Agrochemical compositions

• US 20050043182A1
• Filed: 12/03/2001
• Published: 02/24/2005
• Est. Priority Date: 12/04/2000
• Status: Active Grant

• Current Assignee: Syngenta Crop Protection Incorporated (China National Chemical Corporation)
• Original Assignee: Syngenta Crop Protection Incorporated (China National Chemical Corporation)
• Inventors: Fowler, Jeffrey David, Douglass, Andrew
• Granted Patent: US 8,252,719 B2
• Time in Patent Office: Days
• US Class Current: 504/363
• 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 25/02 containing liquids as carriers, diluents or solvents
• CPC Class Codes: A01N 25/04 Dispersions, emulsions, suspoemulsions, suspension concentrates or gels foams A01N25/16
• CPC Class Codes: A01N 25/06 Aerosols
• CPC Class Codes: A01N 25/30 characterised by the surfactants
• CPC Class Codes: A01N 37/50 the nitrogen atom being doubly bound to the carbon skeleton
• CPC Class Codes: A01N 43/50 1,3-Diazoles; Hydrogenated 1,3-diazoles
• CPC Class Codes: A01N 43/653 1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
• CPC Class Codes: A01N 43/90 having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
• CPC Class Codes: A01N 51/00 Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring

Abstract

Microemulsifiable hydrophobic agrochemical concentrates are provided which are a combination of (A) an alkyl alkanoate with (B) a poyhydric alcohol, a polyhydric alcohol condensate or a mixture thereof and (C) at least one surfactant; the novel compositions are storage stable, easy to apply, ecological and toxicologically favorable and, upon dilution with water, are useful as plant treatment compositions that have good biological efficacy in the target application.

Claims

1. A microemulsifiable concentrate (MEC) of a hydrophobic agrochemical, said concentrate comprising:

(a) at least one hydrophobic agrochemical;

(b) a solvent system comprising;

(i) a first solvent which is selected from the group consisting of alkyl alkanoates; and

(ii) a second solvent which is selected from the group consisting of polyhydric alcohols, condensates of polyhydric alcohols, and mixtures thereof; and

(c) at least one surfactant.

2. The MEC of claim 1 wherein said surfactant component (c) comprises:

(c)(i) at least one cationic surfactant.

3. The MEC of claim 1 wherein said surfactant component (c) comprises:

(c)(ii) at least one nonionic surfactant.

4. The MEC of claim 1 wherein said surfactant component (c) comprises:

(c)(i) at least one cationic surfactant; and

(c)(iii) at least one anionic surfactant.

5. The MEC of claim 1 wherein said surfactant component (c) comprises:

(c)(i) at least one cationic surfactant; and

(c)(ii) at least one nonionic surfactant.

6. The MEC of claim 1 wherein said surfactant component (c) comprises:

(c)(i) at least one cationic surfactant;

(c)(ii) at least one nonionic surfactant; and

(c)(iii) at least one anionic surfactant.

7. The MEC of claim 1 wherein said first solvent component (b)(i) alkyl alkanoate is selected from the group consisting of C₆-C₁₃ alkyl C_1-4 alkanoates.

8. The MEC of claim 7 wherein said C₆-C₁₃ alkyl C_1-4 alkanoates are selected from the group consisting of C₆-C₁₃ alkyl acetates.

9. The MEC of claim 8 wherein said C₆-C₁₃ alkyl acetates are seleceted from the group consisting of oxo-hexyl, oxo-heptyl, oxo-octyl, oxo-2-ethyl-hexyl, oxo-nonyl, oxo-decyl, oxo-dodecyl and oxo-tridecyl acetates.

10. The MEC of claim 1 wherein said second solvent component (b)(ii) is a polydric alcohol.

11. The MEC of claim 1 wherein said second solvent component (b)(ii) is a polydric alcohol condensate.

12. The MEC of claim 1 wherein said second solvent component (b)(ii) is selected from the group consisting of propylene glycol;

dipropylene glycol;

glycerol;

diethyleneglycol;

polyC_2-6alkylene glycols;

mon-di-, and tri-(polyC_2-6alkyloxylated) glycerol;

sugar alcohols;

mono and poly(polyC_2-6alkyloxylated) sugar alcohols;

mono and poly-(hydroxyC_2-6alkyl) sugar alcohol;

glyceroltriacetate;

hexylene glycol (2-methyl-2,4-pentanediol);

1,3-butylene glycol;

1,2,6-hexanetriol;

ethohexadiol USP (2-ethyl-1,3-hexanediol);

C₁₅-C₁₈vicinal glycol;

polyoxyC_2-6alkylene derivatives of trimethylolpropane; and

C_2-6aliphatic glycols.

13. The MEC of claim 12 wherein said second solvent component (b)(ii) is polyethylene glycol 200.

14. The MEC of claim 1 wherein said cationic surfactant component (c)(i) is selected from the group consisting of polyC_2-4alkoxylated fatty amines.

15. The MEC of claim 14 wherein said polyC_2-4alkoxylated fatty amines are selected from polyC_2-4alkoxylated C_14-20fatty amines.

16. The MEC of claim 14 wherein said polyC_2-4alkoxylated fatty amines are selected from the group consisting of C_2-4alkoxylated tallow amine.

17. The MEC of claim 14 wherein said polyC_2-4alkoxylated fatty amines are selected from the group consisting of polyC_2-4alkoxylated fatty amines having 2-18 repeating alkoxy units per molecule.

18. The MEC of claim 16 wherein said polyC_2-4alkoxylated fatty amines are selected from the group consisting of polyC_2-4alkoxylated fatty amines having 2, 5, 8, 15, or 16 repeating alkoxy units per molecule.

19. The MEC of claim 1 wherein said nonionic surfactant component (c)(ii) is selected from the group consisting of mono C_2-6alkyl ether of a polyC_2-4alkylene oxide block copolymer having at least a first polyalkylene oxide block region and a second polyalkylene oxide block region in which the polyalkylene oxide in said first region is different than the polyalkylene oxide in said second region, a condensation product of castor oil and a polyC_2-4alkylene oxide, a mono- or di-ester of a C_12-24fatty acid, and mixtures thereof.

20. The MEC of claim 18 wherein said nonionic surfactant component (c)(ii) mono C_2-6alkyl ether of a polyC_2-4alkylene oxide block copolymer has C_2-6alkyl ether portion which is butyl and/or an alkylene oxide block copolymer portion which is an ethylene oxide/propylene oxide block copolymer.

21. The MEC of claim 18 wherein said nonionic surfactant component (c)(ii) mono C_2-6alkyl ether of a polyC_2-4alkylene oxide block copolymer has an alkylene oxide block copolymer portion which is an ethylene oxide/propylene oxide block copolymer in which ethylene oxide comprises from about 10 mole % to about 90 mole % of the block copolymer.

22. The MEC of claim 18 wherein said nonionic surfactant component (c)(ii) condensation product of castor oil and a polyC_2-4alkylene oxide having about 30 to about 40 alkylene oxide units per molecule.

23. The MEC of claim 18 wherein said nonionic surfactant component (c)(ii) condensation product of castor oil and a polyC_2-4alkylene oxide wherein the alkylene oxide is polyethylene oxide.

24. The MEC of claim 18 wherein said nonionic surfactant component (c)(ii) mono- or di-ester of a C_12-24fatty acid is a mono or diester of a C_12-20fatty acid.

25. The MEC of claim 18 wherein said nonionic surfactant component (c)(ii) mono- or di-ester of a C_12-24fatty acid is a mono or diester of a C_12-16fatty acid.

26. The MEC of claim 18 wherein said nonionic surfactant component (c)(ii) mono- or di-ester of a C_12-24fatty acid is a mono or diester of lauric acid.

27. The MEC of claim 18 wherein said nonionic surfactant component (c)(ii) mono- or di-ester of a C_12-24fatty acid is a polyethyleneoxide ester of a C_12-24fatty acid.

28. The MEC of claim 26 wherein said nonionic surfactant component (c)(ii) mono- or di-ester of a C_12-24fatty acid is a polyethyleneoxide ester of a C_12-24fatty acid having from about 2 to about 40 ethylene oxide units per molecule.

29. The MEC of claim 18 wherein said nonionic surfactant component (c)(ii) mono- or di-ester of a C_12-24fatty acid is polyethyleneoxide mono or di lauric acid ester.

30. The MEC of claim 5 or 7 wherein said anionic surfactant component (c)(i) is selected from the group consisting of poly(oxy-1,2-ethanediyl)-alpha-C_10-15alkyl-omega-hydroxy phosphate and/or a C_10-13alkylbenzenesulfonic acid or a salt thereof.

31. The MEC of claim 29 wherein said anionic surfactant component (c)(i) poly(oxy-1,2-ethanediyl)-alpha-C_10-15alkyl-omega-hydroxy phosphate is selected from the group consisting of poly(oxy-1,2-ethanediyl)-alpha-tridecyl-omega-hydroxy phosphates.

32. The MEC of claim 29 wherein said anionic surfactant component (c)(i) poly(oxy-1,2-ethanediyl)-alpha-C_10-15alkyl-omega-hydroxy phosphate has about 3 to about 9 repeating oxy-1,2-ethanediyl units per molecule.

33. The MEC of claim 29 wherein said anionic surfactant component (c)(i) poly(oxy-1,2-ethanediyl)-alpha-C_10-15alkyl-omega-hydroxy phosphate has about 6 repeating oxy-1,2-ethanediyl units per molecule.

34. The MEC of claim 29 wherein said anionic surfactant component (c)(i) poly(oxy-1,2-ethanediyl)-alpha-C_10-15alkyl-omega-hydroxy phosphate is tridecylalcohol polyethoxylate phosphoric acid or a salt thereof.

35. The MEC of claim 29 wherein said anionic surfactant component (c)(i) C_10-13alkylbenzenesulfonic acid is dodecylbenzenesulfonic acid or a salt thereof.

36. The MEC of claim 1 further comprising (d) a water miscible solvent.

37. The MEC of claim 35 wherein said component (d) water miscible solvent is selected from the group consisting of N—

C_1-4alkyl-2-pyrrolidones;

tetramethylurea;

gamma-butyrolacone;

N,N-diC_1-4alkylformamides;

N,N-diC_1-4alkylacetamides;

dimethylsulfoxide;

C_3-8cycloalkylmethanols, and monohydric C_1-4alkanols.

38. The MEC of claim 35 wherein said component (d) water miscible solvent is selected from the group consisting of N-methyl-2-pyrrolidones;

tetramethylurea;

gamma-butyrolacone;

N,N-dimethylformamides;

N,N-dimethylacetamides;

dimethylsulfoxide;

tetrahydrofurfuryl alcohol, and ethanol.

39. The MEC of claim 35 wherein said component (d) water miscible solvent is tetrahydrofurfuryl alcohol.

40. The MEC of claim 1 wherein said hydrophobic agrochemical is selected from the group consisting of chemical pesticides, herbicide safeners, plant growth regulators, fertilizers and nutrients, gametocides, defoliants, desiccants, and mixtures thereof.

41. The MEC of claim 39 wherein said chemical pesticides are selected from the group consisting of herbicides, algicides, fungicides, bactericides, viricides, insecticides, miticides, nematicides molluscicides, acaricides, ectoparasitcides, and mixtures thereof.

42. The MEC of claim 39 wherein said agrochemical is selected from the group consisting of acylalanines, haloacetanilides, triazole derivatives, phosphoric acid esters, pyrethroids, benzilic acid esters, polycyclic halogenated hydrocarbons, diphenyl ether derivates, formamidines, strobilurines, aryloxyphenoxy-alkanoic acid derivatives and mxitures thereof.

43. The MEC of claim 39 wherein said agrochemical is selected from the group consisting of

(a) Haloacetanilides selected from the group consisting of Dimethachlor, Metolachlor, S-Metolachlor, Pretilachlor, 2-chloro-N-(1-methyl-2-methoxyethyl)-acet-2,6-xylidide, Alachlor, Butachlor, Propachlor, Dimethenamid;

(b) Diphenyl ether derivatives selected from the group consisting of Bifenox, 4-(4-Pentyn-1-yloxy)diphenylether, Acifluorfen, Oxyfluorfen, Fluoroglycofen-ethyl, Fomesafen, and cis-trans-(±

)2-ethyl-5-(4-phenoxy-phenoxymethyl)-1,3-dioxolane;

(c) Phenoxypropionic acid derivatives selected from the group consisting of Fluazifop-butyl, Haloxyfop-methyl, Haloxyfop-(2-ethoxyethyl), Fluorotopic, Fenoxapropethyl, Quizalofopethyl, Propaquizafop, and Diclofop-methyl;

(d) Acylalanines selected from the group consisting of Furalaxyl, Metalaxyl, R-Metalaxyl, Benzoylprop ethyl, Benalaxyl, Oxadixyl, and Flamprop methyl;

(e) Triazole derivatives selected from the group consisting of Difenoconazole, Etaconazol, Propiconazole, Penconazole, Triadimefon, Epoxiconazole, Tebuconazole, Bromuconazole, Fenbuconazole, and Cyproconazole;

(f) Phosphoric acid esters selected from the group consisitng of Piperophos, Anilofos, Butamifos, Azamethiphos, Chlorfenvinphos, Dichlorvos, Diazinon, Methidathion, Azinphos ethyl, Azinphos methyl, Chlorpyrifos, Chlorthiofos, Crotoxyphos, Cyanophos, Demeton, Dialifos, Dimethoate, Disulfoton, Etrimfos, Famphur, Flusulfothion, Fluthion, Fonofos, Formothion, Heptenophos, Isofenphos, Isoxathion, Malathion, Mephospholan, Mevinphos, Naled, Oxydemeton methyl, Oxydeprofos, Parathion, Phoxim, Pyrimiphos methyl, Profenofos, Propaphos, Propetamphos, Prothiophos, Quinalphos, Sulprofos, Phemephos, Terbufos, Triazophos, Trichloronate, Fenamipos, Isazophos, s-benzyl-o,o-diisopropylphosphorothioate, Edinphos, and Pyrazophos;

(g) Pyrethroids selected from the group consisting of Allethrin, Bioallethrin, Bioresmethrin, Cyhalotrin, Cypermethrin, Deltamethrin, Fenpropathrin, Fenvalerate, s-Fenvalerate, Flucythrinate, Fluvalinate, Permethrin, Pyrethrine, Resmethrin, Tetramethrin, Tralomethrin, Ethophenprox, Cyfluthrin, Cycloprothrin, Tefluthrin, Flufenprox, Silafluofen, Bifenthrin, Fenfluthrin, and Bromfenprox;

(h) Benzilic acid esters selected from the group consisting of Brompropylate, Chlorbenzylate, and Chlorpropylate;

(i) Polycyclic halogenated hydrocarbons selected from the group consisting of Aldrin and Endosulfan;

(j) Strobilurines selected from the group consisting of Kresoxim-methyl, Azoxystrobin, Methoxyimino-{2-[1-(3-trifluoromethyl-phenyl)-ethylideneaminooxymethyl]-phenyl}-acetic acid methyl ester, and Trifloxystrobin;

(k) A miscellaneous group selected from the group consisting of Tridemorph, Bromoxynil, Carboxin, Prochloraz, Propargite, Dicamba, Fenpiclonil, Fenpropimorph, Fenpropidin, Fludioxonil, Pymetrozine, Pyrifenox, Pyriproxyfen, Trinexapac-ethyl, Fluazinam, Fludioxonil, Mefenoxam, Cyprodinil, Thiabendazole, Abamectin, Emamectin benzoate, Fenoxycarb, Cyromazine, Prometryne, Ametryne, Prodiamine, Atrazine, Flumeturon, Norflurazon, Pyridate, Flumetsulam, Flumetralin, Cimectacarb, Thiamethoxam, and Acetochlor;

(l) And mixtures thereof.

44. The MEC of claim 39 wherein said agrochemical is selected from the group consisting of

(a) Fungicides selected from the group consisting of propiconazole, difenoconazole, fludioxonil, metalaxyl, mefenoxam (r-metalaxyl), azoxystrobin, trifloxystrobin, furalaxyl, chlorothalonin, fenpropidin, fenpropimorph, cyprodinil, oxadixil, cyproconazole, pyrifenox, fenpiclonil, penconazole, thiabendazole, and pyroquilon;

(b) Insecticides selected from the group consisting of thiamethoxam, abamectin, emamectin benzoate, cypermethrin, fenoxycarb, difenthiuron, methidathion, pymetrozine, tau-fluvalinate, lambda-cybalothrin, permethrin, lufenuron, cyromazine, profenofos, bromopropylate, furathiocarb, organophosphorus compounds, imidacloprid, clothiadin and thiacloprid;

(c) Herbicides selected from the group consisting of metolachlor, S-metolachlor, butafenacil, prometryne, chlortoluron, clodinafop, ametryne, prodiamine, flumeturon, norflurazon, pyridate, flumetsulam, acetochlor, dimethenamid, dimethachlor, tralkoxydim, fluazifop-p-butyl, pretilachlor, and fenclorim;

(d) Growth regulators selected from the group consisting of flumetralin and cimectacarb;

(e) Safeners selected from the group consisting of fluxofenime, benoxacor, cloquintocet, and dichlormid;

(f) Plant activators selected from the group consisting of acibenzolar-s-methyl; and

(g) mixtures thereof

45. The MEC of claim 39 wherein said agrochemical is selected from the group consisting of trifloxystrobin, propiconazole, thiamethoxam, and abamectin, and mixtures thereof.

46. The MEC of claim 39 wherein said agrochemical comprises trifloxystrobin.

47. The MEC of claim 1 further comprising a member selected from the group consisting of conventional agrochemical adjuncts and additives selected from the group consisting of antioxidants, dyes, colorants and fragrances.

48. The MEC of claim 1 wherein said hydrophobic agrochemical is present in an amount of from about 0.1% to about 25% of the MEC.

49. The MEC of claim 1 wherein said first solvent (b)(i) is present in an amount of about 10% to 35% of the MEC.

50. The MEC of claim 1 wherein said second solvent (b)(ii) is present in an amount of about 10% to 45% of the MEC.

51. The MEC of claim 1 wherein said hydrophilic surfactants (c) is present in an amount of about 1% to about 40% of the MEC.

52. The MEC of claim 50 wherein said hydrophilic surfactants (c) comprises (c)(i) at least one cationic surfactant which is present in an amount of about 1% to 20% of the MEC.

53. The MEC of claim 50 wherein said hydrophilic surfactants (c) comprises (c)(ii) at least one nonionic surfactant which is present in an amount of about 1% to 10% of the MEC.

54. The MEC of claim 50 wherein said hydrophilic surfactants (c) comprises (c)(i) at least one cationic surfactant which is present in an amount of about 1% to 20% of the MEC and (c)(iii) at least one anionic surfactant which is present in an amount of about 1% to about 10% of the MEC.

55. The MEC of claim 50 wherein said hydrophilic surfactants (c) comprises (c)(i) at least one cationic surfactant which is present in an amount of about 1% to 20% of the MEC and (c)(ii) at least one nonionic surfactant which is present in an amount of about 1% to about 10% of the MEC.

56. The MEC of claim 50 wherein said hydrophilic surfactants (c) comprises (c)(i) at least one cationic surfactant which is present in an amount of about 1% to 20% of the MEC;

(c)(ii) at least one nonionic surfactant which is present in an amount of about 1% to about 10% of the MEC; and

optionally (c)(iii) at least one anionic surfactant which is present in an amount of up to about 10% of the MEC.

57. The MEC of claim 1 having a pH of about 3 to about 7.

58. The MEC of claim 1 having a pH of about 4 to about 6.

59. The MEC of claim 1 which upon dilution of said concentrate with adequate water, a stable oil-in-water microemulsion is spontaneously formed that is substantially clear in appearance at 25°

C.

60. The MEC of claim 58 which upon dilution of said concentrate with adequate water, a stable oil-in-water microemulsion is spontaneously formed that is substantially clear in appearance at 20-30°

C.

61. The MEC of claim 1 which upon dilution of said concentrate with adequate water, a stable oil-in-water microemulsion is spontaneously formed that is substantially odorless at 25°

C.

62. The MEC of claim 60 which upon dilution of said concentrate with adequate water, a stable oil-in-water microemulsion is spontaneously formed that is substantially odorless at 20-30°

C.

63. The MEC of claim 1 which has sufficiently low eye irritation so as not to fail to qualify for a “

Caution”

Signal Word in its labeling under the United States Environmental Protection Agency criteria therefor as of November 2000.

64. The MEC of claim 1 which has a density of about 0.9 to about 1.1 g/ml.

65. The MEC of claim 1 which upon dilution of said concentrate with adequate water, a stable oil-in-water microemulsion is spontaneously formed that has a droplet particle size of about 20 to about 300 nm.

66. A microemulsion comprising an MEC of claim 1 and water.

67. The microemulsion concentrate of claim 66 in the form of a sprayable composition.

68. The microemulsion in ready to use form of claim 66 which is a sprayable form.

69. A method of dispensing a hydrophobic agrochemical comprising preparing a MEC of claim 1, contacting said MEC with water to result in an aqueous microemulsion thereof, and dispensing said aqueous microemulsion.

72. The MEC of claim 1 comprising:

(a) at least one hydrophobic pesticidal active ingredient;

(b) a solvent system comprising

(i) a first solvent which is selected from the group consisting of alkyl alkanoates; and

(ii) a second solvent which is selected from the group consisting of polydric alcohols, condensates of polyhydric alcohols, and mixtures thereof; and

(c) a mixture of surfactants comprising at least one cationic surfactant, at least one nonionic surfactant, and optionally at least one anionic surfactant.

73. A method of treating a plant with an agrochemical comprising preparing a MEC of claim 1, diluting said MEC with an appropriate amount of water to form a microemulsion, and exposing said plant or portion of said plant to said microemulsion.

74. A method of treating soil with an agrochemical in preparation for planting comprising preparing a MEC of claim 1, diluting said MEC with an appropriate amount of water to form a microemulsion, and exposing said soil to said microemulsion.

75. A method of treating a seed with an agrochemical comprising preparing a MEC of claim 1, diluting said MEC with an appropriate amount of water to form a microemulsion, and exposing said seed to said microemulsion.

76. A method of pre-emergent treatment of planted crops with an agrochemical comprising preparing a MEC of claim 1, diluting said MEC with an appropriate amount of water to form a microemulsion, and exposing said pre-emergent crop area to said microemulsion.

77. A plant or plant part treated with a microemulsion of an agrochemical, said microemulsion being an aqueous dilution of an MEC of claim 1.

70. The method of claim 70 wherein said MEC is contacted with a first fraction of said water to prepare a microemulsion concentrate thereof and said microemulsion concentrate is further diluted with an additional fraction of water to result in said final microemulsion whereby said final microemulsion may result before or during the act of dispensing said agrochemical.

71. A microemulsifiable concentrate system for use with a hydrophobic pesticide comprising

(a) at least one hydrophobic pesticidally active compound;

(b) a solvent system comprising;

(i) a first solvent which is selected from the group consisting of alkyl alkanoates; and

(ii) a second solvent which is selected from the group consisting of polydric alcohols, condensates of polyhydric alcohols, and mixtures thereof; and

(c) at least one hydrophilic surfactant.