FR2763793A1 - Composition for applying to plants to produce biological response - Google Patents

Abstract

Plant treatment composition for application to foliage of a plant to elicit a biological response comprises an aqueous application medium containing colloidally dispersed supramolecular aggregates comprising \- 1 amphiphilic salt having anions of an anionic exogenous chemical substance and cations derived by protonation of \- 1 amine compound of formula R1R2NR3 (I). The composition contains the exogenous chemical in a first molar amount X1 in the form of amphiphilic salts and in a zero or second molar amount X2 in the form of \- 1 salt having anions of the exogenous chemical and cations derived from \- 1 base other than (I). The total molar amount of X1 and X2 is sufficient to elicit the desired biological response when the composition is applied to the foliage of the plant at a rate of 10-1000 l/ha and where X1 as a fraction of X1 + X2 is 0.01-1. R1, R2 = 6-22C hydrocarbyl and R3 = H, 1-5C hydrocarbyl or a linear hydrocarbyl chain no longer than R1 or R2. Also claimed are: (1) a herbicidal composition for application to foliage of a plant which comprises an aqueous application medium containing colloidally dispersed supramolecular aggregates comprising \- 1 amphiphilic salt having anions of N-phosphonomethylglycine and cations derived by protonation of \- 1 (I); (2) an aqueous concentrate composition comprising 5-40 wt.% anionic exogenous chemical substance expressed as acid equivalent which when diluted with water forms the above composition and (3) production of a liquid concentrate composition of an exogenous chemical which comprises neutralising a first molar amount of X1 of an anionic exogenous chemical with \- 1 (I) in liquid medium with agitation and conditioning by continuing the agitation until supramolecular aggregates comprising the amphiphilic salts of the exogenous substance are colloidally dispersed in the liquid medium to form a stable suspension. The exogenous chemical substance is preferably a herbicide (preferably acifluorfen, asulma, benazolin, bentazone, bilanafos, bromacil, bromoxynil, chloramben, clopyralid, 2,4-D, 2,4-DB, dalapon, dicamba, dichlorprop, diclofop, endothall, fenac, fenoxaprop, flamprop, fluazifop, flumiclorac, fluoroglycofen, fomesafen, fosamine, glufosinate, glyphosate, haloxyfop, imazameth, imazamethabenz, mazapyr, imazaquin, imazethapyr, ioxynil, MCPA, MCPB, mecoprop, methylarsonic acid, naptalam, nonanoic acid, picloram, quinclorac, quizalofop, sulfamic acid, 2,3,6-TBA, TCA or triclopyr, or an imidazoline herbicide, especially N-phosphonomethylglycine or DL-homoalanin-4-yl(methyl)phosphinate), plant growth regulator or nematicide (preferably 3,4,4-trifluoro-3-butenoic acid or N-(3,4,4-trifluoro-1-oxo-3-butenyl)glycine) which is systemic in plants.

Description

The field of the present invention is that of phytotoxic agents to

foliar action.

More specifically, the invention relates to phytotoxic agents,

herbicides or plant growth regulators, based on N-

phosphonomethylglycine or its derivatives, such as its salts. These active ingredients are perfectly known and are described, in particular, in US Patents 3,799,758 and 3,977,860, as well as in Patent FR 2,129,327. There are many commercial herbicidal formulations based on water-soluble salts of glyphosate. The most common is the glyphosate salt of

monoisopropylamine.

This active principle also has the advantage of being non-ecotoxic and biodegradable. Nevertheless, this notorious herbicide can still be improved greatly with regard to its bioavailability. It is known, in fact, that only a small fraction of the herbicide applied reaches its specific site of action. This low bioavailability is linked to the fact that glyphosate must cross several barriers before reaching its site of action, namely, among others, the lipophilic cuticle of the leaves.

and the essentially hydrophilic phloem liquid stream.

In this context it therefore appears, a priori, desirable for the glyphosate to be placed in an amphiphilic environment, in order to be compatible both with the hydrophobic barrier and with the hydrophilic barrier. But it turns out that at neutral pH suitable for spreading, glyphosate behaves as a divalent salt in aqueous solution. It follows that in this aqueous liquid form of application, which is the only one conceivable, glyphosate is a strongly hydrophilic compound and therefore, in fact, extremely soluble in water. We can easily see that the crossing

of the lipophilic cuticular barrier is particularly difficult for him.

Faced with this problem, various approaches have been proposed by the prior art, in order to try in vain to improve the bioavailability of glyphosate and

its derivatives.

A first approach was to attempt to improve the "wetting" of the glyphosate spreading solution on the leaves. Such an approach is illustrated, for example, by the content of patent application EP 0 290 416, according to which the surfactant used is an amine substituted by polyoxy-ethylenic or -propylenic residues. None of the prior technical proposals made under this

approach has not improved the bioavailability of glyphosate or its derivatives.

In a second approach, attention has been paid to increasing the permeability of the cuticle to glyphosate by using a lipophilic agent, such as an oil, as excipient / vector of the latter. This concerns water-in-oil microemulsions. Such microemulsions are disclosed, in particular, by applications for

patents CA 2,081,254, EP 0 379 852 and EP 0 244 754.

The major drawback of these microemulsions is that they are subject to an emulsion breaking phenomenon when they are diluted in water at concentrations suitable for spreading, namely e. g. 5 g of glyphosate per liter

emulsion. In other words, these microemulsions do not resist dilution.

Under these conditions, the objective of improving the penetration of the cuticle

hydrophobic, thanks to the lipophilic agent, is not reached.

According to this second approach, oil-in-water emulsions have also been considered. In such systems, glyphosate is predominantly present in the aqueous continuous phase. This is illustrated by application EP 0 485 207 which shows, in particular in the examples, that glyphosate is indeed included in the aqueous continuous phase. This macroemulsion does not give glyphosate an amphiphilic character. It is therefore difficult to expect an increase in the

bioavailability of glyphosate within target plants.

The third approach according to the prior art consists in using amphiphilic salts of glyphosate in which the counteranion is an amphiphilic cation such as, for example, a tetrasubstituted ammonium salt, as described in e. g. in PCT patent application WO 83/03 608. The tetrasubstituted ammonium salts of N-phosphonomethylglycine according to this PCT application are characterized by the fact that the four substituents of the ammonium nitrogen are alkyls in CCC20, C2-C6 alkylenyls, C1-C4 hydroxyalkyls, phenyls which may or may not be substituted by C1-C4 alkyls or else halogens. According to the examples, these substituents are four methyls, one phenyl and three methyls, four hydroxyethyls, four butyls, four isopropyls, one paramethylphenyl and three methyls, one parachlorophenyl and three methyls, one propenyl and three ethyls or even one.

C14H29 and 3 CH3. These quaternary ammoniums are very toxic compounds.

A fourth approach, illustrated in particular by patent application EP 0 148 169, is based on the encapsulation of water-soluble herbicides, such as glyphosate, by interfacial polycondensation. In this technique, a fat-soluble emulsifier based on alkylated polyvinylpyrrolidone is used. Polymerization allows the formation of the wall encapsulating the herbicide. It takes place in a phase

heterogeneous aqueous containing glyphosate, by reaction between two (co) monomers.

Here again the results, obtained in terms of bioavailability, have proved to be largely perfectible, as regards these glyphosate microcapsules. In addition, the

process used is relatively complex and expensive to implement.

Knowing this prior art and all the drawbacks which affect it, the Applicant has set itself the objective of perfecting and developing a new form of implementation of the herbicide and / or growth regulator that

constitutes glyphosate or N-phosphonomethylglycine, its salts or its derivatives.

Another essential objective of the invention is to provide a glyphosate vector allowing efficient delivery of this active principle through the lipophilic cuticular barrier and the hydrophilic systemic barrier to its site.

action, without prejudice to its herbicidal efficacy.

Another essential objective of the invention is to provide a carrier of

glyphosate that is economical and easy to obtain.

Another objective of the invention is to provide a glyphosate transporter, which makes it possible to retain the non-ecotoxic and biodegradable character.

of the last.

Another essential objective of the invention is to provide a glyphosate transporter which can be used in an aqueous liquid medium and which is

stable and efficient at high dilution rates.

Another essential objective of the invention is to provide a method of

preparation of glyphosate vectors meeting the specifications set out below

above, said method having to be easy to implement and inexpensive.

The Applicant has had the merit of achieving these objectives, among others, by devising a new approach as regards the active transport of glyphosate in target plants, to its site of action. This new approach consisted in producing suspensions comprising supra-molecular arrangements and, in particular, nanoparticles using glyphosate itself, as a constituent material, without the integrity and cohesion of these arrangements, e. g. these nanoparticles, do not

depend on the presence of surfactants.

This is how she discovered, after long work and experiments, that it was necessary to judiciously select a particular class of salts of fatty amines of glyphosate to produce, easily and spontaneously and, especially without surfactants, colloidal suspensions. of glyphosate in a liquid, preferably aqueous. Thus, the present invention relates, firstly, to a colloidal suspension, characterized in that it comprises supramolecular arrangements of molecules of at least one glyphosate salt corresponding to at least one of the following formulas: in which: A GH is a glyphosate anionic entity of the formula: 0-

I +

O = -CH2- NH --- CH-2 COO '

OH AA is a cationic entity formed by secondary and / or tertiary ammoniums identical or different from each other and of formula: [HNRIR2R3] + in which at least two of the substituents Rl, R2, R3 each independently represent a long alkyl comprising at least 6, preferably at least 8 and, more preferably still, at least 10 carbon atoms, the optional third substituent, not consisting of a long alkyl as defined above, being hydrogen or a hydrocarbon radical other than alkyls long and preferably representing a short C, 1-C5 alkyl, AB is a cationic entity different from A and formed by monovalent cations, identical or different from each other, A x is a fractional index between 0.30 and 1, preferably between 0.35 and 1,

- (II):

"I yc ++ [G] P AxHYc in which: A G is a glyphosate anionic entity of formula: O

I +

O = P-CH-- NH2-CH2-COO

I - o 'A Al is a cationic entity formed by secondary and / or tertiary ammoniums identical or different from one another and corresponding to the same formula as A of formula (I) above, Al being identical or different from A, AH is hydrogen, AC is a cationic entity formed by monovalent cations, identical or different from each other and meeting the same definition as B, while being able to be identical or different from B, A x '+ y + z = 2, x '> 0.25, y <1, with the condition that when z> 0.5, then C is a primary, secondary and / or tertiary ammonium of the formula [HNR4RSR6] + in which at least one of the substituents R4, R5 , R6 represents a linear or branched alkyl, having at least 8, preferably at least 10 and, more preferably still, at least 12 carbon atoms, (m) -

and the tautomeric forms of formulas (I) and (II).

It is by selecting this particular class of glyphosate salts of formulas (I) and (ô) given above that the applicant has obtained, in a completely unpredictable and surprising manner, this stable colloidal aqueous suspension.

supramolecular arrangements of glyphosate.

Preferably, these arrangements are nanoparticles.

This very advantageous stability must be understood as well with respect to supramolecular arrangements, e. g. nanoparticles themselves than suspension

colloidal containing them.

These supramolecular arrangements, preferably nanoparticles, retain their structural integrity without limitation over time, even at very low concentrations of glyphosate. This is all the more surprising as these arrangements

supramolecular (e. g. nanoparticles) are obtained in the absence of surfactants.

These arrangements, preferably these nanoparticles, also have the capital property of resisting large dilutions. They do not break down into

very dilute suspensions suitable for spreading.

As regards more precisely the colloidal suspension of nanoparticles, its stability is expressed by the fact that no phase separation occurs after 48 hours of

storage at rest, at room temperature.

Another valuable object of the colloidal suspension is that it is easily and

spontaneously obtainable in liquid medium, e. g. aqueous.

These supramolecular arrangements, preferably these nanoparticles are finally advantageous: - in that they behave like a vehicle ensuring an amphiphilic environment for the glyphosate, thus optimizing its transmembrane transport in the target plants, - in that they do not harm not to the herbicidal activity of glyphosate, - and in that ultimately they significantly improve its bioavailability. Beyond the chemical structure of the glyphosate salts which constitute the supramolecular arrangements - preferably the nanoparticles - of the suspension, the latter can be defined by preferred functional characteristics according to which: a-advantageously the suspension subject to phase separation after 48 hours of storage at rest at a temperature between and 40 C, b-the average size of the nanoparticles is less than or equal to 10,000 nm, preferably between 20 and 2,000 nm and, more

more preferably, between 100 and 1000 nm.

These characteristics a, b, are not necessarily cumulative. We

can thus have ab, bc, a or b.

The phase separation stability test is described in the examples below. The performances obtained in stability with respect to settling are

more than one year.

The size of the nanoparticles is measured, for example, by light scattering.

Advantageously, the suspension can exhibit a turbidity measured by absorbance at 400 nm for a concentration of 30 mmol of glyphosate equivalent per liter of

suspension, greater than or equal to 10 dB / cm.

The turbidity test is defined in the examples below.

Nanoparticles can be in various forms: beads, sticks, needles or others. Their morphologies will stand out e. g. observations in

electron microscopy.

In accordance with the invention, the constituent elements of the colloidal arrangements, e. g. nanoparticles, are therefore glyphosate salts of formula (I)

or (l).

The salts of formula (I) are monosalts of glyphosate in which the anionic entity is formed by glyphosate in a state where it presents an oxygen of its terminal phosphoric group in ionized anionic form and forming a zwitterion with the central NH2 + of glyphosate . The other anionic charge O 'is that of the terminal carboxyl group. It is compensated by a counteranion or cation judiciously selected from fatty amines and, more particularly, from secondary or tertiary ammoniums comprising two or three alkyl substituents comprising at least 6, preferably at least 8 and, more preferably still, at least. minus 10 carbon atoms. As regards the AB counteranion of the monosalt of formula (I), it appears that the specific fatty ammonium cation of the invention can be partially substituted by one or more B cations of different natures. For a stoichiometric anion: cation molar ratio of 1: 1, ammonium A represents at least 0.30 in the entity

cationic and preferably at least 0.35.

Formula (11) corresponds to a disalt in which the two phosphoryl and carboxyl ends of glyphosate are negatively charged and are each associated with a counter-anion comprising at least in part an ammonium A 'corresponding to the same formula as A, c' that is, particularly comprising two or three alkyl substituents having 6 or more carbon atoms. This is the reason for

in which the anion: cation molar ratio is 1: 2.

It will be understood, in accordance with the invention, that each group of cations A, B, Al, C can comprise the same species or different species of cations A, B, Al and C. Likewise, the cations A and Al can be identical or different from each other, as well as the cations B and C. It is also conceivable that the supramolecular arrangements, and in particular the nanoparticles, are formed by mixtures of monosalts of formula (I), by mixtures of disalts of formula (H) and / or by mixtures of

monosalts (I) and disalts (11).

One of the specificities of the A and Al counteranions of the nanoparticles of the invention is, as we have seen, to be ammoniums substituted by two or three alkyl or fatty chains, so that this gives them bifid conformations. or trifids respectively. In accordance with a preferred arrangement of the invention, the long chains of entities A and Al of formulas (I) and (II) are alkyls, linear or branched, saturated or not at C6-C30, the short substituents of said entities A and AT'

being either C, -C3 alkyls, preferably CH3, or hydrogen.

Thus, the long alkyl chains of ammoniums are, for example, residues of myristic, lauric, palmitic, stearic, oleic, linolenic fatty acids,

linoleic ...

Advantageously, the cationic entity B different from A in formula (I) or the cationic entity C when z <0.5 in formula (I), is: e a monovalent cation chosen from alkalis, Na + being particularly preferred, e or an ammonium cation substituted by four identical or different radicals, at least one of which is hydrogen and chosen from the group comprising hydrogen and linear or branched alkyls, saturated or not, C 1 -C 30, of preferably in CI-CIO, octylammonium and methylammonium being particularly

favorite.

In the case o z> 0.5 in formula (I), the ammonium forming the cationic entity C comprises at least one substituent R4, R5, R6 representing an alkyl in

C12-C30, the other substituent (s) being either hydrogen or methyl.

According to a preferred embodiment of the colloidal suspension of supramolecular arrangements, e. g. of nanoparticles of glyphosate salts, these arrangements are formed: 1. by glyphosate salts of formula (I) in which: A = [HNRIR2R3] + with R1 = or e R2 = alkyl in C2, Cl4, C16 or Cis and R3 = H or CH3, and, optionally, B = [HNR7RSR9] + with R7 = C6, C8, Co ,, C2, Cl4, Cl, 6 or C, R8 = or R9 = CH3 or IH, or B = Na + , B being # of A; 2. and / or by salts of formula (II) in which: Al = [HNRIORlIRl2] + with Rio = or É Rll = alkyl in C2, C, 4, C, 6 or C, and R'2 = H or CH3, and, optionally,

C corresponding to the same definition as that given above in 1.

for B, except for Na + and R7 = C6 when z> 0.5 in

formula (I).

In practice, the cations A and Al are, for example, formed by tertiary ammoniums comprising two fatty chains at Cl2 and / or at C, 8 and a third methyl substituent, or else by secondary ammoniums comprising two fatty chains at Cl2 and / or Cls, the other two nitrogen substituents being

made up of hydrogen.

The cation B is, for example, Na + or a substituted primary ammonium

by a C chain: monooctylammonium.

It should be emphasized that the colloidal suspensions according to the invention can be provided in more or less diluted form. The preferred dispersant is water, but this is not exclusive of other dispersant liquids. According to an interesting characteristic of the invention, the supramolecular arrangements of glyphosate salts, included in the suspension, contain at least one oil, preferably vegetable. This characteristic is likely to

facilitate the crossing of lipophilic barriers in target plants.

In accordance with a preferred characteristic of the invention, the oil is formed by one or more fatty compounds selected from the following group: * medium-chain fatty ester acid triglyceride (s) of animal, plant or synthetic origin , * paraffin (s), * polysiloxane oil (s), * fatty acids of animal or vegetable origin,

* fatty acids, their esters and / or their salts.

As examples of particularly suitable oils, mention may be made of - triglyceride oils of the coconut oil type (such as that sold under the brand "MYGLIOL" by the company AKZO NOBEL), corn oil, - paraffin, - olive oil, - isopropyl palmitate, - butyl stearate, - ethyl oleate, - esters of eicosapentanoic acids docosahexanolques, - alkyl benzoate, eicosapentanoic acids docosahexanoic, - triglycerides of eicosapentanoic acids docosahexanoic, - triglicerides of caprylic acids,

- silicone oil.

The oil can consist of a single type of liquid fatty substance with

room temperature or by a mixture of several of these.

According to one variant, the oil or oils may or may not be fractionated.

Fractionation makes it possible to eliminate certain cuts of fatty acids, so as to

change the melting temperature and viscosity.

The colloidal suspension according to the invention can also be characterized by its method of obtaining. It is obtained:

- by neutralization in liquid medium, preferably aqueous, of the N-

phosphonomethylglycine using: 0 of at least one fatty amine Ap precursor of ammonium A and corresponding to formula A 'given above and to the same formula as that given above for A, 0 optionally at least a base Bp precursor of the cation B, this neutralization being carried out by using an amount of base Ap and optionally Bp, equivalent to the molar amount of glyphosate used, in accordance with formula (I) given above,

this neutralization preferably being carried out with stirring.

Such a colloidal suspension contains supramolecular arrangements, such as

nanoparticles consisting of a monosalt of formula (I) of glyphosate.

Suspensions including supramolecular arrangements, e. g. nanoparticles, are formed by disalts of formula (U1) as constituent elements are, for their part, obtained:

- by neutralization in liquid medium, preferably aqueous, of N-

phosphonomethylglycine using: 0 of at least one fatty amine Alp precursor of ammonium A 'and corresponding to formula A' given above and to the same formula as that given above for A, 0 optionally at minus one base Cp precursor of the cation C, - this neutralization being carried out by using an amount of base Alp and optionally Cp, equivalent to twice the molar amount of glyphosate used, in accordance with formula (11) given above,

- This neutralization is preferably carried out with stirring.

According to another of its aspects, the invention also relates to a process for obtaining a colloidal suspension of glyphosate consisting of monosalts of

of glyphosate of formula (1).

This first form of implementation of the process is characterized in that it consists, essentially: in neutralizing in liquid medium, preferably in aqueous medium, N-phosphonomethylglycine using: 0 at least one fatty amine Ap precursor of ammonium A and corresponding to the formula [HNRIR2R3] with Rl, R2, R3 as defined above, 0 optionally of at least one base Bp precursor of cation B, - this neutralization being carried out by using an amount of base Ap and optionally Bp equivalent to the molar amount of glyphosate used, in accordance with formula (I) given above,

- + this neutralization being preferably carried out with stirring.

The second embodiment of the method according to the invention relates to supramolecular arrangements, such as nanoparticles based on glyphosate disalt of formula (iI). This second variant consists essentially of: - neutralizing in a liquid medium, preferably in an aqueous medium, N-phosphonomethylglycine using: 0 at least one fatty amine Alp precursor of ammonium A 'and corresponding to the formula A 'given above and with the same formula as that given above for A, optionally 0 of at least one base Cp precursor of the cation C, this neutralization being carried out by using a quantity of base Alp and optionally Bp equivalent to twice the molar amount of glyphosate used, in accordance with formula (I) given above,

this neutralization preferably being carried out with stirring.

In other words, the process according to the invention can be reduced to a neutralization of an acid formed by glyphosate or Nphosphonomethylglycine, using a base consisting of a secondary or tertiary amine and comprising two fatty alkyl substituents. having more than 10 carbon atoms. This neutralization is more or less extensive depending on whether one wishes to neutralize only the first acid function (phosphoryl), or also the second acid function (carboxyl) of glyphosate to obtain, respectively, a monosalt (1) or a disel (HI) . The level of neutralization varies, of course, depending on the amount of base

added to glyphosate acid.

The base used comprises minimum quantities of Ap and Alp precursors, namely 0.30 and 0.25 for 1 and 2 molar of glyphosate anion respectively. Once these minima are satisfied, it is possible to supplement the base with other neutralizing agents, such as the Bp and Cp precursors of the B and C counter-anions. They can be Bp and Cp bases of identical or different natures. , alone or in

mix between them. The invention is not limited to the Bp and Cp neutralizing agents.

This neutralization takes place in an aqueous medium, with stirring, preferably

moderate, eg magnetic.

According to an advantageous arrangement of the invention, the preparation of the colloidal suspension is carried out at a temperature above the melting point of the reactants. In the case of fatty amines used in a privileged way,

this reaction temperature is between 50 and 100 C.

According to a variant of the method according to the invention, it is possible to envisage

using the specific fatty amine Ap or Alp in dispersed form.

The duration of formation of nanoparticles by neutralization varies from

a few minutes to a few hours.

At the end of this process, a colloidal suspension of supramolecular arrangements, such as glyphosate nanoparticles of the type.

mono or disel type. This suspension is stable without the meaning as defined above.

In the case where it is nanoparticles, it is very often turbid.

As regards the industrial applications of the glyphosate suspension according to the invention, it is clear that the main one is the use as a herbicide and / or as a plant growth regulator, knowing that the toxic effect of glyphosate is

variable depending on the nature of the target plant considered.

It follows that a subject of the present invention is also phytotoxic compositions comprising a colloidal suspension of glyphosate as defined above. The glyphosate is more or less diluted in this colloidal aqueous suspension. In practice, the concentrations can range from 1 to 400 g

of glyphosate equivalent per liter of suspension.

Advantageously, these compositions can comprise other functional additives such as, for example, thinning agents, thickening agents or

texture agents.

The examples which follow will make it possible to better understand the invention and to perceive all its advantages and variant embodiments thereof. These examples illustrate, in particular, the preparation and the characterization of suspensions of nanoparticles,

as well as the evaluation of their properties. The examples are given with reference to the appended figures.

DESCRIPTION OF THE FIGURE

Fig. 1 is a photograph of an observation under a transmission electron microscope of a colloidal suspension of nanoparticles of

glyphosate prepared according to Example 1.

EXAMPLES

I - PREPARATION OF A COLLOIDAL SUSPENSION

OF GLYPHOSATE MONO SALT OF THE FORMULA: [GH] -; [A] +

Methodology:

470 mg of "wet cake" glyphosate 86.5% a.e. are introduced into a 30 ml flask.

(MONSANTO EUROPE S.A. rue LAID BURNIAT B 1348 LOUVAIN-LA-

NEW BELGIUM), i.e. the equivalent of 2.4 mMol of acid glyphosate (GH2). Then the amine (Ap 3) is introduced in an amine / glyphosate (Ap / GH) molar ratio equal to 1.

complete with 20 ml of milli Q water (permuted and filtered through 0.2 μm).

The flask is stoppered, then placed in a water bath at 60 ° C. for 2 hours. A

Magnetic stirring ensures the homogenization of the mixture.

A colloidal suspension is then obtained, stable, not very viscous, with a pH of the order of 4. Characterization of the suspension: * The stability of the colloidal suspension is assessed by the experimenter. If no phase separation appears after 48 hours of storage, without stirring, in the preparation flask at room temperature, the suspension is considered

colloidal as stable.

* The turbidity of the colloidal suspension is measured using a LAMDA2 UV-visible spectrophotometer from PERKIN ELMER at a wavelength of 400 nm and at a fixed concentration equivalent to 5 g / l of acid glyphosate. The tanks used have a thickness of 0.5 cm. Expressed in db / cm, the turbidity is given by: Abs. 10 / L, o Abs. represents the absorbance and L the length of the tank

expressed in cm.

* The size of colloidal objects is measured by light scattering at a fixed concentration equivalent to 50 mg / l of glyphosate. The device used is a BROOKHAVEN. The size of colloidal objects can also be observed by transmission electron microscopy (T.E.M.) using the so-called negative staining technique. The dye used is sodium silico tungstate from

formula (NaSiWO4).

EXAMPLE 1:

The amine (Ap) used is N-methyldistearylamine "NORAM M2SH" (CECA S.A.

La Défense 2, cedex 54, 92062 PARIS-LA DEFENSE, FRANCE). The mass

introduced amine is 1.24 g.

EXAMPLE 2:

The amine (Ap) used is N-methyl dilaurylamine “NORAM M2C” (CECA S. A.

La Défense 2, cedex 54, 92062 PARIS-LA DEFENSE, FRANCE). The mass

introduced amine is 0.83 g.

EXAMPLE 3:

The amine (Ap) used is N-dilaurylamine “NORAM 2C” (CECA S.A. La Défense 2, cedex 54, 92062 PARIS-LA DEFENSE, FRANCE). The introduced mass of amine

is 0.79 g.

À8 99 'op + so a! NpoJu! auiuMe, p assutu "'. D3ZX pV'cON." at. wulLmnl! plXq4? w-N el sa aos! l! n ('V) ouI.u'-I: S a3al, x] 8'Z ap sa aa8s8ua a ummwep oz assetu eI'. HSZN rîq oN. at. AmmlVeOas! PNqlaw-N elv so ag s! Ln (dV) au.re, ": t ldl Ix siuapaoaJd saldwaxa salI Jnod aw uo apaoid uo: uo.iws.iqpv.wJ SI Lp oJpadsJo ai p Hd op 'alqis aunsoo aun luowole8a luo! qo uo Z. Il8, a (9 / dV) aolsoqdcL / au.ue ae.loU lioddii un oaA siuapoaJd saldwaxa sol.nod aumuoo apaoojd uo: a.ROlopo, 9 0 LV] - 191: azauo1 ia OJ soiaSOHJ1o laU s Ila al I no'IOT3 ONOISNKadSaS: Ia, (NOIV: 1JdZ - il S 000 zz ap luawass! Sso.g un B, 'i aldwaxa, ap alep! Olloo uo! Suadsns l ap' N'H ' L uailE osqo aun, p aide.8oloqd aun aiuom aaxauue I '"

.................................................. .............. DTD: S91 uor Zit lb nalq ouel I

............, ..................................... ....................... DTD: ...................... DTD: 101 uor il I .. nalq.uelqI Z Ooz uou Z '0ú xnal! l ouelqI I

......., .......................................... ....................... DTD: ......................... ................................... DTD: (wu) assqd Wo / qp uo! Suadsns Oiúeú op uo ! l.redos [! p! qJnL ds x sdwx

E: 6LE9LZ

EXAMPLE 6:

The amine (A ") used is N-dilaurylamine" NORAM 2C "The mass of amine

introduced is 1.58 g.

Results of examples 4 to 6:

.................................................. ................... ".............................. ........................................... .DTD: .... ..DTD: Examples. X Aspect Turbidity Size Separation suspension db / cm phase (nm)

+ ................................................. .......................

.................................................. ....................... DTD: ................. DTD: 4 2 milky white 39 no 380 2 milky white> 50 no 200

...................., ............................. ....................... DTD: ......................- .. ................................................ DTD: ................................. DTD: 6 2 Milky white> 50 no 170

L ..................] ..............,. ,,., C.,. T ... 1I. ......> .. 5..0 ........ L ................ n. .................. L ............ 1 ...... 0 ........... .

... DTD: IM - PREPARATION OF A COLLOIDAL SUSPENSION

OF GLYPHOSATE MONO SALT OF THE FORMULA: [GH] '; [A, By,] + Methodology:

470 mg of "wet cake" glyphosate 86.5% a.e. are introduced into a 30 ml flask.

(MONSANTO EUROPE S.A. rue LAID BURNIAT B 1348 LOUVAIN-LA-

NEW BELGIUM), or the equivalent of 2.4 mMol of acid glyphosate (GH2). The base amine (Ap) is then introduced in a variable amine / glyphosate (A, / GH) molar ratio of between 0.35 and 0.8. Make up with 20 ml of milli Q water (permuted and

filtered through 0.2 grm).

The flask is stoppered, then placed in a water bath at 60 ° C. for 2 hours. Magnetic stirring ensures the homogenization of the mixture. The base complement (Bp) is then added with stirring. Stirring is maintained in the water bath

for '/ 2 hour.

A colloidal suspension is then obtained, stable, not very viscous, with a pH of the order of 4. Characterization of the suspension:

The procedure is as for Examples 1, 2 and 3.

Z aSUaJg 'Q' V'S V393) i ,, HSING IEON .. au.nwueleú? 9s! PliqlOwa! CI-N il 1 SZ (da) aseq, '.. HSZN NVION ,. aUIw.lfe9, ls! ipIqlW-N el 1s ags! p.ln (dV) auIe, -I: 6 Ta] xa'lX la z 'I saldtuwaxa sal inod awuuoo ap? oJd uo: uoIsudsns q ap uo.wms. 5lqDa Oz L oldwaxa, l inod awoo apooiJd uo: a. 2olopo wI4 [[x'gq'xv] '..- []: Iflod <a 31ILVSOH "f19 3a 13S I 3a SI 3IV (aOE1 OD NMOISNIISfas ZaN, (l MOIJLVUVJI d - AI

.................................................. ....................... DTD: ......................... .............. DTD: M; 0I S uouO ç <xnoelj mlq i'o 0 0I Ii uou 6 xnal.re! Dueq} '............... b -.............................. ...

.................................................. .......... ï7 ....... i OLI uou OS <xnal! rel uelq SEO L (wu) oseqd ap w / qp uo! suadsns..DTD: 91HUBI. uoWle.mdoSgl! p! qinj lads. x Qadwox-

.................................................. ...... DTD:: 8 Z Saldwum sap swxlnsy 0I Ijw 81 '[1so al! NpoJlu! apnos ap uo! fnlos ap.l! luenb ea5'0 lsa asuq ap auumep (x) aJ.1row uo! pi.J e "lq I apnos ap uo! lnlos aun lsa (dsI) asq BI '.. HSZN IV' O N .. auU! UelkeIs! PI lqlw- N el 1So agS! I! Ln (dV) aUumMq: 8 3 "hlAIX: [S 8'0 S'O 'Sú'O Op IuOWaACoodsoJ 4uos assq op au.imp ( x) saOJ1eoW SUo! loEJ s -I (Vxri'I HDI3N (IV VNODIS Z-08S-O 4IY) Or.uJIMOl 1so (dg) oseq E "l '.. HSZ' VivION.. aU.ulE8.1i ls! pIq1aW-N el 1so 9, sIl9n (OV) aumn, I1: L 31dW3x [LI

E6LE9LZ

cedex 54, 92062 PARIS-LA DEFENSE, FRANCE). The mole fractions (x) of amine

base equal to 1.

Results of example 9:

r ................................. llS988Z Powfiisbse@o$9*&*v8e.v+ atDfiis iit ** && s . | 2eeu41 ly b.Xib ........................................

....... DTD: Examples x Appearance Turbidity Size Separation I _ suspension db / cm phase (nm)

.................................................. ....................... DTD: ......................... ............................... DTD: V PREPARATION OF A COLLOIDAL NANOPARTICLE SUSPENSION

OF GLYPHOSATE MONO SALT OF THE FORMULA: [GH]; [Ax] + CHARGED WITH OIL.

Methodology: In a 30 ml flask, the base amine (Ap) and the oil are introduced. The flask is stoppered, then stirred in a water bath at 60 ° C. until the amine dissolves in the

oil phase. Then 470 mg of glyphosate "wet cake" 86.5% a.e.

(MONSANTO EUROPE S.A. rue LAID BURNIAT B 1348 LOUVAIN-LA-

NEW BELGIUM), or the equivalent of 2.4 mMol of acid glyphosate (GH2). Then, it is made up with 20 ml of milli Q water (permuted and filtered through 0.2 μm). The bottle is again stoppered and placed in a water bath at 60 ° C. for 2 hours. A

Magnetic stirring ensures the homogenization of the mixture.

A colloidal suspension is then obtained, stable, not very viscous, with a pH of the order of 4. Characterization of the suspension: The procedure is as for Examples 1, 2 and 3

EXAMPLE 10:

The amine (Ap 3) used is N-methyldistearylamine "NORAM M2SH". The mass of amine introduced is 1.24 g. The oil is a fatty ester acid triglyceride

marketed under the brand "MIGLYOL" by the company DYNAMIT NOBEL.

The quantity of oil used is 620 mg.

EXAMPLE 11:

The amine (As,) used is N-methyldilaurylamine “NORAM M2C”. The mass of amine introduced is 0.788 g. The oil is "MIGLYOL". The quantity of oil engaged is 0.620 g. Results of examples 10 to 11: = _......................................... ................ Ma Examples x Appearance Turbidity Size Separation suspension db / cm phase (nm)

.................................................. ....................... DTD: ......................... ............................................ DTD: 10 ... ............... 1 li ux ................... 42 ............ ...........

........ no ......................... 1.4.0 ...... DTD: l .... .................. blancaite ............................... .........

.......... 230..DTD:

Claims (10)

CLAIMS: 1- Colloidal suspension, characterized in that it comprises supramolecular arrangements of molecules of at least one glyphosate salt corresponding to at least one of the following formulas: - * (I): in which: A GH is a glyphosate anionic entity of the formula: O- I + O = P-C2-NH-CH-2 COO- OH AA is a cationic entity formed by secondary and / or tertiary ammoniums identical or different from one another and of formula: [HNRIR2R3] + in which at least two of the substituents R ', R2, R3 each independently represent a long alkyl comprising at least less 6, preferably at least 8 and, more preferably still, at least 10 carbon atoms, the optional third substituent, not constituted by a long alkyl as defined above, being hydrogen or a hydrocarbon radical different from long alkyls and preferably representing a short C 1 -C 5 alkyl, AB is a cationic entity different from A and formed by monovalent cations, identical or different from each other, A x is a fractional index between 0.30 and 1 , preferably between 0.35 and 1, [1 -; (x: HYC B'7 "'' H - '++ in which: A G is a glyphosate anionic entity of the formula: O- I + O = P-CHg-NH2-CH-COO- Io AA 'is a cationic entity formed by secondary and / or tertiary ammoniums identical or different from each other and corresponding to the same formula as A of formula (I) above, A' being identical or different from A, AH is the hydrogen, AC is a cationic entity formed by monovalent cations, identical or different from each other and meeting the same definition as B, while being able to be identical or different from B, A x '+ y + z = 2, x'> 0.25, y 1, with the condition that when z> 0.5, then C is a primary, secondary and / or tertiary ammonium of the formula [HNR4RSR6] + in which at least one of the substituents R4, R5, R6 represents a linear or branched alkyl, having at least 8, preferably at least 10 and, more preferably still, at least 12 carbon atoms, - (ml): and the tautomeric forms of formulas (I) and (1). 2- Suspension according to claim 1, characterized in that the Supramolecular arrangements are differentiated nanoparticles. 3- Suspension according to claim 1 or 2, characterized in that it is not subject to phase separation after 48 hours of storage at rest at temperature between 10 and 40 OC. 4- Suspension according to claim 2 or 3, characterized in that the average size of the nanoparticles it contains is less than or equal to 10,000 nm, preferably between 20 and 2,000 nm and, more preferably still, between and 1000 nm. S - Suspension according to any one of claims 2 to 4, characterized in that it is turbid. 6- Suspension according to any one of claims 1 to 5, characterized in that the long chains of entities A and Al of formulas (I) and (11) are alkyls, linear or branched, saturated or not at C6-C30, the short substituents of said entities A and A 'being, either C, -Cs alkyls, preferably CH3, or hydrogen. 7- Suspension according to any one of claims 1 to 6, characterized: * in that the cationic entity B of formula (I) or C of formula (I) when z> 0.5, is: 0 a monovalent cation chosen from alkalis, Na + being particularly preferred, 0 or an ammonium cation substituted by four radicals which are identical or different from one another, at least one of which is hydrogen and chosen from the group comprising hydrogen and linear or branched alkyls, saturated or not, C1-C30, preferably in CI-C10, octylammonium and methylammonium being particularly preferred, * and in that, in the case oz> 0.5 in formula (11), the ammonium forming the cationic entity C comprises at least one substituent R4, R5, R6 representing a C, 2-C30 alkyl, the one or more other substituents being either hydrogen or methyl. 8- Suspension according to any one of claims 1 to 7, characterized in that the supramolecular arrangements it contains are formed: 1. by glyphosate salts of formula (I) in which: A = [HNRIR2R3] + with Rl = or; R2 = C, 2, C14, C16 or C alkyl, and R3 = H or CH3, and, optionally, B = [HNR7R8R9] + with R7 = C6, C8, C10, C12, C14, C16 or C8, R8 alkyl = or R9 = CH3 or H, or B = Na +, B being different from A; 2. and / or by salts of formula (I1) in which: Al = [HNRI R12] + with RIO = or É R "= alkyl in C2, C14, C, 6 or Cl and R12 = H or CH3, and , eventually, C corresponding to the same definition as that given above in 1. for B, except for Na + and R7 = C6 when z> 0.5 in formula (H). 9- Suspension according to any one of claims 1 to 8, characterized in that the supramolecular arrangements of glyphosate salt (s) which it comprises contain at least one oil, preferably vegetable. - Process for obtaining a colloidal suspension of glyphosate, characterized in that it consists essentially: - in neutralizing in a liquid medium, preferably in an aqueous medium, N-phosphonomethylglycine using: 0 at least one fatty amine Ap precursor of ammonium A and meeting the same definition as that given for A in claims 1 and / or 6 and / or 10 and for A 'in the claim 8, 0 optionally of at least one base Bp precursor of the cation B, - this neutralization being carried out by using an amount of base Ap and optionally Bp, equivalent to the molar amount of glyphosate used, in accordance with formula (I) given above, - This neutralization is preferably carried out with stirring. 11- Process for obtaining a colloidal suspension of glyphosate, characterized in that it is obtained: by neutralization in liquid medium, preferably aqueous, of N- phosphonomethylglycine using: 0 at least one fatty amine Alp precursor of ammonium Al and meeting the same definition as that given for A in the claims 1 and / or 6 and / or 10 and for A 'in the claim 8. 0 optionally at least one base Cp precursor of the cation C, - this neutralization being carried out by using an amount of base Alp and optionally Bp, equivalent to the molar amount of glyphosate used, in accordance with formula ( I) given above, this neutralization preferably being carried out with stirring. 12 - Phytotoxic composition, characterized in that it comprises a colloidal suspension of glyphosate according to any one of claims 1 to 9 or as obtained by the process according to claim 10 or 11.