Herbicidal compositions containing glyphosate and a pyridine analog

Abstract

The present invention is directed to herbicidal compositions or formulations, and to methods of using such compositions or formulations to kill, or control the growth and proliferation of, unwanted plants. In particular, the present invention is directed to herbicidal compositions or formulations, as well as their methods of use, which comprise N-phosphonomethylglycine or a herbicidal derivative thereof, a pyridine analog or a herbicidal derivative thereof, and optionally one or more suitable surfactants, with N-phosphonomethylglycine being in excess relative to the pyridine analog. Such compositions cause early visual symptoms of treatment and/or enhanced effectiveness or control when applied to the foliage of plants.

1 - 62 . (canceled) 
     
     
         63 . An aqueous herbicidal composition useful for killing or controlling the growth of unwanted plants comprising:
 glyphosate, in the form of a salt thereof,   triclopyr, in the form of a salt thereof, and   at least one surfactant;   wherein the composition has a cloud point of at least about 50° C.   
     
     
         64 . The composition of  claim 63  wherein the concentration of the triclopyr is controlled such that it is not substantially antagonistic to the herbicidal activity of the glyphosate within the composition. 
     
     
         65 . The composition of  claim 63  wherein the composition has a cloud point of at least about 60° C. 
     
     
         66 . The composition of  claim 63  comprising a glyphosate salt selected from the group consisting of an alkali metal salt, an amine salt, an ammonium salt, an alkylammonium salt, an alkanolammonium salt, a di-ammonium salt, an alkylamine salt, an alkanolamine salt, an alkylsulfonium salt, and a sulfoxonium salt thereof. 
     
     
         67 . The composition of  claim 66  comprising a glyphosate salt selected from the group consisting of the potassium, isopropylamine, ammonium, di-ammonium, sodium, monoethanolamine, monoethanolammonium, and trimethylsulfonium salts thereof. 
     
     
         68 . The composition of  claim 67  comprising the potassium salt of glyphosate. 
     
     
         69 . The composition of  claim 67  comprising the isopropylamine salt of glyphosate. 
     
     
         70 . The composition of  claim 67  comprising the monoethanolamine salt of glyphosate. 
     
     
         71 . The composition of  claim 63  comprising a triclopyr salt selected from the group consisting of an alkali metal salt, an amine salt, an ammonium salt, an alkylammonium salt, an alkanolammonium salt, a di-ammonium salt, an alkylamine salt, an alkanolamine salt, an alkylsulfonium salt, and a sulfoxonium salt thereof. 
     
     
         72 . The composition of  claim 71  comprising the monoethanolamine salt of triclopyr. 
     
     
         73 . The composition of  claim 71  comprising the isopropylamine salt of triclopyr. 
     
     
         74 . The composition of  claim 71  comprising the triethylamine salt of triclopyr. 
     
     
         75 . The composition of  claim 63  wherein the glyphosate concentration ranges from about 4 grams to about 25 grams acid equivalent per liter. 
     
     
         76 . The composition of  claim 75  wherein the triclopyr concentration ranges from about 0.4 grams to about 6 grams acid equivalent per liter. 
     
     
         77 . The composition of  claim 63  wherein the glyphosate concentration is at least about 75 grams per liter. 
     
     
         78 . The composition of  claim 77  wherein the glyphosate concentration is at least about 100 grams per liter. 
     
     
         79 . The composition of  claim 78  wherein the glyphosate concentration ranges from at least about 100 grams to about 400 grams acid equivalent per liter. 
     
     
         80 . The composition of  claim 79  wherein the triclopyr concentration ranges from at least about 4 to about 60 grams acid equivalent per liter. 
     
     
         81 . The composition of  claim 63  wherein said surfactant is selected from the group consisting of:
 (a) a secondary or tertiary amine having the formula: 
 
       
         
           
           
               
               
           
         
         wherein R 1  and R 2  are hydrocarbyl having from 1 to about 30 carbon atoms, and R 3  is hydrogen or hydrocarbyl having from 1 to about 30 carbon atoms; 
         (b) a monoalkoxylated amine having the formula: 
       
       
         
           
           
               
               
           
         
         wherein R 1  and R 4  are independently hydrocarbyl or substituted hydrocarbyl groups having from 1 to about 30 carbon atoms or —R 5 SR 6 , R 2  in each of the x (R 2 O) groups is independently C 2 -C 4  alkylene, R 3  is hydrogen, or a linear or branched alkyl group having from 1 to about 4 carbon atoms, R 5  is a linear or branched alkyl group having from about 6 to about 30 carbon atoms, R 6  is a hydrocarbyl or substituted hydrocarbyl group having from 4 to about 15 carbon atoms and x is an average number from 1 to about 60; 
         (c) a dialkoxylated quaternary ammonium salt having the formula: 
       
       
         
           
           
               
               
           
         
         wherein R 1  is hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, R 2  in each of the x (R 2 O) and y (R 2 O) groups is independently C 2 -C 4  alkylene, R 3  is hydrogen, or a linear or branched alkyl group having from 1 to about 4 carbon atoms, R 4  is hydrogen or hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, x and y are independently an average number from 1 to about 40, and X— is an agriculturally acceptable anion; 
         (d) a monoalkoxylated quaternary ammonium salt having the formula: 
       
       
         
           
           
               
               
           
         
         wherein R 1  and R 5  are independently hydrogen or hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, R 4  is hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, R 2  in each of the x (R 2 O) groups is independently C 2 -C 4  alkylene, R 3  is hydrogen, or a linear or branched alkyl group having from 1 to about 30 carbon atoms, x is an average number from 1 to about 60, and X— is an agriculturally acceptable anion; 
         (e) a quaternary ammonium salt having the formula: 
       
       
         
           
           
               
               
           
         
         wherein R 1 , R 3  and R 4  are independently hydrogen or hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, R 2  is hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, and X— is an agriculturally acceptable anion; 
         (f) an ether amine having the formula: 
       
       
         
           
           
               
               
           
         
         wherein R 1  is hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms; R 2  is hydrocarbylene or substituted hydrocarbylene having from 2 to about 30 carbon atoms; R 3  and R 4  are independently hydrogen, hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, or —(R 5 O) x R 6 , R 5  in each of the x(R 5 —O) groups is independently C 2 -C 4  alkylene, R 6  is hydrogen, or a linear or branched alkyl group having from 1 to about 4 carbon atoms, and x is an average number from 1 to about 50; 
         (g) a diamine having the formula: 
       
       
         
           
           
               
               
           
         
         wherein R 1 , R 3 , R 4  and R 5  are independently hydrogen, hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, or —(R 6 O) x R 7 ; R 2  and R 8  are independently hydrocarbylene or substituted hydrocarbylene having from 2 to about 30 carbon atoms, R 6  in each of the x (R 6 O) and y (R 6 O) groups is independently 
         C 2 -C 4  alkylene, R 7  is hydrogen, or a linear or branched alkyl group having from 1 to about 30 carbon atoms, x is an average number from 1 to about 30, X is —O—, 
         —N(R 6 )—, —C(O)—, —C(O)O—, —OC(O)—, —N(R 9 )C(O)—, —C(O)N(R 9 )—, —S—, —SO—, or —SO 2 —, y is 0 or an average number from 1 to about 30, n and z are independently 0 or 1, and R 9  is hydrogen or hydrocarbyl or substituted hydrocarbyl; 
         (h) an amine oxide having the formula: 
       
       
         
           
           
               
               
           
         
         wherein R 1 , R 2  and R 3  are independently hydrogen, hydrocarbyl or substituted hydrocarbyl, —(R 4 O) x R 5 , or —R 6 (OR 4 ) x OR 5 ; R 4  in each of the x (R 4 O) groups is independently C 2 -C 4  alkylene, R 5  is hydrogen, or a linear or branched alkyl group having from 1 to about 30 carbon atoms, R 6  is hydrocarbylene or substituted hydrocarbylene having from 2 to about 6 carbon atoms, x is an average number from 1 to about 50, and the total number of carbon atoms in R′, R 2  and R 3  is at least 8; 
         (i) a dialkoxylated amine having the formula: 
       
       
         
           
           
               
               
           
         
         wherein R 1  is a hydrocarbyl or substituted hydrocarbyl having from about 6 to about 30 carbon atoms, or —R 4 SR 5 , R 4  and R 2  in each of the x (R 2 O) and the y (R 2 O) groups is independently C 2 -C 4  alkylene, R 3  is hydrogen, or a linear or branched alkyl group having from 1 to about 4 carbon atoms, R 5  is a linear or branched alkyl group having from about 4 to about 15 carbon atoms, and x and y are independently an average number from 1 to about 40; 
         (j) an aminated alkoxylated alcohol having the structure: 
       
       
         
           
           
               
               
           
         
         wherein R 1 , R 7 , R 8 , and R 9  are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, or —(R 11 ) s (R 3 O) v R 10 ; X is —O—, —OC(O)—, —C(O)O—, —N(R 12 )C(O)—, —C(O)N(R 12 )—, —S—, —SO—, —SO 2 — or —N(R 9 )—; R 3  in each of the n (R 3 O) groups and the v (R 3 O) groups is independently C 2 -C 4  alkylene; R 10  is hydrogen, or a linear or branched alkyl group having from 1 to about 30 carbon atoms; n is an average number from 1 to about 60; v is an average number from 1 to about 50; R 2  and R 11  are each independently hydrocarbylene or substituted hydrocarbylene having from 1 to about 6 carbon atoms; R 4  is hydrocarbylene or substituted hydrocarbylene having from 2 to about 6 carbon atoms; R 12  is hydrogen or hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms; m and s are each independently 0 or 1; R 6  is hydrocarbylene or substituted hydrocarbylene having from 2 to about 30 carbon atoms, —C(═NR 12 )—, —C(S)—, or —C(O)—; q is an integer from 0 to 5; and R 5  is hydrogen or hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms; 
         (k) a quaternary ammonium, sulfonium and sulfoxonium salt having the formula: 
       
       
         
           
           
               
               
           
         
         wherein R 1 , R 7 , R 8 , R 9 , R 10  and R 11  are independently hydrogen, hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, or —(R 13 ) s (R 3 O) v R 12 ; X is —O—, —OC(O)—, —N(R 14 )C(O)—, —C(O)N(R 14 )—, —C(O)O—, or —S—; R 3  in each of the n (R 3 O) groups and v (R 3 O) groups is independently C 2 -C 4  alkylene; R 12  is hydrogen, or a linear or branched alkyl group having from 1 to about 30 carbon atoms; n is an average number from 1 to about 60; v is an average number from 1 to about 50; R 2  and R 13  are each independently hydrocarbylene or substituted hydrocarbylene having from 1 to about 6 carbon atoms; m and s are each independently 0 or 1; R 4  is hydrocarbylene or substituted hydrocarbylene having from 2 to about 6 carbon atoms; R 6  is hydrocarbylene or substituted hydrocarbylene having from 2 to about 30 carbon atoms, —C(═NR 12 )—, —C(S)—, or —C(O)—; R 14  is hydrogen or hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, q is an integer from 0 to 5; R 5  is hydrogen or hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms; and each A −  is an agriculturally acceptable anion; 
         (l) a diamine or diammonium salt having the formula: 
       
       
         
           
           
               
               
           
         
         wherein R 1 , R 4 , R 5 , R 6 , R 7  and R 8  are independently hydrogen or hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, R 2  in each of the m (R 2 O) and n (R 2 O) groups and R 9  are independently C 2 -C 4  alkylene, R 3  is hydrocarbylene or substituted hydrocarbylene having from about 2 to about 6 carbon atoms or —(R 2 O) p R 9 —, m and n are individually an average number from 0 to about 50, and p is an average number from 0 to about 60; 
         (m) an alkoxylated alcohol having the formula:
   R 1 O—(R 2 O) x R 3   (18)
 
 
         wherein R 1  is hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, R 2  in each of the x (R 2 O) groups is independently C 2 -C 4  alkylene, R 3  is hydrogen, or a linear or branched alkyl group having from 1 to about 4 carbon 
         atoms, and x is an average number from 1 to about 60; 
         (n) an alkoxylated dialkylphenol having the formula: 
       
       
         
           
           
               
               
           
         
         wherein R 1  and R 4  are independently hydrogen, or a linear or branched alkyl group having from 1 to about 30 carbon atoms and at least one of R 1  and R 4  is an alkyl group, R 2  in each of the x (R 2 O) groups is independently C 2 -C 4  alkylene, R 3  is hydrogen, or a linear or branched alkyl group having from 1 to about 4 carbon atoms, and x is an average number from 1 to about 60; 
         (o) an alkyl alkoxylated phosphate having the formula: 
       
       
         
           
           
               
               
           
         
         wherein R 1  and R 3  are independently a linear or branched alkyl, linear or branched alkenyl, linear or branched alkynyl, aryl, or aralkyl group having from about 4 to about 30 carbon atoms; R 2  in each of the m (R 2 O) and the n (R 2 O) groups is independently C 2 -C 4  alkylene; and m and n are independently from 1 to about 30; 
         (p) an alkyl alkoxylated phosphate having the formula: 
       
       
         
           
           
               
               
           
         
         wherein R 1  is a linear or branched alkyl, linear or branched alkenyl, linear or branched alkynyl, aryl, or aralkyl group having from about 8 to about 30 carbon atoms; R 2  in each of the m (R 2 O) groups is independently C 2 -C 4  alkylene; and m is from 1 to about 30; 
         and mixtures or combinations thereof. 
       
     
     
         82 . A method for killing or controlling the growth of unwanted plants comprising contacting the foliage of said plants with a herbicidally effective amount of the aqueous herbicidal composition of  claim 63 . 
     
     
         83 . The method of  claim 82  wherein the aqueous herbicidal composition is in the form of a concentrate and is diluted prior to application to the foliage of said plants. 
     
     
         84 . The method of  claim 82  wherein said unwanted plants comprise one or more plants selected from the group consisting of poison ivy, poison oak, kudzu, multiflora rose, golden rod, blue fescue, red maple, and red oak. 
     
     
         85 . The method of  claim 82  wherein the application rate of glyphosate is at least about 3657 grams acid equivalent per acre. 
     
     
         86 . The method of  claim 82  wherein the application rate of triclopyr is at least about 195 grams acid equivalent per acre.