STROBILURIN FORMULATIONS

• US 20140364310A1
• Filed: 08/23/2012
• Published: 12/11/2014
• Est. Priority Date: 12/22/2011
• Status: Active Grant

• Current Assignee: Vive Crop Protection Inc.
• Original Assignee: Vive Crop Protection Inc.
• Inventors: Li, Fugang, Pham, Hung Hoang, Gong, Rachel, Galas, Henry
• Granted Patent: US 10,206,391 B2
• Time in Patent Office: Days
• US Class Current: 504/101
• CPC Class Codes: A01N 2300/00 Combinations or mixtures of active ingredients covered by classes A01N27/00 - A01N65/48 with other active or formulation relevant ingredients, e.g. specific carrier materials or surfactants, covered by classes A01N25/00 - A01N65/48
• CPC Class Codes: A01N 25/04 Dispersions, emulsions, suspoemulsions, suspension concentrates or gels foams A01N25/16
• CPC Class Codes: A01N 25/10 Macromolecular compounds
• CPC Class Codes: A01N 25/14 wettable
• CPC Class Codes: A01N 37/10 Aromatic or araliphatic carboxylic acids, or thio analogues thereof; Derivatives thereof
• CPC Class Codes: A01N 37/50 the nitrogen atom being doubly bound to the carbon skeleton
• CPC Class Codes: A01N 43/40 six-membered rings
• CPC Class Codes: A01N 43/54 1,3-Diazines; Hydrogenated 1,3-diazines
• CPC Class Codes: A01N 43/56 1,2-Diazoles; Hydrogenated 1,2-diazoles
• CPC Class Codes: A01N 43/76 1,3-Oxazoles; Hydrogenated 1,3-oxazoles
• CPC Class Codes: A01N 43/88 six-membered rings with three ring hetero atoms
• CPC Class Codes: A01N 47/24 containing the groups , or; Thio analogues thereof
• CPC Class Codes: A01N 57/20 containing acyclic or cycloaliphatic radicals
• CPC Class Codes: C05G 3/60 Biocides or preservatives, e.g. disinfectants, pesticides or herbicides; Pest repellants or attractants

Abstract

The present disclosure describes a formulation including a nanoparticle including a polymer-associated strobilurin compound with an average diameter of between about 1 nm and about 500 nm; wherein the polymer is a polyelectrolyte, and a dispersant or a wetting agent. The disclosure describes various formulations and formulating agents that can be included in the formulations. Additionally, the disclosures describes application to various plants and fungi as well as advantages of the disclosed formulations.

Claims

1. A formulation comprising:

a nanoparticle comprising a polymer-associated strobilurin compound with an average diameter of between about 1 nm and about 500 nm;

wherein the polymer is a polyelectrolyte; and

a dispersant and/or a wetting agent.

2. The formulation of claim 1, wherein the nanoparticle has a diameter of between about 1 nm and about 100 nm.

3. The formulation of claim 1, wherein the nanoparticle has a diameter of between about 1 nm and about 20 nm.

4. The formulation of any one of claims 1-3, comprising a plurality of nanoparticles, wherein the nanoparticles are in an aggregate and the aggregate has a diameter of between about 10 nm and about 5000 nm.

5. The formulation of any one of claims 1-3, comprising a plurality of nanoparticles, wherein the nanoparticles are in an aggregate and the aggregate has a diameter of between about 100 nm and about 2500 nm.

6. The formulation of any one of claims 1-3, comprising a plurality of nanoparticles, wherein the nanoparticles are in an aggregate and the aggregate has a diameter of between about 100 nm and about 1000 nm.

7. The formulation of any one of claims 1-3, comprising a plurality of nanoparticles, wherein the nanoparticles are in an aggregate and the aggregate has a diameter of between about 100 nm and about 300 nm.

8. The formulation of any one of claims 1-7, wherein the ratio of strobilurin compound to polymer within the nanoparticles is between about 10:

1 and about 1;

10.

9. The formulation of any one of claims 1-7, wherein the ratio of strobilurin compound to polymer within the nanoparticles is between about 5:

1 and about 1;

5.

10. The formulation of any one of claims 1-7, wherein the ratio of strobilurin compound to polymer within the nanoparticles is between about 2:

1 and about 1;

2.

11. The formulation of any one of claims 1-7, wherein the ratio of strobilurin compound to polymer within the nanoparticles is about 1:

3.

12. The formulation of any one of claims 1-7, wherein the ratio of strobilurin compound to polymer within the nanoparticles is about 3:

2.

13. The formulation of any one of claims 1-7, wherein the ratio of strobilurin compound to polymer within the nanoparticles is about 4:

1.

14. The formulation of any one of claims 1-7, wherein the ratio of strobilurin compound to polymer within the nanoparticles is about 2:

1.

15. The formulation of any one of claims 1-7, wherein the ratio of strobilurin compound to polymer within the nanoparticles is about 1:

1.

16. The formulation of any of claims 1-15, wherein the strobilurin compound is azoxystrobin.

17. The formulation of any one of the preceding claims, wherein the polymer is selected from the group consisting of poly(methacrylic acid co-ethyl acrylate);

poly(methacrylic acid-co-styrene);

poly(methacrylic acid-co-butylmethacrylate);

poly[acrylic acid-co-poly(ethylene glycol) methyl ether methacrylate];

poly(n-butylmethacrylcate-co-methacrylic acid) and poly(acrylic acid-co-styrene.

18. The formulation of any one of claims 1-17, wherein the polymer is a homopolymer.

19. The formulation of any one of claims 1-17, wherein the polymer is a copolymer.

20. The formulation of claim 18, wherein the polymer is a random copolymer.

21. The formulation of any one of the preceding claims, wherein the dispersant and/or wetting agent is selected from the group consisting of lignosulfonates, organosilicones, methylated or ethylated seed oils, ethoxylates, sulfonates, sulfates and combinations thereof.

22. The formulation of claim 21, wherein the dispersant and/or wetting agent is sodium lignosulfonate.

23. The formulation of any one of claims 1-21, wherein the dispersant and/or wetting agent is a tristyrylphenol ethoxylate.

24. The formulation of any one of the preceding claims, wherein the wetting agent and the dispersant are the same compound.

25. The formulation of any one of claims 1-21, wherein the wetting agent and the dispersant are different compounds.

26. The formulation of any one of claims 1-21, excluding any wetting agent.

27. The formulation of any one of claims 1-21, excluding any dispersant.

28. The formulation of any one of claim 1-25 or 27, wherein the wetting agent is less than about 30 weight % of the formulation.

29. The formulation of claim 28, wherein the wetting agent is less than about 5 weight % of the formulation.

30. The formulation of any one of claims 1-26, wherein the dispersant is less than about 30 weight % of the formulation.

31. The formulation of claim 30, wherein the dispersant is less than about 5 weight % of the formulation.

32. The formulation of any one of the preceding claims wherein the formulation is in the form of a high solids liquid suspension.

33. The formulation of claim 32, further comprising between about 0.05 weight % and about 5 weight % of a thickener.

34. The formulation of claim 32, wherein the thickener is less than about 1 weight % of the formulation.

35. The formulation of claim 32, wherein the thickener is less than about 0.5 weight % of the formulation.

36. The formulation of claim 32, wherein the thickener is less than about 0.1 weight % of the formulation.

37. The formulation of claim 32, wherein the thickener is selected from the group consisting of guar gum;

locust bean gum;

xanthan gum;

carrageenan;

alginates;

methyl cellulose;

sodium carboxymethyl cellulose;

hydroxyethyl cellulose;

modified starches;

polysaccharides and other modified polysaccharides;

polyvinyl alcohol;

glycerol alkyd, fumed silica and combinations thereof.

38. The formulation of any of the preceding claims, further comprising between about 0.01 weight % and about 0.2 weight % of a preservative.

39. The formulation of claim 38, wherein the preservative is less than about 0.1 weight % of the formulation.

40. The formulation of claim 38, wherein the preservative is less than about 0.05 weight % of the formulation.

41. The formulation of claim 38, wherein the preservative is selected from the group consisting of tocopherol, ascorbyl palmitate, propyl gallate, butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), propionic acid and its sodium salt;

sorbic acid and its sodium or potassium salts;

benzoic acid and its sodium salt;

p-hydroxy benzoic acid sodium salt;

methyl p-hydroxy benzoate;

1,2-benzisothiazalin-3-one, and combinations thereof.

42. The formulation of any of the preceding claims, further comprising between about 0.05 weight % and about 10 weight % of an anti-freezing agent.

43. The formulation of claim 42, wherein the anti-freezing agent is less than about 5 weight % of the formulation.

44. The formulation of claim 42, wherein the anti-freezing agent is less than about 1 weight % of the formulation.

45. The formulation of claim 42, wherein the anti-freezing agent is selected from the group consisting of ethylene glycol;

propylene glycol;

urea and combinations thereof.

46. The formulation of any one of the preceding claims, further comprising water or PBS buffer.

47. The formulation of claim 46, wherein the water or PBS buffer is less than about 50 weight % of the formulation.

48. The formulation of claim 46, wherein the water or PBS buffer is less than about 25 weight % of the formulation.

49. The formulation of claim 46, wherein the water or PBS buffer is less than about 10 weight % of the formulation.

50. The formulation of any of the preceding claims, wherein the nanoparticles of polymer-associated strobilurin comprise less than about 80 weight % of the formulation.

51. The formulation of any of the preceding claims, wherein the nanoparticles of polymer-associated strobilurin comprise between about 20 weight % and about 80 weight % of the formulation.

52. The formulation of any of the preceding claims, wherein the nanoparticles of polymer-associated strobilurin comprise between about 20 weight % and about 60 weight % of the formulation.

53. The formulation of any of the preceding claims, wherein the nanoparticles of polymer-associated strobilurin comprise about 20 weight % and about 50 weight % of the formulation.

54. The formulation of any of the preceding claims, wherein the nanoparticles of polymer-associated strobilurin comprise between about 25 weight % and about 50 weight % of the formulation.

55. The formulation of any of the preceding claims, wherein the nanoparticles of polymer-associated strobilurin comprise about 30 weight % and about 40 weight % of the formulation.

56. The formulation of any of the preceding claims, wherein the polymer-associated strobilurin compound is between about 5 weight % and about 40 weight % of the formulation.

57. The formulation of any of the preceding claims, wherein the polymer-associated strobilurin compound is between about 5 weight % and about 25 weight % of the formulation.

58. The formulation of any of the preceding claims, wherein the polymer-associated strobilurin compound is between about 10 weight % and about 25 weight % of the formulation.

59. The formulation of any of the preceding claims, wherein the polymer-associated strobilurin compound is between about 15 weight % and about 25 weight % of the formulation.

64. The formulation of any one of claims 1-31, wherein the formulation is in the form of a wettable granule.

65. The formulation of any one of claims 1-31, further comprising an inert filler.

66. The formulation of claim 64, wherein the inert filler makes up less than about 90 weight % of the formulation.

67. The formulation of claim 64, wherein the inert filler makes up less than about 40 weight % of the formulation.

68. The formulation of claim 64, wherein the inert filler makes up less than about 5 weight % of the formulation.

69. The formulation of claim 64, wherein the inert filler is selected from the group consisting of saccharides, celluloses, starches, carbohydrates, vegetable oils, protein inert fillers, polymers and combinations thereof.

70. The formulation of claim 64, further comprising water.

71. The formulation of claim 70, wherein the water is less than about 50 weight % of the formulation.

72. The formulation of claim 70, wherein the water is less than about 25 weight % of the formulation.

73. The formulation of claim 70, wherein the water is less than about 10 weight % of the formulation.

74. The formulation of claim 64, further comprising between about 1 weight % and about 20 weight % of a disintegrant.

75. The formulation of claim 74 wherein the disintegrant is selected from the group consisting of polyvinyl pyrrolidone, modified cellulose gum, pregelatinized starch, cornstarch, modified corn starch, sodium carboxymethyl starch, microcrystalline cellulose, sodium starch glycolate, sodium carboxymethyl cellulose, carmellose, carmellose calcium, carmellose sodium, croscarmellose sodium, carmellose calcium, carboxymethylstarch sodium, low-substituted hydroxypropyl cellulose, hydroxypropyl methylcellulose, hydroxypropyl cellulose, soy polysaccharides, alkylcelullose, hydroxyalkylcellulose, alginates, dextrans and poly(alkylene oxide), a combination of citric acid or bicarbonate, a combination of ascorbic acid and bicarbonate, lactose, anhydrous dibasic calcium phosphate, dibasic calcium phosphate, magnesium aluminometasilicate, synthesized hydrotalcite, silicic anhydride synthesized aluminum silicate and combinations thereof.

76. The formulation of any one of the preceding claims, wherein the polymer-associated strobilurin compound has a melting point of less than 100°

C.

77. The formulation of claim 76, wherein the polymer-associated strobilurin compound has a melting point of less than 80°

C.

78. The formulation of claim 76, wherein the polymer-associated strobilurin compound is selected from the group consisting of the following picoxystrobin, pyraclostrobin, orysastrobin, metominostrobin and trifloxystrobin.

79. The formulation of any one of the preceding claims, without a UV-blocker.

80. The formulation of any one of the claims 1-32 or 38-79 without a thickener.

81. The formulation of any one of the preceding claims, further comprising between about 1 weight % and about 20 weight % of a non-ionic surfactant.

82. The formulation of claim 81, wherein the non-ionic surfactant is less than about 1 weight % of the formulation.

83. The formulation of claim 81, wherein the non-ionic surfactant is less than about 0.5 weight % of the formulation.

84. The formulation of claim 81, wherein the non-ionic surfactant is selected from the group consisting of alkylphenol ethoxylates, tristyrylphenol ethoxylates, aliphatic alcohol ethoxylates, aliphatic alkylamine ethoxylates, sorbitan esters and their ethoxylates, castor oil ethoxylates, ethylene oxide/propylene oxide copolymers, polymeric surfactants and combinations thereof.

85. The formulation of any of the preceding claims, further comprising between about 0.1 weight % and about 90 weight % of a solvent.

86. The formulation of claim 85, wherein the solvent is less than about 20 weight % of the formulation.

87. The formulation of claim 85, wherein the solvent is less than about 10 weight % of the formulation.

88. The formulation of claim 85, wherein the solvent is selected from the group consisting of alcohols, alkenes, alkanes, alkynes, phenols, hydrocarbons, chlorinated hydrocarbons, ketones, ethers and combinations thereof.

89. The formulation of any of the preceding claims, further comprising between about 0.05 weight % and about 5 weight % of an anti-foaming agent.

90. The formulation of claim 89, wherein the anti-foaming agent is less than about 1 weight % of the formulation.

91. The formulation of claim 89, wherein the anti-foaming agent is selected from the group consisting of sodium or ammonium phosphates, sodium carbonate or bicarbonate, sodium acetate, sodium metasilicate, magnesium or zinc sulfates, magnesium hydroxide hydrates of any of the forgoing, sodium alkylsulfosuccinates, silicious compounds, magnesium compounds, C10-C22 fatty acids, polyvalent metal salt compounds and combinations thereof.

92. The formulation of any of the preceding claims, further comprising between about 0.05 weight % and about 3 weight % of an anti-caking agent.

93. The formulation of claim 92, wherein the anti-caking agent is less than about 1 weight % of the formulation.

94. The formulation of claim 92, wherein the anti-caking agent is selected from the group consisting of attapulgite clay, kieselguhr, silica aerogel, silica xerogel, perlite, talc, vermiculite, sodium aluminosilicate, zirconium oxychloride, starch, sodium or potassium phthalate, calcium silicate, calcium phosphate, calcium nitride, aluminum nitride, copper oxide, magnesium carbonate, magnesium silicate, magnesium nitride, magnesium phosphate, magnesium oxide, magnesium nitrate, magnesium sulfate, magnesium chloride, and the magnesium and aluminum salts of C10-C22 fatty acids, refined kaolin clay, amorphous precipitated silica dioxide, refined clay, fumed silica, and combinations thereof.

95. The formulation of any of the preceding claims, diluted so that the concentration of the polymer-associated strobilurin compound is between about 0.1 to about 1000 ppm.

96. The formulation of any of the preceding claims, diluted so that the concentration of the polymer-associated strobilurin compound is between about 10 to about 1000 ppm.

97. The formulation of any of the preceding claims, diluted so that the concentration of the polymer-associated strobilurin compound is between about 10 to about 500 ppm.

98. The formulation of any of the preceding claims, diluted so that the concentration of the polymer-associated strobilurin compound is between about 10 to about 100 ppm.

99. The formulation of any of the preceding claims in an aqueous dispersion.

100. The formulation of claim 99, wherein the concentration of the strobilurin in the dispersion is less than solubility limit of the strobilurin in water.

101. The formulation of claim 100, wherein the strobilurin is associated with the polymer in the dispersion.

102. The formulation of claim 99, wherein the water used to form the dispersion has an ionic strength of between about 0 to about 8000 ppm calcium +2 equivalent.

103. The formulation of claim 99, wherein the water used to form the dispersion has an ionic strength of between about 100 to about 2000 ppm calcium +2 equivalent.

104. The formulation of claim 99, wherein the water used to form the dispersion has an ionic strength of between about 100 to about 400 ppm calcium +2 equivalent.

105. The formulation of claim 99, wherein the water used to form the dispersion has an ionic strength of between about 50 to about 400 ppm calcium +2 equivalent.

106. The formulation of claim 99, wherein the water used to form the dispersion has an ionic strength of between about 1000 to about 4000 ppm calcium +2 equivalent.

107. The formulation of any of claims 99-106, wherein the aqueous dispersion further contains an herbicide.

108. The formulation of claim 107, wherein the herbicide is glyphosate.

109. The formulation of any of the preceding claims further comprising a fertilizer.

110. The formulation of claim 109, wherein the fertilizer is a liquid fertilizer.

111. The formulation of either claim 109 or 110, wherein the fertilizer comprises at least one of the elements selected from the group consisting of the following:

boron, copper, manganese, iron, chorine, molybdenum, zinc sulfur, nitrogen, phosphorus and potassium.

112. The formulation of any one of claims 95-98, further comprising between about 0.1 weight % and about 20 weight % of a non-ionic surfactant.

113. The formulation of claim 112, wherein the non-ionic surfactant is less than about 1 weight % of the formulation.

114. The formulation of claim 112, wherein the non-ionic surfactant is less than about 0.5 weight % of the formulation.

115. The formulation of claim 112, wherein the non-ionic surfactant is selected from the group consisting of alkylphenol ethoxylates, tristyrylphenol ethoxylates, aliphatic alcohol ethoxylates, aliphatic alkylamine ethoxylates, sorbitan esters and their ethoxylates, castor oil ethoxylates, ethylene oxide/propylene oxide copolymers, polymeric surfactants and combinations thereof.

116. A method of using the formulation of any one of the preceding claims comprising the steps of:

applying the formulation to a plant.

117. The method of claim 116, wherein the formulation is applied to one part of a plant and the strobilurin translocates to an unapplied part of the plant.

118. The method of claim 117, wherein the unapplied part of the plant comprises new plant growth since the application.

119. A method of inoculating a plant with a strobilurin against fungi by applying the formulation of any one claims 1-115, to the plant.

120. A method of treating a fungal infection of a plant with a strobilurin by applying the formulation of any one claims 1-115, to the plant.

121. A method of increasing a plant'"'"'s fungus resistance by applying the formulation any one claims 1-115, to the plant.

122. The method of any of claims 116-120, wherein the plant is selected from the classes fabaceaae, brassicaceae, rosaceae, solanaceae, convolvulaceae, poaceae, amaranthaceae, laminaceae and apiaceae.

123. The method of claim 122, wherein the plant is selected from oil crops, cereals, pasture, turf, ornamentals, fruit, legume vegetables, bulb vegetables, cole crops, tobacco, soybeans, cotton, sweet corn, field corn, potatoes and greenhouse crops.

124. The method of any of claims 119-123, wherein the fungi is selected from the classes ascomycota, basidiomycota, deuteromycota, blastocladiomycota, chytridiomycota, glomeromycota and combinations thereof.

125. A method of using the formulation of any one of claims 1-115 comprising the steps of:

applying the formulation of any one of claims 1-115 to trees, bushes or shrubs.

126. The method of claim 116, wherein the application is to cure or prevent a fungal infection, and the formulation is applied to a soybean plant at a concentration of between about 11 and about 109 grams of strobilurin compound per hectare and the fungus is selected from the group consisting of Aerial blight (Rhizoctonia solani), Anthracnose (Colletotrichum truncatum), Alternaria leaf spot (Alternaria spp.), Brown spot (Septoria glycines) Cercospora blight and leaf spot (Cercospora kikuchii), Frogeye leaf spot (Cercospora sojina), Pod and stem blight (Diaporthe phaseolorum).

127. The method of claim 126, wherein the strobilurin compound is azoxystrobin or pyraclostrobin.

128. The method of claim 116, wherein the application is to cure or prevent a fungal infection, and the formulation is applied to a corn plant at a concentration of between about 11 and about 109 grams of strobilurin compound per hectare and the fungus is selected from the group consisting of Rust (Puccinia sorghi), anthracnose leaf blight (Colletotrichum graminicola), Gray leaf spot (Cercospora sorghi), Northern corn leaf blight (Setosphaeria turcica), Northern corn leaf spot (Cochliobolus carbonum), Southern corn leaf blight (Cochliobolus heterostrophus) and Eye spot (Aureobasidium zeae).

129. The method of claim 128, wherein the strobilurin compound is azoxystrobin or pyraclostrobin.

130. The method of claim 116, wherein the application is to cure or prevent a fungal infection, and the formulation is applied to a rice plant at a concentration of between about 22 and about 228 grams of azoxystrobin per hectare and the fungus is selected from the group consisting of Aggregate sheath spot (Ceratobasidium oryzae-sativae, Rhizoctonia oryzae-sativae), Black sheath rot (Gaeumannomyces graminis var. graminis), Sheath spot (Rhizoctonia oryzae), Stem rot (Magnaporthe salvinii=Sclerotium oryzae=Nakateae sigmoidea), Brown leaf spot (Cochliobolus miyabeanus), Leaf smut (Entyloma oryzae), Narrow brown leaf spot (Cercospora janseana=Cercospora oryzae), Kernel smut (Tilletia barclayana, Neovossia barclayana) and Panicle blast (Pyricularia grisea).

131. The method of claim 116, wherein the application is to cure or prevent a fungal infection, and the formulation is applied to a wheat plant at a concentration of between about 5 and about 50 grams of azoxystrobin per hectare and the fungus is selected from the group consisting of Bipolaris sorokiniana, Drechslera tritici-repentis, and Puccinia triticina.

132. The method of claim 116, wherein the application is to cure or prevent a fungal infection, and the formulation is applied to a wheat plant at a concentration of between about 11 and about 110 grams of pyraclostrobin per hectare and the fungus is selected from the group consisting of Black Spot, Leaf Rust, Powdery Mildew, Septoria Leaf And Glume Blotch, Spot Blotch, Stem Rust, Stripe Rust, and Tan Spot (Yellow Leaf Spot).

133. The method of claim 116, wherein the application is to cure or prevent a fungal infection, and the formulation is applied to a wheat plant at a concentration of between about 15 and about 150 grams of pyraclostrobin per hectare and the fungus is selected from the group consisting of Drecheslera tritici-repentis, Pucciniatriticina, Bipolaris sorokiniana, Leptosphaeria nodorum, and Septoria tritici.

134. The method of claim 116, wherein the application is to cure or prevent a fungal infection, and the formulation is applied to a rice plant at a concentration of between about 11 and about 139 grams of trifloxystrobilurin per hectare and the fungus is sheath blight (rhizoctonia solani).

60. A formulation comprising:

a nanoparticle comprising a polymer-associated strobilurin compound with an average diameter of between about 1 nm and about 500 nm; and

the polymer is a polyelectrolyte,

a dispersant or a wetting agent

a thickener

a preservative

an anti-freezing agent; and

water or PBS buffer.

62. The formulation of either of claim 60 or 61, wherein the nanoparticles of polymer-associated strobilurin comprise between about 20 weight % and about 80 weight % of the formulation.

63. The formulation of any of claims 60-62, wherein the polymer-associated strobilurin compound is between about 5 weight % and about 25 weight % of the formulation.

61. A formulation comprising:

a nanoparticle comprising a polymer-associated strobilurin compound with an average diameter of between about 1 nm and about 500 nm; and

the polymer is a polyelectrolyte,

between about 1 weight % and about 30 weight % of a dispersant or a wetting agent

between about 0.05 weight % and about 5 weight % of a thickener

between about 0.01 weight % and about 0.2 weight % of a preservative

between about 0.05 weight % and about 10 weight % of an anti-freezing agent; and

water or PBS buffer.

135. A method of making a high solids liquid suspension formulation comprising the steps of

milling nanoparticles of a polymer-associated strobilurin compound with,

a dispersant and/or wetting agent;

and

water.

138. The method of any of claims 135-137, wherein the strobilurin compound has a melting point below 100°

C.

139. The method of any of claims 135-137, wherein the strobilurin compound has a melting point below 80°

C.

140. The method of any of claims 135-137, wherein the polymer-associated strobilurin compound is selected from the group consisting of the following picoxystrobin, pyraclostrobin, orysastrobin, metominostrobin and trifloxystrobin.

141. The method of any of claims 135-137, wherein the strobilurin compound comprises between about 5 weight % and about 25 weight % of the formulation.

142. The method of any of claims 135-137, wherein the strobilurin compound comprises between about 10 weight % and about 25 weight % of the formulation.

143. The method of any of claims 135-137, wherein the strobilurin compound comprises between about 15 weight % and about 25 weight % of the formulation.

144. The method of any of claims 135-137, wherein the polymer nanoparticles and the strobilurin compound comprise between about 20 weight % and about 80 weight % of the formulation.

145. The method of any of claims 135-137, wherein the polymer nanoparticles and the strobilurin compound comprise between about 20 weight % and about 60 weight % of the formulation.

146. The method of any of claims 135-137, wherein the polymer nanoparticles and the strobilurin compound comprise between about 20 weight % and about 50 weight % of the formulation.

147. The method of any of claims 135-137, wherein the polymer nanoparticles and the strobilurin compound comprise between about 30 weight % and about 50 weight % of the formulation.

148. The method of any of claims 135-137, wherein the ratio of strobilurin compound to polymer within the nanoparticles is between about 5:

1 and about 1;

5.

149. The method of any of claims 135-137, further comprising one or more of the following formulating agents:

an anti-freeze, a anti-foaming agent, a thickener, a preservative.

136. A method of making a high solids liquid suspension formulation comprising the steps of

milling polyelectrolyte nanoparticles with,

a strobilurin compound,

a dispersant and/or wetting agent;

and

water.

137. A method of making a wettable granule formulation comprising the steps of:

mixing dried nanoparticles of a polymer-associated strobilurin compound with water,

extruding the mixture through an orifice; and

dividing the extruded material into granules.