FR2782244A1 - Concentrated, stable, solvent-free phytosanitary compositions contain a polyalkoxylated phosphate ester and a polyalkoxylated amidoamine - Google Patents

Abstract

Phytosanitary compositions having at least 450 g/l of an active material, a polyalkoxylated phosphate ester (I) and a polyalkoxylated amidoamine (II) and/or (III). Phytosanitary compositions having at least 450 g/l of an active material, a polyalkoxylated phosphate ester of formula (I) and a polyalkoxylated amidoamine of formula (II) and/or of formula (III). R<1> = 4-12 C saturated or unsaturated hydrocarbon; R<2> = H, methyl or ethyl; n = 2 - 10; M = H, alkali or alkaline earth metal, N(R<3>)4<+>, or R-O(CH2CHR'-O)m-; R<3> = H or 1-6C saturated or unsaturated hydrocarbon, optionally substituted by OH; R = 4-12 C saturated or unsaturated hydrocarbon; R' = H, methyl or ethyl; m = 2 - 10; R<4> = 2 - 22C alkyl or alkenyl, cycloalkyl or alkylaryl; R<5> = H or 1-4C alkyl; and p, q, r, s, and t = zero or a number, such that (p+q) is 1 - 20 and (s+r+t) is 1 - 20. Compounds of formula (I), (II) and (III) may be present as a reaction product of (I) with (II) and/or with (III), or as a mixture of the individual compounds with their reaction products. The weight ratio of (I)/(II) and/or (IIII) is 80/20-20/80, the limits being excluded. Other components of the formulations may include antifreeze agents, colors, antifoaming agents and surfactants.

Description

PHYTOSANITARY FORMULATIONS

WITH A HIGH ACTIVE MATERIAL CONTENT

The present invention relates to phytosanitary formulations, more particularly comprising a liquid, comprising high contents of active material. The application of phytosanitary active materials at the sites to be treated is generally carried out by spraying the 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 solubilization and / or

reinforce the biological activity of the active material considered.

By way of illustration, mention may in particular be made of 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 furthermore leads to a formulation which remains effective whatever the climatic conditions of use. Presumably, the ethoxylated amine activates the diffusion of glyphosate through the cuticular barrier of plants.

and / or plants.

The advantage 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 ethoxylated amines pose obvious toxicity problems. The ethoxylated amines are thus clearly more

irritant and toxic than glyphosate itself.

The increasingly serious consideration of the various problems of an ecological nature has led to the search for phytosanitary compositions, preferably water-soluble, endowed with a biological activity comparable to current formulations and

on the other hand, of markedly reduced toxicity.

Another objective of the formulators is also to develop formulations as concentrated as possible in active matter. However, the higher the concentration of active matter

is higher, the more difficulties are encountered in stabilizing the resulting formulations.

One of the objects of the present invention is therefore to provide phytosanitary formulations combining the double advantage mentioned above, namely low toxicity.

and high concentration.

Thus, the present invention relates to plant protection formulations whose water-soluble active material content is greater than 450 g / l, comprising a mixture of the following compounds: [a] at least one polyalkoxylated phosphate ester of average formula (I):

0-M

/ R1 - O- (CH2- CHR2- O) n- P = O 0-M in which: R1 represents a hydrocarbon radical, linear or not, saturated or not, in C4-C12, R2, identical or not of a 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, identical or not, represent a hydrogen atom, an alkaline earth metal , a radical of the -N (R3) 3+ type for which the radicals R3, which are identical or different, represent a hydrogen atom or a linear or unsaturated C1-C6 hydrocarbon radical, saturated or not, optionally substituted by a group hydroxl, or a radical of RO (CH2CHR'-O) m type in which R represents a hydrocarbon radical, linear or not, saturated or not, C4-C12; 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 arnidoamine of medium formula (11) or (111): R5 / R4- CO - NH- (CH2) 2- N- (CH2- CH2- O) - (CH2- CHO) p - H (II) (CH2- CH- O) q - H R5 R5 R4- CO - N- (CH2- CH2 - O) - (CH2- CHO) r - H (111) (CH2 - CH - O) s - H / /

(CH2) 2 - N R5

\

(CH2 - CH - O) t - H \ R5 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 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 on the other, or else in these two forms, the weight ratio of [a] / [b] being within the range 80/20 - 20/80, of which

bounds are excluded.

It was indeed observed, and this, quite unexpectedly, that the combination of compounds [a] and [b], made it possible to obtain formulations

phytosanitary products higher concentration of active ingredient which are stable.

But other advantages will appear on reading the description and

examples that will follow.

As has been indicated previously, the plant protection formulations according to the invention comprise a high content of active material. Advantageously, the active material content is greater than 450 g / l. More particularly, it is greater than 490 g / l. It should be noted that the formulations according to the invention can contain up to 520 g / t, or even up to 540 g / l in active material, and remain stable in

cold (0 C) or higher temperature (54 C) storage conditions.

Active ingredients likely to be used in the composition of formulations

according to the invention are preferably water-soluble.

By phytosanitary active material is meant according to the invention 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, mention will be made very particularly of aminophosphate derivatives and preferably glyphosate, sulphosate,

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 a salt.

By glyphosate is meant more particularly Nphosphonomethylglycine as well as any derivative thereof leading in aqueous solution to anions

glyphosate.

Mention may more particularly be made, as suitable salts, of alkali metal salts such as sodium or potassium; ammonium salts, of the -N (R) 3+ type for which the R radicals, identical or different, represent a hydrogen atom or a linear or unsaturated C1-C6 hydrocarbon radical, saturated or unsaturated, optionally substituted with a hydroxyl group; or alternatively sulfonium salts; said salts

being present alone or in combination.

Among the ammonium salts, there may be mentioned most 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, mention may be made of

in particular the isopropylamine salt and the trimethylsulfonium salt.

Regarding nutrients, it is preferably salts

metallic such as zinc and iron, for example, and preferably manganese.

These salts are used in the form of E.D.T.A. type chelates. for example or sulphates.

The two compounds [a] and [b] will now be described in more detail.

As was indicated previously, the compound of type [a] represents at least one polyalkoxylated phosphate ester of average formula (I): O-M Rl - O - (CH2 - CHR2 - O) n - P = O

\

OM in which: R1 represents a hydrocarbon radical, linear or not, saturated or not, C4-C12, R2, which may or may not be identical from one group to the other, represent a hydrogen atom or a methyl or ethyl radical, n is an average number of units between 2 and 10, M, identical or not, represent a hydrogen atom, an alkaline earth metal, a radical of the -N (R3) 3+ type for which the R3 radicals, identical or different , represent a hydrogen atom or a C 1 -C 6 hydrocarbon radical, linear or not, saturated or unsaturated, optionally substituted by a hydroxyl group, or a radical of the RO (CH2CHR'-O) m type in which R represents a hydrocarbon radical, linear or not, saturated or not, C4-C12; R ', which may or may not be identical from one group to the other, represent a hydrogen atom or a methyl radical or

ethyl, and m is an average integer number of units from 2 to 10.

Preferably, the polyalkoxylated phosphate ester of formula (I) is such that the radical

R1 is a C4-C12 alkyl radical.

In addition, according to a particular embodiment of the invention, the radical R2

represents a hydrogen atom.

Moreover, 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 else a group of the -N type (R3 ) 3+ for which the radicals R3, which are identical or different, represent a hydrogen atom or, more preferably, a C1-C6 hydrocarbon radical. As radical R3

suitable, there may be mentioned the isopropyl radical.

Preferably, as compound [a], use is made of a mixture of several compounds of formula (I) for which, on average, R1, R2, M and n meet the requirements.

conditions stated above.

The compound [b] entering into the composition of the plant protection formulations according to the invention corresponds to at least one polyalkoxylated amidoamine of average formula (II) or (III): R5 / R4 - CO - NH- (CH2) 2 - N - ( CH2 - CH2 - O) - (CH2 - CH - O) p - H (Il) (CH2- CH - O) q - H \ R5 R5 / R4 - CO - N - (CH2 - CH2 - O) - (CH2 - CH - O) r - H (I) (CH2 - CH - O) s - H

I I

(CH2) 2 - N R5

(CH2 - 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, which are 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

polyalkoxylated amidoamines of average formula (II) and (111).

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 polyalkoxylated amidoamines in which the coefficients p. q. r, s and t, 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 polyalkoxylated amidoamines, mention may be made of polyethoxylated hydroxyethylcocoylamidoamines comprising on average 4 to 7 ethylene oxide units, corresponding to formula (II) and / or (111). According to a mode of

As a preferred embodiment of the invention, such amidoamines are used in admixture.

These polyalkoxylated amidoamines of formulas (II) and (111) can be prepared for example by polycondensation of alkylene oxide on an amidoamine of formulas (IV) or (V) or a mixture of cramidoamines of formulas (IV) and (V) :

R4- CO - NH- (CH2) 2-NH- (CH2) 2-OH (IV)

R4 - CO - N- (CH2) 2-OH (V)

\

(CH2) 2-NH2

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 continuously adding the activated derivative of alkylene glycol in a proportion of the order of 1 to 50 molar equivalents of alkylene oxide relative to the amidoamines of formulas (IV) and (V), more particularly of the order of 1.1 to 25 molar equivalents. Preferably, this proportion is of the order of 2 to 20 molar equivalents. Such a process is for example described in the patent

US -A 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 rheptane or octane, aromatic hydrocarbons, such as toluene, cumene, ketones such as in particular 2-octanone, secondary or tertiary alcohols. , 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 acidic, preferably of the Lewis acid type, such as, for example, boron trifluoride, tin tetrachloride or antimony pentachloride. It is also possible to use a basic catalyst chosen in particular from alkali metal hydroxides, such as NaOH, KOH, alkali metal or alkaline earth metal alcoholates, such as sodium methoxide or else potassium tert-butoxide. Mention may also be made, as suitable catalysts, of rare earth derivatives, such as in particular phosphates,

carbonates, lanthanum oxides.

If a catalyst is used, the amounts used correspond to about 0.05 to 10%, preferably about 0.1 to 1% by weight, relative to the reaction mass. It is specified that the compounds [a] and [b] present in the plant protection formulations according to the invention can be found in combination, that is to say

present as such.

They can also be in the form of 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 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 comprise

simultaneously 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

/ 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 derivatives

phosphates, the ratio by weight is understood as active ingredient expressed in the form

of acid equivalent.

Of course, the composition according to the invention can also contain other additives. They can be, for example, antifreeze agents such as glycerol or ethylene

glycol, colorants, defoamers and / or surfactants.

It can also contain an effective amount of at least one other plant protection active material. They may in particular be herbicides chosen from simazine, isoxaben, atrazine, diuron, terbuthylazine, norflurazon, metamitron,

chloridazon, sulfonyl urea and trifluralin, singly or in combination.

The composition according to the invention is prepared by simple mixing of the water-soluble plant protection active material with the compounds [a] and [b], optionally by

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 plant protection active ingredient, optionally 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 was found that the compounds [a] and [b] as they were defined, are effective biological activators, and that, whatever the formatting of the.

phytosanitary composition (solid, liquid).

Claims (12)

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): OM / R1 - O - (CH2 - CHR2 - O) n - P = O \ OM in which: R1 represents a hydrocarbon radical, linear or not, saturated or not, C4-C12, R2, 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 earth metal, a radical of -N (R3) 3 * type for which the R3 radicals, identical or different, represent a hydrogen atom or a linear or unsaturated C1-C6 hydrocarbon radical, saturated or not, optionally substituted by a hydroxyl group, or else a radical of the RO (CH2CHR'-O) m type in which R represents a hydrocarbon radical, linear or not, saturated or not, C4-C12; 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 arnidoamine of average formula (11l) or (111): R5 / R4 - CO - NH (CH2) 2 - N - (CH2 - CH2 - O) - (CH2 - CH - O) p - H (11) \ (CH2 - CH - O) q- H R5 R5 / R4- CO - N - (CH2 - CH2 - O) - (CH2 - CH - O) r - H (111) (CH2 - CH - O) s - H I I I (CH2) 2 - N R5 \ (CH2 - CH - O) t - H R5 \ 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, which are 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 on the other, or else in these two forms, the weight ratio of [a] / [b] being within the range 80/20 20/80, of which bounds are excluded. 2. Formulation according to claim 1, characterized in that the active ingredient is chosen from glyphosate, sulfosate, glufosinate, as well as organic salts or respective inorganic compounds of the aforementioned 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 alkali metal salts, ammonium salts, of type -N (R) 3 + for which the radicals R, which are identical or different, represent a hydrogen atom or a linear or unsaturated C1-C6 hydrocarbon radical, 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 at least 490 g / l. U '. 5. 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). 6. Formulation according to any one of the preceding claims, characterized in that it comprises a mixture of polyalkoxylated amidoamines of average formulas (II) and (111). 7. Formulation according to any one of the preceding claims, characterized in that it comprises at least one polyalkoxylated amidoamine in in which the radical R2 represents hydrogen or a methyl radical. 8. 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 between 2 and 20, preferably between 3 and 15, and r + s + t is between 2 and 20, preferably between 3 and 15. 9. Formulation according to any one of the preceding claims, characterized in that it comprises, as polyalkoxylated amidoamines, polyethoxylated hydroxyethylcocoylamidoamines comprising on average 4 to 7 units ethylene oxide, corresponding to formula (II) and / or (111). 10. Formulation according to any one of the preceding claims, characterized in that the weighted ratio of [a] / [b] is between 80/20 excluded and / 60, preferably between 80/20 excluded and 45t55. 11. Formulation according to any one of the preceding claims, characterized in that the weighted ratio of the active ingredient to all compounds [a] and [b] varies between 1/5 and 15/1, preferably between 1/5 and 10/1. 12. Formulation according to any one of the preceding claims, characterized in that it further comprises at least one compound chosen from among anti-freeze agents, colorants, anti-foaming agents and surfactants. 1-3. Formulation.seion any of the preceding claims, characterized in that it further 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.