US 2005O227872A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2005/0227872 A1 Volgas et al. (43) Pub. Date: Oct. 13, 2005

(54) HERBICIDE FORMULATION CONTAINING (22) Filed: Mar. 29, 2005 HEXAZINONE Related U.S. Application Data (75) Inventors: Greg Volgas, Bartlett, TN (US); Johnnie R. Roberts, Memphis, TN (60) Provisional application No. 60/560,193, filed on Apr. (US); Trey Baker, Horn Lake, MS 7, 2004. (US) Publication Classification Correspondence Address: CONNOLLY BOVE LODGE & HUTZ, LLP (51) Int. Cl...... A01N 37/00 PO BOX 22O7 (52) U.S. Cl...... 504/307 WILMINGTON, DE 19899 (US) (73) Assignee: HELENA HOLDING COMPANY, (57) ABSTRACT Wilmington, DE A herbicidal composition containing hexaZinone and an (21) Appl. No.: 11/092,093 alkylene carbonate. US 2005/0227872 A1 Oct. 13, 2005

HERBICIDE FORMULATION CONTAINING 0010. These products have been promoted as solvents for HEXAZINONE use in agricultural pesticide formulations. Their typical flash points are between 275 and 320 F., well above the tem RELATED APPLICATIONS perature which would require formulations to be labeled as flammable. 0001. This application claims benefit to provisional application Ser. No. 60/560,193, filed Apr. 7, 2004 which is SUMMARY OF THE INVENTION incorporated by reference in its entirety for all useful pur 0011 What we have surprisingly discovered is that the pOSes. alkylene carbonates are especially good Solvent Systems for heXazinone formulations. The use of these carbonates pro BACKGROUND OF THE INVENTION duces formulations which are both freeze stable down to 15 F. and non-flammable. Prior Art 0012. The invention further relates to a herbicidal con 0002 Hexazinone is a commonly used agricultural and centrate which comprises heXazinone and at least one car forest management herbicide. Commercial formulations of bonate. The concentrate is preferably liquid. this product are currently available in liquid forms. One Such 0013 Whenever the term “% by weight” is used in the liquid formulation of hexazinone is VELPAR(RL is from du Specification, it is understood that it means percent of the Pont. This formulation uses 40-45% ethanol to dissolve the component per the total weight of the composition unless heXazinone. Ethanol can lower the freeze point of Such otherwise Specified. formulations, but it also makes the products flammable. This is a Safety concern for many end users and even distributors. 0014. The invention can be used without the required Furthermore, ethanol does not sufficiently lower the freezing defoaming or foam breaking agents described in the 618 point of the formulation to acceptable levels. The Material patent which are Selected from the group consisting of Safety Data Sheet (“MSDS”) for VELPAR(RL still requires perfluoroalkylphosphonic acids, perfluoroalkylphosphinic that the product not be Stored for prolonged periods below acids and perfluoroaliphatic polymeric esters. However, the 32 degrees F. Since VELPAR(RL is often used and stored in formulation according to the invention can use alternate temperatures below freezing, this formulation problem foam control agents, Such as, but not limited to Silica based requires heated Storage areas. defoamerS. 0.003 Dry formulations of hexazinone have also been DETAILED DESCRIPTION OF THE commercialized. These dry formulations are typically diffi INVENTION cult to mix with other components (i.e. fertilizers, other 0015 The preferred formulation contains at least 5%, pesticides, micronutrients, etc.) of spray mixtures. Further preferably at least 10%, more preferably at least 15% and more, most end-users find measuring liquids much easier even more preferably at least 20% and most preferably at than measuring dry products. least 25% by weight of hexazinone based on the total weight 0004 Alkylene carbonates have been used to formulate of the composition. The preferred formulation is a liquid pesticide products. These formulations typically require a concentrate that contains between 1 and 40% more prefer non-polar co-Solvent to improve Solubility of the pesticide ably 20-30%, and most preferably 25-30% by weight based active. One Such formulation is described by Aven, et. al., of hexaZinone based on the total weight of the composition. U.S. Pat. No. 6,444,618 (“618 patent”). The 618 patent 0016. The preferred formulation does not require the use requires the use of at least one pesticidal crop protection of non-polar organic Solvents, emulsifying Surfactants or active compound, at least one non-polar organic Solvent, an defoaming agents. It may also optionally include any of emulsifying Surfactant System enabling an oil-in-water these components. Again, these ingredients can be present or emulsion to be formed when the formulation is added to optional. water, and at least one defoaming or foam breaking agent Selected from the group consisting of perfluoroalkylphos 0017. The present invention requires a major amount of phonic acids, perfluoroalkylphosphinic acids and perfluoro alkylene carbonate. A major amount is considered of alky aliphatic polymeric esters. Optionally, the patent includes lene carbonate Preferably said alkylene carbonate would be the use of “at least one polar aprotic coSolvent, and lists Selected from the butylenes, ethylene, propylene or glycerin alkylene carbonates as likely candidates. The herbicides carbonates. Most preferably, the alkylene carbonate is buty include numerous candidates of which one is heXazinone. lene carbonate. Mixtures of alkylene carbonates are also The 618 patent requires a Specific defoaming or foam useful. breaking agent Selected from the group consisting of per 0018. The amount of alkylene carbonate is the present fluoroalkylphosphonic acids, perfluoroalkylphosphinic invention is from 10-99% by weight. More preferably, the acids and perfluoroaliphatic polymeric esters. invention would contain between 50-80% by weight alky 0005 Alkylene carbonates are commercially available lene carbonate. Most preferably, the invention would contain from Hunstman under the trade names: between 70-80% by weight alkylene carbonate. 0006 JEFFSOL(R)-ethylene carbonate, 0019. The present invention will benefit greatly from the addition of Surfactants to improve the spreading and wetting 0007 JEFFSOL(R)-propylene carbonate, of Spray droplets on plant Surfaces. The useful Surfactants 0008 JEFFSOL(R)-butylene carbonate, would have as their properties the ability to lower surface tension below 60 dynes/nM when used in water at 1.0% or 0009 JEFFSOL(R)-glycerine carbonate. leSS. US 2005/0227872 A1 Oct. 13, 2005

0020 Useful Surfactants or Solvents include but are not 0058 Sorbitan derivatives including but not limited to: limited to: 0059 Sorbitan esters, Alcohol alkoxylates including but not limited to: 0021) 0060 Alkoxylated Sorbitan esters, Based on branched and linear alcohols 0022) 0061 Sucrose and glucose derivatives including but not 0023 Those containing ethylene oxide or propylene limited to: oxide 0062 Alkylpolyglucosides, 0024 Alcohol alkoxylate Sulfates, 0063 Sulfates and Sulfonates of alkoxylated alkylphe 0025) Alkylphenol alkoxylates including but not limited nols, to: 0064 Sulfates of alcohols, 0026 Nonylphenol and octylphenols. 0065 Tristyrylphenol Alkoxylates, 0027) Those containing ethylene oxide or propylene oxide 0066 Other surfactants are disclosed in McCutcheon's Emulsifiers and Detergents, North American Edition, 2000. 0028) Alkanolamides, 0067. The formulations may also contain oil-based com 0029) Alkylaryl Sulfonates, ponents. 0030) Amine oxides, 0068 The oil or oil substitutes include, but are not limited 0031) Amines including but not limited to: to: 0032) Fatty amine alkoxylates Such as but not limited to 0069. Alkylated fatty acid esters, include but are not tallowamine alkoxylates, limited to: 0033) Betaine derivatives, 0070 Methylated fatty acids, include but not limited to: 0034) Block polymers of ethylene and propylene glycol, 0071 Methylated C6-C19 fatty acids, 0035) Carboxylated alcohol or alkylphenol alkoxylates, 0072 Methylated Tall oil fatty acids, 0036) Diols, including but not limited to Butanediols, 0073 Methylated Oleic acid, 0037) Diphenyl sulfonate derivatives, 0074 Methylated Linoleic acid, 0038 Ethers, including but not limited to 0075 Methylated Linolenic acid, 0039) Butyl celluslove, 0.076 Methylated Stearic acid, 0040 Butyl carbitol, 0.077 Methylated Palmitic acid, 0041) Ethoxylated amines, 0078 And blends thereof; 0042 Ethoxylated fatty acids, 0079 Ethylated fatty acids, include but are not limited to: 0043) Ethoxylated fatty esters and oils, 0080 Ethylated C6-C19 fatty acids, 0044) Ethylene carbonate, 0081 Ethylated Tall oil fatty acids, Fatty esters, 0045 0082) Ethylated Oleic acid, Glycerol esters, 0046) 0083) Ethylated Linoleic acid, 0047 Glycols including but not limited to 0084 Ethylated Linolenic acid, 0048) Propylene glycol, 0085 Ethylated Stearic acid, 0049) Ethylene glycol, 0086) Ethylated Palmitic acid, 0050 Dipropylene glycol, 0087 And blends thereof; 0051) Diethylene glycol, 0088 Butylated fatty acids, include but are not limited to: 0052 Phosphate ester Surfactants including but not lim ited to 0089. Butylated C6-C19 fatty acids, 0053) Phosphate esters of alcohol alkoxylates, 0090. Butylated Tall oil fatty acids, 0054) Phosphate esters of alkylphenol alkoxylates, 0091. Butylated Oleic acid, 0055) Propylene Carbonate, 0092. Butylated Linoleic acid, 0056) Sarcosine derivatives, 0093. Butylated Linolenic acid, 0057) Silicone-based Surfactants, 0094) Butylated Stearic acid, US 2005/0227872 A1 Oct. 13, 2005

0.095 Butylated Palmitic acid, 0136 Palmitic acid, 0096) And blends thereof; 0137 And blends thereof; O097 Alkylated natural oils, include but are not limited 0138 Polybutenes to: 0.139 Epoxified seed oils include but are not limited to: Alkylated soybean oil, include but limited to: 0098) 0140 Epoxified soybean oil and 0099) Methylated soybean oil, 0.141. Other oils or oil substitutes 01.00 Ethylated soybean oil, 0142. The formulation can contain at least one of the 01.01 Butylated soybean oil, above oils or its equivalent. The oil can also be a blend of 0102) And blends thereof; at least two oils. When an oil is used, a Surfactant or emulsifier must also be used if the composition is intended 0103) Alkylated canola oil, include but are not limited to: for aqueous based sprayS. 01.04] Methylated canola oil, 0143. The present invention does not require surfactants 01.05 Ethylated canola oil, (emulsifiers) to mix with water. The addition of surfactants is optional. 01.06) Butylated canola oil, 0144. Other herbicides that will work include one or 01.07 And blends thereof; more herbicidal compounds Selected from the group con 0108) Alkylated coconut oil, include but are not limited Sisting of chloramben, chlorthal, dicamba, naptalam, 2,3,6- to: TBA, clopyralid, diflufenzopyr (SAN 835 H), dithiopyr, Methylated coconut oil, picloran, thiazopyr (MON 13200), quinclorac, quinmerac, 01.09) indanofan (MK-243), benazolin, chlorflurenol, dalapon, 0110 Ethylated coconut oil, endothal, flamprop, flamprop M, flupropanate, flurenol, TCA-Sodium, bromobutide, chlorthiamid, diflufenican, 0111 Butylated coconut oil, diphenamid, ethabenzanid (HW 52), isoxaben, mefenacet, 0112 And blends thereof; monalide, pentanochlor, propanil, propy Zanide, tebutam, fluthiamide (BAY FOE 5043), clodinafop, clomeprop, cyha 0113) Alkylated Sunflower oil, include but are not limited lofop-butyl (XDE-537), 2,4-D, 2,4-DB, dichlorprop, dichlo to: rprop-P, diclofop, fenoxaprop, fenoxaprop-P, fluaZifop, flu 0114 Methylated Sunflower oil, azifop-P, fluroxypyr, haloxyfop, haloxyfop-P-methyl, isoxapyrifop, MCPA, MCPA-thioethyl, MCPB, mecoprop, 0115) Ethylated Sunflower oil, mecoprop-P, naproanilide, napropamide, propaquiazfop, 0.116) Butylated Sunflower oil, quizalofop, quizalofop-P, triclopyr, UBI-C474, bro mofenoxim, bromoxynil, dichlobenil, ioxynil, diguat, 0117) And blend thereof; paraduat, asulam, butylate, carbetamide, chlorbu fam, chlo 0118 Hydrocarbon oils include but are not limited to: rpropham, cycloate, desmedipham, dimepiperate, EPTC, esprocarb, molinate, orbencarb, pebulate, phenmedipham, 0119) Mineral oils, including but are not limited to: propham, proSulfocarb, pyributicarb, thiobencarb, tiocarba 0120 Paraffinic mineral oils, Zil, tri-allate, Vernolate, alloxydim, butroxydim, clethodim, Naphthenic mineral oils, cylcoxydim, Sethoxydim, Sulcotrione, tralkoxydim, 0121) acetochlor, alachlor, butachlor, butenachlor, diethatyl, 0122) Aromatic mineral oils, dimethachlor, dimethenamid, metazochlor, metolachlor, pre tilachlor, propachlor, propisochlor, tenylchlor (NSK-850), 0123) And blends thereof; acifluorfen, aclonifen, bifenox, chlomethoxyfen, chlonitro 0124 Vegetable oils, include but are not limited to: fen, athoxyfenethyl (RC-252), fluoroglycofen, fluoronitro Soybean oil, fen, fomesafen, fuiryloxyfen, lactofen, AKH-7088, oxyfluo 0125) rfen, benfluralin, butralin, dinitramide, ethalfluralin, 0126) Canola oil, fluchloralin, isopropalin, oryzalin, pendimethalin, prodi amine, trifluralin, dinoseb, dinoseb acetate, dinoterb, ami O127) Cottonseed oil, trole, benfureSate, bentazone, benzofenap, cafenstrole (CH 0128 And blends thereof; 900), carfentrazone-ethyl (F-8426), chloridazon, cinmethylin, clomaZone, difenzoquiat, ethofumeSate, 0129 Fatty acids, include but are not limited to: pyraflufen-ethyl (ET-751), flumichlorac-pentyl, flumiox 0130 C6-C19 fatty acids, azin, flumipropin, flupoxam, fluridone, flurochloridone, flur tamone, fluthiacet methyl (KIH-9201), isoxaflutone (RPA 0131) Tall oil fatty acids, 201772), methazole, nipyraclofen, norflurazon, oxadiargyl, oxadiazon, oxaziclomefone (MY-100), pentoxazone (KPP 0132) Oleic acid, 314), pyruZolynate, pyrazoxyfen, pyridate, SulfentraZone, 0133) Linoleic acid, (F6285), thidiazimin, anilofos, bensulide, bilanafos, butami fos, foSamine, glufosinate, glyphosate, LS830556, pipero 0134) Linolenic acid, phos, imazamethabenz, imazamethipyr (AC-263,222), 0135) Stearic acid, imaZamox (AC-299,263), imazapyr, imaZaquin US 2005/0227872 A1 Oct. 13, 2005

imazethapyr, bispyribac-Sodium (KHI-2023), pyribenzoxim dilution in water or oil used as carriers. The amount of (LGC-40863), pyriminobac-methyl (KIH-6127), pyrithio dilution would be from about 2 to about 8 quarts per acre of bac-sodium (KIH-203 1), tioclorim, cloransulam-methyl the concentrate and about 1 to about 100 gallons of water per (XDE-565), diclosulam (XDE-564), flumetsulam (DE-498), acre. The formulation maybe diluted as disclosed in metosulam (XDE-564), flumetSulam (DE-498), metosulam (DE-511), amidosulfuron, azimsulfuron (DPX-A8947), ben duPont's VELPAR L(R) product information (C1998 E.I. du Sulfuron, chlorimuron, chlorSulfliron, cinoSulfuron, cyclo Pont de Nemours and Company, Agricultural Products, sulfamuron (AC-322,140), etha-metsulfuron-methyl (DPX Wilmington, Del. which is incorporated by reference in its A7881), ethoxysulfuron (HOE 095404), flazasulfuron, entirety. flupyrsulfuron (DPX-KE459), halosulfuron (NC-319), ima ZoSulfuron, metSulfuron, NC-300, nicosulfuron, oxasulfuron 0156 Examples of the inventive concentrate composi (CGA-277476), primisulfuron, prosulfuron (CGA-152005), tions include: pyrazolsulfuron, rimsulfuron, sulfometuron (DPX-5648), sulfosulfuiron (MON-37500), thifensulfuron, triasulfuron EXAMPLE 1. (CGA-121036), tribenuron, trifluSulfuron-methyl (DPX 66037), ametryn, atrasin, aziprotryne, cyanazine, desmetryn, O157) dimethame-tryn, dipropetryn, eglinazine, methoprotryne, proglinazine, prometon, prometryne, propazine, Simazine, Simetryn, terbumeton, terbuthylazine, terbutryn, triaziflam (IDH-1105), trietazine, SMY-1500, heXazinone, Propylene carbonate 75.0% metamitron, metribuzin, bromacil, lenacil, terbacil, benz Hexazinone technical (98%) 25.0% thiazuron, chlorbromuron, chloroXuron, chlorotoluron, cumyluron (JC-940), daimuron, difenoxuron, dimefuron, 1-diuron, ethidimuron, fenuron, fluometuron, isoproturon, isouron, linuron, methabenzthiazuron, methyldymron, EXAMPLE 2 metobenzuron, metobromuron, metoxuron, monolinuron, neburon, Siduron, tebuthiuron, thiaZafluoron, isopropaZol 0158 (JV 485), KPP300, KPP 421, BAYYRL2388, DPXT 5975, aZafenidin. 0145 Additional hebicides that will work are disclosed in Butylene carbonate 75.0% The Pesticide Manual published by the British Crop Pro Hexazinone technical (98%) 25.0% tection Council. 0146 The following patents and reference, which include Several ingredients that can be used according to this inven tion, are incorporated by reference in its entirety for all EXAMPLE 3 useful purposes: 0159) 0147 U.S. Pat. No. 5,741,502 entitled Homogeneous, essentially nonaqueous adjuvant compositions with buffer ing capability Ethylene carbonate 75.0% 0148 U.S. Pat. No. 5,725,630 entitled Dry granular fer Hexazinone technical (98%) 25.0% tilizer blend and a method of fertilizing plants 0149 U.S. Pat. No. 5,580,567 entitled Homogeneous, essentially nonaqueous adjuvant compositions with buffer EXAMPLE 4 ing capability 0160 0150 U.S. Pat. No. 5,393,791 entitled Homogeneous, essentially nonaqueous adjuvant compositions with buffer ing capability Propylene carbonate 70.0% 0151 U.S. Pat. No. 5,234,919 entitled Water soluble, Hexazinone technical (98%) 25.0% highly active dimethoate formulations in an alcohol/ester C11 Alcohol (3EO) Ethoxylate 5.0% Solvent System 0152 U.S. Pat. No. 5,178,795 entitled Homogeneous, essentially nonaqueous adjuvant compositions with buffer EXAMPLE 5 ing capability 0161) 0153 U.S. Pat. No. 5,906,961 entitled Alkanolamide Spreader-Sticker Surfactant combination 0154 U.S. Pat. No. 5,877,112 entitled Agricultural for Propylene carbonate 50.0% mulation. Hexazinone technical (98%) 25.0% Nonylphenol (6EO) Ethoxylate 25.0% O155 These formulations are typically concentrates. Typical use of these formulations would include further US 2005/0227872 A1 Oct. 13, 2005

EXAMPLE 6 We claim: 1. A herbicidal composition comprising hexaZinone and 0162 an alkylene carbonate. 2. A composition as claimed in claim 1 which further comprises a Surfactant. Propylene carbonate 50.0% 3. A composition as claimed in claim 1, wherein the Petroleum distillates 30.0% alkylene carbonate is propylene carbonate. Hexazinone technical (98%) 20.0% 4. A composition as claimed in claim 1, wherein the alkylene carbonate is ethylene carbonate. 5. A composition as claimed in claim 1, wherein the EXAMPLE 7 alkylene carbonate is butylene carbonate. 6. A composition as claimed in claim 1, wherein the ratio 0163) of heXaxinone to alkylene carbonate is at most 1:10. 7. A composition as claimed in claim 1, wherein the ratio of heXaxinone to alkylene carbonate is at most 1:5. Butylene carbonate 50.0% 8. A composition as claimed in claim 1, wherein the ratio Methylated soybean oil 30.0% of heXaxinone to alkylene carbonate is at most 1:2. Hexazinone technical (98%) 20.0% 9. A herbicidal composition as claimed in claim 1, wherein the hexazinone comprises at least 5% by weight of the total composition. 0164. The examples 1, 2 and 4 were placed into a freezer 10. A herbicidal composition as claimed in claim 1, at 12 degrees F along with a control Sample of Velpar L. wherein the hexazinone comprises at least 10% by weight of After at least two days in the freezer, the Velpar L. Sample the total composition. crytalized. The crystals did not thaw after Sitting at ambient 11. A herbicidal composition as claimed in claim 1, for 24 hours. The example formulations did not freeze at all. wherein the hexazinone comprises at least 15% by weight of 0.165 Since most uses of the patented formulations will the total composition. be when mixed with water, the example formulations were 12. A herbicidal composition as claimed in claim 1, added to water and were found to mix readily with water. In wherein the hexazinone comprises at least 20% by weight of Some cases, the formulations appeared to actually dissolve the total composition. in water and produce clear Solutions. In other cases, the 13. A herbicidal composition as claimed in claim 1, formulations formed emulsions which were characterized as wherein the hexazinone comprises at least 25% by weight of micro-emulsions, mini-emulsions or emulsions. (AS defined the total composition. by Milton Rosen in his book "Surfactants and Interfacial 14. A herbicidal composition as claimed in claim 1, Phenomena” 2nd edition.) wherein the hexazinone comprises at least 30% by weight of 0166 Carriers other than water are possible. For instance, the total composition. fertilizer or oils may be used as carriers. 15. A herbicidal composition comprising hexaZinone, an alkylene carbonate, and a Surfactant. 0167 All of the examples would have flash points greater 16. A method comprising mixing the composition as than 200 F and would be classified by DOT as non claimed in claim 1 with water and Spraying onto plant flammable. The Velpar L formulation has a flash point of foliage. 73-77 F. according to the MSDS, and would be classified as 17. A herbicidal composition comprising hexaZinone, an a flammable liquid. alkylene carbonate and no other Solvent. 0168 The formulations according to the invention can be 18. A herbicidal composition comprising hexaZinone, an microemulsions, macroemulsions or miniemulsions as alkylene carbonate and another Solvent. defined in Surfactants and Interfacial Phenomena, Milton J. 19. A herbicidal composition comprising hexaZinone and Rosen, John Wiley & Sons 2nd edition (1989) pages 304 a Sufficient amount of alkylene carbonate to completely 336 which is incorporated by reference in its entirety. Solubolize the hexaZinone. 0169 All the references discussed in this application are 20. A herbicidal composition as claimed in claim 1 which incorporated by reference in their entirety for all useful further comprises another herbicide. purposes. 21. A herbicidal composition as claimed in claim 1, wherein the composition does not contain a 0170 While there is shown and described certain specific Structures embodying the invention, it will be manifest to defoaming or foam breaking agent Selected from the those skilled in the art that various modifications and rear group consisting of perfluoroalkylphosphonic acid, per rangements of the parts may be made without departing fluoroalkylphosphinic acid and perfluoroaliphatic poly form the Spirit and Scope of the underlying inventive concept meric ester. and that the same is not limited to the particular forms herein shown and described.