxy and benzyloxy, wherein the cyclic moieties may be unsubstituted or may carry 1, 2, 3, 4, or 5 identical or different substituents R.sup.a; and wherein R.sup.a is selected from CN, halogen, NO.sub.2, C.sub.1-C.sub.4-alkyl, C1-C.sub.4-haloalkyl and C.sub.1-C.sub.4-alkoxy; or two substituents R.sup.a on adjacent C-atoms may be a bridge selected from CH.sub.2CH.sub.2CH.sub.2CH.sub.2, OCH.sub.2CH.sub.2CH.sub.2, CH.sub.2OCH.sub.2CH.sub.2, OCH.sub.2CH.sub.2O, OCH.sub.2OCH.sub.2, CH.sub.2CH.sub.2CH.sub.2, CH.sub.2CH.sub.2O, CH.sub.2OCH.sub.2, O(CH.sub.2)O, SCH.sub.2CH.sub.2CH.sub.2, CH.sub.2SCH.sub.2CH.sub.2, SCH.sub.2CH.sub.2S, SCH.sub.2SCH.sub.2, CH.sub.2CH.sub.2S, CH.sub.2SCH.sub.2, S(CH.sub.2)S, and form together with the C atoms, to which the two R.sup.a are bonded to, a 5-membered or 6-membered saturated carbocyclic or heterocyclic ring; R.sup.b is selected from H, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl, C.sub.1-C.sub.4-haloalkyl, phenyl and benzyl; R.sup.c and R.sup.d are independently of each other selected from the group consisting of H, C.sub.1-C.sub.4-alkyl, and C.sub.1-C.sub.4-haloalkyl; or R.sup.c and R.sup.d together with the N atom to which they are bonded form a 5- or 6-membered, saturated or unsaturated heterocycle, which may carry a further heteroatom being selected from O, S and N as a ring member atom and wherein the heterocycle may be unsubstituted or may carry 1, 2, 3, 4, or 5 substituents which are independently of each other selected from halogen; R.sup.e is selected from CN, halogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-alkoxy, and C.sub.1-C.sub.4-haloalkoxy; Y is O or S; and m is 0, 1 or 2; and a matrix material, which is selected from the group consisting of (c1) a poly(meth)acrylates; and (c2) calcium alginate.

2. The capsules according to claim 1, wherein, in the compounds of formula I, R.sup.1 and R.sup.2 are each H; A is phenyl, wherein said phenyl ring is unsubstituted or carries 1, 2, or 3 identical or different substituents R.sup.A, wherein R.sup.A, if present, is selected from the group consisting of halogen, C.sub.1-C.sub.4-alkyl, and C1-C.sub.4-alkoxy.

3. The capsules according to claim 1, wherein the vapor pressure of the compounds of formula I is more than 0.2 Pa at 20 C.

4. The capsules according to claim 1, wherein the capsules comprise a core (a) and a shell (b), wherein the core (a) is encapsulated by the shell (b), and wherein the weight ratio of the core (a) to the shell (b) is from 70:30 to 98:2.

5. The capsules according to claim 1, wherein the shell material is selected from (b1) polyaddition products of isocyanate, which comprise (b1a) at least one polyfunctional isocyanate and at least one polyfunctional amine in polymerized form; or (b1b) at least one polyfunctional isocyanate and at least one polyfunctional alcohol in polymerized form; or (b1c) at least one polyfunctional isocyanate and at least one polyfunctional amine and at least one polyfunctional alcohol in polymerized form.

6. The capsules according to claim 1, wherein the shell material is (b2a) a poly(meth)acrylate comprising methyl methacrylate and/or methacrylic acid in polymerized form; or (b3a) an aminoplast comprising melamine and formaldehyde in polymerized form.

7. The capsules according to claim 1, wherein the shell (b) of the capsules comprises organic or inorganic protective colloids.

8. The capsules according to claim 1, having a volume median particle size of more than 300 m.

9. A capsule suspension comprising: a suspended phase comprising the capsules according to claim 1, wherein the capsules have a volume median particle size of 300 m or less; and a liquid phase wherein the weight ratio of the suspended phase to the liquid phase is from 1:0.5 to 1:100.

10. A mixture comprising: (i) an inorganic carrier granule, an organic carrier granule, a fertilizer, a composition comprising a fertilizer, or a granule comprising a fertilizer; and (ii) capsules according to claim 1.

11. A method of using the capsules according to claim 1, the method comprising applying the capsules to the root zone of a plant, the soil, soil substituents and/or the locus where a plant is growing or is intended to grow.

12. The method according to claim 11 further comprising using the capsules for reducing nitrification.

13. A method for reducing nitrification comprising applying the capsules according to claim 1 to the root zone of a plant, the soil, soil substituents and/or the locus where a plant is growing or is intended to grow.

14. The method according to claim 13, wherein the root zone of a plant, the soil, soil substituents and/or the locus where a plant is growing or is intended to grow is additionally provided with a fertilizer, wherein the application of the capsules according to claim 1, and the fertilizer may be carried out simultaneously or with a time lag.

15. The mixture according to claim 10, wherein the fertilizer comprises a solid or liquid ammonium-containing inorganic fertilizer, preferably a NPK fertilizer, ammonium nitrate, calcium ammonium nitrate, ammonium sulfate nitrate, ammonium sulfate, or ammonium phosphate; a solid or liquid organic fertilizer, preferably liquid manure, semi-liquid manure, biogas manure, stable manure and straw manure, worm castings, compost, seaweed or guano; or an urea-containing fertilizer such as urea, formaldehyde urea, urea ammonium nitrate (UAN) solution, urea sulphur, stabilized urea, urea based NPK-fertilizers, or urea ammonium sulfate.

16. The capsules according to claim 4 wherein the weight ratio of the core (a) to the shell (b) is from 80:20 to 95:5.

17. The capsules according to claim 8 having a volume median particle size of 1 mm or more.

18. The capsules according to claim 9 wherein the weight ratio of the suspended phase to the liquid phase is from 1:1 to 1:10.

Description

EXAMPLES

[0552] The following abbreviations and terms that are used herein:

TABLE-US-00002 LIST OF ABBREVIATIONS AND TERMS PVA polyvinyl alcohol - 4 wt % solution of Polyvinyl alcohol having a viscosity of 18 mPas according to DIN 53015 and a degree of hydrolysis of 88% MDI 4,4-diphenylmethane diisocyanate MDI-based solvent free polyisocyanate based on 4,4- Polyisocyanate diphenylmethane diisocyanate (MDI) with an average functionality of 2,7, NCO content 32 g/ 100 g) MHPC methylhydroxypropyl cellulose Soprophor 4D384 polyarylphenyl ether sulfate EO ethylene oxide PO propylene oxide DETA diethylene triamine TEPA triethylene pentaamine HNO.sub.3 nitric acid K.sub.2SO.sub.4 potassium sulfate GC gas Chromatograph ECD electron Capture Detector m Micrometer g Gram wt % weight % min Minute h Hour RT room temperature (20 to 25 C.)

Example 1

[0553] Polyurea capsule suspension 1 stabilized by polyvinyl alcohol as a protective colloid was prepared according to the procedure described hereinbelow:

TABLE-US-00003 Ingredient Amount (in g) Initial charge Deionised water 187.50 PVA 45.00 Feed 1 Compound-10 142.5 MDI-based Polyisocyanate 72.5 Feed 2 TEPA (25 wt %) 17.16

[0554] A water phase comprising water and the protective colloid PVA (10 wt %) was introduced as the initial charge at RT. Under stirring conditions, Feed 1 comprising the polyisocyanate and the compound A-10 of Table 1 were added and the mixture dispersed in the aqueous phase for 3 min at 15,000 rpm. Tetraethyl pentaamine solution (25 wt %) was added under stirring for 15 min. The mixture was further heated to 80 C. for 1 h, and maintained at the same temperature for 1 h and further cooled to RT. The dispersion obtained had a solid content of 28.5 wt % and average particle size (D0.5) of 6.66 m.

Example 2

[0555] Polyurea capsule suspension 2 stabilized by polyvinyl alcohol as a protective colloid was prepared in an analogous manner according to the procedure described in Example 1 and by involving the ingredients provided hereinbelow, excepting that the water phase was introduced at 20 C. or less.

TABLE-US-00004 Ingredient Amount (in g) Initial charge Deionised water 208 PVA 30 Feed 1 Compound A-10 85 MDI-based Polyisocyanate 15 Feed 2 TEPA (25 wt %) 34.32
The dispersion obtained had a solid content of 23.1 wt % and average particle size (D0.5) of 8.66 m.

Example 3

[0556] Polyurea capsule suspension 3 stabilized by polyvinyl alcohol as a protective colloid was prepared in an analogous manner according to the procedure described in Example 1 and by involving the ingredients provided hereinbelow, excepting that the water phase was introduced at 20 C.

TABLE-US-00005 Ingredient Amount (in g) Initial charge Deionised water 211 PVA 30 Feed 1 Compound A-10 95 MDI-based Polyisocyanate 5 Feed 2 TEPA (25 wt %) 11.46
The dispersion obtained had a solid content of 29.6 wt % and average particle size (D0.5) of 8.47 m.

Example 4

[0557] Polyurea capsule suspension 4 stabilized by polyvinyl alcohol as a protective colloid was prepared in an analogous manner to the procedure described in Example 1 and by involving the ingredients provided hereinbelow, excepting that the water phase was introduced at 20 C.

TABLE-US-00006 Ingredient Amount (in g) Initial charge Deionised water 196.05 PVA 30.00 Feed 1 Compound A-10 142.50 MDI-based Polyisocyanate 7.50 Feed 2 TEPA (25 wt %) 17.16
The dispersion obtained had a solid content of 33.7 wt % and average particle size (D0.5) of 7.56 m.

Example 5

[0558] Polyurea capsule suspension 5 stabilized with pickering particles was prepared according to the procedure described hereinbelow:

TABLE-US-00007 Ingredient Amount (in g) Initial charge Deionised water 200 Silica sol (50 wt %) having 24 specific surface area of 80 m.sup.2/g MHPC solution (5 wt %) 1.12 having an average molecular weight of 26,000 g/mol Nitric acid solution (20 wt %) 1.20 Feed 1 Compound A-10 76 MDI-based Polyisocyanate 4 Feed 2 TEPA (25 wt %) 9.15

[0559] A water phase comprising water and the pickering system comprising silica sol, MHPC and HNO.sub.3 was introduced as the initial charge below 20 C. Under stirring, the compound A-10 of Table 1 were added and the mixture dispersed in the aqueous phase at 21,000 rpm for 3 min. TEPA solution was added under stirring for 15 min. The mixture was further heated to 80 C. for 1 h, and maintained at the same temperature for 1 h and further cooled to RT. The dispersion obtained had a solid content of 20.3 wt % and average particle size (D0.5) of 4.78 m.

Example 6

[0560] Polyurea capsule suspension 6 stabilized with pickering particles was prepared in an analogous manner to the procedure described in Example 5 and by using the ingredients provided hereinbelow:

TABLE-US-00008 Ingredient Amount (in g) Initial charge Deionised water 200 Silica sol (50 wt %) 24 MHPC solution (5 wt %) 1.12 HNO.sub.3 solution (20 wt %) 1.20 Feed 1 Compound A-10 68.00 MDI-based Polyisocyanate 12.00 Feed 2 TEPA (25 wt %) 27.46
The dispersion obtained had a solid content of 30.7 wt % and average particle size (D0.5) of 4.97 m.

Example 7

[0561] Acrylate capsule suspension 7 stabilized with pickering particles was prepared in an analogous manner to the procedure described in Example 5 and by using the ingredients provided herein below:

TABLE-US-00009 Ingredient Amount (in g) Initial charge Deionised water 175 Silica sol (50 wt %) 36 MHPC solution (5 wt %) 1.68 Sodium nitrite solution in 0.48 water (2.5 wt %) Nitric acid solution (20 wt % 1.80 in water) Feed 1 Compound A-10 96.00 methyl methacrylate 14.40 Pentaerythritol triacrylate 9.60 Feed 2 Tert-butyl perpivalate (as a 0.32 75% solution in aliphatic hydrocarbons) Feed 3 TEPA (25 wt %) 27.46

[0562] The water phase was added at 20 C. When Feed 2 was introduced, the heating program employed was: heating the reaction mixture to 65 C. in 60 min; heating to 90 C. in 60 min and maintaining the reaction mixture at 90 C. for 90 min at 90 C. TEPA was added to the reaction mixture when the reaction mixture was maintained at 90 C.

[0563] The dispersion obtained had a solid content of 22.5 wt % and average particle size (D0.5) of 2.67 m.

Example 8

[0564]

TABLE-US-00010 Acrylate capsule suspension 8 stabilized with the protective colloid PVA was prepared in an analogous manner to the procedure described in Example 1 and by using the ingredients provided herein below: Ingredient Amount (in g) Initial charge Deionised water 204 PVA 36 Feed 1 Compound A-10 80 methyl methacrylate 12 Pentaerythritol triacrylate 8 Feed 2 Tert-butyl perpivalate (75% 0.27 solution in aliphatic hydrocarbons) Feed 3 TEPA (25 wt %) 27.46

[0565] The dispersion obtained had a solid content of 11.5 wt % and average particle size (D0.5) of 25.4 m.

Example 9

[0566] Melamine formaldehyde capsule suspension 9 was prepared in accordance with the procedure described hereinbelow:

TABLE-US-00011 Ingredient Amount (in g) Initial charge Deionised water 222 Poly(2-acrylamido-2- 17.6 methylpropane sulfonic acid) sodium salt having pH 2.5 to 4 Aqueous polymeric solution 19.7 comprising 1,3,5-triazin-2,4,6- triamine (70% strength by weight) reacted with formaldehye having viscosity of 200 to 350 mPa according to DIN EN ISO 3219 at 20 C.) Feed 1 Compound A-10 68 Feed 2 Aqueous solution of formic 2 acid (25% strength by weight)

[0567] A water phase comprising water, sodium salt of Poly(2-acrylamido-2-methylpropane sulfonic acid and aqueous polymeric solution comprising 1,3,5-triazin-2,4,6-triamine (70% strength by weight) reacted with formaldehye was introduced below 20 C. Compound A-10 of Table 1 was added and the mixture dispersed in the aqueous phase for 3 min at 21,000 rpm. Feed 2 comprising aqueous solution of formic acid was added to stabilize the pH value to 4. Stirring was continued for 2 min. The mixture was further heated to 80 C. for 1 h, and maintained at the same temperature for 1 h and further cooled to RT. The dispersion obtained had a solid content of 21.8 wt % and average particle size (D0.5) of 77.98 m.

Example 10

[0568] Melamine formaldehyde capsule suspension 9 was prepared in an analogous manner accordance with the procedure described in Example 9 and by employing the ingredients as herein below:

TABLE-US-00012 Ingredient Amount (in g) Initial charge Deionised water 222 Poly(2-acrylamido-2- 17.6 methylpropane sulfonic acid) sodium salt having pH 2.5 to 4 Aqueous polymeric solution 19.7 comprising 1,3,5-triazin- 2,4,6-triamine (70% strength by weight) reacted with formaldehye having viscosity of 200 to 350 mPa according to DIN EN ISO 3219 at 20 C.) Feed 1 Compound A-10 86.65 Feed 2 Aqueous solution of formic 2 acid (25% strength by weight)
The dispersion obtained had a solid content of 27.2 wt % and average particle size (D0.5) of 29.82 m.

Example 11

[0569] Polyurea capsule suspension stabilized with lignosulfate was prepared in accordance with the procedure described hereinbelow:

TABLE-US-00013 Ingredient Amount (in g) Initial charge Deionised water 339.69 Sodium lignosulfonate 6 Feed 1 Compound A-10 189.99 MDI-based Polyisocyanate 24 Butanol derived EO/PO 7.2 block copolymer Feed 2 DETA 9.12 Feed 3 Glycerine 30 Feed 4 Xanthan gum 30

[0570] A water phase comprising water and sodium lignosulfate was introduced. Under stirring, the mixture comprising compound A-10 of Table 1, MDI based polyisocyanate and butanol derived EO/PO block copolymer was added and the mixture dispersed at 5000 rpm for 3 min. DETA was further added and mixture stirred for 25 min. The mixture was further stirred for 1h at 25 C., cooled to RT further to which glycerine and the thickener xanthan gum were added.

[0571] The dispersion contained an active ingredient of 305 g/l and an average particle size (D0.5) of 3.3 m.

Example 12

[0572] Polyurea capsule suspension stabilized with sodium lignosulfate was prepared in an analogous manner according to the procedure described in Example 11 and by employing the ingredients as provided hereinbelow:

TABLE-US-00014 Ingredient Amount (in g) Initial charge Deionised water 105.75 Sodium lignosulfonate 2.17 Feed 1 Compound A-10 60 MDI-based Polyisocyanate 16 Butanol derived EO/PO 2.4 block copolymer Feed 2 DETA 6.08 Feed 3 Glycerine 20

[0573] The suspension contained an active ingredient of 305 g/l and an average particle size (D0.5) of 2.5 m.

Example 13

[0574] Non-encapsulated emulsion containing the active compound A-10 (of Table 1) was prepared in accordance with the procedure as described hereinbelow:

TABLE-US-00015 Ingredient Amount (in g) Initial charge Deionised water 497 Soprophor 4D384 75 Glycerine 100 Feed 1 Xanthan gum 2 Feed 2 Compound A-10 300

[0575] A water phase comprising water and Soprophor 4D384 was introduced at 20 C. Under stirring, thickener Xanthan gum and the compound A-10 were added and the mixture was dispersed at 5000 rpm for 3 min. The emulsion obtained had an active ingredient content of 300 g/I by weight and an average particle size (D0.5) of 1.2 m.

Example 14

[0576] Soil (100 g) was filled into plastic bottles (500 ml) (e.g. soil sampled from the field) and moistened to 50% water holding capacity. The soil was incubated at 20 C. for one week to activate the microbial biomass. The test solution (1 ml) containing the capsule suspensions 1 to 12 containing the active test compound A-10 in the appropriate concentration (usually 0,3 or 1% of nitrogen N), or DMSO and nitrogen (10 mg) in the form of ammoniumsulfate-N were added to the soil and mixed well. Bottles were capped but loosely to allow air exchange. The bottles were then incubated at 20 C. for 0,14 or 28 days. The same procedure was carried out with the non-encapsulated emulsion comprising the test compound A-10.

[0577] K.sub.2SO.sub.4 solution (1%) (300 ml) was added to the bottle containing the soil and shaken for 2 h in a horizontal shaker at 150 rpm. The whole solution was filtered (Macherey-Nagel Filter MN 807%) and the ammonium and nitrate content were analyzed in the filtrate in an autoanalyzer at 550 nm (Merck, AA11).

[0578] The inhibition (in %) is calculated by the equation [(ab)/(ac)]100; wherein a is the amount of Nitrate-Nitrogen without the test capsule suspensions without the active test compound A-10 at the end of incubation; b is the amount of Nitrate-Nitrogen with the test capsule suspensions containing the active test compound A-10 at the end of incubation; c is the amount of Nitrate-Nitrogen at the beginning. The best inhibition values obtained for the test compounds are provided herein below in Table 2:

TABLE-US-00016 Capsule suspensions prepared according to Inhibition Inhibition (%) Examples 1 to 12 (%) (14 days) (28 days) 1 44 6 2 32 15 3 42 20 4 39 ND 5 47 11 6 44 ND 7 45 11 8 32 0 9 28 16 10 35 21 11 30 11 12 29 19 Non-encapsulated Inhibition (%) Inhibition (%) emulsion (14 days) (28 days) 13 22 9 NDNot determined
The encapsulated capsule suspensions exhibited improved nitrification inhibiting activity as compared to the non-encapsulated emulsion comprising the test compound. The nitrification inhibiting activity was further sustained for an extended period of time.

Example 15

[0579] Green head lettuce was seeded in seedling boxes. Once the 4 leaf stage was reached one plant was potted into a 8 cm pot in standard greenhouse soil (mixture of peat, loam and sand) and grown in the greenhouse at 20 C. and 60% humidity. One week after planting the plants, the pots were separated out and each pot set onto a plant saucer designed with an inner compartment for the pot and an outer ring that is filled with water. At time 0, water with or without various concentrations of fertilizer and with either empty formulation or formulated capsule suspensions was applied to the plant such that the water holding capacity of the soil was around 50%. Then a gas sampling chamber was placed over the plant saucer such that the rim fit into the ring filled with water to create a gas-tight chamber and 20 cc air from the chamber were drawn into a syringe and immediately emptied in to a Vacutainer (Labco, 12 ml volume). This equals the Time Zero measurement for each pot. The same procedure was performed with all pots in the experiment. After incubation time of 1 h, again 20 cc air samples were taken from the gas chambers and emptied into Vacutainers as described above. Plants were then returned to their positions in the greenhouse. The procedure was repeated at precisely the same time of day for the following days until the N.sub.2O emissions were back to background level.

[0580] Samples were analyzed in a Shimadzu 2014 GC equipped with an ECD system. Total cumulated N.sub.2O emissions were calculated and related by calculating the % inhibition compared to control.

TABLE-US-00017 Inhibition (%) N.sub.2O emissions Capsule suspension prepared according to Examples 4 or 6 4 31.44 6 56.93 active test compound A-10 (unformulated) A-10 25
The encapsulated capsule suspensions are more efficacious than the active test compound (unformulated) in reducing N.sub.2O emissions and have enhanced potency as a nitrification inhibitor.