Abstract:
This invention relates to formulations of fluoroxypyr meptyl ester with C 4 -C 8  esters of triclopyr, 2,4-D or MCPA that are free of aromatic hydrocarbon solvents.

Description:
[0001]    This application claims the benefit of U.S. Provisional Application Ser. No. 61/000,250 filed on Oct. 24, 2007. The present invention relates to herbicidal formulations of fluoroxypyr meptyl ester with C 4 -C 8  esters of triclopyr, 2,4-D or MCPA. More particularly, the present invention concerns formulations of fluoroxypyr meptyl ester with C 4 -C 8  esters of triclopyr, 2,4-D or MCPA that are free of aromatic hydrocarbon solvents. 
     
    
     BACKGROUND OF THE INVENTION 
       [0002]    In today&#39;s agrichemical market, it becomes increasingly common to design formulations to contain multiple active ingredients and their required solvents, safeners, and/or adjuvants, etc., in order to achieve the optimal spectrum, efficacy, and delivery efficiency, which consequently makes formulation stability more and more challenging. 
         [0003]    Fluoroxypyr is a known, effective herbicide for the control of broad-leaved weeds. Fluoroxypyr meptyl ester, which is a solid, is typically formulated as an emulsifiable concentrate at a concentration of about 26 weight percent in aromatic hydrocarbon solvents (for example, Dow AgroSciences&#39; Starane™ herbicide). Aromatic hydrocarbon solvents have historically been used to maintain stability at low temperature in fluoroxypyr meptyl formulations. Triclopyr is a known effective herbicide for the control of broad-leaved weeds and woody plants. Triclopyr&#39;s herbicidal activity is complimentary to that of fluoroxypyr. Triclopyr butoxyethyl ester is typically formulated as an emulsifiable concentrate at a concentration of about 61 weight percent in aromatic hydrocarbon solvents (for example, Dow AgroSciences&#39; Garlon 4™ herbicide). (2,4-Dichlorophenoxy)-acetic acid (2,4-D) is a known effective herbicide for the control of broad-leaved weeds. 2,4-D&#39;s herbicidal activity is complimentary to that of fluoroxypyr. 2,4-D 2-ethylhexyl ester is typically formulated as an emulsifiable concentrate at a concentration of about 66 weight percent in kerosene and polyglycol solvents (for example, Nufarm&#39;s Esteron™ herbicide). (4-Chloro-2-methylphenoxy)acetic acid (MCPA) is a known effective herbicide for the control of broad-leaved weeds. MCPA&#39;s herbicidal activity is complimentary to that of fluoroxypyr. MCPA 2-ethylhexyl ester is typically formulated as an emulsifiable concentrate at a concentration of about 68 weight percent in petroleum distillate solvents (for example, Nufarm&#39;s Rhonox™ herbicide). While emulsifiable concentrate formulations can be prepared using chlorinated solvents or 1-methyl-2-pyrrolidinone, these solvents have less than preferred environmental profiles. In fact, some of the compounds used as solvents are being subjected to increasing regulatory scrutiny. Currently, some governing bodies are considering banning or limiting the use of some organic solvents. Removing objectionable solvents from the current herbicide formulations would significantly alter their physical properties including their storage stability and suitability for use. Consequently, it would be preferable to provide alternate formulations that have significantly reduced amounts of solvents or are essentially free of solvents. 
       SUMMARY OF THE INVENTION 
       [0004]    Surprisingly, it has now been found that low-temperature stable, emulsifiable concentrates and emulsion-in-water concentrates of fluoroxypyr meptyl ester with C 4 -C 8  esters of triclopyr, 2,4-D or MCPA can be prepared without aromatic solvents if the weight ratio of fluoroxypyr meptyl ester to the C 4 -C 8  ester of triclopyr, 2,4-D or MCPA is in the range from about 1:1 to about 1:4. This allows less efficient but more environmentally benign adjuvants like seed/vegetable oils and methylated seed/vegetable oils to be used to control concentrate viscosity and commercial active loading levels without sacrificing low temperature physical stability. The formulations of the present invention contain one or more surfactants selected to maintain the herbicidal esters as an emulsion upon dilution; and optionally, one or more adjuvants or compatible ingredients. 
     
    
     DETAILED DESCRIPTION OF THE INVENTION 
       [0005]    In general, the herbicidal formulation includes from about 30 weight percent to about 90 weight percent of the combined fluoroxypyr meptyl ester and the C 4 -C 8  ester of triclopyr, 2,4-D or MCPA. The weight percentage of the C 4 -C 8  ester of triclopyr, 2,4-D or MCPA is preferentially about two to three times that the fluoroxypyr meptyl ester. 
         [0006]    The surfactants can be anionic, cationic or nonionic in character. Typical surfactants include salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkyl and/or arylalkylphenol-alkylene oxide addition products, such as nonylphenol-C 18  ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol-C 16  ethoxylate; soaps, such as sodium stearate; alkylnaphthalenesulfonate salts, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl trimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; salts of mono and dialkyl phosphate esters; and mixtures thereof. The surfactant or mixture of surfactants is usually present at a concentration of from about 2 to about 20 weight percent of the formulation. 
         [0007]    In addition to the formulations set forth above, the present invention also embraces the compositions of these fluoroxypyr meptyl ester/C 4 -C 8  ester of triclopyr, 2,4-D or MCPA formulations in combination with one or more additional compatible ingredients. Other additional ingredients may include, for example, one or more other herbicides, dyes, and any other additional ingredients providing functional utility, such as, for example, stabilizers, fragrants, viscosity-lowering additives, and freeze-point depressants. 
         [0008]    Additional herbicidal compounds employed as supplements or additives should not be antagonistic to the activity of the fluoroxypyr meptyl ester/C 4 -C 8  ester of triclopyr, 2,4-D or MCPA composition as employed in the present invention. Suitable herbicidal compounds include, but are not limited to ametryn, aminopyralid, asulam, atrazine, butafenacil, carfentrazone-ethyl, chlorflurenol, chlormequat, chlorpropham, chlorsulfuron, chlortoluron, cinosulfuron, clethodim, clopyralid, cyclosulfamuron, pyroxsulam, dicamba, dichlobenil, dichlorprop-P, diclosulam, diflufenican, diflufenzopyr, diuron, glyphosate, hexazinone, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, metsulfuron-methyl, picloram, pyrithiobac-sodium, sethoxydim, sulfometuron, sulfosate, sulfosulfuron, tebuthiuron, terbacil, thiazopyr, thifensulfuron, triasulfuron and tribenuron. The herbicidal formulations of the present invention can be co-formulated with the other herbicide or herbicides, tank mixed with the other herbicide or herbicides, or applied sequentially with the other herbicide or herbicides. 
         [0009]    Dyes may be used in the formulated composition as a marker. Generally, a preferred dye can be any oil-soluble dye selected from EPA&#39;s approved list of inerts exempt from tolerance. Such dyes may include, for example, D&amp;C Red #17, D&amp;C Violet #2, and D&amp;C Green #6. Dyes are generally added to the composition by adding the desired amount of dye to the formulated composition with agitation. Dyes are generally present in the final formulation composition in a concentration of about 0.1-1.0% by weight. 
         [0010]    The compositions of the present invention are diluted with water prior to being applied. The diluted compositions usually applied to cereals and range and pastures generally contain about 0.0001 to about 5.0 weight percent of the combined fluoroxypyr meptyl ester and C 4 -C 8  ester of triclopyr, 2,4-D or MCPA. 
       EXAMPLE 1 
     Miscibility of Fluoroxypyr Meptyl Ester and Triclopyr Butoxyethyl Ester 
       [0011]    The following test systems in Table I were prepared by blending molten fluoroxypyr meptyl ester (˜65° C.) into triclopyr butoxyethyl ester at ambient temperature until isotropic. Miscibility behavior is reported in Table I. 
         [0000]    
       
         
               
               
               
             
               
               
               
               
               
             
           
               
                   
                 TABLE I 
               
             
             
               
                   
                   
               
               
                   
                 Weight Ratio of Fluroxypyr 
                 Miscibility Behavior 
               
             
          
           
               
                   
                 MHE to Triclopyr BEE 
                 20° C. 
                 5° C. 
                 −5° C. 
               
               
                   
                   
               
               
                   
                 4:1 
                 NM* 
                 — 
                 — 
               
               
                   
                 3:2 
                 PM* 
                 — 
                 — 
               
               
                   
                 2:3 
                 PM 
                 — 
                 — 
               
               
                   
                 1:4 
                 M* 
                 M 
                 M 
               
               
                   
                 1:3 
                 M 
                 M 
                 M 
               
               
                   
                 1:2 
                 M 
                 M 
                 M 
               
               
                   
                 1:1 
                 PM 
                 — 
                 — 
               
               
                   
                   
               
               
                   
                 *NM = non miscible 
               
               
                   
                 PM = partially miscible, fluroxypyr MHE crystals ovservable 
               
               
                   
                 M = miscible, system is isotropic 
               
             
          
         
       
     
         [0012]    The following test systems in Table II were prepared by blending molten fluoroxypyr meptyl ester (˜65° C.) into 2,4-D 2-ethylhexyl ester at ambient temperature until isotropic. Miscibility behavior is reported in Table II. 
         [0000]    
       
         
               
               
               
             
               
               
               
               
               
             
           
               
                   
                 TABLE II 
               
             
             
               
                   
                   
               
               
                   
                 Weight Ratio of Fluroxypyr 
                 Miscibility Behavior 
               
             
          
           
               
                   
                 MHE to 2,4-D 2EH 
                 20° C. 
                 5° C. 
                 −5° C. 
               
               
                   
                   
               
               
                   
                 4:1 
                 NM 
                 NM 
                 NM 
               
               
                   
                 3:2 
                 NM 
                 NM 
                 NM 
               
               
                   
                 2:3 
                 M 
                 M 
                 NM 
               
               
                   
                 1:4 
                 M 
                 M 
                 M 
               
               
                   
                 1:3 
                 M 
                 M 
                 M 
               
               
                   
                 1:2 
                 M 
                 M 
                 M 
               
               
                   
                 1:1 
                 NM 
                 NM 
                 NM 
               
               
                   
                   
               
               
                   
                 NM = non miscible 
               
               
                   
                 PM = partially miscible, fluroxypyr MHE crystals observable 
               
               
                   
                 M = miscible, system is isotropic 
               
             
          
         
       
     
         [0013]    The following test systems in Table III were prepared by blending molten fluoroxypyr meptyl ester (˜65° C.) into MCPA 2-ethylhexyl ester at ambient temperature until isotropic. Miscibility behavior is reported in Table III. 
         [0000]    
       
         
               
               
               
             
               
               
               
               
               
             
           
               
                   
                 TABLE III 
               
             
             
               
                   
                   
               
               
                   
                 Weight Ratio of Fluroxypyr 
                 Miscibility Behavior 
               
             
          
           
               
                   
                 MHE to MCPA 2EH 
                 20° C. 
                 5° C. 
                 −5° C. 
               
               
                   
                   
               
               
                   
                 4:1 
                 NM 
                 NM 
                 NM 
               
               
                   
                 3:2 
                 M 
                 M 
                 M 
               
               
                   
                 2:3 
                 M 
                 M 
                 M 
               
               
                   
                 1:4 
                 M 
                 M 
                 M 
               
               
                   
                 1:3 
                 M 
                 M 
                 M 
               
               
                   
                 1:2 
                 M 
                 M 
                 M 
               
               
                   
                 1:1 
                 M 
                 M 
                 M 
               
               
                   
                   
               
               
                   
                 NM = non miscible 
               
               
                   
                 PM = partially miscible, fluroxypyr MHE crystals observable 
               
               
                   
                 M = miscible, system is isotropic 
               
             
          
         
       
     
       EXAMPLE 2 
     Emulsifiable Concentrate (EC) 
       [0014]    Formulations A and B were prepared as follows. Molten fluoroxypyr meptyl ester (˜65° C.) was stirred at ambient temperature into triclopyr butoxyethyl ester and the remaining ingredients until an isotropic system was obtained. 
         [0000]    
       
         
               
               
             
               
             
               
               
               
             
               
             
               
               
               
             
           
               
                   
                   
               
               
                   
                 Wt % 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                 Formulation A 
               
             
          
           
               
                   
                 Fluroxypyr MHE 
                 22.7 
               
               
                   
                 Triclopyr BEE 
                 65.7 
               
               
                   
                 Agnique BL 2904 (surfactant blend) 
                 11.6 
               
             
          
           
               
                 Formulation B 
               
             
          
           
               
                   
                 Fluroxypyr MHE 
                 15.3 
               
               
                   
                 Triclopyr BEE 
                 44.4 
               
               
                   
                 Agnique BL 2904 (surfactant blend) 
                 8.0 
               
               
                   
                 Soybean Oil (viscosity modifier) 
                 32.3 
               
               
                   
                   
               
             
          
         
       
     
       EXAMPLE 3 
     Emulsion in Water Concentrate (EW) 
       [0015]    Formulation C was prepared as follows. Molten fluoroxypyr meptyl ester (˜65° C.) was stirred at ambient temperature into a preblend oil phase consisting of triclopyr butoxyethyl ester, Amisoft HS-21P, Nikkol DGMS, Tween 61 and soybean oil until isotropic. This combined oil phase was vigorously mixed with a premix aqueous phase consisting of water, Proxel GXL, monosodium and disodium phosphate and propylene glycol until the total system was homogeneous. 
         [0000]    
       
         
               
             
               
               
             
               
               
               
             
           
               
                   
               
               
                 Formulation C 
               
               
                 Emulsion in Water Concentrate (EW) 
               
             
          
           
               
                   
                 Wt % 
               
               
                   
                   
               
             
          
           
               
                   
                 Fluroxypyr MHE 
                 7.9 
               
               
                   
                 Triclopyr BEE 
                 22.9 
               
               
                   
                 Amisoft HS-21P (surfactant) 
                 0.5 
               
               
                   
                 Nikkol DGMS (surfactant) 
                 2.0 
               
               
                   
                 Tween 61 (surfactant) 
                 1.4 
               
               
                   
                 Soybean Oil (viscocity modifier) 
                 10.0 
               
               
                   
                 Proxel GXL (biocide) 
                 0.3 
               
               
                   
                 NaH 2 PO 4 •H 2 O (buffer) 
                 0.2 
               
               
                   
                 Na 2 HPO 4  (buffer) 
                 0.3 
               
               
                   
                 Proplyene Glycol (antifreeze) 
                 4.0 
               
               
                   
                 Water 
                 50.5