EP1104235A1

EP1104235A1 - Phytosanitary formulations with high active substance content

Info

Publication number: EP1104235A1
Application number: EP99936727A
Authority: EP
Inventors: Valerio Bramati; Antonio Marchetto
Original assignee: Rhodia Chimie SAS
Current assignee: Rhodia Chimie SAS
Priority date: 1998-08-12
Filing date: 1999-08-12
Publication date: 2001-06-06
Also published as: FR2782244A1; AU5171999A; BR9912931A; CA2340022A1; AU749008B2; WO2000008927A1; FR2782244B1

Abstract

The invention concerns phytosanitary formulations whereof the active substance content is higher than 450 g/l, and comprising a mixture [a] of at least a polyalkoxylated phosphate ester, and, [b] of at least a polyalkoxylated amidoamine; said compounds [a] and [b] being present as such, or in a form corresponding to a reaction of one on the other, or further still in both those forms; the weight ratio of [a]/[b] ranging between 80/20 - 20/80 exclusively. Said phytosanitary formulations have the advantage of being stable while being highly concentrated in active substance.

Description

PHYTOSANITARY FORMULATIONS WITH HIGH CONTENT IN ACTIVE MATERIAL

The present invention relates to phytosanitary formulations, more particularly comprising a liquid, comprising high contents of active material.

The application of phytosanitary active ingredients at the sites to be treated is generally carried out by spraying corresponding fluid solutions or dispersions. These are aqueous solutions or dispersions or in oragnic solvents, wettable powders or dispersible granules.

In the case of aqueous solutions, at least one surfactant and / or another compound is generally present in order to promote the solubilization and / or to reinforce the biological activity of the active ingredient considered.

By way of illustration, mention may in particular be made of the conventional aqueous formulations of glyphosate. Glyphosate is a widely used aminophosphate herbicide and its commercial formulations advantageously incorporate an ethoxylated amine.

The presence of this ethoxylated amine considerably strengthens the biological activity of glyphosate and also leads to a formulation which remains effective whatever the climatic conditions of use. Presumably, the ethoxylated amine activates the diffusion of glyphosate across the cuticular barrier of plants and / or plants.

The interest of these compounds, with a synergistic effect on the biological activity, and possibly beneficial on the solubility of the active principle with which they are associated, is unfortunately often affected by their chemical toxicity. Indeed, organic solvents, surfactants or ancillary compounds such as your ethoxylated amines pose obvious toxicity problems. Ethoxylated amines thus prove to be much more irritating and toxic than glyphosate itself.

The increasingly serious consideration of the various ecological problems has led to the search for phytosanitary compositions, preferably water-soluble, with a biological activity comparable to current formulations and, on the other hand, markedly reduced toxicity.

Another objective of formulators is also to develop formulations that are as concentrated as possible in active matter. However, the higher the concentration of active material, the more difficulties are encountered in stabilizing the resulting formulations.

One of the objects of the present invention is therefore to propose phytosanitary formulations combining the double advantage mentioned above, namely low toxicity and high concentration. Thus, the subject of the present invention is phytosanitary formulations whose content of water-soluble active material is greater than 450 g / l, comprising a mixture of the following compounds:

[a] at least one polyalkoxylated phosphate ester of average formula (I):

O - M / R1 - O - (CH ₂ - CHR2 - O) _n - P = O

\ O - M

in which :

R ¹ represents a C4-C12 hydrocarbon radical, linear or not, saturated or unsaturated,

R ² , which may or may not be identical from one group to another, represent a hydrogen atom or a methyl or ethyl radical, n is an average number of units between 2 and 10,

M, which may or may not be identical, represent a hydrogen atom, an alkaline, alkaline-earth metal, an N (R3) ⁺ radical for which the R3 radicals, identical or different, represent a hydrogen atom or a hydrocarbon radical in Ci-Cβ, linear or not, saturated or unsaturated, optionally substituted by a hydroxyl group, or else a radical of type RO (CH2CHR'-O) _m -; formula in which R represents a C4-C-12 hydrocarbon radical, linear or not, saturated or unsaturated; R ′, which may or may not be identical from one group to another, represent a hydrogen atom or a methyl or ethyl radical, and m is an average number of units between 2 and 10;

[b] at least one polyalkoxylated amidoamine of average formula (II) or (III):

R5 / R4 - CO - NH - (CH ₂ ) ₂ - N - (CH ₂ - CH ₂ - O) - (CH ₂ - CH - O) _p - H (II)

\ (CH ₂ - CH - O) _q - H

\ R5

R5 /

R4 - CO - N - (CH ₂ - CH ₂ - O) - (CH ₂ - CH - O) _r - H (III)

I (CH ₂ - CH - O) _s - H

I / /

(CH ₂ ) ₂ - N R5 \

(CH ₂ - CH - O) _t - H \ R5 in which: - R ⁴ , identical or different, represent a C2-C22 hydrocarbon group, alkyl or alkenyl, linear or branched, cycloalkyl or alkylaryl,

- R5, identical or different, represent hydrogen or a C1-C4 alkyl radical,

- p, q, r, s and t, identical or different, represent average numbers of units, which may be zero, with p + q between 1 and 20 and r + s + t between 1 and 20; these compounds being present as such, in a form corresponding to the reaction of one over the other, or alternatively in these two forms, the weight ratio of [a] / [b] being within the range 80/20 - 20/80, the limits of which are excluded. It has indeed been found, and this, quite unexpectedly, that the combination of compounds [a) and [b], makes it possible to obtain phytosanitary formulations with a higher concentration of active material which are stable.

However, other advantages will appear on reading the description and the examples which follow. As indicated previously, the phytosanitary formulations according to the invention comprise a high content of active material. Advantageously, the content of active material is greater than 450 g / l. More particularly, it is greater than or equal to 490 g / l. It should be noted that the formulations according to the invention can contain up to 520 g / l, or even up to 540 g / l in active material, and remain stable under cold storage conditions (0 ° C.) or at higher temperature (54 ° C).

The active materials capable of entering into the composition of the formulations according to the invention are preferably water-soluble.

The term “phytosanitary active material” is intended to denote, according to the invention, pesticides such as insecticides, herbicides, fungicides, but also nutrients promoting the growth and development of plants. They are preferably herbicides.

Among the preferred herbicides according to the invention, there will be mentioned very particularly the aminophosphate derivatives, or aminophosphonates, and preferably glyphosate, sutphosate, glufosinate, as well as the respective organic or inorganic salts of these compounds.

Preferably, the formulations according to the invention comprise glyphosate, and more particularly glyphosate in the form of salt.

By glyphosate is meant more particularly N-phosphonomethylglycine as well as any derivative thereof leading in aqueous solution to glyphosate anions.

Mention may more particularly be made, as suitable salts, of the alkali metal salts such as sodium or potassium; your ammonium salts, type N (R) 4 ⁺ for which radicals R, which are identical or different, represent a hydrogen atom or a linear or unsaturated, saturated or unsaturated hydrocarbon radical, optionally substituted by a hydroxyl group; or alternatively the sulfonium salts; said salts being present alone or in combination. Among the ammonium salts that may be mentioned very particularly, secondary or primary amines such as isopropylamine, dimethylamine or diamines such as ethylenediamine. As for sulfonium salts, trimethylsulfonium is perfectly suitable.

As preferred derivatives of glyphosate in herbicidal application, there may be mentioned in particular the isopropylamine salt and the trimethylsulfonium salt.

As regards the nutrients, it is preferably metallic salts such as zinc and iron, for example, and preferably manganese. These salts are used in the form of E.D.T.A. chelates. for example or sulfates. The two compounds [a] and [b] will now be described in more detail.

As indicated above, the compound of type [a] represents at least one polyalkoxylated phosphate ester of average formula (I):

O - M / R1 - O - (CH ₂ - CHR2 - O) _n - P = O

\ O - M

in which: R ¹ represents a hydrocarbon radical, linear or not, saturated or unsaturated, of C4-C12,

M, which may or may not be identical, represent a hydrogen atom, an alkaline, alkaline-earth metal, a radical of type N (R) 4 ⁺ for which the radicals R3, identical or different, represent a hydrogen atom or a radical hydrocarbon C ^ -CQ, linear or not, saturated or not, optionally substituted by a hydroxyl group, or a radical of type RO (CH2CHR'-O) _m -; formula in which R represents a C4-C-12 hydrocarbon radical, linear or not, saturated or unsaturated; R ', which may or may not be identical from one group to another, represent a hydrogen atom or a methyl or ethyl radical, and m is an average whole number of units between 2 and 10. It should be noted that preferably the compound of formula (I) is in the form of at least one polyalkoxylated phosphate monoester, a polyalkoxylated phosphate diester, or a mixture of these two esters. More particularly, the polyalkoxylated phosphate ester of formula (I) is such that the radical R ¹ is an alkyl radical in C4-Cι ₂ -

In addition, according to a particular embodiment of the invention, the radical R ² represents a hydrogen atom. Furthermore, a preferred variant consists of compounds of formula (I) for which M, which may or may not be identical, represent a hydrogen atom, an alkali metal, preferably sodium, or alternatively a group of type N (R3) ₄ ⁺ for which the radicals R ³ , identical or different, represent a hydrogen atom or, more preferably, a hydrocarbon radical in As an appropriate radical R3, mention may be made of the isopropyl radical.

Preferably, a compound of several compounds of formula (I) is used, as compound [a], for which, on average, R ¹ , R2, M and n meet the conditions set out above.

The compound [b] entering into the composition of the phytosanitary formulations according to the invention corresponds to at least one polyalkoxylated amidoamine of average formula (II) or (III):

R5 / R4 - CO - NH - (CH ₂ ) ₂ - N - (CH ₂ - CH ₂ - O) - (CH ₂ - CH - O) _p - H (II) \

(CH ₂ - CH - O) _q - H \ R5

R5

/ R4 - CO - N - (CH ₂ - CH ₂ - O) - (CH ₂ - CH - O) _r - H (III) l (CH ₂ - CH - O) _s - H

I / / (CH ₂ ) ₂ - N R5

\

(CH ₂ - CH - O) _t - H \ R5 in which:

- R4, identical or different, represent a C ₂ -C ₂ 2 hydrocarbon group _> alkyl or alkenyl, linear or branched, cycloalkyl or alkylaryl,

- R5, identical or different, represent hydrogen or a C1-C4 alkyl radical,

- p, q, r, s and t, identical or different, represent average numbers of units, which may be zero, with p + q between 1 and 20 and r + s + t between 1 and 20;

According to a particularly suitable embodiment of the invention, the phytosanitary composition comprises an effective amount of a mixture of polyalkoxylated amidoamines of average formula (II) and (III). According to a preferred variant of the present invention, the radical R2 represents hydrogen or a methyl radical

A particular embodiment of the invention consists of polyaicoxylated amidoamines in which the coefficients p, q, r, s and t, which are identical or different, are such that the sum of p and q on the one hand, and the sum of r, s and t on the other hand, are each between 2 and 20, more particularly between 3 and 15, preferably between 4 and 7

As particularly suitable polyaoxoxylated amidoamines, mention may be made of polyethoxylated hydroxyethylcocoylamidoamines comprising on average 4 to 7 ethylene oxide units, corresponding to formula (II) and / or (III). According to a preferred embodiment of the invention, such amidoamines are used as a mixture.

These polyaicoxylated amidoamines of formula (II) and (III) can be prepared for example by polycondensation of alkylene oxide on an amidoamine of formulas (IV) or (V) or a mixture of amidoamines of formulas (IV) and ( V)

R4 - CO - NH- (CH ₂ ) ₂ -NH- (CH ₂ ) ₂ -OH (IV)

R4 - CO - N- (CH ₂ ) ₂ -OH (V)

\ (CH ₂ ) ₂ -NH ₂

formulas in which R4 has the definition given above

This operation can be carried out at a temperature of the order of 70 to 180 ° C, preferably of the order of 110 to 150 ° C, by continuous addition of the activated derivative of alkylene glycol in a proportion of the on the order of 1 to 50 molar equivalents of alkylene oxide relative to the amidoamines of formula (IV) and (V), more particularly on the order of 1, 1 to 25 molar equivalents Preferably, this proportion is order of 2 to 20 molar equivalents Such a process is for example described in US Pat. No. 2,681,354 This operation can also be carried out in the presence of a third solvent. By way of example of a solvent, mention may be made of saturated aliphatic hydrocarbons, such as heptane or octane, aromatic hydrocarbons, such as toluene, cumene, ketones such as in particular octanone-2, secondary alcohols or tertiary, such as isopropanol, tert-butanol, and water The reaction can be carried out in the absence of a catalyst, or if necessary in the presence of a catalyst This catalyst can be acid, preferably of the acid type of Lewis, such as for example boron tπfluoride, tin tetrachloride, antimony pentachloride It is likewise possible to use a basic catalyst chosen in particular from alkali metal hydroxides, such as NaOH, KOH, alkali or alkaline earth metal alcoholates, such as sodium methylate or potassium tert-butoxide. Mention may likewise be made, as suitable catalysts, of rare earth derivatives, such as in particular phosphates, carbonates, lanthanum oxides. If a catalyst is used, the quantities used correspond to approximately 0.05 to 10%, preferably approximately 0.1 to 1% by weight relative to the reaction mass.

It is specified that the compounds [a] and [b] present in the phytosanitary formulations according to the invention, can be found in association, that is to say present as such. They can also be found as a combination. By this term is meant a form corresponding to the reaction of one on the other. More particularly, the mixture results from the neutralization of the compound [a] by the compound [b]. In this particular case, the compound [a] is found, before neutralization, in a form in which at least one of the radicals M corresponds to a hydrogen atom.

Obviously, the formulations according to the invention can simultaneously comprise the associated and combined forms.

The phytosanitary formulations according to the present invention are such that the weight ratio [a] / [b] is between 80/20 and 20/80, these two limits being excluded. More particularly, said ratio is 80/20 excluded to 40/60. Preferably, the ratio is between 80/20 excluded and 45/55. Note that in the case where the compounds are in combined form, said ratio is calculated from the "isolated" compounds.

According to a very advantageous embodiment of the present invention, the formulations are such that the weight ratio of [a] / [b] is between 70/30 and 45/55, these two limits being included.

In the formulations according to the invention, the weight ratio of the active material to the sum of the compounds [a] and [b] can vary between 1/5 and 15/1, preferably 1/5 to 10/1. In the particular case of active materials such as amino phosphate derivatives, the weight ratio is understood to be active material expressed in the form of an acid equivalent.

Of course, the composition according to the invention may also contain other additives. They may, for example, be antifreeze agents such as glycerol or ethylene glycol, dyes, anti-foaming agents and / or surfactants. It can also contain an effective amount of at least one other phytosanitary active ingredient. It may in particular be herbicides chosen from simazine, isoxaben, atrazine, diuron, terbuthylazine, norflurazon, metamitron, chloridazon, sulfonyl urea and trifluralin, alone or in combination. The composition according to the invention is prepared by simple mixing of the water-soluble phytosanitary active ingredient with the compounds [a] and [b], optionally in the presence of other additives.

The composition according to the invention can be prepared well before its use but also just before it. In the latter case, the compounds [a] and [b] are added to the phytosanitary active ingredient, possibly to the other additives, during the dilution of the formulation in the spray tank (tank mix).

The formulations according to the invention can be applied as an insecticide, herbicide, fungicide or fertilizer. Finally, it has been found that the compounds [a] and [b] as they have been defined, are effective biological activators, and this, whatever the form of the phytosanitary composition (solid, liquid).

Concrete but nonlimiting examples of the invention will now be presented.

EXAMPLE 1

A formulation is prepared, the glyphosate concentration of which is 490 g / l expressed in acid equivalent, by mixing, with stirring, the following compounds:

( ^* ) the amidoamine used corresponds to a mixture of polyethoxylated hydroxyethyl cocoylamidoamines comprising 4.2 moles of ethylene oxide on average. ( ^** ) Geronol CF / AR (marketed by the company Rhodia Geronazzo) is a mixture of mono- and di-ester phosphates of formula (I) derived from aliphatic alcohols saturated with C4-C10, and comprising on average 3 to 8 ethylene oxide units, and M is isopropyl ammonium.

The table below shows that the formulation obtained is stable over time at different storage temperatures:

EXAMPLE 2

( ^* ) the amidoamine used corresponds to a mixture of polyethoxylated hydroxyethyl cocoylamidoamines comprising 6.8 moles of ethylene oxide on average.

Claims

1. Phytosanitary formulation with an active ingredient content greater than 450 g / l, comprising a mixture of the following compounds:

[a] at least one polyalkoxylated phosphate ester of formula (I):

O - M / R1 - O - (CH ₂ - CHR2 - O) _n - P = O \

O - M

in which :

R1 represents a hydrocarbon radical, linear or not, saturated or unsaturated, in C4-C12, R ² , identical or not from one group to another, represent a hydrogen atom or a methyl or ethyl radical, n is a average number of patterns between 2 and 10,

M, which may or may not be identical, represent a hydrogen atom, an alkali, alkaline-earth metal, a radical of type N (R3) 4 ⁺ for which the radicals R3, identical or different, represent a hydrogen atom or a radical C1-Ce hydrocarbon, linear or not, saturated or unsaturated, optionally substituted by a hydroxyl group, or alternatively a radical of type RO (CH2CHR'-O) _m -; formula in which R represents a C4-C-12 hydrocarbon radical, linear or not, saturated or unsaturated; R ′, which may or may not be identical from one group to another, represent a hydrogen atom or a methyl or ethyl radical, and m is an average number of units between 2 and 10;

[b] at least one polyalkoxylated amidoamine of average formula (II) or (III):

\

(CH ₂ - CH - O) _q - H \ R5 R5 / R4 - CO - N - (CH ₂ - CH ₂ - O) - (CH ₂ - CH - O) _r - H (III)

(CH ₂ - CH - O) _s - H / /

(CH ₂ ) ₂ - N R5 \

(CH ₂ - CH - O) _t - H \ R5 in which:

- R4, identical or different, represent a C2-C22 hydrocarbon group. alkyl or alkenyl, linear or branched, cycloalkyl or alkylaryl,

- R5, identical or different, represent hydrogen or a C1-C4 alkyl radical, - p, q, r, s and t, identical or different, represent average numbers of units, which can be zero, with p + q between 1 and 20 and r + s + t between 1 and 20; these compounds being present as such, in a form corresponding to the reaction of one over the other, or alternatively in these two forms, the weight ratio of [a] / [b] being within the range 80/20 - 20/80, the limits of which are excluded.

2. Formulation according to claim 1, characterized in that the active material is chosen from aminophosphates or aminophosphonates, such as glyphosate, sulfosate, glufosinate, as well as the respective organic or inorganic salts of the above-mentioned compounds.

3. Formulation according to the preceding claim, characterized in that the active material is chosen from glyphosate, more particularly in the form of a salt, such as the alkali metal salts, the ammonium salts, of type N (R) 4 ⁺ for which the radicals R, identical or different, represent a hydrogen atom or a hydrocarbon radical in Ci-Cβ, linear or not, saturated or not, optionally substituted by a hydroxyl group, or alternatively the sulfonium salts, alone or in combination.

4. Formulation according to any one of the preceding claims, characterized in that the concentration of active material is greater than or equal to 490 g / l.

5. Formulation according to any one of the preceding claims, characterized in that the compound of formula (I) is in the form of at least one polyalkoxylated phosphate monoester, a polyalkoxylated phosphate diester or a mixture of these two esters.

6. Formulation according to any one of the preceding claims, characterized in that the polyalkoxylated phosphate ester of average formula (I) is a mixture of several compounds of average formula (I).

7. Formulation according to any one of the preceding claims, characterized in that it comprises a mixture of polyaicoxylated amidoamines of average formulas (II) and (III).

8. Formulation according to any one of the preceding claims, characterized in that it comprises at least one polyalkoxylated amidoamine in which the radical

R ² represents hydrogen or a methyl radical.

9. Formulation according to any one of the preceding claims, characterized in that it comprises at least one polyalkoxylated amidoamine in which the coefficients p, q, r, s and t, identical or different, are such that p + q is included between 2 and 20, preferably between 3 and 15, and r + s + t is between 2 and 20, preferably between 3 and 15.

10. Formulation according to any one of the preceding claims, characterized in that it comprises, as polyaicoxylated amidoamines, polyethoxylated hydroxyethylcocoylamidoamines comprising on average 4 to 7 ethylene oxide units, corresponding to formula (II) and / or (III).

11. Formulation according to any one of the preceding claims, characterized in that the weight ratio of [a] / [b] is between 80/20 excluded and 40/60, preferably between 80/20 excluded and 45/55 .

12. Formulation according to any one of the preceding claims, characterized in that the weight ratio of the active ingredient to all of the compounds [a] and [b] varies between 1/5 and 15/1, preferably between 1 / 5 and 10/1.

13. Formulation according to any one of the preceding claims, characterized in that it also comprises at least one compound chosen from antifreeze agents, dyes, anti-foaming agents and surfactants.

14. Formulation according to any one of the preceding claims, characterized in that it also comprises an effective amount of at least one other active material such as a herbicide chosen from the following products: simazine, ixobazen, atrazine, diuron, terbuthylazine, norflurazon, metamitron, chloridazon, sulfonyl urea, or trifluralin, alone or in combination.