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Publication numberUSRE37866 E1
Publication typeGrant
Application numberUS 09/569,800
Publication dateOct 1, 2002
Filing dateMay 12, 2000
Priority dateApr 10, 1995
Fee statusPaid
Also published asCA2214376A1, CA2214376C, CN1075352C, CN1187105A, DE69605660D1, DE69605660T2, EP0820231A2, EP0820231B1, WO1996032839A2, WO1996032839A3
Publication number09569800, 569800, US RE37866 E1, US RE37866E1, US-E1-RE37866, USRE37866 E1, USRE37866E1
InventorsDaniel R. Wright, Ronald J. Brinker, Joseph J. Sandbrink, Al S. Wideman
Original AssigneeMonsanto Technology, Llc
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Glyphosate formulations containing etheramine surfactants
US RE37866 E1
Abstract
Herbicidal compositions are provided comprising glyphosate or a salt thereof and an etheramine surfactant having the representative chemical structure (a)
wherein R1 is a straight or branched chain C6 to about C22 alkyl, aryl or alkylaryl group, m is an average number from 1 to about 10, R2 in each of the m (O由2) groups is independently C1-C4 alkylene, R3 groups are independently C1-C4 alkylene, and x and y are average numbers such that x+y is in the range from 2 to about 60; or (b)
wherein R1 is a straight or branched chain C6 to about C22 alkyl, aryl or alkylaryl group, m is an average number from 1 to about 10, R2 in each of the m (O由2) groups is independently C1-C4 alkylene, R3 groups are independently C1-C4 alkylene, R4 is C1-C4 alkyl, x and y are average numbers such that x+y is in the range from 0 to about 60, and Ais an agriculturally acceptable anion; or (c)
wherein R1 is a straight or branched chain C6 to about C22 alkyl, aryl or alkylaryl group, m is an average number from 1 to about 10, R2 is each of the m (O由2) groups is independently C1-C4 alkylene, R3 groups are independently C1-C4 alkylene, and x and y are average numbers such that x+y is in the range from 2 to about 60.
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Claims(97)
What is claimed is:
1. A herbicidal composition comprising
(a) a herbicidally effective amount of glyphosate or a salt thereof; and
(b) an effective herbicidal activity enhancing amount of a surfactant having the chemical structure
wherein R1 is a straight or branched chain C6 to about C22 alkyl, aryl or alkylaryl group, m is an average number from 1 to about 10, R2 in each of the m (O由2) groups is independently C1-C4 alkylene, R3 groups are independently C1-C4 alkylene, and x and y are average numbers such that x+y is in the range from 2 to about 60.
2. A herbicidal composition comprising
(a) a herbicidally effective amount of glyphosate or a salt thereof; and
(b) an effective herbicidal activity enhancing amount of a surfactant having the chemical structure
wherein R1 is a straight or branched chain C6 to about C22 alkyl, aryl or alkylaryl group, m is an average number from 1 to about 10, R2 in each of the m (O由2) groups is independently C1-C4 alkylene, R3 groups are independently C1-C4 alkylene, R4 is C1-C4 alkyl, x and y are average numbers such that x+y is in the range from 0 to about 60, and Ais an agriculturally acceptable anion.
3. A herbicidal composition comprising
(a) a herbicidally effective amount of glyphosate or a salt thereof; and
(b) an effective herbicidal activity enhancing amount of a surfactant having the chemical structure
wherein R1 is a straight or branched chain C6 to about C22 alkyl, aryl or alkylaryl group, m is an average number from 1 to about 10, R2 in each of the m (O由2) groups is independently C1-C4 alkylene, R3 groups are independently C1-C4 alkylene, and x and y are average numbers such that x+y is in the range from 2 to about 60.
4. A herbicidal composition in the form of a spray solution prepared on site by tank-mixing
(a) a herbicidally effective amount of a composition comprising glyphosate or a salt thereof;
(b) an effective herbicidal activity enhancing amount of a composition comprising a surfactant having the chemical structure
wherein R1 is a straight or branched chain C6 to about C22 alkyl, aryl or alkylaryl group, m is an average number from 1 to about 10, R2 in each of the m (O由2) groups is independently C1-C4 alkylene, R3 groups are independently C1-C4 alkylene, and x and y are average numbers such that x+y is in the range from 2 to about 60; and
(c) water.
5. A herbicidal composition in the form of a spray solution prepared on site by tank-mixing
(a) a herbicidally effective amount of a composition comprising glyphosate or a salt thereof;
(b) an effective herbicidal activity enhancing amount of a composition comprising a surfactant having the chemical structure
wherein R1 is a straight or branched chain C6 to about C22 alkyl, aryl or alkylaryl group, m is an average number from 1 to about 10, R2 in each of the m (O由2) groups is independently C1-C4 alkylene, R3 groups are independently C1-C4 alkylene, R4 is C1-C4 alkyl, x and y are average numbers such that x+y is in the range from 0 to about 60, and Ais an agriculturally acceptable anion; and
(c) water.
6. A herbicidal composition in the form of a spray solution prepared on site by tank-mixing
(a) a herbicidally effective amount of a composition comprising glyphosate or a salt thereof;
(b) an effective herbicidal activity enhancing amount of a composition comprising a surfactant having the chemical structure
wherein R1 is a straight or branched chain C6 to about C22 alkyl, aryl or alkylaryl group, m is an average number from 1 to about 10, R2 in each of the m (O由2) groups is independently C1-C4 alkylene, R3 groups are independently C1-C4 alkylene, and x and y are average numbers such that x+y is in the range from 2 to about 60; and
(c) water.
7. A herbicidal composition of claim 1, 2 or 3 wherein the glyphosate or salt thereof and the surfactant are dissolved in water and the composition is ready to use.
8. A herbicidal composition of claim 7 wherein the glyphosate or salt thereof is present at about 1 to about 50 g a.e./l.
9. A herbicidal composition of claim 8 wherein the glyphosate or salt thereof is present at about 5 to about 20 g a.e./l.
10. A herbicidal composition of claim 7 wherein said surfactant is present at about 0.125% to about 2% weight/volume.
11. A herbicidal composition of claim 1 wherein the glyphosate or salt thereof is present at about 5 to about 20 g a.e./l; the surfactant is present at about 0.125% to about 2% weight/volume; the glyphosate or salt thereof and the surfactant are dissolved in water and the composition is ready to use; and, in the chemical structure of said surfactant, R1 is C8-C18 alkyl, R2 is linear propylene, isopropylene or ethylene, R3 is ethylene, m is in the range from 1 to about 5 and x+y is in the range from 2 to about 20.
12. A herbicidal composition of claim 11 wherein, in the chemical structure of said surfactant, R2 is isopropylene or ethylene.
13. A herbicidal composition of claim 11 wherein, in the chemical structure of said surfactant, R2 is linear propylene and m is 1.
14. A herbicidal composition of claim 2 wherein the glyphosate or salt thereof is present at about 5 to about 20 g a.e./l; the surfactant is present at about 0.125% to about 2% weight/volume; the glyphosate or salt thereof and the surfactant are dissolved in water and the composition is ready to use; and, in the chemical structure of said surfactant, R1 is C8-C18 alkyl, R2 is linear propylene, isopropylene or ethylene, R3 is ethylene, R4 is methyl, m is in the range from 1 to about 5, x+y is in the range from 0 to about 20 and Ais an anion selected from the group consisting of halide, phosphate and sulfate.
15. A herbicidal composition of claim 14 wherein, in the chemical structure of said surfactant, R2 is linear propylene and m is 1.
16. A liquid concentrate herbicidal composition of claim 1, 2 or 3 which further comprises water and wherein the glyphosate or salt thereof is present at about 50 to about 500 g a.e./l.
17. A herbicidal composition of claim 16 wherein the glyphosate or salt thereof is present at about 200 to about 500 g a.e./l.
18. A herbicidal composition of claim 17 wherein the glyphosate or salt thereof is present at about 350 to about 500 g a.e./l.
19. A herbicidal composition of claim 18 wherein the glyphosate or salt thereof is present at about 450 to about 500 g a.e./l.
20. A herbicidal composition of claim 16 wherein the glyphosate is present at a salt selected from the group consisting of the ammonium, alkylamine, alkanolamine, alkylsulfonium and alkali metal salts of glyphosate.
21. A herbicidal composition of claim 20 wherein the glyphosate is present as its isopropylamine salt.
22. A liquid concentrate herbicidal composition of claim 1 which further comprises water; wherein the glyphosate or salt thereof is present at about 50 to about 500 g a.e./l; and wherein, in the chemical structure of said surfactant, R1 is C8-C18 alkyl, R2 is linear propylene, isopropylene or ethylene, R3 is ethylene, m is in the range from 1 to about 5 and x+y is in the range from about 2 to about 20.
23. A herbicidal composition of claim 22 wherein the weight/weight ratio of said surfactant to glyphosate a.e. is in the range from about 1:20 to about 1:1.
24. A herbicidal composition of claim 23 wherein the weight/weight ratio of said surfactant to glyphosate a.e. is in the range from about 1:10 to about 1:2.
25. A herbicidal composition of claim 22, 23 or 24 wherein, in the chemical structure of said surfactant, R2 is isopropylene or ethylene.
26. A herbicidal composition of claim 25 wherein, in the chemical structure of said surfactant, R1 is C12-C14 alkyl, R2 is isopropylene, m is 2 and x+y is 5.
27. A herbicidal composition of claim 25 wherein, in the chemical structure of said surfactant, R1 is C12-C14 alkyl, R2 is ethylene, m is 3 and x+y is 5.
28. A herbicidal composition of claim 22, 23 or 24 wherein, in the chemical structure of said surfactant, R2 is linear propylene and m is 1.
29. A herbicidal composition of claim 28 wherein, in the chemical structure of said surfactant, R1 is a straight or branched chain alkyl group having from about 10 to about 15 carbon atoms, and x+y is in the range from 2 to about 10.
30. A herbicidal composition of claim 29 wherein, in the chemical structure of said surfactant, x+y is in the range from 2 to about 5.
31. A liquid concentrate herbicidal composition of claim 2 which further comprises water; wherein the glyphosate or salt thereof is present at about 50 to about 500 g a.e./l; and wherein, in the chemical structure of said surfactant, R1 is C8-C18 alkyl, R2 is linear propylene, isopropylene or ethylene, R3 is ethylene, R4 is methyl, m is in the range from 1 to about 5, x+y is in the range from about 0 to about 20, and Ais an anion selected from the group consisting of halide, phosphate and sulfate.
32. A herbicidal composition of claim 31 wherein the weight/weight ratio of said surfactant to glyphosate a.e. is in the range from about 1:20 to about 1:1.
33. A herbicidal composition of claim 32 wherein the weight/weight ratio of said surfactant to glyphosate a.e. is in the range from about 1:10 to about 1:2.
34. A herbicidal composition of any of claim 31, 32 or 33 wherein, in the chemical structure of said surfactant, R2 is linear propylene and m is 1.
35. A herbicidal composition of claim 34 wherein, in the chemical structure of said surfactant, R1 is a straight or branched chain alkyl group having from about 10 to about 15 carbon atoms, and x+y is in the range from 2 to about 10.
36. A herbicidal composition of claim 35 wherein, in the chemical structure of said surfactant, x+y is in the range from 2 to about 5.
37. A storage stable liquid concentrate herbicidal composition of either of claim 22 or claim 31 wherein
(a) the glyphosate is present at its isopropylamine or trimethylsulfonium salt at a concentration in the range from about 450 to about 500 g a.e./l;
(b) the weight/weight ratio of glyphosate a.e. to total surfactant is in the range from about 5:1 to about 8:1; and
(c) the etheramine surfactant comprises from about 75% to 100% by weight of the total surfactant present.
38. A herbicidal composition of claim 37 wherein
(a) the glyphosate is present as its isopropylamine salt at a concentration of about 480 g a.e./l;
(b) total surfactant concentration is about 80 g/l;
(c) the etheramine surfactant comprises about 80% by weight of the total surfactant present;
(d) in the chemical structure of said etheramine surfactant, R1 is a straight or branched chain alkyl group having from about 10 to about 15 carbon atoms, R2 is isopropylene or ethylene, and x+y is in the range from 2 to about 5; and
(e) the composition further comprises, at about 20% by weight of the total surfactant present, a nonionic surfactant.
39. A herbicidal composition of claim 37 wherein
(a) the glyphosate is present as its isopropylamine salt at a concentration of about 480 g a.e./l;
(b) total surfactant concentration is about 80 g/l;
(c) the etheramine surfactant comprises about 80% by weight of the total surfactant present;
(d) in the chemical structure of said etheramine surfactant, R1 is a straight or branched chain alkyl group having from about 10 to about 15 carbon atoms, R2 is linear propylene, m is 1, and x+y is in the range from 2 to about 5; and
(e) the composition further comprises, at about 20% by weight of the total surfactant present, a nonionic surfactant.
40. A dry concentrate herbicidal composition of claim 1, 2 or 3 wherein the glyphosate or salt thereof is present at about 20% to about 80% weight/weight.
41. A herbicidal composition of claim 40 wherein the glyphosate or salt thereof is present at about 50% to about 76% weight/weight.
42. A herbicidal composition of claim 41 wherein the glyphosate or salt thereof is present at about 60% to about 72% weight/weight.
43. A herbicidal composition of claim 40 wherein the glyphosate is present as a salt selected from the group consisting of the ammonium, alkylamine, alkanolamine, alkylsulfonium and alkali metal salts of glyphosate.
44. A herbicidal composition of claim 43 wherein the glyphosate is present as its ammonium salt.
45. A dry concentrate herbicidal composition of claim 1 wherein the glyphosate or salt thereof is present at about 20% to about 80% weight/weight; and wherein, in the chemical structure of said surfactant, R1 is C8-C18 alkyl, R2 is linear propylene, isopropylene or ethylene, R3 is ethylene, m is in the range from 1 to about 5 and x+y is in the range from about 2 to about 20.
46. A herbicidal composition of claim 45 wherein the weight/weight ratio of said surfactant to glyphosate a.e. is in the range from about 1:20 to about 1:1.
47. A herbicidal composition of claim 46 wherein the weight/weight ratio of said surfactant to glyphosate a.e. is in the range from about 1:10 to about 1:2.
48. A herbicidal composition of claim 45, 46 or 47 wherein, in the chemical structure of said surfactant, R2 is isopropylene or ethylene.
49. A herbicidal composition of claim 48 wherein, in the chemical structure of said surfactant, R1 is C12-C14 alkyl, R2 is isopropylene, m is 2 and x+y is 5.
50. A herbicidal composition of claim 48 wherein, in the chemical structure of said surfactant, R1 is C12-C14 alkyl, R2 is ethylene, m is 3 and x+y is 5.
51. A herbicidal composition of claim 45, 46 or 47 wherein, in the chemical structure of said surfactant, R2 is linear propylene and m is 1.
52. A herbicidal composition of claim 51 wherein, in the chemical structure of said surfactant, R1 is a straight or branched chain alkyl group having from about 10 to about 15 carbon atoms, and x+y is in the range from 2 to about 10.
53. A herbicidal composition of claim 52 wherein, in the chemical structure of said surfactant, x+y is in the range from 2 to about 5.
54. A dry concentrate herbicidal composition of claim 2 wherein the glyphosate or salt thereof is present at about 20% to about 80% weight/weight; and wherein, in the chemical structure of said surfactant, R1 is C8-C18 alkyl, R2 is linear propylene, isopropylene or ethylene, R3 is ethylene, R4 is methyl, m is in the range from 1 to about 5, x+y is in the range from about 0 to about 20, and Ais an anion selected from the group consisting of halide, phosphate and sulfate.
55. A herbicidal composition of claim 54 wherein the weight/weight ratio of said surfactant to glyphosate a.e. is in the range from about 1:20 to about 1:1.
56. A herbicidal composition of claim 55 wherein the weight/weight ratio of said surfactant to glyphosate a.e. is in the range from about 1:10 to about 1:2.
57. A herbicidal composition of any of claims 54-56 wherein, in the chemical structure of said surfactant, R2 is linear propylene and m is 1.
58. A herbicidal composition of claim 57 wherein, in the chemical structure of said surfactant, R1 is a straight or branched chain alkyl group having from about 10 to about 15 carbon atoms, and x+y is in the range from 2 to about 10.
59. A herbicidal composition of claim 58 wherein, in the chemical structure of said surfactant, x+y is in the range from 2 to about 5.
60. A method of killing or controlling weeds or unwanted vegetation comprising the steps of
(a) diluting a composition of claim 16 in a convenient amount of water to form a spray solution; and
(b) applying a herbicidally effective amount of the spray solution to the foliage of the weeds or unwanted vegetation.
61. A method of killing or controlling weeds or unwanted vegetation comprising the steps of
(a) dissolving or dispersing a composition of claim 40 in a convenient amount of water to form a spray solution; and
(b) applying a herbicidally effective amount of the spray solution to the foliage of the weeds or unwanted vegetation.
62. A herbicidal concentrate composition comprising an aqueous solution of glyphosate, predominately in the form of one or a mixture of the potassium and monoethanolammonium salts thereof, said solution having a glyphosate concentration in excess of about 350 g a.e./l.
63. A herbicidal composition as set forth in claim 62 wherein the glyphosate or salt thereof is present at about 350 to 500 g a.e./l.
64. A herbicidal composition as set forth in claim 63 wherein the monoethanolamine salt is present at a concentration of about 350 to 500 g a.e./l.
65. A herbicidal composition as set forth in claim 63 wherein the potassium salt is present at a concentration of about 350 to 500 g a.e./l.
66. A herbicidal composition as set forth in claim 63 wherein the concentration of a potassium salt, a monoethanolamine salt or mixture of potassium and monoethanolamine salts of glyphosate is present at a concentration of 450 to 500 g a.e./l.
67. A herbicidal composition of claim 20 wherein the glyphosate salt is present at about 200 to about 500 g a.e./l.
68. A herbicidal composition of claim 67 wherein the glyphosate salt is present at about 350 to about 500 g a.e./l.
69. A herbicidal composition of claim 68 wherein the glyphosate salt is present at about 450 to about 500 g a.e./l.
70. A herbicidal composition of claim 67, 68, or 69 wherein the glyphosate salt is present as an alkali metal salt.
71. A herbicidal composition of claim 70 wherein the alkali metal is potassium.
72. A herbicidal composition of claim 70 further comprising a second surfactant selected from the group consisting of primary or secondary alcohol ethoxylates, an alkyl ester of sucrose or sorbitan, or an alkyl polyglucoside.
73. A herbicidal composition of claim 72 wherein the alkali metal is potassium.
74. A herbicidal composition of claim 67, 68, or 69 wherein the glyphosate is present as an alkanolamine salt.
75. A herbicidal composition of claim 74 wherein the alkanolamine is monoethanolamine.
76. A herbicidal composition of claim 74 further comprising a second surfactant selected from the group consisting of primary or secondary alcohol ethoxylates, an alkyl ester of sucrose or sorbitan, or an alkyl polyglucoside.
77. A herbicidal composition of claim 74 wherein the alkanolamine is monoethanolamine.
78. A herbicidal composition of claim 67, 68, or 69 wherein the glyphosate is present as an alkylsulfonium salt.
79. A herbicidal composition of claim 78 wherein the alkylsulfonium is trimethylsulfonium.
80. A herbicidal composition of claim 78 further comprising a second surfactant selected from the group consisting of primary or secondary alcohol ethoxylates, an alkyl ester of sucrose or sorbitan, or an alkyl polyglucoside.
81. A herbicidal composition of claim 80 wherein the alkylsulfonium is trimethylsulfonium.
82. A herbicidal composition of claim 20 further comprising a second surfactant selected from the group consisting of primary or secondary alcohol ethoxylates, an alkyl ester of sucrose or sorbitan, or an alkyl polyglucoside.
83. A herbicidal composition comprising:
an herbicidally effective amount of glyphosate or a salt thereof;
a surfactant having the chemical structure:
where R 1 is a straight or branched chain C 6 to about C 22 alkyl, aryl or alkylaryl group, m is an average number from 1 to about 10, R 2 in each of the m (O由 2) groups is independently C 1 -C 4 alkylene, R 3 groups are independently C 1 -C 4 alkylene, and x and y are average numbers such that x+y is in a range from 2 to about 60; and
a nonionic surfactant, said surfactants together being present in an herbicidally effective amount.
84. A herbicidal composition as set forth in claim 83 wherein said nonionic surfactant is selected from the group consisting of a primary alcohol ethoxylate, a secondary alcohol ethoxylate, an alkyl ester of sucrose, an alkyl ester of sorbitan and an alkyl polyglucoside.
85. A herbicidal composition comprising:
an herbicidally effective amount of glyphosate or a salt thereof;
a surfactant having the chemical structure:
where R 1 is a straight or branched chain C 6 to about C 22 alkyl, aryl or alkylaryl group, m is an average number from 1 to about 10, R 2 in each of the m (O由 2) groups is independently C 1 -C 4 alkylene, R 3 groups are independently C 1 -C 4 alkylene, and x and y are average numbers such that x+y is in a range from 2 to about 60, and A is an agriculturally acceptable anion; and
a nonionic surfactant, said surfactants together being present in an herbicidally effective amount.
86. A herbicidal composition as set forth in claim 85 wherein said nonionic surfactant is selected from the group consisting of a primary alcohol ethoxylate, a secondary alcohol ethoxylate, an alkyl ester of sucrose, an alkyl ester of sorbitan and an alkyl polyglucoside.
87. A herbicidal composition comprising:
an herbicidally effective amount of glyphosate or a salt thereof;
a surfactant having the chemical structure:
where R 1 is a straight or branched chain C 6 to about C 22 alkyl, aryl or alkylaryl group, m is an average number from 1 to about 10, R 2 in each of the m (O由 2) groups is independently C 1 -C 4 alkylene, R 3 groups are independently C 1 -C 4 alkylene, and x and y are average numbers such that x+y is in a range from 2 to about 60; and
a nonionic surfactant, said surfactants together being present in an herbicidally effective amount.
88. A herbicidal composition as set forth in claim 87 wherein said nonionic surfactant is selected from the group consisting of a primary alcohol ethoxylate, a secondary alcohol ethoxylate, an alkyl ester of sucrose, an alkyl ester of sorbitan and an alkyl polyglucoside.
89. A herbicidal composition as set forth in claim 66 wherein the monoethanolamine salt is present at a concentration of 450 to 500 g a.e./l.
90. A herbicidal composition as set forth in claim 66 wherein the potassium salt is present at a concentration of 450 to 500 g a.e./l.
91. A herbicidal concentrate composition comprising: an aqueous solution comprising a surfactant and glyphosate, predominantly in the form of one or a mixture of the potassium and monoethanolammonium salts thereof, said solution having a glyphosate concentration in excess of about 350 g a.e./l.
92. A herbicidal composition as set forth in claim 91 wherein the glyphosate or salt thereof is present at about 350 to 500 g a.e./l.
93. A herbicidal composition as set forth in claim 92 wherein the monoethanolamine salt is present at a concentration of about 350 to 500 g a.e./l.
94. A herbicidal composition as set forth in claim 92 wherein the potassium salt is present at a concentration of about 350 to 500 g a.e./l.
95. A herbicidal composition as set forth in claim 91 wherein the concentration of a potassium salt, a monoethanolamine salt or mixture of potassium and monoethanolamine salts of glyphosate is present at a concentration of 450 to 500 g a.e./l.
96. A herbicidal composition as set forth in claim 95 wherein the monoethanolamine salt is present at a concentration of 450 to 500 g a.e./l.
97. A herbicidal composition as set forth in claim 95 wherein the potassium salt is present at a concentration of 450 to 500 g a.e./l.
Description
CROSS-REFERENCE TO RELATED APPLICATION

This is a continuation-in-part of application Ser. No. 08/419,299 filed Apr. 10, 1995, abandoned.

FIELD OF THE INVENTION

Novel agriculturally acceptable formulations of the herbicide N-phosphonomethylglycine (glyphosate) comprising tertiary or quaternary etheramine or etheramine oxide surfactants are provided.

BACKGROUND OF THE INVENTION

Glyphosate is well known as a highly effective and commercially important herbicide useful for combating the presence of a wide variety of unwanted vegetation, including a agricultural weeds. Glyphosate is conventionally applied as a formulated product dissolved in water to the foliage of annual and perennial grasses and broad leaf plants and the like, is taken up over a period of time into the leaves, and thereafter translocates throughout the plant.

Usually, glyphosate is formulated in commercial compositions in the form of a water-soluble salt. Salts in commercial use include the ammonium salt, alkylamine salts, such as the isopropylamine salt, alkali metal salts, such as the sodium salt, and the trimethylsulfonium salt. However, formulations of glyphosate in its acid form are also used. Typical glyphosate salt formulations include aqueous concentrates, requiring simple dilution and distributions in water for application by the end-user, and water-soluble or water-dispersible dry formulations, especially granules, requiring dissolution or dispersion in water prior to application.

Under most application conditions, the herbicidal efficacy of glyphosate can be significantly enhanced by including one or more surfactants in the composition to be applied. It is believed that such surfactants act partly by facilitating the penetration of glyphosate, a relatively hydrophilic compound, through the rather hydrophobic cuticle which normally covers the external above-ground surfaces of higher plants.

Wyrill and Burnside, Weed Science, Vol. 25 (1977), pp. 275-287, conducted a wide-ranging study of different classes of surfactants as agents for enhancing the herbicidal activity of glyphosate, applied as the isopropylamine salt. They demonstrated that the choice of surfactant has a pronounced effect on the herbicidal performance of a glyphosate formulation, but beyond showing a general tendency for surfactants having high values of hydrophile-lipophile balance (HLB) to be more efficacious than surfactants of the same class having low HLB values, they did not observe any predictive relationship between efficacy and surfactant chemical class. Some of the most effective surfactants identified in the Wyrill and Burnside study were ethoxylated tertiary and quaternary alkylamines.

Commercial formulations of glyphosate have frequently used ethoxylated tertiary alkylamine surfactants, for example an ethoxylated tallowamine having an average of about 15 moles of ethylene oxide (EO) per mole of tallowamine. Monsanto Company of St. Louis, Mo. has for many years sold, under the trademark Roundupョ herbicide, glyphosate formulations containing various concentrations of such an ethoxylated tallowamine surfactant.

European Patent No. 0 290 416 to Forbes et al. discloses compositions of glyphosate salts comprising ethoxylated tertiary alkylamine surfactants having less than 15 moles of EO. For example a composition is disclosed comprising the isopropylamine salt of glyphosate and an ethoxylated cocoamine surfactant having an average of 5 moles of EO. It is taught by Forbes et al. that certain herbicidal efficacy advantages are obtainable with such compositions by comparison with compositions where the EO level in the surfactant is around 15 moles.

European Patent No. 0 274 369 to Sato et al. discloses glyphosate compositions comprising ethoxylated quaternary alkylamine surfactants. Several examples are shown wherein the surfactant is an ethoxylated N-methyl cocoammonium chloride surfactant having 2 moles of EO.

A drawback of ethoxylated tertiary alkylamine surfactants of prior art is that when included in concentrate formulations at levels consistent with good herbicidal performance, they tend to be irritant to eyes. In some, but not all, cases, eye irritancy can be reduced by converting the tertiary alkylamine to the corresponding quaternary (N-methyl) alkylamine. U.S. Pat. No. 5,317,003 to Kassebaum discloses that a glyphosate composition containing as the surfactant an ethoxylated N-methyl cocoammonium chloride surfactant having 15 moles of EO is less irritant to eyes than an otherwise identical composition wherein the surfactant is an ethoxylated tertiary cocoamine surfactant having 15 moles of EO.

An alternative solution to the eye irritancy problem is suggested in U.S. Pat. No. 5,118,444 to Nguyen, wherein ethoxylated tertiary alkylamine surfactants are converted to their N-oxides. Examples are shown of glyphosate compositions wherein the surfactant is an ethoxylated tallowamine oxide surfactant having 10, 15 or 20 moles of EO.

A further drawback of ethoxylated tertiary alkylamine surfactants of the prior art is that when water is added to them, they tend to form a stiff gel which adds to the complexity and expense of manufacturing formulations containing such surfactants, by making it difficult to clean vessels and pipes. In practice, this problem is ameliorated by adding an anti-gelling agent, such as polyethylene glycol, to the surfactant.

Never previously disclosed as components of concentrate glyphosate formulations are alkoxylated tertiary or quaternary etheramine or etheramine oxide surfactants. United Kingdom Patent No. 1,588,079 to Texaco Development Corporation discloses examples of ethoxylated alkyloxyisopropylamine and alkylpoly(isopropyl)amine surfactants and methods of preparing them, and suggests they are useful as detergents, dispersants, wetting agents and emulsifiers. Surfactants disclosed have the representative chemical structure

wherein R1 is C8-C18 alkyl, m is a number from 1 to 5, and x and y are average numbers such that x+y is in the range from 2 to 20.

Tomah Products, Inc. of Milton, Wis. in a brochure titled 摘thoxylated Amines, dated Aug. 22, 1994, disclose, together with a series of ethoxylated tertiary alkylamines, a number of ethoxylated tertiary etheramine surfactants having the representative chemical structure

wherein R1 is C10-C26 alkyl and x and y are average numbers such that x+y is in the range from 2 to 15. Suggested uses of the Tomah ethoxylated amines include 殿gricultural adjuvants, a well-known application of the ethoxylated tertiary alkylamines listed. No suggestion is made that the ethoxylated tertiary etheramines included in the list would have advantages over the ethoxylated tertiary alkylamines as agricultural adjuvants, nor is there any teaching relevant to the making of concentrate glyphosate compositions with ethoxylated tertiary etheramines.

Another brochure from Tomah Products titled 轍uaternaries, dated Sep. 1, 1994, includes in a list of quaternary amine surfactants a number of ethoxylated quaternary etheramines having the representative chemical structure

wherein R1 is an aliphatic group exemplified by isodecyl or isotridecyl and x+y is 2. The list of suggested uses for Tomah's quaternaries does not include agricultural adjuvants.

Another brochure from Tomah Products titled 鄭O-14-2, dated Aug. 24, 1994, discloses an ethoxylated etheramine oxide which can be deduced to have the representative chemical structure

wherein R1 is an aliphatic group exemplified by isodecyl and x+y is 2. The list of suggested uses for AO-14-2 does not include agricultural adjuvants.

It is an object of the present invention to provide novel compositions of glyphosate herbicide containing an etheramine surfactant which imparts good herbicidal efficacy, yet having low irritancy to eyes.

It is a further object of the present invention to provide the commercial formulator of glyphosate with an alternative to ethoxylated alkylamine surfactants that (1) allows elimination or substantial reduction of the need for the use of an anti-gelling agent, (2) is soluble in aqueous formulations having higher glyphosate acid equivalent loadings than prior art formulations having comparable efficacy, and (3) provides herbicidal efficacy superior to that obtainable with comparable amounts of said ethoxylated alkylamine surfactants having similar degrees of ethoxylation.

It is a further object of the present invention to provide concentrate liquid and dry formulations of glyphosate with an etheramine surfactant having good storage stability.

These and other objectives are satisfied by the compositions disclosed herein. defined as an amine surfactant in which the hydrophobe is connected to the amine group via a series of up to about 10 oxyalkylene groups.

Specifically, the etheramine surfactant may be a tertiary amine having the representative chemical structure

wherein R1 is a straight or branched chain C6 to about C22 alkyl, aryl or alkylaryl group, m is an average number from 1 to about 10. R2 in each of the m (O由2) groups are independently C1-C4 alkylene, and x and y are average numbers such that x+y is in the range from 2 to about 60.

Alternatively, the etheramine surfactant may be a quaternary amine having the representative chemical structure

wherein R1 is a straight or branched chain C6 to about C22 alkyl, aryl or alkylaryl group, m is an average number from 1 to about 10, R2 in each of the m (O由2) groups is independently C1-C4 alkylene, R3 groups are independently C1-C4 alkylene, R4 is C1-C4 alkyl, x and y are average numbers such that x+y is in the range from 0 to about 60, and Ais an agriculturally acceptable anion.

As a third possibility, the etheramine surfactant may be an amine oxide having the representative chemical structure

wherein R1 is a straight or branched chain C6 to about C22 alkyl, aryl or alkylaryl group, m is an average number from 1 to about 10, R2 in each of the m (O由2) groups is independently C1-C4 alkylene, R3 groups are independently C1-C4 alkylene, and x and y are average numbers such that x+y is in the range from 2 to about 60.

Compositions of the invention may be prepared on site by the end-user shortly before application to the foliage of vegetation to be killed or controlled, by mixing in aqueous solution a glyphosate containing composition and a composition comprising a surfactant having a chemical structure encompassed by those represented immediately above. Such compositions of the invention are referred to herein as 鍍ank-mix compositions.

Alternatively, compositions of the invention may be provided to the end-user already formulated, either at the desired dilution for application (途eady to use compositions) or requiring dilution, dispersion or dissolution in water by the end-user (田oncentrate compositions). Such preformulated compositions of the invention are storage-stable and may be liquid or dry.

A method of use of compositions of the invention to kill or control weeds or other unwanted vegetation is also provided.

DETAILED DESCRIPTION OF THE INVENTION

Compositions of the invention may contain glyphosate in its acid form. However, because of the relatively low solubility of glyphosate acid in water, more soluble salts of glyphosate are generally preferred. As in commercial compositions of prior art, an especially preferred salt for aqueous compositions of the invention is the isopropylamine salt of glyphosate, while an especially preferred salt for dry compositions of the invention is the ammonium salt. Many other salts may be used either in aqueous or in dry formulations, including but not restricted to alkylamine, such as dimethylamine and n-propylamine, alkanolamine, such as monoethanolamine, alkylsulfonium, such as trimethylsulfonium, and alkali metal, such as sodium and potassium, salts of glyphosate. Regardless of whether acid or a salt is used, it is generally preferred to refer to the amount of glyphosate applied or contained in a formulation in terms of glyphosate acid equivalent, conventionally abbreviated as 殿.e..

Tank-mix and ready to use compositions of the invention are aqueous solutions comprising from about 1 to about 50 g glyphosate a.e./l, occasionally more. A preferred range for tank-mix and ready to use compositions is from about 5 to about 20 g a.e./l.

Concentrate compositions of the invention may be aqueous solutions comprising from about 50 to about 500 g glyphosate a.e./l or more, preferably from about 200 to about 500 g a.e./l and most preferably from about 350 to about 500 g a.e./l. An example of an especially preferred aqueous concentrate composition of the invention contains the isopropylamine salt of glyphosate at about 360 g a.e./l, the same level as is present in commercial compositions being sold as Roundupョ herbicide by Monsanto Company.

A surprising advantage of aqueous compositions of the invention over prior art compositions is that the glyphosate concentration can be increased to very high levels, for example from about 450 to about 500 g a.e./l, yet the surfactant concentration is still adequate to give excellent herbicidal performance without the end-user requiring to add more surfactant in the spray tank. Many such highly concentrated compositions have remarkably good storage stability under a wide range of temperature conditions.

Alternatively, concentrate compositions of the invention may be dry formulations, presented for example in the form of powders, pellets, tablets or, preferably, granules, to be dispersed or dissolved in water prior to use. Typically no water-insoluble ingredients are present at substantial levels in such compositions and the formulations are therefore fully water-soluble. Dry water-soluble or water-dispersible compositions of the invention comprise from about 20% to about 80% weight/weight glyphosate a.e., preferably from about 50% to about 76%, and most preferably from about 60% to about 72%. An example of an especially preferred water-soluble granular composition of the invention contains the ammonium salt of glyphosate at about 72% weight/weight, the same level as is present in commercial compositions being sold as Scoutョ herbicide by Monsanto Company.

In dry compositions of the invention glyphosate may itself provide the support for other formulation ingredients, or there may additionally be present one or more inert ingredients providing such support. An example of an inert support that may be used is ammonium sulfate. The term 電ry as used herein does not imply that dry compositions are totally free of water; typically dry compositions of the invention comprise from about 0.5 to about 5 percent by weight, preferably less than about 1 percent by weight water.

Dry water-soluble or water-dispersible granular formulations of the invention can be made by any process known in the art, including but not restricted to spray drying, fluid-bed agglomeration, pan granulation, or extrusion. In dry formulations, glyphosate may be present as a salt, for example the sodium or ammonium salt, or as the acid. Formulations containing glyphosate acid may optionally contain an acid acceptor such as an ammonium or alkali metal carbonate or bicarbonate, ammonium dihydrogen phosphate or the like, so that upon dissolution or dispersion in water by the end user a water soluble salt of glyphosate is produced.

What distinguishes compositions of the invention from all previously described glyphosate compositions is the presence therein of an alkoxylated tertiary or an alkoxylated or non-alkoxylated quaternary etheramine or an alkoxylated etheramine oxide surfactant having the representative chemical structure (a)

wherein R1 is a straight or branched chain C6 to about C22 alkyl, aryl or alkylaryl group, m is an average number from 1 to about 10, R2 in each of the m (O由2) groups is independently C1-C4 alkylene, R3 groups are independently C1-C4 alkylene, and x and y are average numbers such that x+y is in the range from 2 to about 60; or (b)

wherein R1 is a straight or branched chain C6 to about C22 alkyl, aryl or alkylaryl group, m is an average number from 1 to about 10, R2 in each of the m (O由2) groups is independently C1-C4 alkylene, R3 groups are independently C1-C4 alkylene, R4 is C1-C4 alkyl, x and y are average numbers such that x+y is in the range from 0 to about 60, and Ais an agriculturally acceptable anion; or (c)

wherein R1 is a straight or branched chain C6 to about C22 alkyl, aryl or alkylaryl group, m is an average number from 1 to about 10, R2 in each of the m (O由2) groups is independently C1-C4 alkylene, R3 groups are independently C1-C4 alkylene, and x and y are average numbers such that x+y is in the range from 2 to about 60.

Alkylamine or alkylamine oxide surfactants in glyphosate compositions of prior art have no (O由2) groups, in other words m=0. We have found that surprisingly improved properties can be imparted to glyphosate compositions when from 1 to about 10 (O由2) groups are inserted in the surfactant structure between the R1 group and the nitrogen atom.

Aryl groups, if present in R1, have 5-7, preferably 6, carbon atoms and may or may not be substituted with moieties. The alkyl portion in any alkylaryl group comprising R1 has 1-16 carbon atoms. An example of such an alkylaryl group is alkylphenyl, for example nonylphenyl.

However, in preferred surfactants of the invention R1 is a straight or branched chain alkyl group having about 8 to about 18, for example about 10-15, carbon atoms, and are derived from the corresponding alcohol. For example, the alkyl group may be of natural derivation, such as from coconut or tallow, or may be derived from a synthetic alcohol such as isodecyl, isotridecyl, linear C12-C14 or octadecyl alcohols.

The R2 substituent closest to the nitrogen atom (the proximal R2 group) is in preferred examples a linear propylene (佑H2CH2CH2), isopropylene (佑H2CH(CH3)) or ethylene (佑H2CH2) group. Preferred examples where the proximal R2 group is linear propylene have m=1. Where the proximal R2 group is isopropylene or ethylene, m is preferably in the range from 1 to 5, most preferably from 2 to 3, and all R2 groups are preferably the same.

R3 substituents in preferred examples are independently selected from isopropylene and ethylene. In especially preferred examples all R3 groups are ethylene. In tertiary etheramines and etheramine oxides of the invention it is preferred that x+y is in the range from 2 to about 20. In quaternary etheramines of the invention it is preferred that x+y is in the range from 0 to about 20. A particularly preferred range for x+y in tertiary and quaternary etheramines and etheramine oxides of the invention is from 2 to about 10, more particularly from 2 to about 5.

In quaternary etheramines of the invention R4 is preferably methyl and Ais preferably a halide, for example chloride or bromide, a phosphate or a sulfate ion, or alternatively may be a glyphosate ion or may be contributed by an anionic surfactant included with the etheramine in the formulation. It will be recognized by those skilled in the art that a low pH, such as may well exist in a glyphosate formulation, tertiary etheramines will most likely be protonated at the nitrogen atom and may be associated with a counterion; in such cases the tertiary etheramine can be represented by the chemical structure shown above for a quaternary etheramine, except that R4 is hydrogen. The counterion Ain a low pH glyphosate formulation comprising a tertiary etheramine is most likely glyphosate itself.

One especially preferred surfactant useful in compositions of the invention is a tertiary etheramine having R1=C12-C14 alkyl, R2=isopropylene, m=2, R3=ethylene and x+y=5.

Another especially preferred surfactant useful in compositions of the invention is a tertiary etheramine having R1=C12-C14 alkyl, R2=ethylene, m=3, R3=ethylene and x+y=5.

Two other especially preferred surfactants useful in compositions of the invention are tertiary etheramines having R1=isodecyl, R2=linear propylene, m=1, R3 ethylene and x+y=2 or 5 respectively..

Another series of especially preferred surfactants useful in compositions of the invention is a tertiary etheramine having R1=coco alkyl, R2=linear propylene, m=1, R3=ethylene and x+y=a number in the range from 2 to 10.

Two other especially preferred surfactants useful in compositions of the invention are tertiary etheramines having R1=isotridecyl, R2=linear propylene, m=1, R3=ethylene and x+y=2 or 5 respectively.

Two other especially preferred surfactants useful in compositions of the invention are quaternary etheramines having R1=isodecyl or isotridecyl respectively, R2=linear propylene, R3=ethylene, R4=methyl, m=1 and x+y=2.

Any convenient and effective herbicidal activity enhancing amount of the etheramine surfactant can be used in compositions of the invention. In tank-mix and ready to use formulations very high levels of surfactant are achievable. for example up to 5% weight/volume or even higher, but for reasons of economy it will be more normal to use a concentration in the range from about 0.125% to about 2% weight/volume. One of ordinary skill in the art will be able to determine from tests on different plant species an appropriate level of etheramine surfactant to include for any particular glyphosate application.

In concentrate liquid or dry compositions of the invention, the etheramine surfactant is preferably included at a weight/weight ratio to glyphosate a.e. in the range from about 1:20 to about 1:1, most preferably from about 1:10 to about 1:2, for example about 1:6.

Long-term storage stability is an important commercial attribute of concentrate formulations. In the case of aqueous concentrate formulations of glyphosate salts, it is particularly important that surfactants in the formulation do not separate concentrates made with surfactants of prior art show a tendency for phase separation at high temperatures. It is a feature of the etheramine surfactants herein disclosed that they show good compatibility with glyphosate salts, particularly the isopropylamine salt, as evidenced by relatively high cloud points even in aqueous solutions having high glyphosate concentrations. In general for most applications, a cloud point higher than about 50ー C. is desirable.

In addition to glyphosate or a salt thereof and the etheramine surfactant, any of a variety of further ingredients or adjuvants may be included in formulations of the present invention, as long as such added materials are not significantly antagonistic to the glyphosate herbicidal activity. Examples of such added materials illustratively include anti-gelling agents, antifreezes, thickeners, dyes, antimicrobial preservatives or additives to further enhance herbicidal activity, such as ammonium sulfate or fatty acids.

A second surfactant of a class other than etheramines, for example a primary or secondary alcohol ethoxylate, an alkyl ester of sucrose or sorbitan, or an alkyl polyglucoside, may also be included. When such a second surfactant is present, it is preferable that the weight/weight ratio of etheramine to the second surfactant is greater than about 1:1, most preferably greater than about 2:1, for example around 4:1.

Preferably when a second surfactant is included in a highly concentrated glyphosate formulation of the invention, for example one containing about 450 to about 500 g a.e./l, the etheramine surfactant comprises at least about 75% by weight of the total surfactant present.

Mixtures of glyphosate with other herbicides are also within the scope of the present invention if an etheramine surfactant is included in the formulation. Examples of such other herbicides include bialaphos, glufosinate, 2,4-D, MCPA, dicamba, diphenylethers, imidazolinones and sulfonylureas.

Methods of use of glyphosate formulations are well known to those of skill in the art. Aqueous concentrate formulations of the invention are diluted in an appropriate volume of water and applied, for example by spraying, to the weeds or other unwanted vegetation to be killed or controlled. Dry concentrate formulations of the invention are dissolved or dispersed in an appropriate volume of water and applied in the same way. For most purposes, compositions of the invention are applied at glyphosate a.e. rates in the range from about 0.1 to about 5 kg/ha, occasionally more. Typical glyphosate a.e. rates for control of annual and perennial grasses and broadleaves are in the range from about 0.3 to about 1.5 kg/ha. Compositions of the invention may be applied in any convenient volume of water, most typically in the range from about 50 to about 1000 l/ha.

The present invention is illustrated by but not limited to the following Examples.

EXAMPLES

Cloud point was determined for certain liquid compositions of the Examples as follows. A sample of the composition in a test tube was heated in a water bath until it became cloudy. The test tube was then removed from the water bath and the sample stirred with a thermometer until it became clear. The temperature at which the sample became clear was recorded as the cloud point of the composition.

Percentages expressed as % in the following Examples are by weight/weight unless otherwise indicated.

Example 1

The surfactant used in Example 1 is a tertiary etheramine having the chemical structure represented above in which R1 is C12-C14 alkyl, m is 3, x+y is 5 and R2 and R3 are each ethylene.

The aqueous concentrate composition of Example 1 was prepared by mixing the following ingredients in the order given:

(1) aqueous solution of glyphosate isopropylamine salt containing 46% glyphosate a.e., 67.4 g.

(2) surfactant as defined above, 10.0 g.

(3) deionized water, 22.6 g.

The composition can be calculated to contain 31% glyphosate a.e. and 10% surfactant. Specific gravity of the composition at 20/15.6ー C. was determined to be 1.1628. Cloud point of the composition was >90ー C.

Example 2

The surfactant used in Example 2 is the same as that used in Example 1. The aqueous concentrate composition of Example 2 was prepared by mixing the following ingredients in the order given:

(1) aqueous solution of glyphosate isopropylamine salt containing 46% glyphosate a.e., 1348 g.

(2) surfactant as defined above, 110 g.

(3) deionized water, 542 g.

The composition can be calculated to contain 31% glyphosate a.e. and 5.5% surfactant. Specific gravity of the composition at 20/15.6ー C. was determined to be 1.1630. Cloud point of the composition was >90ー C.

The composition of Example 2 was submitted for eye irritation testing according to the standard procedure prescribed in US Environmental Protection Agency (EPA) Publication 540/9-82-025, November 1982, entitled Pesticidal Assessment Guidelines, Subdivision F. Hazard Evaluation: Human and Domestic Animals. The study was conducted in compliance with EPA Good Laboratory Practice (GLP) standards. Results were obtained placing the composition in toxicity category III, indicating low irritancy to eyes.

Example 3

The surfactant used in Example 3 is a tertiary etheramine having the chemical structure represented above in which R1 is C12-C14 alkyl, m is 2, x+y is 5, R2 is isopropylene and R3 is ethylene.

The aqueous concentrate composition of Example 3 was prepared by mixing the following ingredients in the order given:

(1) aqueous solution of glyphosate isopropylamine salt containing 46% glyphosate a.e., 1348 g.

(2) surfactant as defined above, 200 g.

(3) deionized water, 452 g.

The composition can be calculated to contain 31% glyphosate a.e. and 10% surfactant. Specific gravity of the composition at 20/15.6ー C. was determined to be 1.1618. Cloud point of the composition was >90ー C.

Example 4

The surfactant used in Example 4 is the same as that used in Example 3. The aqueous concentrate composition of Example 4 was prepared by mixing the following ingredients in the order given:

(1) aqueous solution of glyphosate isopropylamine salt containing 46% glyphosate a.e., 1348 g.

(2) surfactant as defined above, 110 g.

(3) deionized water, 542 g.

The composition can be calculated to contain 31% glyphosate a.e. and 5.5% surfactant. Specific gravity of the composition at 20/15.6ー C. was determined to be 1.1617. Cloud point of the composition was >90ー C.

The composition of Example 4 was submitted for eye irritation testing according to the standard procedure prescribed in EPA Publication 540/9-82-025, November 1982 cited above. The study was conducted in compliance with GLP standards. Results were obtained placing the composition in in toxicity category III, indicating low irritancy to eyes.

Examples 5-7

The surfactants used in Examples 5-7 are tertiary etheramines having the chemical structure represented above in which R1 is C12-C14 alkyl, m is 3 and R2 and R3 are each ethylene. The value of x+y is varied as shown in the table below.

Aqueous concentrate compositions containing 31% glyphosate a.e. in the form of the isopropylamine salt and 11% surfactant were prepared by a procedure similar to that of Examples 1-4. Cloud point of each composition was determined as shown in the table below.

Example x + y Cloud point (ー C.)
5  5 >95 
6 10 81
7 15 66

Examples 8-11

The surfactants used in Examples 8-11 are tertiary etheramines having the chemical structure represented above in which R1 is C12-C14 alkyl, m is 2, R2 is isopropylene and R3 is ethylene. The value of x+y is varied as shown in the table below.

Aqueous concentrate compositions containing 31% glyphosate a.e. in the form of the isopropylamine salt and 11% surfactant were prepared by a procedure similar to that of Examples 1-4. Cloud point of each composition was determined as shown in the table below.

Example x + y Cloud point (ー C.)
8 2 76
9 5 >95
10 10 >95
11 15 71

Example 12

Comparative herbicidal efficacy was determined in a field test at Jerseyville, Ill. Treatments were applied post-emergence to plants which had grown from seeds planted mechanically in rows. A randomized block design with three replicates was used. Applications were made with a backpack sprayer with multiple nozzles giving an overlapping spray pattern to maximize uniformity of application. Herbicidal efficacy was evaluated as percent control estimated visually by comparison with untreated plots.

Plant species on which herbicidal efficacy was evaluated were Japanese millet (Echinochloa crus-galli, ECHCF), broadleaf signalgrass (Brachiaria platphylla, BRAPP), prickly sida (Sida spinosa, SIDSP), redroot pigweed (Amaranthus retroflexus, AMARE), hemp sesbania (Sesbania exaltata, SEBEX), morningglory (Ipomoea sp., IPOSS) and velvetleaf (Abutilon theophrasti, ABUTH).

All glyphosate formulations in this test were aqueous concentrates diluted in water to give an application volume of 93 l/ha. Dilutions were made so as to give three glyphosate application rates of 314, 628 and 840 g a.e./ha for each formulation.

Standard treatments used for reference in this field test were made with concentrate formulations A and B containing glyphosate isopropylamine salt at 360 g a.e./l and respectively 15.4% and 7.7% of MON 0818, a surfactant based on ethoxylated tallowamine having an average of 15 moles of EO.

Concentrate formulations C-J of the invention contained glyphosate in the form of the isopropylamine salt at 360 g a.e./l. Concentrate formulations C-F further contained, as sole surfactant, a tertiary etheramine having the chemical structure represented above in which R1 is C12-C14 alkyl, m is 2, x+y is 5, R2 is isopropylene and R3 is ethylene. Surfactant contents in concentrate formulations C, D, E and F were respectively 3.5%, 5.5%, 7.5% and 10%. Concentrate formulations D and F are essentially identical to the compositions of Examples 4 and 3 above, respectively. Concentrate formulations G-J contained, as sole surfactant, a tertiary etheramine having the chemical structure represented above in which R1 is C12-C14 alkyl, m is 3, x+y is 5, and R2 and R3 are each ethylene. Surfactant contents in concentrate formulations G, H, I and J were, respectively, 3.5%, 5.5%, 7.5% and 10%. Concentrate formulations H and J are essentially identical to the compositions of Examples 2 and 1 above respectively.

Concentrate formulations K and L of the invention contained glyphosate in the form of the isopropylamine salt at 420 g a.e./l and a tertiary etheramine surfactant having the chemical structure represented above in which R1 is C12-C14 alkyl, m is 3, x+y is 5, and R2 and R3 are each ethylene. Etheramine surfactant contents in concentrate formulations K and L were respectively 5.5% and 3.5%. Concentrate formulation L additionally contained 3.9% of an alkyl polyglucoside surfactant having a C9-C11 alkyl chain and an alkyl/glucose molar ratio of 1:1.6.

Results of the field test are tabulated below.

Percent control
Formula- g a.e./
tion ha ECHCF BRAPP SIDSP AMARE SEBEX IPOSS ABUTH
A 314 97 96 70 96 99 59 59
B 314 97 98 81 95 98 52 52
C 314 100 100 68 98 100 49 50
D 314 98 98 73 96 100 48 50
E 314 100 100 52 95 100 46 50
F 314 100 100 75 96 100 58 59
G 314 100 100 66 94 99 53 52
H 314 99 100 50 88 98 53 55
I 314 97 98 65 97 97 60 63
J 314 98 100 74 95 97 60 56
K 314 92 96 76 93 98 54 53
L 314 97 98 77 95 97 55 56
A 328 100 100 96 100 100 73 75
B 628 100 100 95 99 99 68 66
C 628 100 100 94 99 100 71 70
D 628 100 98 95 100 100 85 78
E 628 100 100 98 99 99 77 77
F 628 100 100 93 100 100 81 79
G 628 100 100 99 99 100 87 84
H 628 100 100 97 98 100 74 72
I 628 100 100 97 100 100 83 78
J 628 100 100 98 99 100 77 70
K 628 100 98 92 99 99 72 73
L 628 100 100 94 99 100 79 81
A 840 100 100 97 99 100 90 78
B 840 100 100 99 99 100 87 81
C 840 100 100 100 100 100 90 90
D 840 100 98 100 100 100 89 83
E 840 100 100 98 100 100 91 86
F 840 100 100 99 99 100 90 88
G 840 100 100 96 100 100 86 83
H 840 100 100 100 100 100 86 83
I 840 100 100 96 98 100 88 80
J 840 100 100 98 100 100 92 82
K 840 100 100 100 100 100 92 92
L 840 100 100 99 99 99 88 86

Example 13

The surfactant used in Example 13 is the same as that used in Example 1. The dry water-soluble granular composition of Example 13 was prepared by adding to a small food-processor bowl the following ingredients:

(1) powdered ammonium glyphosate containing 86.6% glyphosate a.e., 37.5 g.

(2) surfactant as defined above, 12.5 g.

(3) water, 2.5 g.

No gelling of the surfactant was observed. The ingredients were mixed, forming homogeneous small granules. The granules were dried in a fluid-bed dryer at 65ー C. for 15 minutes.

The composition can be calculated to contain, on a dry weight basis, 25% surfactant. Glyphosate assay was determined to be 61.8% a.e.

Example 14

The surfactant used in Example 14 is the same as that used in Example 3. The dry water-soluble granular composition of Example 14 was prepared by adding to a small food-processor bowl the following ingredients:

(1) powdered ammonium glyphosate containing 86.6% glyphosate a.e., 37.5 g.

(2) surfactant as defined above, 12.5 g.

(3) water, 2.5 g.

No gelling of the surfactant was observed. The ingredients were mixed, forming homogeneous small granules. The granules were dried in a fluid-bed dryer at 65ー C. for 15 minutes.

The composition can be calculated to contain, on a dry weight basis, 25% surfactant. Glyphosate assay was determined to be 66.2% a.e.

Example 15

For comparative greenhouse testing of herbicidal efficacy, aqueous concentrate compositions containing 31% glyphosate a.e. in the form of the isopropylamine salt and 5.5% surfactant were prepared by a procedure similar to that of Examples 1-4.

Formulations C1 and C2 were made using tertiary alkylamine surfactants of prior art. The surfactant in C1 is an ethoxylated cocoamine having 5 moles of EO. If the representative chemical structure shown for a tertiary etheramine of the invention is applied to the surfactant of C1, it will be seen that R1 is coco alkyl of average carbon chain length about 12, m is 0, R3 is ethylene and x+y is 5. The surfactant in C2 is an ethoxylated tallowamine having 5 moles of EO. If the representative chemical structure shown for a tertiary etheramine of the invention is applied to the surfactant of C2, it will be seen that R1 is tallow alkyl of average carbon chain length about 18, m is 0, R3 is ethylene and x+y is 5.

Formulations E1-E9 were made using tertiary or quaternary N-methyl etheramine surfactants of the invention. The chemical structures of these surfactants can be deduced from the following table, by reference to the representative structures shown above.

Formu- Surfactant x +
lation type R1 R2 R3 m y A
E1 tertiary C12-14 CH2CH(CH3) CH2CH2 2  5
alkyl
E2 tertiary coco CH2CH2CH2 CH2CH2 1 10
alkyl
E3 tertiary isodecyl CH2CH2CH2 CH2CH2 1 2
E4 tertiary isodecyl CH2CH2CH2 CH2CH2 1 5
E5 tertiary iso- CH2CH2CH2 CH2CH2 1 2
tridecyl
E6 tertiary iso- CH2CH2CH2 CH2CH2 1 5
tridecyl
E7 tertiary C15 CH2CH2CH2 CH2CH2 1 2
alkyl
E8 quaternary isodecyl CH2CH2CH2 CH2CH2 1 2 Cl
E9 quaternary iso- CH2CH2CH2 CH2CH2 1 2 Cl
tridecyl

For greenhouse testing, seeds of velvetleaf (Abutilon theophrasti, ABUTH) and Japanese millet (Echinochloa crus-galli, ECHCF) were planted in 10.2 cm square pots of soil with added fertilizer. Plants were allowed to grow until the desired growth stage of size (3-leaf stage for ABUTH, 20-25 cm height for ECHCF) for spraying. Pots were selected for uniformity before treatment and four replicate pots were assigned to each treatment, including an untreated control. Spray solutions were prepared by dilution of the concentrate glyphosate formulations in water. Spraying was performed with a device which simulates agricultural field spraying equipment, delivering a fine spray at a pressure of about 207 kilopascals. Speed of travel of the spray device over the plants was adjusted to give the desired spray volume of 187 l/ha. For logistical reasons, all four replicates of each treatment were sprayed together. After spraying, the plants were returned to the greenhouse. Herbicidal efficacy was evaluated by visual assessment 16 days after treatment and recorded as 菟ercent control on an arbitrary scale by comparison with untreated plants. On this scale 0 means no visible effect and 100 means death of all plants. In the table below, percent control values given are the means of four replicates.

Percent control
g a.e./ha: ABUTH ECHCF
Formulation 112 224 336 448 112 224 336 448
C1 0 1 60 50 6 30 61 50
C2 0 6 53 79 0  6 53 79
E1 1 13 58 78 10 55 78 86
E2 3 15 49 65 3 15 49 91
E3 0 9 50 60 9 53 69 89
E4 0 4 35 65 10 53 55 78
E5 0 0 n.d. 53 5 50 n.d. 95
E6 0 6 55 65 15 55 71 81
E7 0 5 50 71 6 55 75 86
E8 0 5 40 73 10 61 76 97
E9 3 13 71 70 5 58 73 75
n.d. = no data

Example 16

To determine compatibility of surfactants of the invention with very concentrated aqueous formulations of glyphosate, aqueous concentrate compositions containing 480 g/l glyphosate a.e. in the form of the isopropylamine salt and 80 g/l surfactant were prepared by a procedure similar to that of Examples 1-4. The compositions of Example 16 are approximately one-third more concentrated in respect of glyphosate a.e. than those of Example 15.

Formulations C3 and C4 were made using tertiary alkylamine surfactants of prior art. The surfactant in C3 is the same as that in formulation C1 of Example 15. The surfactant in C4 is the same as that in formulation C2 of Example 15.

Formulations E10, E11, E12 and E13 were made using the same tertiary or quaternary N-methyl etheramine surfactants of the invention as are present in formulations E1, E6, E8 and E9 respectively of Example 15.

Surfactant compatibility was determined by measuring cloud point of the formulations, as shown in the table below.

Formulation Cloud point (ー C.)
C3  >90
C4  >90
E10 >90
E11 >90
E12 >90
E13 >90

Example 17

Compositions of the invention were prepared by a procedure similar to that of Examples 1-4 to illustrate the incorporation of a sonionic surfactant together with the etheramine surfactant in a highly concentrated aqueous glyphosate formulation. In formulations E14-E25 glyphosate is present as its isopropylamine salt at 480 g a.e./l and the total surfactant (etheramine plus nonionic surfactant) concentration is 80 g/l. In all cases the weight/weight ratio of etheramine to the nonionic surfactant is 4:1.

The etheramine surfactant in formulation E14 is the same as that in formulation E1 of Example 15. The nonionic surfactant in formulation E14 is an ethoxylated C14-C16 linear primary alcohol having an average of 7 moles of EO.

The etheramine surfactant in formulation E15 is the same as that in formulation E1 of Example 15. The nonionic surfactant in formulation E15 is an ethoxylated C12-C13 linear primary alcohol having an average of 5 moles of EO.

The etheramine surfactant in formulation E16 is the same as that in formulation E1 of Example 15. The nonionic surfactant in formulation E16 is an ethoxylated C11 linear primary alcohol having an average of 7 moles of EO.

The etheramine surfactant in formulation E17 is the same as that in formulation E1 of Example 15. The nonionic surfactant in formulation E17 is an ethoxylated C11-C12 linear primary alcohol having an average of 6 moles of EO.

The etheramine surfactant in formulation E18 is the same as that in formulation E1 of Example 15. The nonionic surfactant in formulation E18 is an ethoxylated C12-C15 secondary alcohol having an average of 9 moles of EO.

The etheramine surfactant in formulation E19 is the same as that in formulation E1 of Example 15. The nonionic surfactant in formulation E19 is an alkyl polyglucoside having a C8-C10 alkyl chain and an average of 1.7 moles of glucose.

The etheramine surfactant in formulation E20 is the same as that in formulation E6 of Example 15. The nonionic surfactant in formulation E20 is an ethoxylated C14-C16 linear primary alcohol having an average of 7 moles of EO.

The etheramine surfactant in formulation E21 is the same as that in formulation E6 of Example 15. The nonionic surfactant in formulation E21 is an ethoxylated C12-C15 secondary alcohol having an average of 9 moles of EO.

The etheramine surfactant in formulation E22 is the same as that in formulation E8 of Example 15. The nonionic surfactant in formulation E22 is an ethoxylated C14-C16 linear primary alcohol having an average of 7 moles of EO.

The etheramine surfactant in formulation E23 is the same as that in formulation E8 of Example 15. The nonionic surfactant in formulation E23 is an ethoxylated C12-C15 secondary alcohol having an average of 9 moles of EO.

The etheramine surfactant in formulation E24 is the same as that in formulation E9 of Example 15. The nonionic surfactant in formulation E24 is an ethoxylated C14-C16 linear primary alcohol having an average of 7 moles of EO.

The etheramine surfactant in formulation E25 is the same as that in formulation E9 of Example 15. The nonionic surfactant in formulation E25 is an ethoxylated C12-C15 secondary alcohol having an average of 9 moles of EO.

Cloud points of formulations E14-E25 are shown in the table below.

Formulation Cloud point (ー C.)
E14 79
E15 73
E16 63
E17 71
E18 77
E19 >90
E20 >90
E21 >90
E22 >90
E23 >90
E24 >90
E25 >90

An attempt was made to make formulations similar to E14-E25, but containing, in place of the etheramine component, an ethoxylated tertiary alkylamine surfactant of prior art. Whether a cocoamine with 5 moles of EO or a tallowamine with 5 moles of EO was used, the prior art surfactant was found to be incompatible with any of the ethoxylated primary or secondary alcohol surfactants used in formulations E14-E25, at equal glyphosate, amine surfactant and nonionic surfactant loadings as in these same formulations. Thus, a further unexpected advantage of etheramine surfactants of the present invention over alkylamine surfactants of prior art is their relatively good compatibility with nonionic surfactants in highly concentrated aqueous glyphosate formulations.

While the illustrative embodiments of the invention have been described with particularity, it will be understood that various other modifications will be apparent to and can be readily made by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is not intended that the scope of the claims appended hereto be limited to the examples and descriptions set forth hereinabove but rather that the claims be construed as encompassing all the features of patentable novelty which reside in the present invention, including all features which would be treated as equivalents thereof by those skilled in the art to which the invention pertains.

Example 18

Further to the compositions of Example 15, aqueous concentrate compositions containing 31% glyphosate a.e. in the form of the isopropylamine salt and 5.5% surfactant were prepared by a procedure similar to that of Examples 1-4.

Formulations C1 and C2 are as in Example 15.

Formulations C3 and C4 were likewise made using tertiary alkylamine surfactants of prior art. The surfactant in C3 is an ethoxylated cocoamine having 2 moles of EO. The surfactant in C4 is an ethoxylated tallowamine having 2 moles of EO.

Formulation C5 was made using a quaternary alkylamine surfactant of prior art, which is N-methyl cocoammonium chloride having 2 moles of EO.

Formulation C6 was made using an alkylamine oxide surfactant of prior art, supplied by Tomah Products, Inc. as 鄭O-728 Special. It is an alkylamine N-oxide having 2 moles of EO; the chain length or origin of the alkyl chain is not disclosed by Tomah.

Formulations E1-E9 are as in Example 15.

Formulation E26 was made using an etheramine oxide surfactant of the invention. Its chemical structure can be deduced from the following table, by reference to the representative structures shown above.

For-
mula- Surfactant
tion type R1 R2 R3 m x + y A
E26 N-oxide isodecyl CH2CH(CH3) CH2CH2 1 2

Greenhouse testing was conducted exactly as described in Example 15, except that herbicidal efficacy was evaluated 17 days after treatment. Average percent control is shown in the table below.

Percent control
g a.e./ha: ABUTH ECHCF
Formulation 224 336 448 672 224 336 448 672
C1 33 58 69 83 41 69 66 95
C2 44 58 74 78 39 60 63 95
C3 44 49 85 84 50 64 83 81
C4 41 51 65 85 54 66 84 88
C5 31 41 66 76 51 71 86 96
C6 34 38 60 69 46 64 65 81
E1 46 65 83 91 48 71 81 99
E2 50 59 75 85 40 60 81 93
E3 46 56 68 73 39 55 66 95
E4 39 55 78 80 49 59 79 89
E5 40 51 73 75 51 63 79 89
E6 49 60 83 86 51 63 80 90
E7 31 39 75 75 46 63 75 95
E8 43 55 73 80 46 58 73 93
E9 48 50 84 85 51 60 85 98
 E26 48 59 73 83 48 61 84 94

While the illustrative embodiments of the invention have been described with particularity, it will be understood that various other modifications will be apparent to and can be readily made by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is not intended that the scope of the claims appended hereto be limited to the examples and descriptions set forth hereinabove but rather that the claims be construed as encompassing all the features of patentable novelty which reside in the present invention, including all features which would be treated as equivalents thereof by those skilled in the art to which the invention pertains.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3799758Aug 9, 1971Mar 26, 1974Monsanto CoN-phosphonomethyl-glycine phytotoxicant compositions
US4159901Dec 27, 1977Jul 3, 1979Monsanto CompanyAminomethylenephosphonic acid, thiol
US4405531Mar 8, 1982Sep 20, 1983Monsanto CompanySalts of N-phosphonomethylglycine
US4936901Jun 16, 1987Jun 26, 1990Monsanto CompanyFormulations of water-dispersible granules and process for preparation thereof
US5317003Jul 16, 1992May 31, 1994Monsanto CompanyHerbicidal compositions comprising glyphosate salts and alkoxylated quaternary amine surfactants
US5389598 *Dec 17, 1993Feb 14, 1995Monsanto CompanyAqueous concentrate formulations having reduced eye irritancy
US5464807Sep 23, 1994Nov 7, 1995Monsanto CompanyMethods of using glyphosate compositions comprising alkoxylated quaternary ammonium surfactants
US5668085Jun 2, 1995Sep 16, 1997Monsanto CompanyGlyphosate formulations comprising alkoxylated amine surfactants
US5683958May 31, 1995Nov 4, 1997Monsanto CompanyOxyalkylated fatty amine, reduction of eye irritation
US5703015Dec 19, 1994Dec 30, 1997Monsanto CompanyAqueous solution of glyphosate and polyoxyalkylene alkylamine surfactant, containing phosphate monoester and/or diester to reduce eye irritation
US5750468Mar 15, 1996May 12, 1998Monsanto CompanyHerbicide
US5849663May 24, 1995Dec 15, 1998Kao CorporationEnhancer for agricultural chemicals, enhancer composition for agricultural chemicals and method for enhancing the efficacy of agricultural chemical
US5948421Mar 5, 1997Sep 7, 1999Kao CorporationOrganophosphorus herbicides, cationic surfactant mixtures
US6008158Oct 2, 1998Dec 28, 1999Kao CorporationEnhancer composition for agricultural chemicals and method for enhancing the efficacy of agricultural chemical
US6063733Sep 18, 1997May 16, 2000Monsanto CompanyAqueous or water soluble composition comprising glyphosate herbicide, alkoxylated amine surfactant, acidic compound to reduce eye irritation
EP0274369A1Dec 3, 1987Jul 13, 1988Monsanto CompanyGlyphosate-ammonium sulfate herbicidal formulation
EP0290416A2Apr 26, 1988Nov 9, 1988Monsanto Europe S.A.Improved glyphosate formulations
EP0472310A1Aug 1, 1991Feb 26, 1992Monsanto CompanyNew surfactant compositions, method for their preparation, and pesticidal compositions containing same
GB1588079A Title not available
WO1995033379A2May 24, 1995Dec 14, 1995Keiko HasebeEnhancer composition for agricultural chemicals and method for enhancing the efficacy of agricultural chemical
Non-Patent Citations
Reference
1Brochure: Tomah Products, Inc., dated Aug. 22, 1994, "Ethoxylated Amines".
2Brochure: Tomah Products, Inc., dated Sep. 1, 1994, "Quaternaries".
3McWhorter, C.G. "The Physiologocal Effects of Adjuvants on Plants" Chapter 6 in S. O. Duke, ed., Weed Physiology: vol. II: Herbicide Physiology, CRC Press, Boca Raton, Florida, 141-158, 1985.
4Wyrill and Burnsid, Weed Science, vol. 25 (1977), pp. 275-287.
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US7622641Aug 22, 2006Nov 24, 2009Pioneer Hi-Bred Int'l., Inc.5-enolpyruvylshikimate-3-phosphate synthase inhibition; tolerant to acetolactate synthase inhibitors; glyphosate-N-acetyltransferase
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US7973218Aug 22, 2006Jul 5, 2011Pioneer Hi-Bred International, Inc.Methods and compositions for controlling weeds
US8203033Apr 2, 2009Jun 19, 2012Pioneer Hi-Bred International, Inc.glyphosate-N-acetyltransferase polypeptide; enolpyruvylshikimate-3-phosphate synthase-5 inhibition; tolerant to glyphosate/acetolactate synthase inhibitors
US8455396Jul 11, 2011Jun 4, 2013Stepan CompanyAlkali metal glyphosate compositions
US8536095Jun 30, 2009Sep 17, 2013Monsanto Technology LlcCombinations of derivatized saccharide surfactants and etheramine oxide surfactants as herbicide adjuvants
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Classifications
U.S. Classification504/206
International ClassificationA01N25/30, A01P13/00, A01N57/20, A01N25/00
Cooperative ClassificationA01N57/20
European ClassificationA01N57/20
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