HUT54273A - Concentrated liquid herbicidal compositions comprising n-phosphonomethylglycine - Google Patents

Abstract

Liquid suspensions in an organic or aqueous organic solvent medium, contain: a) herbicidal N-phosphonomethylglycine and/or one of its derivatives having an inherent solubility in water of more than 5 g/l, this N-phosphonomethylglycine and/or its derivative being present in the compositions in a proportion of at least 100 g/l glyphosate equivalent, at least part of this N-phosphonomethylglycine or its derivatives being in a form insoluble in the medium under consideration, and b) a surfactant having an activator character and having the formula <IMAGE> in which R is a straight-chain or branched alkyl or alkenyl hydrocarbon chain (8 to 22 carbon atoms), A represents an alkylene group, n + n' is between 2 and 40 and preferably between 20 and 25. R<1> is H or acyl.

Description

The present invention relates to a new concentrated composition comprising N-phosphonomethylglycine and compounds containing N-phosphonomethylglycyl.

N-phosphonomethylglycine (commonly known as glyphosate) and its analogs, as well as their herbicidal properties and compositions containing them, are described, inter alia, in U.S. Patent No. 3,799,758. Many water-soluble and water-insoluble derivatives of glyphosate are known, but the use of water-soluble derivatives is generally preferred and, therefore, N-phosphonomethylglycine salts, including the isopropylamine salt, have generally been developed and marketed.

Recently, an N-phosphonomethylglycine salt-based concentrate has been developed (European Patent Application No. 290,416), which may also contain N-phosphonomethylglycine in acid form, but in any case contains soluble or soluble N-phosphono methylglycine and / or its derivatives and a special type of alkoxylated amine activator. This alkoxylated amine must contain at least 12 alkbxicsbpbrt per molecule, be surfactant and promote the herbicidal activity of the N-phosphonomethylglycine derivatives.

The amount of alkoxylated amine is at least less than that of the surfactants used in the known N-phosphonomethylglycine formulations in concentrates suitable for the preparation of field sprays which are sprayed at a dose of 100 to 600 l / ha.

A composition comprising a substantially water-insoluble N-phosphonomethylglycine tetraaluminium salt and a special type of surfactant is disclosed in U.S. Patent 4,528,023. One consequence of the insolubility of the active ingredient is that, if the concentrate is diluted as required for spraying, the resulting spraying agent will not be a perfect solution, adversely affecting both applicability and efficacy. Those skilled in the art have not attempted to use the formulations described in the above patent for higher solubility agents, since experience has shown that the preparation of concentrated suspensions from partially soluble active agents is very difficult due to the tendency of the concentrated suspensions to solidify. One explanation for this is that continuous (aqueous) suspensions tend to crystallize, and that crystal growth can be quite extreme, that is, until it solidifies.

It is an object of the present invention to provide formulations containing N-phosphonomethylglycine or derivatives thereof which have a much higher active ingredient content than similar formulations known hitherto.

It was another object of the present invention to provide formulations containing N-phosphonomethylglycine or derivatives thereof which contain much greater amounts of active ingredients, such as inorganic ammonium salts, than prior art formulations.

It was another object of the present invention to provide concentrates containing N-phosphonomethylglycine or derivatives thereof which can be well diluted into suitable herbicidal compositions.

• ·

It has also been an object of the present invention to provide concentrates containing N-phosphonomethylglycine or derivatives thereof which also contain one or more activator surfactants, i.e., agents that enhance the biological, particularly herbicidal, action of the active ingredient.

It was also an object of the present invention to provide concentrates containing N-phosphonomethylglycine or derivatives thereof which disperse well and rapidly in water.

It was a further object of the present invention to provide concentrated formulations containing N-phosphonomethylglycine or derivatives thereof which perform well at low temperatures.

It was also an object of the present invention to provide concentrated formulations containing N-phosphonomethylglycine or derivatives thereof which have a low tendency to foaming and therefore require only a small amount of antifoaming agent.

It was a further object of the present invention to provide concentrated agents or compositions (also called concentrates) containing N-phosphonomethylglycine, in particular poorly water-soluble N-phosphonomethylglycine.

It was also an object of the present invention to provide concentrated formulations based on N-phosphodi-methylglycine containing one or more other herbicides.

The compositions of the present invention fulfill all or part of the above objectives. In the following, unless otherwise indicated, the% symbol is% w / v.

In the following description, the glyphosate equivalent term is the total N-phosphonomethylglycine in the composition.

5-derivative represents the equivalent of N-phosphonomethylglycine.

The compositions of the present invention are liquid compositions comprising the following ingredients in a suspension in an organic or suitable aqueous-organic solvent medium (concentrated):

a) N-phosphonomethylglycine and / or a derivative thereof having a water solubility higher than 5 g / l, preferably 9 g / l, and N-phosphonomethylglycine and / or its derivative at least 100 g / l equivalent of glyphosate is present in the composition, at least part of the N-phosphonomethylglycine or derivative thereof is insoluble in the medium (insolubility is due to the presence of N-phosphonomethylglycine or its derivatives medium solubility);

b) an activator surfactant of the formula I in the formula

R is a straight or branched alkyl or alkenyl group containing from 8 to 22 carbon atoms;

A is alkylene, preferably ethylene or propylene;

n and n 'are integers such that the sum of n + n' is between 2 and 40, preferably between 16 and 30, more preferably between 25 and 25; and r! represents a hydrogen atom or an acyl group such as formyl, acetyl, propionyl (i.e., CH3-CH2 -CO) or benzoyl.

The term N-phosphonomethylglycine refers to a compound containing a -CO-CH 2 -N-Ch 3 -P 4 group, preferably a salt, ester or amide. The term is understood in such a broad sense as to include, for example, these compounds ·· ··

- 6 also sulfonamides.

Of course, a single activator-acting surfactant may also be substituted by a mixture of surfactants which are also of formula (I) wherein R, n and n 'are as defined above.

According to the above, the herbicidal active ingredient of the composition according to the invention is N-phosphonomethylglycine or a derivative thereof which is soluble in water in an amount greater than 5 g / l, preferably 9 g / l. The preparation may contain a variety of derivatives of N-phosphonomethylglycine, in particular salts, either alone or in admixture. The most suitable derivatives are the sodium, potassium, or organic or inorganic ammonium salts, in particular the isopropylammonium salts, and the sulfonium salts; N-methyl-N- (methylsulfonyl) -N0, N * -phosphonomethylglycylamine; but aluminum salts are not within the scope of the present invention. When using these products, of course, the volume and solubility conditions stated elsewhere must be taken into account.

The present invention preferably relates to concentrated formulations as described above which have one or more of the following properties.

a) the N-phosphonomethylglycine or derivative thereof is present in an amount, preferably in the range of 120 to 250 g / l, more preferably 160 to 220 g / l, which is greater than its solubility in the medium; and the amount of undissolved N-phosphonomethylglycine derivative is greater than 30%, preferably greater than 75%;

b) the insoluble N-phosphonomethylglycine or derivative thereof is present in the form of solid particles having a particle size of less than 1 µm, preferably 1-20 µm;

c) the concentrated composition contains from 100 to 500 g / l, preferably from 200 to 350 g / l, of an ammonium salt (NH ⁴⁺ ) such as nitrate, phosphate, sulfate, thiocyanate or preferably sulfate;

(d) dilution of the concentrated preparation at the point of application by agricultural professionals in a tank containing water;

the dilution is such that the application rate of the diluted spray is 100-600 l / ha and the application rate is 0.125-1.5 kg / ha;

e) the weight ratio of glyphosate to equivalent surfactant (activator) is 0.5 to 6, preferably 0.6 to 2; it is noted that this relatively high amount of surfactant applies only to the biologically active herbicidal surfactants and not to the other components of the formulations which will be described later, in particular surfactants having a very different wetting, dispersing or emulsifying properties; their amount used is much less than that of the activator;

f) as a solvent, the composition comprises an organic solvent which is preferably miscible with water, containing up to 50%, preferably less than 30% water, and the solvent is only slightly soluble in N-phosphonomethylglycine, meaning that its solubility is lower such as 80 g / l, preferably 40 g / l.

The concentrated suspensions of the present invention are formulated to give non-settling stable liquids (fine grinding).

The compositions of the present invention are generally 10 to 75% active ingredient (herbicide), 0.5 to 40% activator surfactant, 10 to 50% ammonium salt (active ingredient), 0.1 to 10% common surfactant which is a dispersant and / or a moisturizing and / or emulsifying agent, and 0 to 30% of a suitable additive such as antifoam, corrosion inhibitor, protective colloid, thickener, sequestering agent, thixotropic or pseudoplastic material, stabilizer, penetration enhancer and adhesive, they contain an organic liquid in which the active ingredient is poorly soluble or insoluble.

Also, any solid organic matter or inorganic salt may be dissolved or suspended in the carrier material to prevent sedimentation or gelling. The active ingredient of the composition of the present invention may be combined (mixed) with any solid or liquid excipient commonly used in the formulation process.

The composition of the invention may also contain other herbicides or plant growth regulators.

Examples of herbicides that can be combined with glyphosate derivatives in the compositions of the present invention include acifluorfen, aclonifen, bifenox, diflufenican, azulem, triazines (particularly simazine and atrazine) diuron and oxadiazone, hormone or phenoxytype herbicides, 2,4-DB, MCPP, hydroxybenzonitriles (primarily bromoxynil and ioxynil), imidazolinones (primarily imazaquin and imazapur) · · · · · · · · · · · · · · And sulfonite ureas (primarily chlorosulfuron and methsulfuron). The names described above are standardized terms used to denote herbicides.

These herbicides are generally used in an amount of from 1 to 400 parts by weight, based on 100 parts by weight of glyphosate or glyphosate. By using glyphosate equivalents, all glyphosate derivatives are simply considered as present in the form of N-phosphonomethylglycine when calculating fractions.

More particularly, when other herbicides other than glyphosate are used in admixture with glyphosate, the following weight ratios will generally be used:

glyphosate or glyphosate equivalent

Weight ratio (i.e.) = ____________________________________ other herbicides

glyphosate + acifluorfen glyphosate + diuron or 4 100 T. Z 9 100 oxadiazor 1; 2 THE T. THE 4 glyphosate + acionifen: 1 y 2 ^ T. Δ- 10 glyphosate + bifenox: 1 3 THE t. the THE 1 glyphosate + diflufenican: 2 Δ- T. Z_ 20 glyphosate + barban 1 4 Α. T. Z 1 glyphosate + phenoxy 2 3 Λ- T. Z. 4 glyphosate + hydroxy-benz nitrile: 1 Α T. 10

glyphosate + triazine: 1 3 z. t. the. Z. 1 glyphosate + imidazolinone: 1 Z_ t. the. Z. 4 glyphosate + sulfone -urea: 100 6 THE. t. the. 100

Concentrated suspensions of the present invention, as mentioned above, contain a solvent (also known as a carrier). Solvent is an organic or inorganic substance of natural or synthetic origin which, in combination with the active ingredient or compounds, facilitates its application to the plant or soil. The solvent should therefore be acceptable in agriculture or in agriculture, especially in the treated crop. The composition of the present invention is an organic liquid such as esters, in particular methyl glycol acetate, which satisfies the above requirements as a solvent; ketones, especially cyclohexanone and isophorone, petroleum fractions; aromatic hydrocarbons, in particular xylenes or paraffinic hydrocarbons; chlorinated, aliphatic or aromatic hydrocarbons, in particular chlorobenzenes; glycols, low molecular weight liquid oligoglycols or polyglycols or optionally esterified vegetable oils.

The concentrated compositions of the present invention, as described above, may contain one or more other surfactants in addition to the activator surfactants also described above. Such surfactants include ionic or nonionic emulsifiers, dispersants or wetting agents, or mixtures thereof, such as polyacrylic acid salts, lignosulfonic acid salts, phenolic sulfonic acid or naphthalenesulfonic acid salts, polycondensed products of phenols with alkylene or fatty acids, ), sulfonic succinic acid salts, taurine derivatives (in particular alkyl taurates), alcohol phosphoric acid esters, polycondensation products of ethylene oxide and phenol, esters of fatty acids and polyols, and derivatives of the compounds listed above such as sulfate, sulfonate and fumarate.

The following examples illustrate the compositions of the present invention, in particular concentrated suspensions, and their application.

Example 1

A concentrated preparation of the following ingredients was prepared:

- N-phosphonomethylglycine (acid): 200 g / L - Ammonium sulphate (adjuvant): 200 g / L - surfactant (activator) described below: 200 g / L - dispersant / wetting agent, polycondensation product of ethylene phosphate: 20 g / L ammonium dodecyl benzene sulfonate: 10 g / L - Organic polysiloxane oil (antifoaming agents): 2 g / L bentonite (thixotropic substance): 2 g / L - Polyvinyl alcohol (protective colloid): 8 g / L - solvent: propylene glycol: 300 g / L water 250 g / L

The surfactant used is the compound of formula (1).

The mixture containing the components was ground in a ball mill. Grinding was carried out to obtain a concentrated microsuspension of 73¾ N-phosphonomethylglycine containing 5-20 µm particles. A fraction of the concentrated suspension thus obtained was centrifuged and, after analysis of the liquid phase, the liquid phase contained 27 g / l of N-phosphonomethylglycine:

Concentrated preparation

(a) for one month at 50 ° C, and

(b) one month, including eight equal periods,

It was kept 4 times at 35 ° C and 4 times at -10 ° C, whereby the preparation retained its original physico-chemical properties.

The preparation prepared above was then diluted with 100 liters of water per liter of concentrate. This resulted in an immediate dilution and homogeneous spray of 250 l / ha on the following weeds: Portulaca oleraceae, Centauria cyanus, Sinapis arvensis, Panicum trichoides and Abutilon theophrasti. At the application rate of 500 g / ha, the above weeds showed 95%, 100%, 98%, 100% and 100% mortality respectively.

Example 2

A concentrated preparation of the following ingredients was prepared:

- N-phosphonomethylglycine (acid) 200 g / l

- Ammonium sulphate (additive) 200 g / l surfactant, activator, identical

as in Example 1: 200 g / l

dispersant / wetting agent polycondensation of ethylene oxide and tris (phenylethyl) phenol phosphate

products 20 g / l ammonium dodecylbenzenesulfonate: 10 g / l - Organic polysiloxane oil (antifoam) 2 g / l - Polyvinyl alcohol (protective colloid) 8 g / l - bentonite (thixotropic agent) 2 g / l

- solvent:

poly (ethylene glycol)

(molecular weight: 400): 552 g / l

The mixture containing the above components was ground according to the procedure described in Example 1 to give a concentrated composition having the properties of the concentrated composition described in Example 1.

Example 3

A concentrated preparation of the following ingredients was prepared:

- N-phosphonomethylglycine (acid): 125 g / l - Oxadiazon 125 g / l

- the surfactant of Example 1,

activator: 125 g / l - ammonium sulphate 125 g / l

- polycondensation product of dispersant / wetting agent, ethylene oxide and tris (phenylethyl) phenol phosphate: 20 g / l ammonium dodecylbenzene sulphonate: 10 g / l polycondensation product of ethylene oxide and dodecanol: 20 g / l

lead of organic polysiloxane 2g / l

- bentonite (thixotropic agent): 2 g / l

- polyvinyl alcohol (protective colloid): 8 g / l

solvent: polyethylene glycol (M = 400): 410 g / l

The mixture containing the above components was ground according to the procedure described in Example 1 to give a concentrated composition having the properties of the concentrated composition of Example 1.

Example 4

A concentrated preparation was prepared from the following ingredients:

N-phosphonomethylglycine (acid): 125 g / l acionifen: 250 g / l

The surfactant of Example 1,

activator: 125 g / l ammonium sulfate: 125 g / l

dispersing / wetting agent:

ethylene oxide and tris (phenylethyl) -

Polycondensation product of phenol phosphate: 30 g / l propylene glycol: 270 g / l WATER: 175 g / l

• »

The mixture containing the above components was milled according to the procedure of Example 1 to give a concentrated composition having the properties of the concentrated composition of Example 1.

Example 5

Concentrated preparation was prepared from ingredients:

- N-phosphonomethylglycine (acid):

- Chlorosulfuron:

- Surfactant, activator according to Example 1:

- ammonium sulphate

- dispersing / wetting agent:

polycondensation product of ethylene oxide and tris (phenylethyl) phenol phosphate:

Condensation product of 4: 1 ethylene oxide and dodecanol:

Condensation product of 6: 1 ethylene oxide and decanol:

attapulgitis (thixotropic agent):

next Total 200 g / 1 g / 1

200 g / l

200 g / 1 g / 1 g / 1 g / 1 g / 1

- Solvent containing an additional quantity of aromatic hydrocarbons, distillation fractions containing 9 to 11 carbon atoms per liter.

The mixture containing the above components was ground according to the procedure described in Example 1 to give a concentrated composition having the properties of the concentrated composition of Example 1.

This concentrated preparation is applied at 3C0 1 / ha at 750 g / ha • · ♦. · * »· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · To Similar end

- 16 doses of the active ingredient were diluted into sprays and sprayed on weed-infested areas.

The effect of the preparation on weeds was as follows:

Centauria cyanus: 99.7% + chrysanthemum: 97.5%; Galium aparine: 80%; Synapse alba: 85%; In synapse numerensis: 92.5%; Stellarie Media: 92.5%; Agrotis tenuis: 93.5%; Alopecurus myosuroides: 96.5%; Avena fatua: 98.5%; Lolium multiflorum: 97.6%; Phalaris canariensis: 97.6%; and Poa annua: 82.5%.

Claims (10)

Claims Claims 1. A concentrated liquid preparation containing N-phosphonomethylglycine and / or a derivative thereof, characterized in that it is an organic or suitable organic -contains, in suspension in an aqueous solvent medium: a) N-phosphonomethylglycine and / or a derivative thereof having a water solubility of greater than 5 g / l, preferably 9 g / l, and N-phosphonomethylglycine and / or a derivative thereof the composition is present in an amount of at least 100 g / l glyphosate and at least a portion of the N-phosphonomethylglycine and / or derivative thereof is insoluble in the medium; and b) an activator surfactant of the formula I in the formula R is a straight or branched alkyl or alkenyl group containing from 8 to 22 carbon atoms; A is alkylene, preferably ethylene or propylene; n and n 'are integers such that the sum of n + n * is between 20 and 40; and R 'is hydrogen or acyl such as formyl, acetyl, propionyl or benzoyl. Composition according to Claim 1, characterized in that, as component (b), it comprises a compound of formula (I) wherein A is ethylene or propylene and / or π + n 'is 16 and 30, preferably 20 and 25. between. • · · ···· Composition according to claim 1 or 2, characterized in that the N-phosphonomethylglycine derivative contains sodium, potassium or organic or inorganic ammonium or sulphonium salts, either alone or in a mixture. 4. Composition according to any one of claims 1 to 3, characterized in that the N-phosphonomethylglycine or its derivative is present in an amount above the solubility limit in the medium, preferably in the range of 120 to 250 g / l. Composition according to claim 4, characterized in that the N-phosphonomethylglycine or derivative thereof is present in an amount of 90 to 220 g / l. 6. A composition according to claim 4 or 5, wherein the undissolved N-phosphonomethylglycine derivative is present in an amount greater than 30% w / v, preferably greater than 75% w / v. 7. A composition according to any one of claims 1 to 3, wherein the insoluble N-phosphonomethylglycine or derivative thereof is less than 30 µm, preferably It is in the form of solid particles with a diameter of 1-20 µm. 8. Composition according to any one of claims 1 to 3, characterized in that it also contains an active ingredient which may be an ammonium salt, in particular nitrate, phosphate, sulfonate, thiocyanate or sulfate. Composition according to Claim 8, characterized in that the active ingredient is present in an amount of 50 to 500 g / l, preferably 100 to 350 g / l. 10. A composition according to any one of claims 1 to 4, 1 * 99 »· 9« 99 9 · · 9 9 · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · Characterized in that it is a concentrate to be diluted into a spraying agent at a dose of from 0.125 to 1.5 kg / ha at a dose of 100 to 600 l / ha.