AU5171999A

AU5171999A - Phytosanitary formulations with high active substance content

Info

Publication number: AU5171999A
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: 2000-03-06
Anticipated expiration: 2019-08-12
Also published as: BR9912931A; FR2782244B1; AU749008B2; CA2340022A1; WO2000008927A1; EP1104235A1; FR2782244A1

Description

WO 00/08927 1 PCT/FR99/01977 PLANT PROTECTION FORMULATIONS WITH A HIGH CONTENT OF ACTIVE MATERIAL The present invention relates to plant 5 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. 10 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 15 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 20 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 25 considerably reinforces the biological activity of glyphosate and also gives a formulation which remains Uw effective irrespective of the climatic conditions in 2 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 5 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, 10 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 15 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 20 toxicity. Another objective of formulators is also to develop formulations that are as concentrated as possible in active material. However, the higher the concentration of active material, the greater the 25 problems of stabilizing the resulting formulations. One of the aims of the present invention is thus to propose plant protection formulations which 3 combine the twofold advantage mentioned above, namely low toxicity and high concentration. Thus, a subject of the present invention is plant protection formulations whose content of water 5 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 10 in which: R' represents a linear or branched, saturated or unsaturated C 4 -C1 2 hydrocarbon-based radical, 2 R , which may be identical or different from one group to another, represent a hydrogen atom or a methyl or 15 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 + for which the 20 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 25 which formula R represents a linear or branched, 4 saturated or unsaturated C 4

-C

12 hydrocarbon-based radical; R', 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 5 units of 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 - 0)-(CH 2 - CH - O)p - H (II)

(CH

2 - CH - O)q - H R5 R5 R4 - CO - N -(CH2 - CH 2 - O) -(CH 2 - CH - O)rH (II)

(CH

2 - CH O)s - H

(CH

2

)

2 - N R5

(CH

2 - CH - O)t - H R5 10 in which: - R 4 , which may be identical or different, represent a linear or branched C 2

-C

2 2 alkyl or alkenyl, cycloalkyl or alkylaryl hydrocarbon-based group, - R 5 ,\ which may be identical or different, represent 15 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 may be zero, with p + q between 1 and 20 and r + s + t 5 between 1 and 20; these compounds being present in unmodified form, in a form corresponding to the reaction of one with the other, or in these two forms, the weight ratio of [a]/[b] being in the range 80/20 5 20/80, limits excluded. Specifically, it has been found, entirely unexpectedly, that the combination of compounds [a] and [b] makes it possible to obtain plant protection formulations with a higher concentration of active 10 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 15 protection formulations according to the invention comprise a high content of active material. The content of active 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 20 according to the invention may contain up to 520 g/l, or even up to 540 g/l, of active material, and remain stable under cold (0 0 C) storage conditions or at a higher temperature (54 0 C). The active materials which may be included in 25 the composition of the formulations according to the invention are preferably water-soluble.

6 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 5 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 10 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 15 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. 20 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 25 branched, saturated or unsaturated Cl-C 6 hydrocarbon sRAL/ based radical, optionally substituted with a hydroxyl

W,

7 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 5 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 10 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 15 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 [a] and (b] will now be described in greater detail. 20 As has been mentioned previously, 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=0 0-M R in which: 77- 8

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 5 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 ) for which the 10 radicals R 3 , which may be identical or different, represent a hydrogen atom or a linear or branched, saturated or unsaturated C1-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 15 which formula R represents a linear or branched, saturated or unsaturated C 4

-C

12 hydrocarbon-based radical; R', 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 20 units of between 2 and 10. It is 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. 25 More particularly, the polyalkoxylated phosphate ester of formula (I) is such that the radical R is a C 4

-C

12 alkyl radical.

9 In addition, according to one particular embodiment of the invention, the radical R 2 represents a hydrogen atom. Moreover, a preferred variant consists of 5 compounds of formula (I) for which M, which may be identical or different, represent a hydrogen atom, an alkali metal, preferably sodium, or a group of the type

N(R

3 )W for which the radicals R , which may be identical or different, represent a hydrogen atom or, more 10 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, R1, R , M and n satisfy the 15 conditions mentioned above is preferably used as compound [a]. The compound [b] included in the composition of the plant protection formulations according to the invention corresponds to at least one polyalkoxylated 20 amidoamine of average formula (II) or (III): N~s~~4j, -6 10 R5 R4- CO - NH - (CH 2

)

2 - N -(CH 2 - CH 2 - 0)-(CH 2 - CH - O)p - H (11)

(CH

2 - CH - O)q - H R5 R5 R4 -CO - N -(CH 2 - CH 2 - 0) - (CH 2 - H - O)r H(I) (CH2 - CH - O)s - H

(CH

2

)

2 - N R5

(CH

2 - CH - O)t - H R5 in which: - R 4 , which may be identical or different, represent a linear or branched C 2

-C

2 2 alkyl or alkenyl, cycloalkyl 5 or alkylaryl hydrocarbon-based group, - R , 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 10 may be zero, with p + q between 1 and 20 and r + s + t between 1 and 20. According to one particularly suitable embodiment of the invention, the plant protection composition comprises an effective amount of a mixture 15 of polyalkoxylated amidoamines of average formulae (II) C RA and

(III).

11 According to a preferred variant of the present invention, the radical R2 represents hydrogen or a methyl radical. One particular embodiment of the invention 5 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 10 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, 15 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 20 polycondensation of alkylene oxide with an amidoamine of formula (IV) or (V) or a mixture of amidoamines of formulae (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 12 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 150OC, by continuous addition of the 5 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 (V), more particularly of about from 1.1 to 25 molar equivalents. This proportion is preferably 10 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 15 hydrocarbons, such as heptane or octane, aromatic hydrocarbons, such as toluene or cumene, ketoies, in particular such as 2-octanone, secondary or tertiary alcohols, such as isopropanol or tert-butanol, and water. 20 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 25 pentachloride. Similarly, a basic catalyst chosen in particular from alkali metal hydroxides, such as NaOH or KOH, and alkali metal alkoxides or alkaline-earth 13 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 5 phosphates, carbonates and 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 pointed out that compounds [a] and [b] 10 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 15 the reaction of one with the other. More particularly, the mixture results from the neutralization of compound [a] with compound [b]. In this particular case, compound [a] is, before the neutralization, in a form in which at least one of the radicals M corresponds to 20 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 25 to the present invention are such that the weight ratio [a]/[b] is between 80/20 and 20/80, limits excluded. More particularly, the said ratio is from 80/20 14 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. 5 According to one 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, limits excluded. In the formulations according to the 10 invention, the weight ratio of the active material to the sum of compounds [a] and [b] may vary between 1/5 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 15 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 20 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 25 simazine, isoxaben, atrazine, diuron, terbuthylazine, norflurazon, metamitron, chloridazon, sulphonylurea and trifluralin, alone or combined. Lid 15 The composition according to the invention is prepared by simply mixing the water-soluble plant protection active material with compounds [a] and [b], optionally in the presence of other additives. 5 The composition according to the invention may be prepared well before its use, but also just before use. In the latter case, compounds [a] and [b] are added to the plant protection active material, and optionally to the other additives, during the dilution 10 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] 15 and [b] 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. 20 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: 16 * 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 5 Geronazzo) is a mixture of phosphate mono- and diesters of formula (I) derived from saturated C 4 -Cio aliphatic alcohols, and comprising on average 3 to 8 ethylene oxide units, and M is isopropylammonium. 10 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 0 C 1 phase clear 2 months at 54 0 C 1 phase clear 2 months at 60 0 C 1 phase clear 15 EXAMPLE 2 A formulation with a glyphosate concentration ~AL of 490 g/l, expressed as acid equivalent, is prepared LjI 17 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 5 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 10 temperatures: STORAGE CONDITIONS RESULTS Initially 1 phase clear 2 months at 0 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, 5 comprising a mixture of the following compounds: [a] at least one polyalkoxylated phosphate ester of formula (I): 0-M R1 -O-(CH 2 -CHR2-O)n-P=0 0 - M in which: 10 R1 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, 15 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 ) for which the radicals R 3 , which may be identical or different, 20 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, 19 saturated or unsaturated C 4 -C 12 hydrocarbon-based radical; R', 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 5 units of 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 (11) (CH 2 - CH - O)q - H R5 R5 R4 - CO - N -(CH 2 - CH 2 - 0) - (CH 2 - CH -0)rH (I) (CH 2 - CH - O)s - H / / (CH 2 ) 2 - N R5 (CH 2 - CH - O)t - H 10 RS in which: 4 - R , which may be identical or different, represent a linear or branched C 2 -C 22 alkyl or alkenyl, cycloalkyl or alkylaryl hydrocarbon-based group, 15 - 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 20 between 1 and 20; these compounds being present in unmodified form, in a form corresponding to the reaction of one with the other, or in these two forms, the weight ratio of [a]/[b] being in the range 80/20 5 20/80, limits excluded.

2. Formulation according to Claim 1, characterized in that the active material is chosen from aminophosphates and aminophosphonates, such as glyphosate, sulphosate or glufosinate, as well as the 10 respective organic or inorganic salts of the abovementioned compounds.

3. Formulation according to the preceding claim, characterized in that the active material is chosen from glyphosate, more particularly in salt form, 15 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 or a linear or branched, saturated or unsaturated Ci-C 6 hydrocarbon based radical, optionally substituted with a hydroxyl 20 group, or sulphonium 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. 25

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 21 polyalkoxylated phosphate monoester, polyalkoxylated phosphate diester or a mixture of these two esters.

6. Formulation according to any one of the preceding claims, characterized in that the 5 polyalkoxylated phosphate ester of average formula (I) is a mixture of several compounds of average formula ().

7. Formulation according to any one of the preceding claims, characterized in that it comprises a 10 mixture of polyalkoxylated amidoamines of average formulae (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 15 radical R2 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, which may be identical 20 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.

10. Formulation according to any one of the preceding claims, characterized in that it comprises, 25 as polyalkoxylated amidoamines, polyethoxylated hydroxyethylcocoylamidoamines comprising on average 4 22 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 5 ratio of [a]/[b] is between 80/20 exclusive and 40/60, preferably between 80/20 exclusive and 45/55.

12. Formulation according to any one of the preceding claims, characterized in that the weight ratio of the active material to the combination of 10 compounds [a] and [b] ranges 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 15 agents, colorants, antifoams 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 20 following products: simazine, ixobazen, atrazine, diuron, terbuthylazine, norflurazon, metamitron, chloridazon, sulphonylurea or trifluralin, alone or combined.