Fertilizer-compatible composition

Abstract

This invention relates to compositions compatible with liquid fertilizers and methods of use thereof.

Claims

1. A fluid thixotropic fertilizer-compatible pesticidal composition substantially free of surfactants comprising: (a) at least one agrochemically active compound; (b) a metal lignosulfate salt, wherein said metal lignosulfate salt is a non-surface active dispersant; (c) a at least one lubricant selected from silica or alumina; (d) a water soluble salt of a strong acid; and (e) water; wherein the agrochemically active compound is in the form of solid particles, wherein the solid particles have an average diameter from 1 nm to 100 microns and are of a sufficiently small average diameter to be effectively dispersed in the composition and the metal lignosulfate salt and water soluble salt are present in a ratio of from about 2:1 to about 1:20 and are combined in amounts effective to disperse the particles in the water.

2. A fluid thixotropic composition according to claim 1 wherein the agrochemically active compound is an insecticide.

3. A fluid thixotropic composition according to claim 1 wherein the agrochemically active compound is a insecticide of formula (I) ##STR00006## wherein R is hydrogen, acyl, alkyl, aryl, aralkyl, heteroaryl or heteroarylalkyl; A is hydrogen, acyl, alkyl, aryl, or a bifunctional group that is linked to Z; E is NO.sub.2, CN, or a halogenoalkylcarbonyl group; X is CR or N, wherein R is hydrogen or a bifunctional group linked to Z; Z is alkyl, OR, SR, or NRR, or Z is a group linked to (i) the radical A or (ii) the radical X or (iii) both A and X; provided that when E is CN, Z is not methyl and R is not a (6-chloro-3-pyridyl)methyl ##STR00007## radical.

4. A fluid thixotropic composition according to claim 1 wherein the agrochemically active compound is ##STR00008## ##STR00009## ##STR00010## ##STR00011##

5. A fluid thixotropic composition according to claim 1 wherein the agrochemically active compound is imidacloprid, thiamethoxam, thiacloprid, clothianidin, nitenpyram, nithiazine, or dinotefuran.

6. A fluid thixotropic composition according to claim 1 wherein the agrochemically active compound is a herbicide.

7. A fluid thixotropic composition according to claim 1 wherein the agrochemically active compound is a fungicide.

8. A fluid thixotropic composition according to claim 1 wherein the agrochemically active compound is a plant growth regulant.

9. The composition of claim 1 wherein the agrochemically active compound and metal lignosulfate salt are present at a ratio of from about 60:1 to about 1:10.

10. The composition of claim 1 wherein the particles are from about 2 to 4 microns average diameter.

11. The composition of claim 1 wherein the metal lignosulfate salt is an alkali metal lignosulfate salt or an alkaline earth metal lignosulfate salt.

12. The composition of claim 1 wherein the water soluble salt of a strong acid is LiCl, NaCl, KCl, MgCl.sub.2, CaCl.sub.2, FeCl.sub.3, NH.sub.4NO.sub.3, Mg(NO.sub.3).sub.2, NaNO.sub.3, K.sub.3PO.sub.4, (NH4).sub.2SO.sub.4, Na.sub.2SO.sub.4, or ZnSO.sub.4.

13. A product comprising a composition according to claim 1 and an agriculturally acceptable liquid fertilizer for simultaneous, separate, or sequential application for control of pests at a locus.

14. A fluid thixotropic composition of claim 1, wherein said agrochemically active compound is imidacloprid.

15. A fluid thixotropic composition of claim 1, wherein said at least one lubricant is silica and alumina.

16. A fluid thixotropic composition of claim 1, wherein said metal lignosulfate salt comprises sodium lignosulfate, potassium lignosulfate, lithium lignosulfate, or calcium lignosulfate.

17. A fluid thixotropic composition of claim 16, wherein said metal lignosulfate salt comprises sodium lignosulfate.

18. A fluid thixotropic composition of claim 1, wherein said water soluble salt of a strong acid comprises KCl.

19. A fluid thixotropic composition of claim 1 further comprising an organic sulfonate.

20. A fluid thixotropic composition of claim 19, wherein said organic sulfonate comprises ammonium salt of alkyl naphthalene sulfonate, sodium salt of alkyl naphthalene sulfonate, or calcium salt of alkyl naphthalene sulfonate.

21. A fluid thixotropic composition of claim 1, wherein (a) said at least one agrochemically active compound comprises imidacloprid; (b) said metal lignosulfate salt comprises sodium lignosulfate, potassium lignosulfate, lithium lignosulfate, or calcium lignosulfate; and (c) said water soluble salt of a strong acid comprises LiCl, NaCl, KCl, MgCl.sub.2, CaCl.sub.2, FeCl.sub.3, NH.sub.4NO.sub.3, Mg(NO.sub.3).sub.2, NaNO.sub.3, K.sub.3PO.sub.4, (NH4).sub.2SO.sub.4, Na.sub.2SO.sub.4, or ZnSO.sub.4.

22. A fluid thixotropic composition of claim 1, wherein said fluid thixotropic fertilizer-compatible pesticidal composition is free of surfactants.

23. A fluid thixotropic composition free of a surfactant comprising: (a) an agrochemically active compound; (b) a metal lignosulfate salt, wherein said metal lignosulfate salt is a non-surface active dispersant; (c) a water soluble salt of a strong acid; and (d) water; wherein the compound is in the form of solid particles and/or liquid globules of sufficiently small average diameter to be effectively dispersed in the composition and wherein the metal lignosulfate salt and water soluble salt are combined in amounts effective to disperse the particles and/or globules in the water.

Description

EXAMPLES

Example 1Liquid Phase Study

(1) This study was done to determine that the medium viscosity is low when there is no active ingredient present. The following solutions were prepared by adding ingredients and mixing using a Ross mixer. A 10 mL sample was added to a 50 mL graduated cylinder and the cylinder was shaken vigorously 20 times. The amount of foam was measured as the percent of the 50 mL volume. The viscosity of each sample was measured using Brookfield viscometer, LVTD, #3 spindle and a speed of 30 rpm with a setting of F=2 for all readings. Specific Gravity measurements were taken performed using a neat sample. Measurements of pH were taken of neat samples. Freezing and thawing temperatures were determined by placing samples in a 20 C. freezer overnight and then allowing the samples to warm. A freezing temperature was recorded when the sample became completely fluid with no noticeable ice crystals present. Tables 2 and 3 show the results of the liquid phase study. There was noticeably more foaming when Agnique PG 9116 was present. Agnique PG 9116 is a C.sub.9-C.sub.11 alkyl polyglycoside non-ionic surfactant with a 1.6% average degree of polymerization available from Cognis Chemicals, website http://www.cognis.com/cognis.html.

(2) TABLE-US-00002 TABLE 2 Liquid Phase Study 1 1 2 3 4 5 6 7 8 9 Deionized Water 96 g 96 g 96 g 96 g 96 g 96 g 96 g 96 g 96 g Glycerin 36 g 36 g 36 g 36 g 36 g 36 g 36 g 36 g Borresperse NA 10.5 g 10.5 g 10.5 g 10.5 g Agnique PG 9116 1.5 g 1.5 g 1.5 g 1.5 g Potassium chloride 12 g 12 g 12 g 12 g Appearance clear dark clear clear clear dark clear clear dark clear dark clear clear brown liquid, colorless colorless brown liquid, colorless brown liquid, brown colorless colorless slight foam liquid with liquid, no with liquid with slight foam liquid, with liquid, no liquid, significant foam significant significant significant foam slight foam foam foam foam foam Foaming, vol. % 8 80 0 76 60 10 80 0 0 Viscosity, cps 7.0 4.0 2.8 3.4 3.6 4.4 4.2 2.0 2.4 Specific gravity 1.098 1.067 1.119 1.098 1.117 1.144 1.136 1.000 1.067 pH 7.5 8.85 6.74 7.47 6.93 7.45 7.49 9.19 8.42 Freeze/thaw 8 C. 6 C. 12 C. 9 C. 13 C. 13 C. 13 C. 0 6 C. Temp. C.

(3) TABLE-US-00003 TABLE 3 Liquid Phase Study 2 10 11 12 13 14 15 16 Deionized water 96 g 96 g 96 g 96 g 96 g 96 g 96 g Borresperse NA 10.5 g 10.5 g 10.5 g 10.5 g Agnique PG 9116 1.5 g 1.5 g 1.5 g 1.5 g Potassium chloride 12 g 12 g 12 g 12 g Appearance clear dark clear colorless clear colorless clear dark clear colorless clear dark clear dark brown liquid, liquid with liquid, no foam brown liquid, liquid with brown liquid, brown liquid slight foam significant foam with significant significant foam slight foam with significant foam foam Foaming, vol % 14 84 0 78 94 16 90 Viscosity 4.0 2.6 2.6 3.6 2.8 3.0 4.0 Specific gravity 1.044 1.001 1.072 1.044 1.072 1.109 1.108 pH 7.63 8.78 7.63 7.44 7.42 7.49 Freeze/thaw Temp 0 C. 0 C. 1 C. 0 C. 2 C. 4 C. 6 C.

Example 2Aqueous Suspension Phase Study

(4) The procedures of Example 1 were performed on the compositions of Tables 4 and 5. The mixtures were prepared by mixing the ingredients first, followed by grinding the contents using a Silverson mixer. The lignin sulfonate medium is studied to show that generally the medium viscosity is low when there is no Al involved. It was observed that some formulation media foamed a lot when there is nonionic surfactant such as Agnique PG 9116 is present in the medium. Freezing and thawing points were not measured. Borresperse NA is sodium lignosulfate (CAS number 8061-51-6) supplied by Lignotech. Hi-Sil 233 is Hydrated Amorphous Silica Gel, CAS number 112926-00-8, available from PPG Industries, Inc. Attagel 50 is an attapulgite clay available from Engelhard Corporation.

(5) TABLE-US-00004 TABLE 4 Suspension Study 1 17 18 19 20 21 22 23 24 25 26 27 Deionized water 96 g 96 g 96 g 96 g 96 g 96 g 96 g 96 g 96 g 96 g 96 g Glycerin 36 g 36 g 36 g 36 g 36 g 36 g 36 g 36 g 36 g 36 g 36 g Borresperse NA 10.5 g 10.5 g 10.5 g 10.5 g 10.5 g 10.5 g 10.5 g 10.5 g 10.5 g 10.5 g 10.5 g Potassium chloride 12 g 12 g 12 g 12 g 12 g 12 g Aluminum oxide C 1.2 g 1.2 g 1.2 g 1.2 g 1.2 g 1.2 g Hi-Sil 233 0.3 g 0.3 g 0.3 g 0.3 g 0.3 g 0.3 g 0.3 g Attagel 50 0.3 g 0.3 g 0.3 g 0.3 g 0.3 g Appearance hazy clear clear hazy hazy clear clear clear hazy hazy hazy brown brown brown brown brown brown brown brown brown brown brown liquid liquid liquid liquid liquid liquid liquid liquid liquid liquid liquid with with with with with with with with with with with slight slight slight slight slight slight slight slight slight slight slight foam foam foam foam foam foam foam foam foam foam foam Foaming vol. % 8 8 8 8 10 8 8 10 12 8 8 Viscosity, cps 5.8 7.8 9 4.2 5.2 5.6 5.6 3.6 5.8 4.8 4.4 Specific gravity 1.105 1.095 1.099 1.104 1.106 1.140 1.145 1.140 1.148 1.149 1.148 pH 7.61 7.63 7.66 7.59 7.65 7.34 7.45 7.4 7.35 7.32 7.4

(6) TABLE-US-00005 TABLE 5 Suspension Study 2 Suspension Study 2 28 29 30 31 32 33 34 35 36 37 38 Deionized water 96 g 96 g 96 g 96 g 96 g 96 g 96 g 96 g 96 g 96 g 96 g Borresperse NA 10.5 g 10.5 g 10.5 g 10.5 g 10.5 g 10.5 g 10.5 g 10.5 g 10.5 g 10.5 g 10.5 g Potassium chloride 12 g 12 g 12 g 12 g 12 g 12 g Aluminum oxide C 1.2 g 1.2 g 1.2 g 1.2 g 1.2 g 1.2 g Hi-Sil 233 0.3 g 0.3 g 0.3 g 0.3 g 0.3 g 0.3 g 0.3 g Attagel 50 0.3 g 0.3 g 0.3 g 0.3 g 0.3 g Appearance hazy clear clear hazy hazy clear clear clear hazy hazy hazy brown brown brown brown brown brown brown brown brown brown brown liquid liquid liquid liquid liquid liquid liquid liquid liquid liquid liquid with with with with with with with with with with with slight slight slight slight slight slight slight slight slight slight slight foam foam foam foam foam foam foam foam foam foam foam Foaming, vol. % 14 14 14 18 16 16 16 16 16 16 16 Viscosity, cps 2.4 2 2.4 2.6 2.4 2.2 2 2.8 3 2.6 3.2 Specific gravity 1.051 1.045 1.045 1.04 1.054 1.102 1.109 1.109 1.114 1.115 1.117 pH 7.54 7.44 7.63 7.55 7.57 7.26 7.37 7.34 7.34 7.25 7.3

Example 3

(7) Samples 39 through 42 were prepared from a wet-milled master batch of 328 g imidacloprid, 32 g, Borresperse NA, and 540 g water. The milling was carried out in a lab Dynomil milling device. After the particle size had reached 2.6 micron (<50% volume average), the resultant mill base was collected and subdivided. To each sample salt and/or glycerin was added to finish the formulations (Samples 39 to 42). The formulations demonstrated surprising compatibility with fertilizers tested (Table 6, 10-34-0, 3-18-18, and 6-24-6). A reference formula (Samples 43, Table 6) using the traditional surfactants alone was prepared for comparison. The fertilizer compatibility test in this invention is carried out to simulate the field test conditions (0.22 lb active ingredient per 5 gallons fertilizer); and the corresponding laboratory rate is 0.375 g active ingredient per 100 g fertilizer. Then the whole mixture is filtered through a screen of US Mesh 50, the net retained residues are measured and reported. The results demonstrated the superior compatibility of the Borresperse NA plus salt as a synergistic dispersant system to that using common surfactants. Morwet D425 is the sodium salt of alkylnaphthalenesulfonate formaldehyde polymer CAS #9084-06-4, alternatively identified with CAS numbers 68425-94-5, 83453-42-3, and 9008-63-3. Alkamuls EL 620 is a fatty acid ethoxylate non-ionic surfactant from Rhodia, Inc.

(8) Samples 44 to 49 (Table 7) were prepared like those in Tables 4, 5 and 6. All ingredients including imidacloprid were mixed well before wet milling. The mixture was milled to an average particle size of 2.8 microns before discharge. Formulation specific gravity and viscosities were measured before testing for fertilizer compatibilities. It is surprising that the combined Ingredients of aluminum oxide, Attagel 50, and Hi Sil 233 further improved the integrity of the resultant formulations. Furthermore, fertilizer tests of these examples showed the significance of glycerin stabilizing the fertilizer dilutions. Lastly the controlled flocculation phenomena with shear thinning effect are clearly shown due to the presence of salt (e.g., potassium chloride).

(9) TABLE-US-00006 TABLE 6 39 40 41 42 43 Imidacloprid 31 31 31 31 31 Morwet D425 2 Alkamuls EL 620 1 Borresperse NA 3 3 3 3 KCl 2 2 Zn sulfate 0.2 0.2 Glycerin 13 14.8 Water 65.8 64 51 51 66 Total (% weight) 100 100 100 100 100 Specific gravity, g/ml 1.133 1.145 1.191 1.177 1.127 Viscosity, cps, set 83 56 64 54 12 Viscosity, cps, stirred 15 8 14 20 9.6 10-34-0 fertilizer + 0 0 0 0 0 50 mesh net retain, %* 3-18-18 fertilizer + 0.09 0.17 0.06 0.06 0.18 50 mesh net retain, %* 6-24-6 fertilizer + 0.01 0.09 0.1 0.04 0.13 50 mesh net retain, %*

(10) TABLE-US-00007 TABLE 7 Basic Formulation Study 44 45 46 47 48 49 Imidacloprid 47.1 g 47.1 g 47.1 g 47.1 g 47.1 g 47.1 g Borresperse NA 3.50 g 3.50 g 3.50 g 3.50 g 3.50 g 3.50 g Agnique PG 9116 0.50 g 0.50 g 0.50 g 0.50 g 0.50 g 0.50 g Glycerin 12.00 g 12.00 g 12.00 g Aluminum oxide C 0.40 g 0.40 g 0.40 g 0.40 g Attagel 50 0.10 g 0.10 g 0.20 g 0.10 g 0.10 g 0.20 g Potassium chloride 4.00 g 4.00 g 4.00 g 4.00 g Hi-Sil 233 0.10 g 0.10 g 0.20 g 0.10 g 0.10 g 0.20 g Water 32.00 g 32.00 g 32.00 g 44.00 g 44.00 g 44.00 g Results Formulation 1.302 1.276 1.294 1.259 1.231 1.257 Specific gravity, g/ml Formulation viscosity, >4000 492 >4000 2400 480 >4000 cps (set) Formulation viscosity, 480 180 956 276 84 352 cps (stirred) Dilution in 342 ppm <0.1 ml <0.1 ml <0.1 ml 0.1 ml 0.1 ml 0.1 ml water* sediment, good sediment, good sediment, sediment, sediment, sediment, resuspension resuspension good some residue some residue some residue after 24 hours after 24 hours resuspension on on on after 24 hours resuspension resuspension resuspension Dilution in 10-34-0 good good good good good good Fertilizer after pre- dispersion, dispersion, dispersion, dispersion, dispersion, dispersion, dilution with water** good good good some sticky some sticky some sticky resuspension. resuspension resuspension residues with residues with residues with resuspension resuspension resuspension *Water dilution test: 0.31 ml/95 g 342 ppm water **1:2 dilution with water at 0.95 ml/99 g 10-34-0 fertilizer

Example 4

(11) Two reference formulations (Table 8, Samples 50 and 51) with 25 weight % imidacloprid in 300 g batch were prepared in traditional suspension concentrate technology using standard wet-milling technique. All ingredients except Keizan (xanthan gum) were charged to a container beforehand and pre-ground using a rotary Silverson mixer followed by wet milling. The milling was carried out in a lab Dynomil apparatus until the particle size reached 2.5 micron (<50% volume average). To finish the formulation, Keizan was post added to the discharged mill bases.

(12) Samples 52 to 54 (Table 9) are formulations containing 25 weight % insecticide with various salts; Samples 55 to 58 (Table 10) are formulations with various lignin sulfonate dispersant combinations. Shear thinning effect is prominent throughout the examples. Samples 59 to 62 (Table 11) are formulations containing nonionic surfactant in addition to the lignin sulfonate. Relatively speaking, the shear thinning in this systems is minimized, clearly due to the effect of the nonionic surfactants.

(13) TABLE-US-00008 TABLE 8 50 51 Imidacloprid 25.0 25.0 Morwet D425 2.0 Geropon T 36 2.25 Alkamul EL620 1.0 APG 9116 0.5 Vangel B 0.5 0.3 Hi Sil 233 0.2 Kelzan 0.5 0.5 Water 71.0 71.25 Total 100 100 Specific gravity, g/ml 1.065 1.004 Viscosity*, cps (set) 2544 3208 Viscosity*, cps (stirred) 2496 3104

(14) TABLE-US-00009 TABLE 9 52 53 54 Imidacloprid 25.00 25.00 25.00 Borresperse NA 2.50 2.50 2.50 Glycerin 8.00 8.00 8.00 Aluminum oxide C 0.30 0.30 0.30 Attagel 50 2.50 2.50 2.50 Hi-Sil 233 1.50 1.50 1.50 Sodium sulfate 3 Calcium chloride 0.5 Zinc sulfate 0.5 Water 57.2 59.7 59.7 Total 100 100 100 Specific gravity, g/ml 1.159 1.186 1.168 Viscosity, cps, set 2280 2300 1040 Viscosity, cps, stirred 1160 1648 864

(15) TABLE-US-00010 TABLE 10 55 56 57 58 Imidacloprid 25.00 25.00 25.00 25.00 Borresperse NA 1.50 1.50 1.50 1.50 Glycerin 8.00 8.00 8.00 8.00 Aluminum oxide C 0.30 0.30 0.30 0.30 Attagel 50 2.50 2.50 2.50 2.50 Hi-Sil 233 1.50 1.50 1.50 1.50 Potassium chloride 3 3 3 3 Ultrazine CA 1 Supragil WP 1 Geropon SDS 1 Lignosperse AGK 200 1 Water 57.2 57.2 57.2 57.2 Total 100 100 100 100 Specific gravity, g/ml 1.183 1.18 1.185 1.183 Viscosity, cps, set 4040 10160 4120 3320 Viscosity, cps, stirred 3064 8560 3332 1044

(16) TABLE-US-00011 TABLE 11 59 60 61 62 Imidacloprid 25.00 25.00 25.00 25.00 Borresperse NA 1.50 1.50 1.50 1.50 Glycerin 8.00 8.00 8.00 8.00 Aluminum oxide C 0.30 0.30 0.30 0.30 Attagel 50 2.50 2.50 2.50 2.50 Hi-Sil 233 1.50 1.50 1.50 1.50 Potassium chloride 3 3 3 3 Pluronic P 65 1 Iconol DA-6 1 Soprophor 796P 1 Alkamul EL-620 1 Water 57.2 57.2 57.2 57.2 Total 100 100 100 100 Specific gravity, g/ml 1.176 1.176 1.184 1.18 Viscosity, cps, set 8460 3320 1920 1780 Viscosity, cps, stirred 13200 2744 1624 1432

Example 5

(17) Samples 50-62 were tested for fertilizer compatibility. Three fertilizers known for their harsh compatibility with many pesticides used in the filed were selected for testing purposes. They are (NPK) 10-34-0, 3-18-18 and 6-24-6. The same tank mixing method as in Table 6 was used and the results are compared in Table 12. It is clear that the new technology from this invention is superior to the traditional suspension concentrate in the area of fertilizer compatibility. A commercial pesticide formulation, Admire 2F, is included in the test. It is known that Admire 2F is made with old suspension concentrate technology.

(18) TABLE-US-00012 TABLE 12 50 51 Admire 2F (ref) (ref) (control) 52 53 54 55 56 57 58 59 60 61 62 10-34-0 fertilizer + 1.92 1.26 1.31 0.30 0.05 0.00 0.16 0.14 0.06 0.20 0.14 0.00 0.16 0.00 50 mesh net retain, %* 3-18-18 fertilizer + 1.65 0.62 0.27 0.16 0.19 0.13 0.15 0.54 0.24 0.05 0.03 0.09 0.12 0.05 50 mesh net retain, %* 6-24-6 fertilizer + 2.42 1.87 1.28 0.32 0.35 0.19 0.43 0.46 0.43 0.62 0.20 0.22 0.45 0.55 50 mesh net retain, %*

Example 6

(19) Reference Sample 63 as indicated in Table 13 was prepared in the same manner as in Samples 50-51. The Reference Sample, along with the Samples 64-71 in Tables 14-15 were tested for fertilizer compatibility as indicated in Table 16.

(20) TABLE-US-00013 TABLE 13 63 Imidacloprid 43.32 Soprophor S25 1.5 Atlox 4913 4.5 Glycerin 14 Proxel GXL 0.25 Hi-Sil 233 0.1 Antifoam 8830 FG 0.1 Water 36.23 Total 100 Specific gravity, g/ml 1.229 Viscosity, cps, stirred 612

(21) TABLE-US-00014 TABLE 14 64 65 66 67 Imidacloprid 43.30 43.30 43.30 43.30 Norlig 11 D 4.00 4.00 Diwatex S-3 4.00 4.00 Glycerin 14.00 14.00 14.00 14.00 Aluminum oxide C 0.40 0.40 0.40 0.40 Attagel 50 0.30 0.30 0.30 0.30 Zinc sulfate 0.50 0.50 Potassium chloride 4.00 4.00 Hi-Sil 233 0.30 0.30 0.30 0.30 Proxel GXL 0.20 0.20 0.20 0.20 Deionized water 33.50 37.00 33.50 37.00 Total 100 100 100 100 Specific gravity, g/ml 1.295 1.256 1.284 1.242 Viscosity, cps, set 11840 4320 5480 19640 Viscosity, cps, stirred 7300 712 436 424

(22) TABLE-US-00015 TABLE 15 68 69 70 71 Imidacloprid 43.88 43.88 43.88 43.88 Borresperse NA 3.5 3.5 3.5 3.5 Morwet D425 0.5 0.5 0.5 0.5 Glycerin 14 14 14 14 Aluminum oxide C 0.4 0.4 0.4 0.4 Attagel 50 0.3 0.3 0.3 0.3 Potassium chloride 3 Sodium chloride 3 Zinc sulfate 0.5 Magnesium chloride 0.5 Proxel GXL 0.1 0.1 0.1 0.1 Hi-Sil 233 0.3 0.3 0.3 0.3 Antifoam 8830 FG 0.3 0.3 0.3 0.3 Water 33.72 33.72 36.22 36.22 Total 100 100 100 100 Specific gravity, g/ml 1.281 1.286 1.261 1.254 Viscosity, cps, set 728 604 180 400 Viscosity, cps, stirred 188 176 60 128

(23) TABLE-US-00016 TABLE 16 43% formulations 63 64 65 66 67 68 69 70 71 342 ppm hard water + 50 0 0 0 0 0 0.04 0.07 0.02 0.00 mesh net retain, % 10-34-0 fertilizer + 50 1.65 0.94 0.01 0.70 0.17 0.83 0.50 0.85 0.81 mesh net retain, % 6-24-6 fertilizer + 50 0.43 0.05 0.16 0.69 0.14 0.29 0.29 0.40 0.75 mesh net retain, % Formulation diluted with water 1:1 beforehand 10-34-0 fertilizer + 50 1.02 0 0 0 0 0.48 0.21 0.18 0.08 mesh net retain, % 6-24-6 fertilizer + 50 0.6 0.024 0.032 0.014 0.011 0.16 0.13 0.29 0.10 mesh net retain, %

Example 7

(24) Preparation of Sample 68 in industrial batch scale. An industrial batch of high concentration imidacloprid suspension concentrate (550 g/l) was manufactured as follows. Charged to a mixing vessel of 150 gallon (568 liter) capacity in the order listed, water, 246 lb (112 kg); Borresperse NA, 30 lb (14 kg); Morwet D425, 4.3 lb (2.0 kg); glycerin, 120.5 lb (55 kg); aluminum oxide, 3.44 lb (1.6 kg); Attagel 50, 2.6 lb (1.2 kg); Hi-Sil 233, 2.6 lb (1.2 kg); Proxel GXL, 0.9 lb (0.41 kg); and Antifoam 8830 FG, 2.6 lb (1.2 kg). The ingredients were then well mixed followed by addition of 377 lb (171 kg) imidacloprid technical. Wet milling was carried out in a bead mill with a 5 liter chamber. Zirconium beads of 1.4 mm diameter were used. The ground formulation mill base was then discharged after the particle size reached <50% volume average of 2.75 microns. To the recovered mill base (762 lb, or 346 kg) was added 43.5 lb (19.7 kg) of water, 25 lb (11.3 kg) potassium chloride and 0.87 lb (0.39 kg) FD&C Blue 1 dye to complete the final formulation. The product afforded the following properties, specific gravity of 1.282, set viscosity, 728 cps and stirred viscosity, 188 cps. The initial viscosity was surprisingly low; however, given time the viscosity was found to have increased after 4 weeks at room temperature to a set viscosity of 1040 cps, stirred viscosity 80 cps; another sample after 4 weeks at 40 C provided a set viscosity of 3130 cps; stirred viscosity, 112 cps).

Example 8

(25) The product of Example 7 was mixed with various liquid fertilizers under laboratory conditions. 500 mL of the following liquid fertilizers were placed into a clear container: local tap water; 7-30-3; 7-26-0-8; and 10-34-0. Admire 2F and Sample 68 were added at rates below for a 20 grams per acre application of imidacloprid to the soil. This represented about 3.1 mL of Admire 2F per 500 mL fertilizer and about 1.3 mL of Sample 68 per 500 mL fertilizer. Combinations were inverted four times and left to stand for 10 minutes. Observations were made immediately after inversion and after standing for 10 minutes. If combinations were not in solution after 10 minutes, an additional 250 mL of water was added to aid the product's entry into solution. Combination was inverted an additional four times and observations were taken after 10 minutes of standing. The following results shown in Tables 17-22 were obtained.

(26) TABLE-US-00017 TABLE 17 (Mixing +10 minutes +10 min. + 250 with water) Initial mixing standing mL water Admire 2F Mixed into solution Normal product Not necessary No scum layer settling No initial precipitates Foam Foam Sample 16 Mixed into solution Normal product Not necessary No scum layer settling No initial precipitates No foam No foam

(27) TABLE-US-00018 TABLE 18 Mix with +10 minutes +10 min. + 250 7-30-3 Initial mixing standing mL water Admire 2F Mixed into suspension Normal product Addition of water of suspended bodies settling did not change No scum layer nor mixture initial precipitates No foam Sample 68 Mixed into suspension Normal product Addition of water of suspended bodies settling did not change No scum layer mixture No initial precipitates No foam

(28) TABLE-US-00019 TABLE 19 Mix with +10 minutes +10 min. + 250 7-26-0-8 Initial mixing standing mL water Admire 2F Mixed into suspension Suspended bodies of suspended bodies dissolved into No scum layer a true solution No initial precipitates No settling No foam Sample 68 Mixed into suspension Suspended bodies of suspended bodies dissolved into No scum layer a true solution No initial precipitates No settling No foam

(29) TABLE-US-00020 TABLE 20 Mix with +10 minutes +10 min. + 250 10-34-0 Initial mixing standing mL water Admire 2F Mixed into suspension Product settled Addition of water of suspended bodies out did not change Scum layer mixture No initial precipitates No foam Sample 68 Mixed into suspension Product settled Addition of water of suspended bodies out did not change No scum layer mixture No initial precipitates No foam

(30) TABLE-US-00021 TABLE 21 Mix with +10 minutes +10 min. + 250 5-17-0 Initial mixing standing mL water Admire 2F Mixed into suspension Product settled of suspended bodies out Scum layer No precipitates No foam Sample 68 Mixed into a true Normal product solution settling No scum layer No precipitates No foam

(31) TABLE-US-00022 TABLE 22 +10 minutes +10 min. + 250 Initial mixing standing mL water Admire 2F Mixed into suspension Product settled of suspended bodies out No scum layer No precipitates No foam AMSI 302 Mixed into a true Normal product 550SC solution settling No scum layer No precipitates No foam

Example 9

(32) Solid insecticides, fungicides, and their mixture suspension concentrates (SC) were prepared using the same procedures as detailed in Example 3. The insecticides and fungicides encompass not only CNI compounds but a wide variety of other chemistries, yet the resultant suspensions surprisingly showed the same pattern of stability and induced shear thinning (Table 23). All samples showed the same fertilizer compatibility (Table 24).

(33) TABLE-US-00023 TABLE 23 72 73 74 75 76 77 78 Imidacloprid 32.80 Trifloxystrobin 14.10 Clothianidin 46.55 23.30 Carbaryl 30.00 Thiodicarb 35.00 17.50 Aldicarb 40.00 BYI 8330 (spirotetramat) 23.00 Borresperse NA 4.00 3.00 3.00 9.00 3.00 3.50 3.80 Morwet D425 0.50 0.20 0.30 0.50 0.50 0.40 0.50 Citric Acid 0.10 Glycerin 8.00 16.00 12.00 10.00 16.00 10.00 8.00 Potassium chloride 2.00 8.00 4.00 6.50 4.00 3.00 2.00 Aluminum oxide 0.40 0.80 0.40 0.50 0.50 0.40 0.40 Attagel 50 0.20 0.30 0.50 0.10 1.20 0.35 0.30 Hi Sil 233 0.30 1.00 1.00 0.50 1.00 0.65 0.20 Antifoam 8830FG 0.30 0.30 0.30 0.15 0.20 0.30 0.20 Proxel GXL 0.10 0.10 0.10 0.10 0.10 0.10 0.10 Water 37.65 40.30 43.40 32.55 50.50 40.50 37.60 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Special gravity 1.30 1.20 1.23 1.25 1.20 1.25 1.29 Viscosity, set 2264 2332 1464 1550 1215 1650 1320 Viscosity, stirred 532 228 210 330 255 345 264

(34) TABLE-US-00024 TABLE 24 Fertilizer test results 3-18-18 fertilizer + 0.15 0.48 0.21 0.18 50 mesh net retain, %

Example 10

(35) Solid insecticides, fungicides, and their mixture suspension concentrates (SC) were prepared using the same procedures as detailed in Example 3 and then further mixed with emulsifiable concentrate (EC) of other insecticides or fungicides to form resultant suspoemulsions (SE). The insecticides and fungicides encompass a wide variety of chemistries, yet the resultant suspoemulsions surprisingly showed the same pattern of physical stability and induced shear thinning (Table 25). All samples showed the same fertilizer compatibility (Table 26).

(36) TABLE-US-00025 TABLE 25 79 80 81 Tebuconazole 9.20 Trifloxystrobin 38.00 19 Prothioconazole tech 9.2 Clothianidin 23.3 Ufoxane 3 A 4.50 2.3 Borresperse NA 3.5 2 Morwet D425 0.50 0.00 0.25 Glycerin 14.00 12.00 10 Potassium chloride 3.00 4.00 3 Aluminum oxide 0.40 0.40 0.4 Attagel 50 0.50 0.20 0.2 Hi Sil 233 0.30 1.00 0.65 Antifoam 8830FG 0.30 0.30 0.3 Proxel GXL 0.10 0.10 0.1 Water 59 39.50 38.5 Total 100.00 100.00 100.00 Special gravity 1.137 1.23 1.25 Viscosity, set 550 1350 1345 Viscosity, stirred 252 420 355

(37) TABLE-US-00026 TABLE 26 Fertilizer test results 3-18-18 fertilizer + 50 0.56 0.14 mesh net retain, %

Example 11

(38) Solid insecticides, fungicides and their mixture suspension concentrate (SC) were prepared using the same procedures as detailed in Example 3, and then further mixed with emulsifiable concentrates (EC) of other insecticides or fungicides to form suspoemulsions (SE). The insecticides and fungicides encompass a wide variety of chemistry, yet the resultant suspoemulsions surprisingly showed the same pattern of physical stability and induced shear thinning (Table 27). All samples showed the same fertilizer compatibility (Table 28).

(39) TABLE-US-00027 TABLE 27 82 83 84 Imidacloprid 16.10 Clothianidin 35.59 Cyfluthrin 9.93 16.10 Trifloxystrobin 19.00 Propiconazole 36.70 Ufoxane 3 A 2.30 Borresperse NA 4.00 3.50 Morwet D425 0.50 0.50 Glycerin 6.00 8.00 12.00 Potassium chloride 2.00 3.00 5.00 Aluminum oxide 0.20 0.40 0.35 Attagel 50 0.10 0.60 1.20 Hi Sil 233 0.50 0.50 1.00 Antifoam 8830FG 0.15 0.40 0.30 Proxel GXL 0.05 0.10 0.10 Water 19.80 31.98 37.35 Aromatic A-150 9.20 Methylene chloride 2.00 2.00 Soprophor FLK 4.00 Pluraflo E5B 2.00 1.50 Atlox 4912 1.00 3.00 Total 100 100 100 Special gravity 1.156 1.228 1.25 Viscosity, stirred 220 430 250 Viscosity, set 750 2250 1540

(40) TABLE-US-00028 TABLE 28 Fertilizer test results 3-18-18 fertilizer + 0.44 1.02 0 50 mesh net retain, % Formulation Diluted with Water 1:1 Beforehand 3-18-18 fertilizer + 0 0.33 0 50 mesh net retain, %

Example 12

(41) Suspension concentrate mixture formulations of insecticides ethiprole, fipronil, and imidacloprid were prepared using essentially the same procedure as described in Example 3, and fertilizer compatibility tests were conducted. Each SC formulation contained 200 g/L of the active compounds and surprisingly exhibited very good compatibility with an NPK plus iron fertilizer (Wuxal) (Tables 29 and 30).

(42) TABLE-US-00029 TABLE 29 85 86 Ethiprole 8.33 Imidacloprid 8.33 8.31 Fipronil 8.31 Borresperse NA 4.00 2.91 Morwet D425 0.58 0.42 Propylene glycol 14.57 11.63 Potassium chloride 3.33 2.49 Aluminum oxide 0.58 0.33 Attagel 50 0.33 0.25 Tixosil 38 0.33 0.25 Silicone antifoam 0.33 0.25 Proxel GXL 0.17 0.08 Water 59.12 64.77 Total 100.00 100.00 Special gravity 1.14 1.14 Dynamic viscosity at 18 19 7.5 per sec, mPa .Math. s Dynamic viscosity at 16 16 20 per sec, mPa .Math. s Dynamic viscosity at 13 13 100 per sec, mPa.Math. s

(43) TABLE-US-00030 TABLE 30 Fertilizer test results 8-8-6 plus Fe fertilizer + 0 0 50 mesh retain, %

Example 13

(44) Suspension concentrates of herbicides and their mixtures were prepared using the procedures detailed in Example 3. The herbicides encompass a wide variety of chemistry yet the resultant suspensions surprisingly showed not only the same pattern of stability and induced shear thinning (Table 31) but also the same fertilizer compatibility (Table 32).

(45) TABLE-US-00031 TABLE 31 87 88 89 Metribusin 40 Flufenacet 40 Isoxaflutole 46 Borresperse NA 4 4 4 Morwet D425 0.5 0.5 0.5 Glycerin 16 16 16 Potassium chloride 6 6 6 Aluminum oxide 0.4 0.4 0.4 Attagel 50 0.2 0.2 0.3 Hi Sil 233 0.4 0.4 1 Antifoam 8830FG 0.3 0.3 0.3 Proxel GXL 0.1 0.1 0.1 Water 32.1 32.1 25.4 Total 100 100 100 Special gravity 1.175 1.18 1.23 Viscosity, set 6800 7000 15800 Viscosity, stirred 3000 3000 2200

(46) TABLE-US-00032 TABLE 32 Fertilizer test results 32-0-0 fertilizer + 0.15 0 0.12 50 mesh retain, %

Example 14

(47) Solid herbicides and their mixed suspension concentrates (SC) were prepared separately with the same procedures as detailed in Example 3 and then further mixed with emulsifiable concentrates (EC) of other herbicides to form resultant suspoemulsions (SE). The insecticides encompass a wide variety of chemistry, yet the resultant suspoemulsions surprisingly showed the same pattern of physical stability and induced shear thinning (Table 33). All samples showed the same fertilizer compatibility (Table 34).

(48) TABLE-US-00033 TABLE 33 90 91 92 Metribusin 20 Isoxaflutole 23 Flufenacet 20 Broxynil octanoate 20.8 20.8 Broxynil heptanoate 21.2 21.2 Acetochlor 26.05 Borresperse NA 2 2 2 Morwet D425 0.25 0.25 0.25 Glycerin 8 8 8 Potassium chloride 3 3 3 Aluminum oxide 0.2 0.2 0.2 Attagel 50 0.15 0.1 0.1 Hi Sil 233 0.5 0.2 0.2 Antifoam 8830FG 0.15 0.15 0.15 Proxel GXL 0.05 0.05 0.1 Water 12.7 16 16 Aromatic A-150 5 20 5 Ca DDBS 0.5 1 0.5 Ethoxylated alcohol 2.5 3 2.5 Total 100 100 100 Special gravity 1.2 1.195 1.3 Viscosity, set 1550 1255 1340 Viscosity, stirred 250 150 310

(49) TABLE-US-00034 TABLE 34 Fertilizer test results 32-0-0 fertilizer + 0.02 0 0 50 mesh retain, %

Example 15

(50) A plant growth regulator cyclanilide suspension concentrate (SC) was prepared using the same procedures as detailed in Example 3 and then further mixed with the water-soluble mepiquat chloride to form a suspension solution mixture. The resultant liquid mixture surprisingly showed not only the same pattern of stability and induced shear thinning (Table 35) but also the same fertilizer compatibility (Table 36).

(51) TABLE-US-00035 TABLE 35 93 Cyclanilide 30 Borresperse NA 2.5 Morwet D425 0.5 Hi Sil 233 0.2 Attagel 50 0.3 Aluminum oxide 0.4 Glycerin 10 KCl 3 Water 43.1 Mepiquat chloride 10 Total 100 Particle size, micron 2.50 Specific gravity, g/ml 1.201 Viscosity, cps, set 160 Viscosity, cps, stirred 80

(52) TABLE-US-00036 TABLE 36 Fertilizer test results 3-18-18 fertilizer + 50 mesh retain, % 0.02 32-0-0 fertilizer + 50 mesh retain, % 0 10-34-0 fertilizer + 50 mesh retain, % 0

Example 16

(53) Insecticide and herbicide suspension concentrates (SC) were prepared with the same procedures as detailed in Example 3, and then further mixed with emulsifiable concentrates (EC) of oil adjuvants to form resultant suspoemulsions (SE). The resultant suspoemulsion surprisingly showed the same pattern of stability and induced shear thinning (Table 37). All samples showed the same fertilizer compatibility (Table 38)

(54) TABLE-US-00037 TABLE 37 94 95 96 Imidacloprid 550 SC 64 (Sample 68) BYI 8330 260 SC 20 (Sample 76) Isoxaflutole 560 SC 50 (Sample 89) Atlox 4914 4 Agnique ME -181 U 34.2 45 (methyl oleate) Atlox 4912 1.8 Soprophor TS 29 5 Halcomid 810 76 (methyl carprylate caprate) Total 100 100 100

(55) TABLE-US-00038 TABLE 38 Fertilizer test results 3-18-18 fertilizer + 0 0 50 mesh retain, % 32-0-0 fertilizer + 0.08 50 mesh retain, %