RU2781896C2 - Herbicidal composition - Google Patents

Abstract

FIELD: agriculture.

SUBSTANCE: invention relates to agriculture, in particular to herbicidal compositions. An aqueous herbicidal composition contains from 100 to 750 g/l (in the form of acidic equivalents) of glyphosate or its agriculturally acceptable salt and from 1 to 30 wt.% of ethoxylated amine of composite ester, where the specified ethoxylated amine of composite ester has the formula (I):

(I),

where: a) R, R’, and R”, each independently, is an alkylene group with 1-8 carbon atoms, b) X, Y, and Z is selected from H, O-(CH₂CH₂O)_nH, O-(CH₂CH₂O)_n-COR’’’, or O-COR’’’, and one of X, Y, and Z is O-(CH₂CH₂O)_n-COR’’’ or O-COR’’’, where n=1-40, and R’’’ is a saturated or unsaturated C₆-C₃₀alkyl group; provided that: i) if one of X, Y, or Z is O-(CH₂CH₂O)_n-COR’’’, each of two other substitutes is independently H or O-(CH₂CH₂O)_nH; ii) if one of X, Y, or Z is O-COR’’’, two other substitutes are H or O-(CH₂CH₂O)_nH, and at least one of them is O-(CH₂CH₂O)_nH, where the specified ethoxylated amine of composite ester of the formula (I) is a product of a reaction of saturated or unsaturated C6-C30 aliphatic monocarboxylic acid and tertiary hydroxylamine, where ethoxylation is carried out directly on tertiary hydroxylamine before esterification or on a product of an esterification reaction. The aqueous herbicidal composition is used in a method for destruction of weeds in crops of agricultural plants and in a method for control of weed growth.

EFFECT: proposed aqueous herbicidal composition has improved physical and chemical indicators, in particular, shows high stability and has an improved ecotoxic profile.

12 cl, 8 tbl, 14 ex

Description

FIELD OF TECHNOLOGY

The present invention relates to herbicidal compositions, and in particular to stable herbicidal compositions containing glyphosate or an agriculturally acceptable salt thereof and an adjuvant.

BACKGROUND OF THE INVENTION

Glyphosate (N-(phosphonomethyl)glycine in acid or salt form) is one of the most commonly used herbicides for the non-selective control of weeds and unwanted plants in agricultural and non-agricultural areas. It works through the inhibition of 5-enolpyruvylshikimate-3-phosphate synthase (EPSPS), an enzyme in the aromatic acid biosynthetic pathway, thereby preventing the synthesis of essential aromatic amino acids that are essential for protein biosynthesis.

The acidic form of glyphosate is poorly soluble in water, and for this reason glyphosate is usually sold as a salt that has sufficient water solubility to make concentrated herbicide formulations that are diluted by the end user in the field. Commonly used glyphosate salts include sodium salt, potassium salt, ammonium salt, sulfonium salts such as trimethylsulfonium, amine salts such as monoisopropylamine, dimethylamine, diamines (eg ethylenediamine) and alkanolamines (eg monoethanolamine).

Glyphosate is typically applied by the end user as a diluted aqueous spray solution. The diluted aqueous spray solution of glyphosate typically includes at least one surfactant that acts as an adjuvant. The presence of a surfactant is highly desirable, as surfactants reduce the interfacial tension between the aqueous spray and the treated material (foliage) (i.e. they improve wetting), thereby facilitating the distribution of droplets on the treated surface, the penetration of the active ingredient into the materials and the overall bioefficiency of the solution.

The original glyphosate patent US 3,799,758, which is incorporated herein by reference in its entirety, includes in the herbicidal formulation a surfactant adjuvant including, but not limited to: alkylbenzene sulfonates or alkylnaphthalene sulfonates, sulfated fatty alcohols, amines or acid amine derivatives, sodium sulfosuccinate esters, sulfonated vegetable oils; and an ethoxylated alkylamine, the latter being preferred in most commercial formulations due to its low cost and reasonable efficacy.

Alkylamine ethoxylates, and in particular ethoxylated tallow amine, are most commonly used as pesticide adjuvants, in particular as glyphosate adjuvants. Various other alkylamine-based surfactants have been described that provide superior glyphosate bioefficiency. However, these surfactants are dangerous and can be serious eye, skin, and respiratory irritants, and are highly toxic to plants and animals, especially aquatic plants and animals, even at low concentrations.

In addition, it has become increasingly desirable to increase the concentration of active herbicide in formulations so that a given dose of herbicide can be provided in a smaller volume of liquid, which offers advantages in terms of transport, storage, handling and disposal of the container. In terms of glyphosate formulations, concentrations of at least 480 g/L are desirable. Highly concentrated herbicidal formulations tend to crystallize and exhibit phase separation upon prolonged storage at low temperatures. Conventional surfactants that attempt to accommodate high concentration glyphosate formulations are problematic because the high concentration of surfactants required causes immiscibility between the surfactants and glyphosate.

In the field of alternatives to classical adjuvants such as tallow amine ethoxylate, EP 1289362 describes ester amines derived from an ethoxylated alcohol that has been carboxymethylated and then esterified with a tertiary hydroxylamine (alkanolamine) and amidoamines obtained by reacting a fatty acid or fatty acid methyl ester and diamine.

We have found that ethoxylated amine esters, which are the reaction product of a saturated or unsaturated C ₆ -C ₃₀ aliphatic monocarboxylic acid and a tertiary hydroxylamine, where the ethoxylation is carried out directly on the tertiary hydroxylamine prior to esterification or on the product of the esterification reaction, can be used to obtain stable herbicidal formulations. containing glyphosate or its agriculturally acceptable salt. This is particularly surprising since not only are these ethoxylated ester amines as effective as tallow amine ethoxylate, but they also show a much better ecotoxicological profile.

SUMMARY OF THE INVENTION

Therefore, the object of this invention is an aqueous herbicidal composition containing from 1 to 30 wt.% (wt.%) ethoxylated amine ester, where the specified ethoxylated amine ester has the formula (I):

(I),

(I)

where:

a) R, R' and R'' are each independently an alkylene group having 1-8 carbon atoms

b) X, Y and Z are selected from H, O-(CH ₂ CH ₂ O) _n H, O-(CH ₂ CH ₂ O) _n -COR''' or O-COR''', and one of X , Y and Z is O-(CH ₂ CH ₂ O) _n -COR''' or O-COR'''

where n=1-40, and R''' is a saturated or unsaturated C ₆ -C ₃₀ alkyl group;

provided that:

i) if one of X, Y or Z is O-(CH ₂ CH ₂ O) _n -COR''', each of the other two substituents is independently H or O-(CH ₂ CH ₂ O) _n H

ii) if one of X, Y or Z is O-COR''', the other two substituents are H or O-(CH ₂ CH ₂ O) _n H and at least one of them is O-(CH ₂ CH ₂ O) _n H.

Another object of this invention is a method of killing or controlling the growth of weeds, which includes applying to the fields a diluted aqueous herbicidal composition containing 0.01-3 wt.% glyphosate (a.e.) or its agriculturally acceptable salt and an ethoxylated amine ester of the formula ( I) as an adjuvant, in an amount sufficient to kill or control the growth of weeds.

Another object of this invention is a diluted sprayable herbicidal composition (tank mix) containing 0.01-10 wt.%, preferably 0.01-5 wt.%, at least one herbicide, and 0.01-5 wt. %, preferably 0.01-3 wt.% ethoxylated amine ester of formula (I).

Throughout the description, unless otherwise indicated, the amounts of glyphosate and its salts are given in terms of acid equivalent (a.e.).

DETAILED DESCRIPTION OF THE INVENTION

Preferably, the aqueous herbicidal composition according to the present invention contains 100-750 g/l, preferably 300-600 g/l (acid equivalent (a.e.)) of glyphosate or an agriculturally acceptable salt thereof and 2-10% by weight ( wt.%) ethoxylated amine ester, where the specified ethoxylated amine ester has the formula (I):

(I),

(I)

where:

a) R, R' and R'' are each independently an alkylene group having 2 carbon atoms

b) X, Y and Z are selected from O-(CH ₂ CH ₂ O) _n H, O-(CH ₂ CH ₂ O) _n -COR''' or O-COR''', and one from X, Y and Z is O-(CH ₂ CH ₂ O) _n -COR''' or O-COR'''

where n=3-20, preferably 10-20, and R''' is a saturated or unsaturated C ₁₆ -C ₂₂ alkyl group;

provided that:

i) if one of X, Y or Z is O-(CH ₂ CH ₂ O) _n -COR''', both other substituents are O-(CH ₂ CH ₂ O) _n H

ii) if one of X, Y or Z is O-COR''', both other substituents are O-(CH ₂ CH ₂ O) _n H.

According to the invention, the ethoxylated ester amines used as adjuvants for glyphosate compositions are the reaction product of a saturated or unsaturated C ₆ -C ₃₀ aliphatic monocarboxylic acid and a tertiary hydroxylamine, wherein the ethoxylation is carried out directly on the tertiary hydroxylamine prior to esterification or on the reaction product esterification.

Examples of C ₆ -C ₃₀ aliphatic unsaturated monocarboxylic acids suitable for this invention include both unsaturated and polyunsaturated aliphatic carboxylic acids with 6-30 carbon atoms. Examples of these acids are palmitoleic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid and the like.

Examples of C ₆ -C ₃₀ aliphatic saturated monocarboxylic acids include decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and the like.

Mixtures of C ₆ -C ₃₀ saturated and unsaturated aliphatic monocarboxylic acids can also be used.

Also, refined oils from vegetable waste are useful sources of aliphatic monocarboxylic acids.

Preference is given to mixtures of monocarboxylic acids derived from natural oils such as coconut oil, mustard oil, palm oil, olein, soybean oil, rapeseed oil, tall oil, sunflower oil, and mixtures thereof. Particularly preferred are blends derived from tall oil.

In particular, the most preferred tall oil fatty acids are those that have a certain amount of rosin acids that are also capable of reacting with tertiary hydroxylamine or ethoxylated tertiary hydroxylamine; preferably, the tall oil fatty acids are those having less than 6 wt%, more preferably 0.5-6 wt% resin acids.

Also suitable are mixtures of saturated or unsaturated aliphatic C ₆ -C ₃₀ monocarboxylic acids obtained as a by-product from the biodiesel production process.

In accordance with this invention, the tertiary hydroxylamine is selected from trialkanolamines, monoalkyldialkanolamines and dialkylmonoalkanolamines, where the alkyl and hydroxyalkyl substituents have 1-8 carbon atoms.

Specific examples of said tertiary hydroxylamines are triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-diisopropylethanolamine, N,N-dibutylethanolamine and N, N-dimethylisopropanolamine.

Preferably, the tertiary hydroxylamine is a trialkanolamine. The most preferred trialkanolamine is triethanolamine.

As stated above, the ethoxylated amine esters of the present invention are the reaction product of a saturated or unsaturated C ₆ -C ₃₀ aliphatic monocarboxylic acid and a tertiary hydroxylamine, where the ethoxylation is carried out directly on the tertiary hydroxylamine prior to esterification, or on the product of the esterification reaction. Preferably, the tertiary hydroxylamine is ethoxylated and then esterified with a saturated or unsaturated C ₆ -C ₃₀ aliphatic monocarboxylic acid by reacting in a 1:1 molar ratio to minimize the formation of diesters and other byproducts, typically polyethylene glycol monoesters and diesters, which may be detrimental to the effectiveness of the product.

In accordance with this invention, the herbicidal composition contains the herbicide, which is glyphosate, and the above ethoxylated ester amine as an adjuvant.

Any agriculturally acceptable water soluble salt of glyphosate can be used in herbicidal compositions according to the practice of this invention.

Glyphosate is an organic compound that contains three acidic protonated groups and, in its acidic form, is relatively insoluble in water. Therefore, glyphosate is usually formulated and applied as a water-soluble salt. While monobasic, dibasic, and tribasic salts of glyphosate can be prepared, it is generally preferred to formulate and apply glyphosate in the form of a monobasic salt, such as a potassium or monoalkylammonium salt. Suitable salts include isopropylamine salts; sodium; potassium; ammonium; mono-, di-, tri- and tetra-C _1-4 -alkylammonium; mono-, di- and tri-C _1-4 alkanolammonium; mono-, di- and tri-C _1-4 -alkylsulfonium; and sulfoxin. Salt mixtures may also be used in certain formulations.

Preferred forms of glyphosate in herbicidal compositions are the isopropylamine salt of glyphosate and the potassium salt of glyphosate.

In addition to the ethoxylated ester amine and glyphosate, the herbicidal composition according to the invention may also contain, as additional ingredients:

- other surfactants such as cationic, anionic, nonionic and amphoteric surfactants such as nonionic or anionic alkyl polyglycosides, alkoxylated fatty alcohols or amines, anionic esters of (alkoxylated) fatty alcohols, C ₆ -C ₁₈ alkyl dimethyl betaine;

- other herbicides such as glufosinate salts, bentazon, fomesafen, 2,4-D and its derivatives, dicamba, MCPA, MCPP, MCRV, paraquat, clopyralid, dichlorprop, imazalil, picloram, diquat, terbutylazine, florasulam, isoproturon, diuron, diflufenican and mixtures thereof;

- other biocidal active ingredients or compositions, for example insecticides, fungicides, bactericides, acaricides, nematicides and/or plant growth regulators, to broaden the spectrum of activity;

- fertilizers (nitrogen source) such as ammonium sulfate, ammonia solutions, ammonium nitrate, ammonium hydrogen sulfate, ammonium acetate, ammonium formate, ammonium oxalate, ammonium carbonate, ammonium hydrogen carbonate, ammonium thiosulfate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, sodium hydrogen phosphate -ammonium, ammonium thiocyanate, urea, thiourea and mixtures thereof;

- water-soluble organic solvents such as glycerin, ethylene glycol, propylene glycol, dipropylene glycol methyl ether (Dovanol DPM), dipropylene glycol, butyldiglycol, dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone, dibutoxymethane (Butylal), methanol, ethanol, ethanol isopropanol, ethyl lactate (Purasolve), propylene carbonate and mixtures thereof;

- other conventional agrochemical composition additives such as defoamers, antifreezes, colorants, stabilizers, buffers, thickeners, flow enhancers, wetting agents, lubricants, fillers, drift controls, stickers, flame retardants, preservatives and the like.

Preferably, when the composition of the present invention contains additives, such additional components are environmentally friendly, substantially non-toxic to aquatic organisms, and have acceptable efficacy.

The herbicidal composition according to the present invention may be a concentrated aqueous composition or a diluted, ready-to-use, sprayable aqueous solution.

The concentrated aqueous herbicidal composition usually contains 100-750 g/l, preferably 300-600 g/l in acid equivalent of glyphosate salts and 1-30 wt.%, preferably 2-10 wt.% ethoxylated amine ester.

The concentrated aqueous herbicidal composition according to the invention contains at least 10% by weight, preferably 20-40% by weight, of water. The concentrated aqueous herbicidal composition of the present invention can generally be prepared by mixing the ethoxylated ester amine and optionally the other ingredients listed above and then mixing them with glyphosate salt solutions and water, in a suitable mixing vessel equipped with a stirrer, such as mixer. Preferably, the concentrated aqueous herbicidal composition has a Brookfield® viscosity at 25° C. of less than 1500 mPa.s and in particular less than 300 mPa.s.

A diluted herbicidal composition according to the present invention is prepared by diluting a concentrated composition with water, and this is an aqueous herbicidal composition, preferably a solution, possibly ready for spray application, which comprises 0.01%-3 wt.% a.e. glyphosate, an ethoxylated ester amine adjuvant, and optionally other ingredients listed above such as other active ingredients, fertilizers, microfertilizers, surfactants and/or other additives commonly used in agricultural compositions.

The present invention also provides a method of killing or controlling weed growth by applying to fields an aqueous herbicidal composition containing glyphosate and an adjuvant according to the present invention in a diluted form, typically containing 0.01-3 wt.% glyphosate (a.e.), and in an amount sufficient to kill or control the growth of weeds. The herbicidal compositions of the present invention are usually applied in diluted form as foliar non-selective herbicides or in combination with a post-emergence herbicide.

The method according to the invention is used to control and/or prevent the growth of unwanted plants in cereals or useful plants. The method of the present invention is also suitable for controlling and/or preventing the growth of undesirable plants in locations physically distant from crop areas, such as in non-crop areas, along unplanted roadsides, or under power lines.

Another object of this invention is represented by diluted sprayable herbicidal compositions (tank mixes) containing 0.01-10 wt.%, preferably 0.01-5 wt.%, at least one herbicide, and 0.001-5 wt.%, preferably 0.01-3% by weight of an ethoxylated amine ester of formula (I). Said diluted sprayable herbicidal compositions are prepared by adding an ethoxylated amine ester of formula (I) to water or other suitable vehicle, either before or after the formulated herbicide. Alternatively, the formulated herbicide and/or the ethoxylated ester amine of formula (I) may be pre-diluted and then mixed.

Said sprayable herbicidal tank mixes contain herbicidal active compounds such as, Acetochlor, Acibenzolar, Acibenzolar-S-methyl, Acifluorfen, Acifluorfen-sodium, Aclonifen, Alachlor, Allidochlor, Alloxydinn, Alloxydinn-sodium, Ametrin, Amicarbazone, Amidochlor, Amidosulfuron, Aminocyclopyrachlor , Aminopyralid, Amitrol, Ammonium Sulfamate, Ancimidol, Anilofos, Asulam, Atrazine, Azafenidine, Azimsulfuron, Aziprotrin, Beflubutamide, Benazolin, Benazolin-ethyl, Bencarbazone, Benfluralin, Benfuresat, Bensulide, Bensulfuron, Bensulfuron-methyl, Bentazone, Benzfendizon, Benzobicyclone, Benzofenap, Benzofluor, Benzoylprop, Bicyclopyrone, Bifenox, Bispyribac, Bispyribac-sodium, Bromacil, Bromobutide, Bromphenoxime, Bromoxynil, Bromuron, Buminaphos, Busoxinone, Butachlor, Butafenacyl, Butamiphos, Butenachlor, Butralin, Butroxidim, Butylate, Kafenstrol, Carbetamide, Carfentrazone, Carfentrazone-ethyl, Chlomethoxifen, Chloramben, Chlorazifop, Chlorazifop-butyl, Chlorbromuron, Chlorbufam, Chlorfenac, Chlorf Enac-sodium, Chlorfenprop, Chlorflurenol, Chlorflurenol-methyl, Chloridazon, Chlorimuron, Chlorimuron-ethyl, Chlormequat-chloride, Chlornitrofen, Chlorphthalim, Chlorthal-dimethyl, Chlortoluron, Chlorsulfuron, Cinidone, Cinidone-ethyl, Cinmethylin, Cinosulfuron, Cletodiium (C10) , Clodinafop, Clodinafop-propargyl, Clofencet, Clomazone, Clomeprop, Cloprop, Clopyralid (C1), Cloransulam, Cloransulam-methyl, Cumiluron, Cyanamide, Cyanazine, Cyclanilide, Cycloate, Cyclosulfamuron, Cycloxidim (C11), Cycluron, Cyhalofop, Cyhalofop-butyl , Cyperquat, Ciprazine, Ciprazol, 2,4-D (and its salts and esters such as 2,4-D-butotyl, 2,4-D-butyl, 2,4-D-dimethylammonium, 2,4- D-diolamine, 2,4-D-ethyl, 2,4-D-ethylhexyl, 2,4-D-isobutyl, 2,4-D-isoctyl, 2,4-D-isopropyl, 2,4-D- isopropylammonium, 2,4-D-sodium, 2,4-D-triisopropanolammonium, 2,4-D-trolamine), 2,4-DB, Dalapon, Daminozid, Dazomet, n-Decanol, Desmedifam, Desmetrin, Detosyl-Pyrazolate (DTP), Diallat, Dicamba (and its salts or esters such as Dicamba-butotyl, diglycolamine Dicamba salt, Dicamba-dimethylammonium, Dicamba-diolamine, Dicamba-isopropylammonium, Dicamba-potassium, Dicamba-sodium, Dicamba-trolamine), Dichlobenil, Dichlorprop, Dichlorprop-P, Diclofop, Diclofop-methyl, Diclofop-P-methyl, Diclozulam, Dietatil, Dietatyl-ethyl, Difenoxuron, Difenzocquat, Diflufenican, Diflufenzopyr, Diflufenzopyr-sodium, Dimefuron, Dikegulac-sodium, Dimefuron, Dimepiperate, Dimethachlor (C2), Dimethamethrin, Dimethenamid, Dimethenamid-P, Dimetipine, Dimetrasulfuron, Dinitramine, Dinoseb, Dinoterb , Diphenamide, Dipropetrin, Diquat, Diquat-dibromide, Dithiopyr, Diuron, DNOC, Eglinazine-ethyl, Endothal, EPTC, Esprocarb, Etalfluralin, Etametsulfuron, Etametsulfuron-methyl, Ethephon, Ethidimuron, Ethiosin, Ethofumesate, Ethoxyfen, Ethoxyphen-ethyl, Ethoxysulfuron , Etobenzanide, F-5331, i.e. N-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-4,5-dihydro-5-oxo-1H-tetrazol-1-yl]phenyl]ethanesulfonamide, F-7967, v. e. 3-[7-chloro-5-fluoro-2-(trifluoromethyl)-1H-benzimidazol-4-yl]-1-methyl-6-(trifluoromethyl)pyrimidine-2,4(1H,3H)-dione, Fenoprop, Fenoxaprop, Fenoxaprop-P, Fenoxaprop-ethyl, Fenoxaprop-P-ethyl (C3), Fenoxasulfone, Fentrazamide, Fenuron, Flamprop, Flamprop-M-isopropyl, Flamprop-M-methyl, Flazasulfuron, Florasulam, Fluazifop, Fluazifop-P, Fluazifop -butyl, Fluazifop-P-butyl, Fluazolate, Flucarbazone, Flucarbazone-sodium, Flucetosulfuron, Fluchloralin, Flufenacet (Thiafluamide), Flufenpir, Flufenpir-ethyl, Flumetraline, Flumetsulam, Flumyclorac, Flumyclorac-pentyl, Flumioxazine, Flumipropine, Fluometuron, Fluordifen, Fluorglycofen, Fluorglycofen-ethyl, Flupoxam, Flupropacil, Flupropanate, Flupyrsulfuron, Flupyrsulfuron-methyl-sodium, Flurenol, Flurenol-butyl, Fluridon, Flurochloridone, Fluroxypyr, Fluroxypyr-meptyl, Flurprimidol, Flurtamon, Flutiacet, Flutiacet-methyl, Fluthiamide, Fomesafen, Foramsulfuron, Forchlorfenuron, Fosamine, Furyloxifene, Glufosinate, Ammonium Glufosinate, Glyphosate, Diammonium Glyphosate, Gli Isopropylammonium Phosate, Potassium Glyphosate, H-9201, i.e. O-(2,4-dimethyl-6-nitrophenyl)-O-ethylisopropyl phosphoramidothioate, Halosafen, Halosulfuron, Halosulfuron-methyl, Haloxyfop, Haloxifop-p (C4), Haloxifop-ethoxyethyl, Haloxifop-P-ethoxyethyl, Haloxifop-methyl, Haloxyfop-P-methyl, Hexazinon, HW-02 i.e. 1-(Dimethoxyphosphoryl)ethyl(2,4-dichlorophenoxy)acetate, Imazametabenz, Imazametabenz-methyl, Imazamox (C9), Imazamox-ammonium, Imazapik, Imazapir, Imazapyr-isopropylammonium, Imazaquin, Imazaquin-ammonium, Imazethapyr, Imazethapyr-ammonium, Imazosulfuron, Inabenfid, Indanophane, Indaziflam, Indoleacetic acid (IAA), 4-indol-3-ylbutyrrhic acid (IBA), Iodsulfuron, Iodsulfuron-methyl-sodium, Ioxynil, Ipfencarbazone, Isocarbamide, Isopropaline, Isoproturon, Isouron, Isoxaben, Isoxachlorothol, Isoxaflutol, Isoxapirifop, KUH-043, i.e. 3-({[5-(difluoromethyl)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfonyl)-5,5-dimethyl-4,5-dihydro-1,2- oxazol, Carbutylate, Ketospiradox, Lactofen, Lenacil, Linuron, MCPA, MCPB, MCPB-methyl, -ethyl and -sodium, Mecoprop, Mecoprop-sodium, Mecoprop-butotyl, Mecoprop-P-butyl, Mecoprop-P-dimethylammonium, Mecoprop- P-2-Ethylhexyl, Mecoprop-P-potassium, Mefenacet, Mefluidide, Mepiquat Chloride, Mesosulfuron, Mesosulfuron-methyl, Mesosulfuron-methyl-Na, Mesotrione, Metabenzthiazuron, Metam, Metamifop, Metamitron, Metazachlor (C5), Metazasulfuron, Metazol , Methiopyrsulfuron, Metiozolin, Methoxyphenone, Methyldymron, 1-Methylcyclopropene, Methylisocyanate, Metobenzuron, Metobromuron, Metolachlor, S-Metolachlor, Metosulam, Methoxuron, Metribuzin, Metsulfuron, Metsulfuron-methyl, Molinate, Monalide, Monocarbamide, Monocarbamide dihydrosulfate, Monolinuron, Monosulfuron , Monosulfuron-ester, Monuron, MT-128, i.e. 6-chloro-N-[(2E)-3-chloroprop-2-en-1-yl]-5-methyl-N-phenylpyridazin-3-amine, MT-5950, i.e. N-[3-chloro-4-(1-methylethyl)phenyl]-2-methylpentanamide, NGGC-011, Naproanilide, Napropamide (C6), Naptalam, NC-310, i.e. 4-(2,4-dichlorobenzoyl)-1-methyl-5-benzyloxypyrazole, Neburon, Nicosulfuron, Nipyraclofen, Nitralin, Nitrofen, Sodium Nitrophenolate (mixture of isomers), Nitrofluorfen, Nonansur, Norflurazon, Orbencarb, Orthosulfamuron, Orizalin, Oxadiargyl, Oxadiazon, Oxasulfuron, Oxaziclomefon, Oxyfluorfen, Paclobutrazol, Paraquat, Paraquat dichloride, Pendimethalin, Pendralin, Penoxsulam, Pentanochlor, Pentoxazon, Perfluidone, Petoxamide, Phenizofam, Phenmedifam, Phenmedifam-ethyl, Picloram, Picolinafen, Pinoxaden, Piperophos, Pyrifenop, Pyrifenop- butyl, Pretilachlor, Primisulfuron, Primisulfuron-methyl, Probenazole, Profluazole, Procyazine, Prodiamine, Prifluralin, Profoxidim, Prohexadione, Prohexadione-calcium, Prohydroyasmon, Prometon, Prometrin, Propachlor, Propanil, Propaquizafop, Propazine, Profam, Propizochlor, Propoxycarbazone, Propoxycarbazone- Sodium, Propyrisulfuron, Propizamide, Prosulfaline, Prosulfocarb, Prosulfuron, Prinachlor, Pyraclonil, Piraflufen, Piraflufen-ethyl, Pirasulfotol, Pyrazolinate (Pi razolate), Pyrazosulfuron, Pyrazosulfuron-ethyl, Pyrazoxifen, Pyribambenz, Pyribambenz-isopropyl, Pyribambenz-propyl, Pyribenzoxime, Pyributicarb, Pyridafol, Pyridate (C7), Pyrifthalide, Pyriminobac, Pyriminobac-methyl, Pyrimisulfan, Pyritiobac, Pyritiobac-sodium, Pyroxasulfone, Piroxsulam, Quinclorac, Quinmerac, Quinoclamin, Quizalofop, Quizalofop-ethyl, Quizalofop-R, Quizalofop-R-ethyl, Quizalofop-R-tefuryl, Rimsulfuron, Saflufenacil, Secbumeton, Setoxydim, Siduron, Simazine, Simetrin, SN-106279, v. e. methyl-(2R)-2-({7-[2-chloro-4-(trifluoromethyl)phenoxy]-2-naphthyl}oxy)propanoate, Sulcotrione, Sulfallate (CDEC), Sulfentrazone, Sulfonneturon, Sulfonneturon-methyl, Sulfosate ( Glyphosate trimesium), Sulfosulfuron, SYN-523, SYP-249, i.e. 1-ethoxy-3-methyl-1-oxobut-3-en-2-yl-5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate, SYP-300, i. e. 1-[7-fluoro-3-oxo-4-(prop-2-yn-1-yl)-3,4-dihydro-2H-1,4-benzoxazin-6-yl]-3-propyl-2- thioxoimidazolidin-4,5-dione, Tebutam, Tebuthiuron, Teknazen, Tefuryltrione, Tembotrione, Tepraloxidim, Terbacil, Terbucarb, Terbuchlor, Terbumeton, Terbutylazine, Terbutrin, Tenylchlor, Thiaffluamide, Thiazofluron, Thiazopyr, Thidiazimin, Thidiazuron, Thiencarbazone, Thiencarbazone-methyl, Tifensulfuron, Tifensulfuron-methyl, Thiobencarb, Thiocarbazil, Topramesone, Tralkoxydim, Triallate, Triasulfuron, Triaziflam, Triazofenamide, Tribenuron, Tribenuron-methyl, Trichloroacetic acid (TCA), Triclopyr, Tridifan, Trietazine, Trifloxysulfuron, Trifloxysulfuron sodium, Trifluralin (C8) , Triflusulfuron, Triflusulfuron-methyl, Trimeturon, Trinexapak, Trinexapak-ethyl, Tritosulfuron, Cytodef, Uniconazole, Uniconazole-P, Vernolate, ZJ-0862, i.e. 3,4-dichloro-N-{2-[(4,6-dimethoxypyrimidin-2-yl)oxy]benzyl}aniline, salts thereof and mixtures thereof.

Preferred herbicidal active compounds are Glyphosate, 2,4-D, Dicamba, Cletodym, Metribuzin or derivatives thereof.

Other biologically active ingredients such as other pesticides, plant growth regulators, algicides, fungicides, bactericides, viricides, insecticides, acaricides, nematicides can be added as partners in herbicide spray tank mixes.

The diluted sprayable herbicidal compositions (tank mixes) of the present invention may further comprise at least one oil selected from: vegetable oil, modified vegetable oil, seed oil, modified soybean oil (e.g., methylated soybean oil), modified palm oil, modified rapeseed oil, vegetable oil concentrate, petroleum hydrocarbons, mineral oil, paraffin oil, naphthenic oil, aromatic oil, emulsified petroleum distillates, unsaturated fatty acids, paraffin oil, tall oil. Modified oils may include oils that are, for example, methylated, ethylated, propylized, or bottled.

The diluted sprayable herbicidal compositions (tank mixes) of this invention may further comprise other conventional additives, including thickeners, flow enhancers, wetting agents, buffers, lubricants, fillers, drift control agents, settling enhancers, evaporation retarders, anti freezing agents, insect-attracting fragrances, UV protection agents, fragrances, defoamers, and the like.

The following examples illustrate the preparation of an ethoxylated ester amine in accordance with the present invention. They also serve to illustrate the comparable bioefficacy and lower ecotoxicity of the herbicidal compositions of the present invention compared to those containing a commonly known adjuvant such as thalamine ethoxylate.

EXAMPLES

Example 1 - Preparation of amine ester 1

a) Preparation of tall oil fatty acid ester with triethanolamine

Tall oil fatty acids (1650 g; resin acid content: 2 wt%) and triethanolamine (840 g) are added to a reaction vessel equipped with a heater, stirrer, thermometer, reagent introduction system, connected to a cooler equipped with a water manifold. The reaction mixture is slowly heated to 180° C. with stirring and under a stream of nitrogen. The reaction mixture is kept at 180-185°C until the acid number reaches a value below 5 mg KOH/g.

b) Ethoxylation

To a stirred stainless steel reactor equipped for temperature measurement and control, pressure measurement, vacuum and inert gas purge, sampling, and for introducing ethylene oxide as a liquid, add the ester obtained in step a) (965 g) at 60° C. The reactor is heated to 115°C and kept under vacuum and nitrogen flow for 1 hour, then cooled to 80°C. Add potassium hydroxide (35 wt.%) in aqueous solution (8 g), the contents of the reactor are heated to 130°C and maintained in vacuum and a stream of nitrogen for 45 minutes to reduce the moisture content to less than 0.1%. The reactor is pressurized with nitrogen up to 110-140 kPa and heated to 150°C. Ethylene oxide (2001 g) is then added while maintaining the temperature at 150-160°C. The reaction mixture is kept for 30 minutes at the reaction temperature, then it is cooled to 80°C and acetic acid (80 wt.%) in an aqueous solution (4 g) is added.

Example 2 - Preparation of an amine ester 2

a) Preparation of ethoxylated triethanolamine

To a stirred stainless steel reactor equipped for temperature measurement and control, pressure measurement, vacuum and inert gas purge, sampling, and injection of ethylene oxide as a liquid, add triethanolamine (860 g) and sodium methoxide (30 wt.%) in methanol solution (20 g). The reactor is pressurized, then vented three times to remove atmospheric oxygen. The reactor is heated to 90°C and kept under vacuum and nitrogen flow for 30 minutes. In the reactor create a nitrogen pressure of 110-140 kPa and heated to 125°C. Ethylene oxide (4904 g) is then added while maintaining the temperature at 125-130°C. The reaction mixture is kept for 30 minutes at the reaction temperature, then it is cooled to 80°C and acetic acid (80 wt.%) in an aqueous solution (4 g) is added.

b) Preparation of tall oil fatty acid ester with ethoxylated triethanolamine

To a reaction vessel equipped with a heater, stirrer, thermometer, reagent introduction system, connected to a cooler equipped with a water manifold, ethoxylated triethanolamine (1754 g) and tall oil fatty acids (965 g; resin acid content: 2 wt.%) are added. At a temperature of about 60°C, p-toluenesulfonic acid monohydrate (5.6 g) and hypophosphoric acid (50 wt.%) in aqueous solution (1.1 g) are added with stirring. The reaction mixture is slowly heated to 195° C. with stirring and under a stream of nitrogen. The reaction mixture is kept at 195-200° C. until the acid number reaches a value below 15 mg KOH/g. When the acid number is reached, at a temperature of 195-200°C, a vacuum (70±5 mm Hg) is applied and the reaction mixture is kept under these conditions until the acid number is below 10 mg KOH/g.

Example 3-5 - Preparation of concentrated aqueous herbicidal compositions of isopropylamine salt of glyphosate (Glyphosate IPA)

The compositions of Examples 3-5 are prepared by mixing at room temperature an aqueous concentrate of glyphosate IPA (62 wt%) with the appropriate amount of an ethoxylated ester amine and water as shown in Table 1. The characteristics of aqueous concentrated glyphosate compositions are presented in Table 2.

Table 1

Examples Component (wt%) 3 four 5 Amine ester 1 2.55 Amine ester 2 2.55 7.16 Glyphosate IPA (62%) 67.00 67.00 67.00 Water 30.45 30.45 25.84

table 2

Examples 3 four 5 Glyphosate content (a.e.) 360 g/l 360 g/l 360 g/l Density 1.17 g/ml 1.17 g/ml 1.17 g/ml Appearance clear liquid clear liquid clear liquid Stability testing (7 days at 4°C) stable stable stable Stability testing (14 days at 54°C) stable stable stable pH 4.7 4.7 4.7

Bioefficacy Testing (Greenhouse Testing)

The compositions of Examples 3-5 are diluted and tested for bioefficacy in greenhouse trials on the following weeds: common barnyard grass (Echinochloa crus-galli) , Theophrasto's ropeweed (Abutilon theophrasti) and white gooseberry (Chenopodium album) . Greenhouse testing is carried out in comparison with comparative glyphosate compositions obtained by diluting similar concentrated glyphosate compositions containing 2.5 wt.% (TAE 1) or 7.0 wt.% (TAE 2) talamine ethoxylated with 20 moles of ethylene oxide.

The diluted compositions are tested under the following conditions:

- on a regular barnyard for 3, 7 and 10 days of treatment (respectively, 3 DAT, 7 DAT and 10 DAT) with 0.75 ft. glyphosate (a.e.)/acre (a);

- on the Theophrastus cable car for 7, 11 and 14 days of treatment (respectively, 7 DAT, 11 DAT and 14 DAT) from 1 ft. glyphosate (a.e.)/acre (a);

- on mari white within 5 and 9 days of treatment (respectively, 5 DAT and 9 DAT) from 0.313 ft. glyphosate (a.e.)/acre (a).

Spray volume is 15 gal/a applied through 8002 flat spray nozzles 4 times. The test results are shown as “% control”, meaning 0% as no control and 100% as complete weed control, and are shown in the following tables (Tables 3-5).

Table 3

Composition % control for common barnyard 3 DAT (%) 7 DAT (%) 10 DAT (%) Example 3 58.0 77.8 84.5 Example 4 57.5 78.8 85.8 TAE 1* 56.3 80.8 87.0 Example 5 60.8 85.0 86.3 TAE 2* 60.0 84.8 91.0

*Comparative

Table 4

Composition % control of Theophrastus rope 7 DAT (%) 11 DAT (%) 14 DAT (%) Example 3 81.0 95.0 98.0 Example 4 83.8 97.3 97.0 TAE 1* 84.0 97.3 99.0 Example 5 87.8 97.0 99.0 TAE 2* 81.8 94.8 97.8

*Comparative

Table 5

Composition % control for marya white 5 DAT (%) 9 DAT (%) Example 3 69.0 86.0 Example 4 69.0 86.5 TAE 1* 69.0 82.7 Example 5 71.7 94.5 TAE 2* 75.9 91.3

*Comparative

Tests show that the adjuvants according to the invention show substantially the same efficacy as compared to a known adjuvant such as thalamine ethoxylate.

Ecotoxicological tests

The adjuvants according to the invention have a better ecotoxicological profile compared to thalamine ethoxylated with 20 moles of ethylene oxide (ETA), showing relatively low activity against various algae as measured in tests carried out according to standard method ISO 10253:2006 (Water Quality - Test inhibition of algae growth with Skeletonema costatum and Phaeodactylum tricornutum ).

The results of ecotoxicological tests are presented in Table 6.

Table 6

Adjuvant EU _fifty EU _90-100 Amine ester 1 >1.00 mg/l >1.00 mg/l Amine ester 2 >1.00 mg/l >1.00 mg/l THIS 0.19 mg/l 0.37 mg/l

EC ₅₀ = effective concentration that inhibits the growth of 50% of algae.

EC _90-100 = effective concentration that inhibits the growth of 90-100% of algae.

Examples 6-14 Emulsion Stability Test

The suitability of the ethoxylated amine esters of the present invention for use in diluted spray herbicide compositions (tank mixes) is assessed by conducting an emulsion stability test.

This test is carried out according to the standard method CIPAC MT 36.

The tested products are mixed with methylated soybean oil (MSM) and then diluted with water to a dilution ratio of 1%.

Emulsions are considered stable if there is no phase separation or a slight amount of cream at the top of the emulsion. The results of the emulsion stability test are shown in Table 7a-b.

In the emulsion stability test, the amine ester 2 shows greater efficacy than commercially available emulsifiers or mixtures thereof and comparable efficacy to thalamine ethoxylate.

Table 7a

Examples Component (wt%) 6* 7* eight* 9 ten* MSM 85 85 85 85 80 Emulsion AG/18C ¹ fifteen twenty Rolfor TR8 L ² fifteen Ethoxylated (40 EO) castor oil TAE-20 ³ fifteen Amine ester 2 fifteen Appearance of the emulsion after 2 hours Separation stable stable stable Separation Appearance of the emulsion after 24 hours Separation Separation stable stable Separation

1 - Emulsion AG/18C=ethoxylated castor oil condensed with olein (Lamberti)

2 - Rolfor TR8 L=branched fatty alcohol ethoxylate (Lamberti)

3 - Tatal amine ethoxylate (with 20 moles of ethylene oxide)

* Comparative

Table 7b

Examples Component (wt%) eleven* 12* 13* fourteen MSM 80 80 80 80 Emulsion AG/18C ¹ ten ten ten ten Rolfor TR8 L ² ten Ethoxylated (40 EO) castor oil ten TAE-20 ³ ten Amine ester 2 ten Appearance of the emulsion after 2 hours stable stable stable stable Appearance of the emulsion after 24 hours Separation Separation stable stable

1 - Emulsion AG/18C=ethoxylated castor oil condensed with olein (Lamberti)

2 - Rolfor TR8 L=branched fatty alcohol ethoxylate (Lamberti)

3 - Tatal amine ethoxylate (with 20 moles of ethylene oxide)

* Comparative.

Claims (29)

1. An aqueous herbicidal composition containing from 100 to 750 g/l (in the form of acid equivalents) of glyphosate or its agriculturally acceptable salt and from 1 to 30 wt.% ethoxylated ester amine, where the specified ethoxylated ester amine has the formula (I) :

(I) where: a) R, R' and R'' are each independently an alkylene group having 1-8 carbon atoms, b) X, Y and Z are selected from H, O-(CH ₂ CH ₂ O) _n H, O-(CH ₂ CH ₂ O) _n -COR''' or O-COR''', and one of X , Y and Z is O-(CH ₂ CH ₂ O) _n -COR''' or O-COR''', where n=1-40, and R''' is a saturated or unsaturated C ₆ -C ₃₀ alkyl group; provided that: i) if one of X, Y or Z is O-(CH ₂ CH ₂ O) _n -COR''', each of the other two substituents is independently H or O-(CH ₂ CH ₂ O) _n H ii) if one of X, Y or Z is O-COR''', the other two substituents are H or O-(CH ₂ CH ₂ O) _n H and at least one of them is O-(CH ₂ CH ₂ O) _n H, wherein said ethoxylated ester amine of formula (I) is the reaction product of a saturated or unsaturated C6-C30 aliphatic monocarboxylic acid and a tertiary hydroxylamine, wherein the ethoxylation is carried out directly on the tertiary hydroxylamine prior to esterification or on the product of the esterification reaction. 2. An aqueous herbicidal composition according to claim 1, wherein the ethoxylated ester amine has the formula (I):

(I) where: a) R, R' and R'' are each independently an alkylene group having 2 carbon atoms, b) X, Y and Z are selected from O-(CH ₂ CH ₂ O) _n H, O-(CH ₂ CH ₂ O) _n -COR''' or O-COR''', and one from X, Y and Z is O-(CH ₂ CH ₂ O) _n -COR''' or O-COR''', where n=3-20, and R''' is a saturated or unsaturated C ₁₆ -C ₂₂ alkyl group; provided that: i) if one of X, Y or Z is O-(CH ₂ CH ₂ O) _n -COR''', both other substituents are O-(CH ₂ CH ₂ O) _n H ii) if one of X, Y or Z is O-COR''', both other substituents are O-(CH ₂ CH ₂ O) _n H. 3. An aqueous herbicidal composition according to claim 1, wherein said aqueous herbicidal composition contains 300 to 600 g/L (as acid equivalents) of glyphosate or an agriculturally acceptable salt thereof and 2 to 10% by weight of an ethoxylated amine ester of formula (I ). 4. An aqueous herbicidal composition according to claim 1, wherein in formula (I), R''' is a saturated or unsaturated alkyl group derived from tall oil. 5. Aqueous herbicidal composition according to claim 1, containing at least 10 wt.% water. 6. Aqueous herbicidal composition according to claim 5, containing from 20 to 40 wt.% water. 7. The aqueous herbicidal composition of claim 1, wherein the glyphosate, or an agriculturally acceptable salt thereof, is glyphosate isopropylamine salt or glyphosate potassium salt. 8. Aqueous herbicidal composition according to claim 1, additionally containing a water-soluble organic solvent. 9. The aqueous herbicidal composition of claim 1 further comprising one or more additives selected from defoamers, antifreezes, colorants, stabilizers, buffers, thickeners, flow enhancers, wetting agents, lubricants, fillers, drift control agents, sedimentation enhancers, evaporation retarders . 10. A method of weed control which comprises applying to fields a diluted aqueous herbicidal composition containing 0.01 to 3 wt % glyphosate (a.e.) or an agriculturally acceptable salt thereof and an ethoxylated ester amine of formula (I) as listed in paragraph 1, as an adjuvant, in an amount sufficient to kill weeds. 11. A method of controlling weed growth, which includes applying to the fields a diluted aqueous herbicidal composition containing from 0.01 to 3 wt.% glyphosate (a.e.) or its agriculturally acceptable salt and an ethoxylated amine ester of formula (I), as it is listed in point 1 as an adjuvant in an amount sufficient to control the growth of weeds. 12. A diluted sprayable herbicidal composition containing from 0.01 to 10% by weight of at least glyphosate and from 0.001 to 5% by weight of an ethoxylated amine ester of formula (I) as defined in claim 1.