AU749008B2

AU749008B2 - Phytosanitary formulations with high active substance content

Info

Publication number: AU749008B2
Application number: AU51719/99A
Authority: AU
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: 2002-06-13
Anticipated expiration: 2019-08-12
Also published as: FR2782244B1; AU5171999A; WO2000008927A1; FR2782244A1; CA2340022A1; BR9912931A; EP1104235A1

Description

WO 00/08927 PCT/FR99/01977 PLANT PROTECTION FORMULATIONS WITH A HIGH CONTENT OF ACTIVE MATERIAL The present invention relates to plant protection formulations, more particularly comprising a liquid, comprising high contents of active material.

Plant protection active materials are generally applied to the sites to be treated by spraying corresponding solutions or fluid dispersions.

These are solutions or dispersions that are aqueous or in organic solvents, wettable powders or dispersible granules.

In the case of aqueous solutions, at least one surfactant and/or one other compound is generally present in order to promote the dissolution and/or to reinforce the biological activity of the active material under consideration.

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

The presence of this ethoxylated amine considerably reinforces the biological activity of glyphosate and also gives a formulation which remains effective irrespective of the climatic conditions in which it is used. The ethoxylated amine quite probably activates the diffusion of glyphosate across the cuticular barrier of the plants and/or vegetation.

The advantage of these compounds, which have a synergistic effect on the biological activity, and possibly a beneficial effect on the solubility of the active principle with which they are combined, is, unfortunately, often affected by their chemical toxicity. Specifically, the organic solvents, surfactants or associated compounds, such as the ethoxylated amines, pose obvious toxicity problems. The ethoxylated amines are thus found to be markedly more irritant and toxic than glyphosate itself.

The increasingly serious consideration given to the various problems of ecological nature has led to the search for plant protection compositions, preferably water-soluble, whose biological activity is comparable with that of the current formulations, but which, •on the other hand, are of markedly lower toxicity.

Another objective of formulators is also to develop formulations that are as 15 concentrated as possible in active material. However, the higher the concentration of active material, the greater the problems of stabilizing the resulting formulations.

•"It is an object of the present invention to overcome or ameliorate at least one of •the disadvantages of the prior art, or to provide a useful alternative.

Unless the context clearly requires otherwise, throughout the description and the 20 claims, the words 'comprise', 'comprising', and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in the sense of "including, but not limited to".

Thus, a subject of the present invention is plant protection formulations whose content of active material is greater than 450 g/l, comprising a mixture of the following Tcompounds: at least one polyalkoxylated phosphate ester of average formula P compounds: at least one polyalkoxylated phosphate ester of average formula 839aupOO.doci./CMW

O-M

R'-O-(CH

2

-CHR

2 -O)n-P O

O-M

in which: R' represents a linear or branched, saturated or unsaturated C 4

-C

1 2 hydrocarbon-based radical, R 2 which may be identical or different from one group to another, represent a hydrogen atom or a methyl or ethyl radical, n is an average number of units of between 2 and 10, M, which may be identical or different, represent a hydrogen atom, an alkali metal, an alkaline-earth metal, a radical of the type N(R 3 4 for which the radicals R 3 which may be identical or different, represent a hydrogen atom or a linear or branched, saturated or unsaturated Ci-C 6 hydrocarbonbased radical optionally substituted with a hydroxyl group, or alternatively a radical of the type R-O(CH 2 CHR'-O)m-; in which formula R represents a linear or branched, e 839aupO.docCMW saturated or unsaturated C 4

-C

1 2 hydrocarbon-based radical; which may be identical or different from one group to another, represent a hydrogen atom or a methyl or ethyl radical, and m is an average number of units of between 2 and at least one polyalkoxylated amidoamine of average formula (II) or (III): 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 R4 CO N -(CH 2 CH2 (CH2 CH O)r- H (111)

(CH

2 CH O)s -H

(CH

2 2 N

(CH

2 CH O)t H in which:

R

4 which may be identical or different, represent a linear or branched C 2

-C

22 alkyl or alkenyl, cycloalkyl or alkylaryl hydrocarbon-based group,

R

5 which may be identical or different, represent hydrogen or a Ci-C 4 alkyl radical, p, q, r, s and t, which may be 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; compounds and being present in unreacted form, in reacted form, or in a combination of unreacted and reacted forms, the weight ratio of being more than 20/80 and less than 80/20.

Preferably, the active material is water soluble and stable.

Specifically, it has been found, entirely unexpectedly, that in certain preferred embodiments the combination of compounds and makes it possible to obtain plant protection formulations with a higher concentration of active material which are stable.

However, other advantages will become apparent on reading the description and the examples which follow.

As has been mentioned previously, the plant protection formulations according to the invention comprise a high content of active material. The content of active i material is advantageously 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 may 15 contain up to 520 g/l, or even up to 540 g/l, of active material, and remain stable under cold storage conditions or at a higher temperature (54°C).

The active materials which may be included in the composition of the formulations according to the invention are preferably water-soluble.

oooo 839aup0.doc/CMW According to the invention, the expression "plant protection active material" is intended to denote pesticides such as insecticides, herbicides and fungicides, and also nutrient elements which promote the growth and development of plants. The expression preferably denotes herbicides.

Among the herbicides that are preferred according to the invention, mention will be made most particularly of aminophosphate or aminophosphonate derivatives, and preferentially glyphosate, sulphosate and glufosinate, as well as the respective organic or inorganic salts of these compounds.

The formulations according to the invention preferably comprise glyphosate, and more particularly glyphosate in salt form.

The term "glyphosate" more particularly denotes N-phosphonomethylglycine, as well as any derivative thereof which gives glyphosate anions in aqueous solution.

Suitable salts which may be mentioned more particularly are alkali metal salts such as the sodium or potassium salt; ammonium salts, of the type N(R)4 for which the radicals R, which may be identical or different, represent a hydrogen atom or a linear or branched, saturated or unsaturated Ci-C 6 hydrocarbonbased radical, optionally substituted with a hydroxyl group; or alternatively sulphonium salts; the said salts being present alone or in combination.

Among the ammonium salts which may be mentioned most particularly are secondary or primary amines such as isopropylamine and dimethylamine, or diamines such as ethylenediamine. As regards the sulphonium salts, trimethylsulphonium is entirely suitable.

As preferred glyphosate derivatives for herbicidal application, mention may be made in particular of the isopropylamine salt and the trimethylsulphonium salt.

As regards the nutrient elements, these are preferably metal salts such as zinc and iron, for example, and preferentially manganese salts. These salts are used in the form of chelates of EDTA type, for example, or in the form of sulphates.

The two compounds and will now be described in greater detail.

As has been mentioned previously, the compound of type represents at least one polyalkoxylated phosphate ester of average formula

O-M

Ri -O-(CH 2 -CHR2-O)n -P=O

O-M

in which:

R

1 represents a linear or branched, saturated or unsaturated C 4

-C

12 hydrocarbon-based radical,

R

2 which may be identical or different from one group to another, represent a hydrogen atom or a methyl or ethyl radical, n is an average number of units of between 2 and M, which may be identical or different, represent a hydrogen atom, an alkali metal, an alkaline-earth metal, a radical of the type N(R 3 4 for which the radicals R 3 which may be identical or different, represent a hydrogen atom or a linear or branched, saturated or unsaturated C 1

-C

6 hydrocarbon-based radical optionally substituted with a hydroxyl group, or alternatively a radical of the type R-O(CH 2 CHR'-O)m-; in which formula R represents a linear or branched, saturated or unsaturated C 4

-C

12 hydrocarbon-based radical; which may be identical or different from one group to another, represent a hydrogen atom or a methyl or ethyl radical, and m is an average integer of units of between 2 and 10. It is noted that, preferably, the compound of formula 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 is such that the radical

R

1 is a C 4

-C

12 alkyl radical.

In addition, according to one particular embodiment of the invention, the radical R 2 represents a hydrogen atom.

Moreover, a preferred variant consists of compounds of formula for which M, which may be identical or different, represent a hydrogen atom, an alkali metal, preferably sodium, or a group of the type 3 3 N(R 3)4 for which the radicals R 3 which may be identical or different, represent a hydrogen atom or, more preferably, a C 1

-C

6 hydrocarbon-based radical. A suitable radical R 3 which may be mentioned is the isopropyl radical.

A mixture of several compounds of formula (I) 1 2 for which, on average, R R 2 M and n satisfy the conditions mentioned above is preferably used as compound [a] The compound included in the composition of the plant protection formulations according to the invention corresponds to at least one polyalkoxylated amidoamine of average formula (II) or (III): 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 R CO N -(CH 2

CH

2

(CH

2 CH O)r H (III) (CH2-CH-O) -H

(CH

2 2 N

(CH

2 CH O) H

R

in which:

R

4 which may be identical or different, represent a linear or branched C 2

-C

22 alkyl or alkenyl, cycloalkyl or alkylaryl hydrocarbon-based group,

R

5 which may be identical or different, represent hydrogen or a Ci-C 4 alkyl radical, p, q, r, s and t, which may be 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 According to one particularly suitable embodiment of the invention, the plant protection composition comprises an effective amount of a mixture of polyalkoxylated amidoamines of average formulae (II) clland (III).

According to a preferred variant of the present invention, the radical R 2 represents hydrogen or a methyl radical.

One particular embodiment of the invention consists of polyalkoxylated amidoamines in which the coefficients p, q, r, s and t, which may be 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 polyalkoxylated amidoamines that are particularly suitable, 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 one preferred embodiment of the invention, such amidoamines are used as a mixture.

These polyalkoxylated amidoamines of formulae (II) and (III) may be prepared, for example, by polycondensation of alkylene oxide with an amidoamine of formula (IV) or or a mixture of amidoamines of formulae (IV) and R CO NH-(CH 2 2 -NH-(CH2) 2 -OH (IV) R4 CO N-(CH 2 2 -OH

(V)

(CH

2 2

-NH

2 in which formulae R 4 has the definition given above.

This operation may be carried out at a temperature of about from 70 to 1800C, preferably of about from 110 to 150 0 C, by continuous addition of the activated derivative of the alkylene glycol in a proportion of about from 1 to 50 molar equivalents of alkylene oxide relative to the amidoamines of formulae (IV) and more particularly of about from 1.1 to molar equivalents. This proportion is preferably about from 2 to 20 molar equivalents. Such a process is disclosed, for example, in patent US-A-2 681 354.

This operation may also be carried out in the presence of an intermediary solvent. Examples of solvents which may be mentioned are saturated aliphatic hydrocarbons, such as heptane or octane, aromatic hydrocarbons, such as toluene or cumene, ketones, in particular such as 2-octanone, secondary or tertiary alcohols, such as isopropanol or tert-butanol, and water.

The reaction may be carried out in the absence of catalyst or, if necessary, in the presence of a catalyst. This catalyst may be acidic, preferably of the Lewis acid type, such as, for example, boron trifluoride, tin tetrachloride or antimony pentachloride. Similarly, a basic catalyst chosen in particular from alkali metal hydroxides, such as NaOH or KOH, and alkali metal alkoxides or alkaline-earth metal alkoxides, such as sodium methoxide or potassium tert-butoxide, may be used. Similarly, suitable catalysts which may be mentioned include rare-earth derivatives such as, in particular, lanthanum phosphates, carbonates and oxides.

If a catalyst is used, the amounts used correspond to about 0.05 to 10%, preferably about 0.1 to by weight relative to the reaction mass.

It is pointed out that compounds and [b] present in the plant protection formulations according to the invention may be in association, i.e. present as such.

They may also be in the form of a combination. This term means a form corresponding to the reaction of one with the other. More particularly, the mixture results from the neutralization of compound with compound In this particular case, compound is, before the neutralization, in a form in which at least one of the radicals M corresponds to a hydrogen atom.

Needless to say, the formulations according to the invention may simultaneously comprise the associated and combined forms.

The plant protection formulations according to the present invention are such that the weight ratio is between 80/20 and 20/80, limits excluded.

More particularly, the said ratio is from 80/20 exclusive to 40/60. Preferably, the ratio is between 80/20 exclusive and 45/55. It should be noted that, when the compounds are in combined form, the said ratio is calculated on the basis of the "isolated" compounds.

According to one very advantageous embodiment of the present invention, the formulations are such that the weight ratio of is between 70/30 and 45/55, limits excluded.

In the formulations according to the invention, the weight ratio of the active material to the sum of compounds and may vary between and 15/1, preferably from 1/5 to 10/1.

In the particular case of active materials such as aminophosphate derivatives, the weight ratio is understood as active material expressed in the form of acid equivalent.

Needless to say, the composition according to the invention may also contain other additives. These may be, for example, antifreeze agents such as glycerol or ethylene glycol, colorants, antifoams and/or surfactants.

It may also contain an effective amount of at least one other plant protection active material. This material may be, in particular, herbicides chosen from simazine, isoxaben, atrazine, diuron, terbuthylazine, norflurazon, metamitron, chloridazon, sulphonylurea and Strifluralin, alone or combined.

The composition according to the invention is prepared by simply mixing the water-soluble plant protection active material with compounds and optionally in the presence of other additives.

The composition according to the invention may be prepared well before its use, but also just before use. In the latter case, compounds and [b] are added to the plant protection active material, and optionally to the other additives, during the dilution of the formulation in the spraying tank (tank mix).

The formulations according to the invention may be applied as insecticide, herbicide, fungicide or fertilizer.

Finally, it has been found that compounds [a] and as have just been defined are effective biological activators, irrespective of the formulation of the plant protection composition (solid or liquid) Concrete but non-limiting examples of the invention will now be given.

EXAMPLE 1 A formulation with a glyphosate concentration of 490 g/l expressed as acid equivalent is prepared by mixing together the following compounds with stirring: isopropylamine salt of glyphosate (46% acid) 1065 g amidoamine 48 g Geronol CF/AR 72 g water 37 g the amidoamine used corresponds to a mixture of polyethoxylated hydroxyethylcocoylamidoamines comprising 4.2 mol of ethylene oxide on average Geronol CF/AR (sold by the company Rhodia Geronazzo) is a mixture of phosphate mono- and diesters of formula derived from saturated C 4

-C

1 0 aliphatic alcohols, and comprising on average 3 to 8 ethylene oxide units, and M is isopropylammonium.

.0 The table below shows that the formulation obtained is stable over time at various storage temperatures: STORAGE CONDITIONS RESULTS Initially 1 phase clear 2 months at 0°C 1 phase clear 2 months at 54 0 C 1 phase clear 2 months at 60 0 C 1 phase clear EXAMPLE 2 A formulation with a glyphosate concentration of 490 g/l, expressed as acid equivalent, is prepared by mixing together the following compounds with stirring: isopropylamine salt of glyphosate (46% acid) 1065 g amidoamine 60 g Geronol CF/AR 60 g water 37 g the amidoamine used corresponds to a mixture of polyethoxylated hydroxyethylcocoylamidoamines comprising 6.8 mol of ethylene oxide on average The table below shows that the formulation obtained is stable over time at various storage temperatures: STORAGE CONDITIONS RESULTS Initially 1 phase clear 2 months at 0°C 1 phase clear 2 months at 54 0 C 1 phase clear 2 months at 60 0 C 1 phase clear

Claims

1. Plant protection formulation whose content of active material is greater than 450 g/l, comprising a mixture of the following compounds: at least one polyalkoxylated phosphate ester of formula O-M R1 -O-(CH 2 -H2CHR2-O)n-P O O-M in which: R 1 represents a linear or branched, saturated or unsaturated C 4 -C 12 hydrocarbon-based radical, R 2 which may be identical or different from one group to another, represent a hydrogen atom or a methyl or ethyl radical, n is an average number of units of between 2 and M, which may be identical or different, represent a hydrogen atom, an alkali metal, an alkaline-earth metal, a radical of the type N(R 3 )4 for which the radicals R 3 which may be identical or different, represent a hydrogen atom or a linear or branched, saturated or unsaturated Ci-C 6 hydrocarbon-based radical optionally substituted with a hydroxyl group, or alternatively a radical of the type R-O(CH 2 CHR'-O)m-; in which formula R represents a linear or branched, saturated or unsaturated C 4 -C 12 hydrocarbon-based radical; which may be identical or different from one group to another, represent a hydrogen atom or a methyl or ethyl radical, and m is an average number of units of between 2 and at least one polyalkoxylated amidoamine of average formula (II) or (III): R4 CO NH (CH 2 2 N -(CH 2 CH 2 O)-(CH 2 CH O)p H (II) (CH2 CH- O)q-H R4 CO N -(CH 2 CH2 O) (CH 2 CH H (III) (CH 2 CH O)s H (CH 2 2 N (CH2 CH O)t-H in which: R 4 which may be identical or different, represent a linear or branched C 2 -C 22 alkyl or alkenyl, cycloalkyl or alkylaryl hydrocarbon-based group, R 5 which may be identical or different, represent hydrogen or a C 1 -C 4 alkyl radical, p, q, r, s and t, which may be identical or different, represent average numbers of units, which Smay be zero, with p q between 1 and 20 and r s t between 1 and 20; compounds and being present in unreacted form, in reacted form, or in a combination of unreacted and reacted forms, the weight ratio of being more than 20/80 and less than 80/20.

2. Formulation according to Claim 1, wherein the active material is chosen from aminophosphates and aminophosphonates, such as glyphosate, sulphosate or glufosinate, as well as the respective organic or inorganic salts of the abovementioned compounds.

3. Formulation according to the preceding claim, wherein the active material is chosen from glyphosate, more particularly in salt form, such as alkali metal salts, ammonium salts, of the type N(R) 4 for which the radicals R, which may be identical or different, represent a hydrogen atom of a linear or branched, saturated or unsaturated C 1 -C 6 hydrocarbon-based radical, optionally substituted with a hydroxyl group, or sulphonium salts, alone or in combination.

4. Formulation according to any one of the preceding claims, wherein the Sconcentration of active material is greater than or equal to 490 g/1. i: 15 5. Formulation according to any one of the preceding claims, wherein the compound of formula is in the form of at least one polyalkoxylated phosphate S"monoester, polyalkoxylated phosphate diester or a mixture of these two esters.

6. Formulation according to any one of the preceding claims, wherein the polyalkoxylated phosphate ester of average formula is a mixture of several 20 compounds of average formula

7. Formulation according to any one of the preceding claims, comprising a mixture of polyalkoxylated amidoamines of average formulae (II) and (III).

8. Formulation according to any one of the preceding claims, comprising at least &lkoxylated amidoamine in which the radical R 5 represents hydrogen or a 839up00.doCNVIW -21-

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

10. Formulation according to any one of the preceding claims, comprising as polyalkoxylated 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, wherein the weight ratio of is less than 80/20 exclusive and greater than or equal to 40/60.

12. Formulation according to any one of the preceding claims, wherein the weight ratio of is less than 80/20 and greater than or equal to 45/55.

13. Formulation according to any one of the preceding claims, wherein the weight ratio of the active material to the combination of compounds and ranges between S. 15 1/5 and 15/1.

14. Formulation according to any one of the preceding claims, wherein the weight S.i ratio of the active material to the combination of compounds and ranges between 1/5 and 10/1. Formulation according to any one of the preceding claims, also comprising at 20 least one compound chosen from antifreeze agents, colorants, antifoams and surfactants.

16. Formulation according to any one of the preceding claims, also comprising 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, sulphonylurea or trifluralin, alone or combined. 839aupOO.doJCMW -22

17. A plant protection formulation substantially as herein described with reference to any one of the examples. DATED this 18th Day of April 2002 RHODIA CHIIMIE Attorney: CHARLES W. TANSEY Registered Patent and Trade Mark Attorney of Australia of BALD WIN SHELSTON WATERS S.00 o o 0 0 005 0**0. 839aupOO.docCMW