Potassium glyphosate formulations

1. A formulation useful in retarding the growth of vegetation comprising an aqueous mixture containing a surfactant, glyphosate, primaraly in the form of the potassium salt thereof, and a dicarboxylic acid, the nature of said surfactant and the composition of said formulation being such that, upon application of the formulation to a plant, anisotropic aggregates comprising said surfactant are formed on the foliage of said plant.

2. A formulation as set forth in claim 1 wherein the nature of said surfactant and the composition of said formulation are such that, upon application of the formulation to a plant, liquid crystals comprising said surfactant are formed in the foliage of said plant.

3. A formulation as set forth in claim 1 wherein the glyphosate concentration is from about 400 g a.e./L to about 600 g a.e./L.

4. A formulation of claim 1 wherein the formulation has a cloud point of at least about 50° C. and a crystallization point of not higher than about 0° C.

5. A formulation of claim 4 wherein the formulation has a cloud point of at least about 60° C. and a crystallization point of not higher than about −10° C.

6. A formulation of claim 1 wherein the weight ratio of the surfactant to the dicarboxylic acid is from about 50:1.

7. A formulation of claim 1 wherein the formulation has a density of at least about 1.210 grams/liter.

8. A formulation of claim 1 wherein the formulation has a viscosity of less than about 1000 c.p. at 0° C. at 45/s shear rate.

9. A formulation of claim 8 wherein the formulation has a viscosity of less than about 250 c.p. at 0° C. at 45/s shear rate.

10. A formulation of claim 1 wherein the surfactant comprised by the formulation is not substantially antagonistic to the herbicidal activity of the glyphosate.

11. A formulation useful in retarding the growth of vegetation comprising an aqueous mixture containing a surfactant, glyphosate, predominantly in the form of the potassium salt thereof, and a dicarboxylic acid, the nature of said surfactant and the composition of said formulation being such that, upon application of the formulation to a plant, anisotropic aggregates comprising said surfactant are formed on the foliage of said plant, and wherein the growth of the plant is controlled to a greater extent than in a plant treated with a reference application mixture devoid of the dicarboxylic acid but otherwise having the same composition as said formulation.

12. A formulation as set forth in claim 11 wherein the nature of said surfactant and the composition of said formulation are such that, upon application of the formulation to a plant, liquid crystals comprising said surfactant are formed in the foliage of said plant.

13. A formulation as set forth in claim 11 wherein the glyphosate concentration is from about 400 g a.e./L to about 600 g a.e./L.

14. A formulation of claim 11 wherein the formulation has a cloud point of at least about 50° C. and a crystallization point of not higher than about 0° C.

15. A formulation of claim 14 wherein the formulation has a cloud point of at least about 60° C. and a crystallization point of not higher than about −10° C.

16. A formulation of claim 11 wherein the weight ratio of the surfactant to the dicarboxylic acid is from about 5:1 to about 50:1.

17. A formulation of claim 11 wherein the formulation has a density of at least about 1.210 grams/liter.

18. A formulation of claim 11 wherein the formulation has a viscosity of less than about 1000 c.p. at 0° C. at 45/s shear rate.

19. A formulation of claim 18 wherein the formulation has a viscosity of less than about 250 c.p. at 0° C. at 45/s shear rate.

20. A formulation of claim 11 wherein the surfactant comprised by the formulation is not substantially antagonistic to the herbicidal activity of the glyphosate.

21. A formulation useful in retarding the growth of vegetation comprising an aqueous mixture containing a surfactant, glyphosate or a salt or ester thereof, and a dicarboxylic acid, said surfactant and said dicarboxylic acid being present is a weight ratio of between about 5:1 and about 50:1, the nature of said surfactant and the composition of said formulation being such that, upon application of the formulation to a plant, anisotropic aggregates comprising said surfactant are formed on the foliage of said plant.

22. A formulation as set forth in claim 21 wherein the nature of said surfactant and the composition of said formulation are such that, upon application of the formulation to a plant, liquid crystals comprising said surfactant are formed in the foliage of said plant.

23. A formulation as set forth in claim 21 wherein the glyphosate concentration is from about 400 g a.e./L to about 600 g a.e./L.

24. A formulation of claim 21 wherein the formulation has a cloud point of at least about 50° C. and a crystallization point of not higher than about 0° C.

25. A formulation of claim 24 wherein the formulation has a cloud point of at least about 60° C. and a crystallization point of not higher than about −10° C.

26. A formulation of claim 21 wherein the formulation comprises a salt of glyphosate selected from the group consisting of potassium glyphosate, monoammonium glyphosate, diammonium glyphosate, sodium glyphosate, monoethanolamine glyphosate, n-propylamine glyphosate, ethylamine glyphosate, ethylenediamine glyphosate, hexamethylenediamine glyphosate, trimethylsulfonium glyphosate and mixtures thereof.

27. A formulation of claim 21 wherein the formulation has a density of at least about 1.210 grams/liter.

28. A formulation of claim 21 wherein the formulation has a viscosity of less than about 1000 c.p. at 0° C. at 45/s shear rate.

29. A formulation of claim 28 wherein the formulation has a viscosity of less than about 250 c.p. at 0° C. at 45/s shear rate.

30. A formulation of claim 21 wherein the surfactant comprised by the formulation is not substantially antagonistic to the herbicidal activity of the glyphosate.

31. A formulation of any one of claims 1 , 11 , or 21 wherein the surfactant is selected from the group consisting of:

(a) monoalkoxylated amines having the formula:

wherein R 1 is hydrogen or hydrocarbyl or substituted hydrocarbyl having at least 7 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 a hydrocarbylene or substituted hydrocarbylene having from 2 to about 6 carbon atoms; R 4 and R 5 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, —(R 6 ) n —(R 2 O) y R 7 , or R 4 and R 5 , together with the nitrogen atom to which they are attached, form a cyclic or heterocyclic ring; R 6 is hydrocarbylene or substituted hydrocarbylene containing from 1 to about 6 carbon atoms, R 7 is hydrogen or a linear or branched alkyl group having 1 to about 4 carbon atoms, n is 0 or 1, and x and y are independently an average number from 1 to about 60, provided, however, that when R 2 and R 3 in each of the x (R 2 O) groups is ethylene, R 1 is other than unsubstituted alkyl or R 4 is other than hydrogen or unsubstituted alkyl when R 5 is hydrogen or unsubstituted alkyl, and when R 2 and R 3 are isopropylene and x is 1, R 1 is other than unsubstituted alkyl or R 4 is other than —(R 2 O) y R 7 ;

(b) alkoxylated poly(hydroxyalkyl)amines having the formula:

wherein R 1 and R 3 are independently hydrogen, 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 4 is hydrocarbylene or substituted hydrocarbylene having from 1 to about 30 carbon atoms, R 5 is hydroxyalkyl, polyhydroxyalkyl, or poly(hydroxyalkyl)alkyl; x is an average number from 0 to about 30, and y is 0 or 1;

(c) di-poly(hydroxyalkyl)amines having the formula:

wherein R 1 and R 3 are independently hydrogen or hydrocarbyl or substituted hydrocarbyl having from 1 to about 22 carbon atoms, R 2 is hydrocarbylene or substituted hydrocarbylene having from 2 to about 18 carbon atoms, R 4 and R 5 are independently hydroxyalkyl, polyhydroxyalkyl, or poly(hydroxyalkyl)alkyl, provided, however, that when R 1 and R 3 are methyl, R 2 is other than octylene;

(d) alkoxylated triamines having the formula:

wherein R 1 is hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms; R 2 , R 3 , R 4 and R 5 are independently hydrogen, hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, or —(R 8 ) s (R 7 —O) n R 6 ; R 6 is hydrogen, or a linear or branched alkyl group having from 1 to about 4 carbon atoms; R 7 in each of the n (R 7 O) groups is independently C 2 -C 4 alkylene; R 8 is hydrocarbylene or substituted hydrocarbylene having from 1 to about 6 carbon atoms; n is an average number from 1 to about 10; s is 0 or 1; and x and y are independently an integer from 1 to about 4; provided, however, that when R 1 is alkyl, R 2 is other than hydrogen, x is 3 or 4, or R 4 is other than —(R 7 —O) n R 6 ;

(e) monoalkoxylated amines having the formula:

wherein R 1 is a hydrocarbyl or substituted hydrocarbyl group having from 1 to about 30 carbon atoms, R 2 is 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 a linear or branched alkynyl, aryl, or aralkyl group having from 1 to about 30 carbon atoms, and x is an average number from 1 to about 60;

(f) amine oxides having the formula:

wherein R 1 is hydrocarbyl or substituted hydrocarbyl having from about 8 to about 30 carbon atoms, R 2 and R 3 are independently —(R 4 O) x R 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 hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, x is an average number from 1 to about 50.

(g) an alkoxylated amine oxide having the formula:

wherein R 1 is hydrogen or 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 a hydrocarbylene or substituted hydrocarbylene having from 2 to about 6 carbon atoms; R 4 and R 5 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, —(R 6 ) n —(R 2 O) y R 7 ; R 6 is hydrocarbylene or substituted hydrocarbylene containing from 1 to about 6 carbon atoms, R 7 is hydrogen or a linear or branched alkyl group having 1 to about 4 carbon atoms, n is 0 or 1, and x and y are independently an average number from 1 to about 60;

(h) alkoxylated diamines having the formula:

wherein R 1 is hydrocarbyl or substituted hydrocarbyl having from about 8 to about 30 carbon atoms; R 2 in each of the x (R 2 O) groups and the y (R 2 O) groups is independently C 2 -C 4 alkylene; R 3 , R 5 and R 6 are independently hydrogen, hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, or —(R 2 O) y R 7 ; R 4 is hydrocarbylene or substituted hydrocarbylene having from 2 to about 6 carbon atoms, —C(═NR 11 )NR 12 R 13 —, —C(═O)NR 12 R 13 —, —C(═S)NR 12 R 13 —, —C(═NR 12 )—, —C(S)—, or —C(O)—; R 7 is hydrogen, or a linear or branched alkyl group having from 1 to about 4 carbon atoms; R 11 , R 12 and R 13 are hydrogen, hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms x is an average number from 1 to about 30; and y is an average number from 1 to about 50, provided, however, that at least one of R 3 , R 5 and R 6 is —(R 2 O) y R 7 , at least one R 2 is other than ethylene, R 4 is other than unsubstituted propylene, R 1 is other than unsubstituted alkyl, or x is from 2 to about 30;

(i) dialkoxylated amines 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) dialkoxylated alcohols having the formula:

R 1 (OR 2 ) x O—R 3 —O—(R 2 O) y R 1   (35)

wherein R 1 is independently hydrogen, or a linear or branched alkyl group having from 1 to about 4 carbon atoms, 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 hydrocarbylene or substituted hydrocarbylene having from 2 to about 30 carbon atoms, and x and y are independently an average number from 1 to about 60; and

(k) compounds of the formula:

wherein R 1 , R 9 , and R 12 are independently hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, or —(R 2 O) p R 13 ; R 2 in each of the m (R 2 O), n (R 2 O), p (R 2 O) and q (R 2 O) groups is independently C 2 -C 4 alkylene; R 3 , R 8 , R 11 , R 13 and R 15 are independently hydrogen, or a hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms; R 4 is —(CH 2 ) y OR 13 or —(CH 2 ) y O(R 2 O) q R 3 ; R 5 , R 6 and R 7 are independently hydrogen, hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, or R 4 ; R 10 is hydrocarbylene or substituted hydrocarbylene having from 2 to about 30 carbon atoms; R 14 is hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, or —(CH 2 ) z O(R 2 O) p R 3 ; m, n, p and q are independently an average number from 1 to about 50; X is —O—, —N(R 14 )—, —C(O)—, —C(O)O—, —OC(O)—, —N(R 15 )C(O)—, —C(O)N(R 15 )—, —S—, —SO—, or —SO 2 —; t is 0 or 1; A− is an agriculturally acceptable anion; and y and z are independently an integer from 0 to about 30.

32. A formulation of any one of claims 1 , 11 or 21 wherein the surfactant is selected from the group consisting of:

(a) aminated alkoxylated alcohol having the formula:

wherein R 1 is hydrocarbyl or substituted hydrocarbyl containing at least 7 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 and R 6 are each independently hydrocarbylene or substituted hydrocarbylene having from 1 to about 6 carbon atoms; R 4 is hydrogen, hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, hydroxy substituted hydrocarbyl, —(R 6 ) n —(R 2 O) y R 7 , —C(═NR 11 )NR 12 R 13 , —C(═O)NR 12 R 13 , —C(═S)NR 12 R 13 or together with R 5 and the nitrogen atom to which they are attached, form a cyclic or heterocyclic ring; R 5 is hydrogen, hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, hydroxy substituted hydrocarbyl, —(R 6 ) n —(R 2 O) y R 7 , —C(═NR 11 )NR 12 R 13 , —C(═O)NR 12 R 13 , —C(═S)NR 12 R 13 , or together with R 4 and the nitrogen atom to which they are attached, form a cyclic or heterocyclic ring; R 7 is hydrogen or a linear or branched alkyl group having 1 to about 4 carbon atoms; R 11 , R 12 and R 13 are hydrogen, hydrocarbyl or substituted hydrocarbyl, R 14 is hydrogen, hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, hydroxy substituted hydrocarbyl, —(R 6 ) n —(R 2 O) y R 7 , —C(═NR 11 )NR 12 R 13 , —C(═O)NR 12 R 13 , or —C(═S)NR 12 R 13 , n is 0 or 1, x and y are independently an average number from 1 to about 60, and A− is an agriculturally acceptable anion, provided, however, that when R 2 and R 3 are isopropylene and x is 1, R 1 is other than alkyl or R 4 is other than —(R 2 O) y R 7 ;

(b) hydroxylated amines having the formula:

wherein R 1 is hydrocarbyl or substituted hydrocarbyl having from about 4 to about 30 carbon atoms, R 2 is hydrogen or hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, and R 3 is hydroxyalkyl, polyhydroxyalkyl, or poly(hydroxyalkyl)alkyl;

(c) diamines having the formula:

wherein R 1 , R 2 and R 5 are independently hydrogen or hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms or —R 8 (OR 9 ) n OR 10 , R 3 is hydrocarbylene or substituted hydrocarbylene having from 2 to about 18 carbon atoms, R 8 and R 9 are individually hydrocarbylene or substituted hydrocarbylene having from 2 to about 4 carbon atoms, R 4 and R 10 are independently hydrogen or hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, m is 0 or 1, n is an average number from 0 to about 40, X is —C(O)— or —SO 2 —, and A − is an agriculturally acceptable anion;

(d) mono- or di-ammonium salts having the formula:

wherein R 1 , R 2 , R 4 , R 5 and R 7 are independently hydrogen or hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms or —R 8 (OR 9 ) n OR 10 , R 6 is hydrocarbyl or substituted hydrocarbyl having from about 1 to about 30 carbon atoms, R 3 is hydrocarbylene or substituted hydrocarbylene having from 2 to about 18 carbon atoms, R 8 , R 9 and R 11 are individually hydrocarbylene or substituted hydrocarbylene having from 2 to about 4 carbon atoms, R 10 is hydrogen or hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, m is 0 or 1, n is an average number from 0 to about 40, X is —C(O)— or —SO 2 —, Z is —C(O)—, and A − is an agriculturally acceptable anion;

(e) poly(hydroxyalkyl)amines having the formula:

wherein R 1 is hydrocarbyl or substituted hydrocarbyl having from about 4 to about 30 carbon atoms or —R 4 OR 5 , R 2 is hydrogen or hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, R 3 is hydroxyalkyl, polyhydroxyalkyl, or poly(hydroxyalkyl)alkyl, R 4 is hydrocarbylene or substituted hydrocarbylene having from 2 to about 18 carbon atoms, and R 5 is hydrogen or hydrocarbyl or substituted hydrocarbyl having from about 1 to about 30 carbon atoms.

(f) di-poly(hydroxyalkyl)amine having the formula:

wherein R 1 and R 3 are independently hydrogen or hydrocarbyl or substituted hydrocarbyl having from 1 to about 22 carbon atoms, R 2 is hydrocarbylene or substituted hydrocarbylene having from 2 to about 18 carbon atoms, and R 4 and R 5 are independently hydroxyalkyl, polyhydroxyalkyl, or poly(hydroxyalkyl)alkyl;

(g) quaternary poly(hydroxyalkyl)amine salts having the formula:

wherein R 1 is hydrocarbyl or substituted hydrocarbyl having from about 4 to about 30 carbon atoms, R 2 and R 3 are independently hydrogen or hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, and R 4 is hydroxyalkyl, polyhydroxyalkyl, or poly(hydroxyalkyl)alkyl;

(h) triamines having the formula:

wherein R 1 is hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms; R 2 , R 3 , R 4 and R 5 are independently hydrogen, hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms, or —(R 8 ) s (R 7 O) n R 6 ; R 6 is hydrogen or a linear or branched alkyl group having from 1 to about 4 carbon atoms, R 7 in each of the n (R 7 O) groups is independently C 2 -C 4 alkylene; R 8 is hydrocarbylene or substituted hydrocarbylene having from 1 to about 6 carbon atoms, n is an average number from 1 to about 10, s is 0 or 1, and x and y are independently an integer from 1 to about 4;

and mixtures thereof, wherein the pesticide is other than a bacteriocide if the composition includes a surfactant of group (a) or (d).