FR2692439A1 - Phytotoxic agent contg. glyphosate ammonium salt - as stable, non-toxic, easily transported water-soluble form of herbicide N-phosphono:methyl-glycine - Google Patents

Abstract

Product for application as phytotoxic agent contains as active agent an ammonium salt (I) of N-(phosphonomethyl)-glycine (NPMG). (I) is pref. the monoammonium salt (IA). Also claimed are: (i) conc. compsns. for on-site prepn. of phytotoxic formulatons by dissolution in water, consisting of powder or granules contg. (I) and one or more adjuvants selected from wetting agents, surfactants and powders; and (ii) phytotoxic prepns. contg. (I) and a vehicle. USE/ADVANTAGE - (I) is a water-soluble form of the phytotoxic agent (herbicide) NPMG, i.e. glyphosate, NPMG is useful for post-emergence control of undesirable vegetation, including established and aquatic vegetation. Compared with the monoisopropanolamine salt (II) of NPMG (previously used as water-soluble form of NPMG). (I) have comparabel activity, lower toxicity and higher content of NPMG. (I) are stable crystalline solids, which are easier and cheaper to transport in bulk (e.g. in sacks) than (II) (transported as 48% aq. soln.). Pref. concn. (I)-contg. compsns. contain kaolin, attapulgite, silica or diatomaceous earth as powder additive, polyethoxylated nonylphenol or sodium lanylsulphate as surfactant; and polyvinyl alcohol or sodium naphthalenesulphonate as dispersant. In an example, powdered NPMG was added iin portions to a stirred soln. of ammonium carbonate (96g) in water (200 ml) at room temp. The soln. was stirred until CO2 evolution ceased, filtered and concn. to 50 ml. (IA) was pptd. as white crystals. No examples of compsns. contg. (I) are given, although tests are described showing that 90% (IA) has comparable activity with 48% (II).

Description

 The present invention relates to a product to be applied as a phytotoxic agent, and a concentrated composition and a phytotoxic preparation containing such a product.

 N- (phosphonomethyl) glycines are a family of compounds well known for its phytotoxic action (see Argentinian Patent AR-A-188,592).

One of them, whose trade name is "Glyphosate", is a very effective phytotoxic tricarboxylic acid (see the Merck index) although its use on an industrial scale has not been successful because is a compound having reduced solubility in aqueous medium and in organic solvents compatible with the agricultural operation; it is the same with other compounds of this family.

This adaptability and the reduced ability of this acid (ie Glyphosate) to form solutions of commercial interest has led to the substitution of acid for its salts, which are generally much more soluble, such as This is the case for Group IA and Group IIA salts as well as for amine salts, especially primary organic amine salts (see Merck Index). In practice these are compounds from the salification of at most two protonizable atoms of N- (phosphonomethyl) glycine corresponding to the formula:

Among all the salts proposed and tested, the monosel of isopropylamine of Glyphosate (or monobasic salt) known under the name of MIPA (mono
N- (isopropylamine phosphonomethylglycinate) is remarkable for its very general use, because of its efficiency and its ability to formulate commercial formulations.

 The post-emergence treatment of unwanted vegetation and established herbaceous vegetation (including aquatic plants) found in the isopropylamine monosel of Glyphosate, a very effective ally (both for its phytotoxic activity on weeds and for its safety for the cultures) of very widespread use compared to other salts of N-phosphonomethylglycine.

MIPA is commercially available in concentrated aqueous solution (48%) ready for dilution "in situ" in water as a step prior to its application.

 Despite its broad acceptance, MIPA has some practical and economic disadvantages. Indeed it is a concentrated aqueous solution that is distributed packaged in barrels or plastic drums not recoverable. At the unrecoverable cost of packaging is added that of the transport of a product containing 52% of inert mass. In addition, the toxicity of isopropylamine undesirably increases the toxicity of the final product, since GLyphosate is less toxic and less corrosive than the isopropylamine salt (MIPA).

 This disadvantage, common to all distributed products that are formulated in whole or in part to be diluted "in situ" was analyzed by the applicant in order to be able to have a product with the phytotoxic properties of Glyphosate but without the disadvantages mentioned above of its isopropylamine monosalt (MIPA).

The solution found by the plaintiff now makes it possible to have, at the commercial level, the
Ammonium glyphosate, a solid, crystallized, stable and readily soluble product in water with which it is possible to prepare "in situ" aqueous solutions with the same utility and effectiveness as MIPA preparations ( by diluting the concentrated solution) and of lower toxicity.

 In AR-A-188 592 and US-A-3 977 860, the description of N- (phosphonomethyl) glycines is always associated with the mention of alkali or alkaline earth metal salts, amine salts and ammonium salts of transition metals.

In particular, reference is made only to the possible obtaining and application of the potassium, calcium and magnesium monosels and of the dimethylamine monosel already mentioned in the aforementioned prior art. By contrast, the ammonium salts are generically mentioned in the form of a simple list of bases that are strong enough to salify at least one of the three protonizable hydrogen atoms of the molecule.
Glyphosate.

 Nevertheless, the production of ammonium monosels is not expressly mentioned, but in addition the process detailed in example 6 of US Pat. No. 3,977,860 seems to contradict the information previously given in the same text (column 5 lines 3-6), where it is claimed to obtain N- (phosphonomethyl) glycine salts by neutralization with "appropriate bases, carbonates, ammonia, organic amines".

Indeed, according to the example 6 mentioned, the treatment under reflux of N- (phosphonomethyl) glycine with NH3 (aqueous) gives the corresponding amide; it is the same in Example 9 when using pyrolidine instead of ammonia while the same reaction conducted at room temperature would prepare the piperidine monosel as described in the generalities that supplement the text of example 4.

 Despite the time elapsed since the promotion and disclosure of Glyphosate substitution by the previously mentioned salified Glyphosate, this aspect of agrochemicals has been covered by the widespread use of isopropylamine monosel on which there is abundant information, although that there is no complete information on the possibilities of ammonium salts.

The field of the present invention is also described in the following documents and works: AR-A-221 857; "Agricultural adjuvant spray", by Lori. A. THOMSSO; "Revised EPA Lest of inerts of toxicological concen" (November 22, 1989); Round Up,
Vision, POER, and 1,4-Dioxin: Mary O'Brien - Journal of Pesticide
Reform, Vol. 9, No. 4, winter 1990; Ecological and Public
HealthImplications Associated with the USA of fliphovate
Herbicide - David H. Monroe Ph.D. - ECN October 1, 1988.

The object of the present invention is to upgrade the application of the other salts of the
N- (phosphonomethyl) glycine, in particular ammonium salts, more particularly ammonium monosalt, marginalized or displaced from the agrochemical domain by the monopolistic application of isopropylamine monosalt (MIPA).

 The main object of the present invention is thus constituted by the ammonium salts of N- (phosphonomethyl) glycine as phytotoxic agent "per se" in particular the ammonium monosalt of N- (phosphonomethyl) glycine.

Another object of the invention is the preparation of compositions concentrated in particles, in powder or in granules, soluble in water comprising ammonium salts, such as the monoammonium salts of the
N- (phosphonomethyl) glycine as a phytotoxic agent and comprising at least one of the following additives: adjuvants, humectants and surfactants. These concentrates make it possible to transport and distribute the harmful agent, without burdening the transport costs because of the dead weight or useless that represent the bulky diluents as it is the case for the water in the classic preparations of MIPA. In addition, the concentrated compositions according to the invention can be stored and transported in bags or cans, the cost of which is certainly smaller than that of the bulk transport of MIPA in drums or in bulk. Moreover, this makes it possible to formulate "in situ phytotoxic compositions ready for use, by dissolution in water or by mixing with inert diluents powder.

 Another object of the invention is the phytotoxic preparations which contain ammonium salts of N- (phosphonomethyl) glycine, such as ammonium monosalt, by dilution with water or with inert diluents. powder, said ammonium salts or particular concentrated compositions mentioned.

 Ammonium Glyphosate (or ammonium monosalt of N- (phosphonomethyl) glycine) (which will subsequently be referred to as monoammonium salt of N- (phosphonomethyl) glycine or monoammonium salt) is a crystalline solid of color white water, the phytotoxic activity of which is similar, under the same conditions, to those of aqueous solutions of N- (phosphonomethyl) glycine isopropylamine monosalt, as has been demonstrated by the experiments or by the "field tests" which will be detailed later.

 The product or composition concentrated according to another object of the invention, is in the form of powder or granules (pellets) soluble in water, in combination with adjuvants, or wetting additives and / or dispersing or emulsifying agents depending on the type of preparation you want to apply. Water is obviously the most advantageous solvent when it comes to liquid preparations, whether solutions or emulsions and dispersions. The concentrated monoammonium N- (phosphonomethyl) glycinate compositions according to the present invention do not depend on a particular class of wetting agents. Wetting agents and dispersing or emulsifying, anionic, cationic and nonionic agents are used interchangeably. Among the most suitable wetting agents are, inter alia, nonylphenolpolyethoxylated, lanylsulphonates (for example sodium).

 Among the preferred dispersants there may be mentioned polyvinyl alcohol, methylcellulose, sodium naphthalenesulphonate, etc.

 The powdered or granular compositions or the preparations according to the present invention may be presented in the form of products or dry preparations for spraying, by diluting these compositions or ammonium glyphosate with inert solid diluents known as "extenders" such as kaolin, attapulgite, silica, diatomaceous earth, etc., in varying proportions depending on the final type of preparation.

 As is usual in the agrochemical field, the powdered or granulated compositions of the present invention may include additional bioactive components such as fertilizers (eg urea), insecticides (carbamates, triazines, acetic anilides, etc.).

Obtaining ready-to-use products from the ammonium salts of Glyphosate or concentrated compositions according to the invention corresponds to the technique which is applicable in the conventional practice for preparing solutions, emulsions or dispersions. from a powdery or granular material. Those skilled in the art will certainly not need any additional information on this subject. Nor is it necessary to detail how the diluted forms (solutions, dispersions, etc.) should be used from the powdered or granulated concentrate material of the present invention; it follows the technique employed in the classical practice of
N- (phosphonomethyl) glycine already described in Argentinian Patent 188,592, hereby incorporated by reference.

 In the following examples and tests, the preparation of ammonium monosalt of N- (phosphonomethyl) glycine and the results of the field tests are described by way of illustration.

EXAMPLE 1
Preparation of N- (phosphonomethyl) glycinate
mono ammonium
Fractionally N- (phosphonomethyl) glycine is finely pulverized fractionally to an ammonium carbonate solution (96 g of ammonium carbonate in 200 ml of water) at room temperature and stirring constantly until stopping the release of CO2. The solution is filtered and concentrated by distillation to 50 ml. Concentrate (50 ml) is separated at room temperature by a white crystalline mass which corresponds to the title compound.

TEST 1 (1) PRE-INSTALLATION DATA
Location: Tunuyan - Mendoza Location: Route 40
Km 82.

(2) DATA ON CULTURE
Culture: apple
Variety / hybrid. Growth level
* Red Delicious with fruits 2 cm in diameter.

Planting date:
Density: traditional culture: plants at 8 x 8 m.

 Health status of culture: very good.

(3) CLIMATE CHARACTERISTICS
Dry with a relative humidity of 60 to 70% and a
temperature between 200C and 220C for the month
of November.

(4) CHARACTERISTICS OF THE PLOT
Soil type: clayey free.

 Soil moisture: good.

Parcel history: ---
Previous culture: -----
Culture work: ----- (5) ADVENTICES / PARASITES / DISEASES TO STUDY
Vulgar Name: Scientific name Development status
* Sorghum Aleppo Sorghum HalepensisTallage, flowering 40%
* Quackgrass Cynodon dactylon Vegetative state:
flowering 20%
Other pests / diseases present: (6) INSTALLATION DATA
Processing Date: November 20, 1991
Temperature: 210C
Relative humidity: 60%
cloudiness:
Wind: ---- Km / h Clear / fog: ----
Start time: 18:00 hours
End of treatment time:
CO2 backpack sprayer
Dose: 215 1 / Ha
Pressure: 317 kPa (46 psi)
Spouts: 11003
Speed: (7) TREATMENT

<tb> PRODUCT <SEP> A <SEP> DILUTION <SEP> A
<tb><SEP> USE <SEP> USE
<tb> TRAIT. <SEP> PRODUCT <SEP> IA <SEP> PC <SEP> cc / par.cc / sob
<tb><SEP> 1 <SEP> Witness
<tb><SEP> 2 <SEP> Salt <SEP> MIPA <SEP> 48% <SEQ> 2.880 <SEP> g / ha <SEP> 6 <SEP> 1 / ha
<tb><SEP> 3 <SEP> Salt <SEP> monoammonium <SEP> 90% <SEP> 2.880g / ha <SEP> 3.2 <SEP> 1 / ha
<tb><SEP> 4
<tb><SEP> 5
<tb> 6
<tb> 7
<tb> 8
<tb> 9
<tb><SEP> 10
<tb> 11
<tb> 12
<Tb>
Prepared volume / treatment: liters.

adjuvants:
Observations: Only one dose was tried for each
produced with three treatments.

Plots of 2 mx 8 m = 16
IA: Active ingredient.

PC: Commercial product.

As:
Comparative test of the behavior of herbicides
Monoammonium Glyphosate 90% (= Salt of
monoammonium 90%) and Isopropylamine Glyphosate 48%
(= 48% MIPA salt) for weed control
in apple crops.

B. Objective:
Compare the behavior and action of the herbicide
90% ammonium salt compared to Sel herbicide
MIPA 48%.

C. Culture:
Apples.

D. Locality:
Tunuyan-Mendoza area.

E. Statistical con- ception:
F. Size of parcels:
2 x 8 m = 16 m2.

G. Evaluation Method:
Visual percentage of control.

H. Application:
Moment: in full vegetation (30-80 cm high
weeds).

 Number of treatments: 1 dose with 3 passages.

 Volume used: 215 1 / Ha.

(9) EVALUATION

<SEP> AVERAGE <SEP> OF <SEP> BLOCKS <SEP> A <SEP> - <SEP> B <SEP> - <SEP> C <SEP> AVERAGE <SEP> OF <SEP> BLOCKS <SEP> A <SEP > - <SEP> B <SEP> - <SEP> C
<tb><SEP> Days <SEP> since <SEP><SEP> Days <SEP> since <SEP> on
<tb><SEP> Date: <SEP> 28-12-91 <SEP> Date: <SEP> 10-1-92
<tb><SEP> treatment <SEP>: <SEP> 38 <SEP> treatment <SEP>: <SEP> 51
<tb><SEP> COUNT <SEP> FX <SEP> COUNT
<tb><SEP> CULTURE
<tb> A <SEP> B <SEP> C <SEP> D <SEP> E <SEP> F <SEP> G <SEP> H <SEP> A <SEP> B <SEP> C <SEP> D <SEP > K <SEP> @ <SEP><SEP> @ <SEP> H
<tb> 0 <SEP> - <SEP> - <SEP> 0 <SEP> - <SEP>
<tb><SEP> 1 <SEP> 65 <SEP> 70 <SEP> 1 <SEP> 85 <SEP> 80
<tb> 2 <SEP> 68 <SEP> 70 <SEP> 2 <SEP> 85 <SEP> 88
<tb><SEP> AVERAGE <SEP><SEP> BLOCKS <SEP> A <SEP> - <SEP> B <SEP> - <SEP> C
<tb><SEP> Date: <SEP> 28.2.92 <SEP> Days <SEP> since <SEP> the
<tb><SEP> processing <SEP>: <SEP> 99
<tb><SEP> 0 <SEP> - <SEP>
<tb><SEP> 1 <SEP> 95 <SEP> 90
<tb><SEP> 2 <SEP> 95 <SEP> 95
<Tb>
A: Sorghum of Aleppo D: G:
B: Quackgrass R: H:
C: F: (10) Conclusions:
90% monoammonium salt had a similar herbicide behavior as salt
MIPOA 48% using the same dose of active ingredient per hectare.

Monoammonium salt 90% just like salt
MIPA 48% were effective as herbicides against weeds studied at the indicated dosages and conditions.

TEST 2: TEST OF GLYPHOSATE HERBICIDE
MONOAMMONIUM CONCENTRATED WITH 90% SOLUBLE POWDER:
Goal:
Comparison of two formulas based on glyphosate for the treatment of weeds in citrus cultivation.

Location of the test:
Property "La Concepcion".

Locality: Fighieras.

Responsible:
Ing. Luis Carranzio.

Culture:
Citrus - 400 trees / Ha.

Vegetative state:
Flowering.

Soil moisture:
Good.

Adventists present:
Aleppo sorghum (Sorghum Halepensis).

Vegetative state of the weed:
Tallage and 10% flowering.

Processing date: 18.11.90.

Temperature: 250C.

Treatment equipment:
CO2 backpack sprayer.

Size of the nozzle: 8002. Even distribution.

Volume used by Ha: 200 1.

General observations:
Adventures well developed.

Product to be tested: - Isopropylamine glyphosate 48% = MIPA salt 48%.

- Ammonium glyphosate 90% = 90% monoammonium salt.

treatments:
One dose of each product with three repetitions.

<Tb>

I <SEP> I <SEP> I
<tb> g <SEP> Treat <SEP><SEP><SEP><SEP><SEP>SEP>SEP><SEP>SEP><SEP>SEP><SEP> Dose % <SEP> I
<tb> ment <SEP> Product <SEP> principle <SEP> formulation <SEP> control
<tb> N <SEP> active / Ha
<tb> Ol <SEP> Salt <SEP> from <SEP> MIPA <SEP> 2.880 <SEP> g <SEP> 6 <SEP> 1 / Ha <SEP> 90%
<tb><SEP> 48% <SEP> I <SEP> I <SEP>
<tb><SEP> 02 <SEP> Salt <SEP> of ammo- <SEP> 2.880 <SEP> g <SEP> 1 <SEP><SEP> 3.2 <SEP> Kg / Ha <SEP> I <SEP><SEP> 92% <SEP> I <SEP>
<tb> nium90%
<Tb>
Evaluation::
The effect of the herbicide on each of them was evaluated 20 days and 32 days after treatment with a mean control for both observations of 90-92% with both herbicides.

 The doses of active ingredient / Ha used are identical.

Conclusion:
The observations obtained after the trial show:
1. Glyphosate Monoammonium 90% Herbicide has a similar action as Glyphosate Salt MIPA 48%.

 2. Both herbicides were effective in the control of Aleppo sorghum at the tested doses and under the conditions described.

TEST 3: TESTING THE GLYPHOSATE HERBICIDE
MONOAMMONIUM 90% COMPARISON WITH ANOTHER
FORMULATION
Place:
Rosario, Zabella (experimental field).

authors:
Ing. Agr. Luis Carrancio
Products tested: - 90% monoammonium glyphosate (= 90% ammonium salt).

- Isopropylamine glyphosate 48% (= MIPA salt 48%).

Purpose: * Analysis of behavior and herbicidal action.

* Comparison of behavior and action with 48% MIPA salt herbicide.

 This trial was conducted in Rosario on an uncultivated area dominated by quackgrass (Cynodon dactylon).

 During the test, the weather conditions and the state of the weed were appropriate to allow adequate treatment and subsequent satisfactory development of the latter.

The test diagram was as follows:
Four treatments and one control were performed with 4 replicates. The size of each plot was 14 m2.

 The treatment was carried out with a 3 head spout and 11003 nozzle CO2 backpack sprayer.

 The results obtained were satisfactory.

The behavior of 90% monoammonium salt herbicide was similar to that of 48% MIPA salt herbicide.

Introduction:
The purpose of this test is to evaluate the behavior, action and yield of 90% ammonium salt as a herbicide.

Four treatments were done with a control. One of the treatments was performed with MIPA salt herbicide 48%.

Materials and methods:
The trial was conducted on a non-cropped area with absolute predominance of quackgrass (Cynodon dactylon) at vegetative growth level; he completely covered the ground.

 Plots of 14 m2 each (2.80 x 5 m) were used with 4 repetitions.

 The treatment was carried out with a CO2 spool, 3-spout head and nozzles 11003. This scheme covered half of the width of the plot for which two passes were made (return) by superimposing the range of the internal nozzle during the second pass. The 2.80 meters of the plot width were covered in this way.

Volume sprayed by Ha: 215 1.

Working pressure: 317 kPa (46 psi).

Temperature: 250C.

Relative humidity: 65%.

Wind:
cloudiness:
Spray time: 10:30.

Date of spraying: 20.09.89.

treatments:
IA Product
Commercial 1. Monoammonium salt
90% (1) 1,800 g / Ha 2 kg / Ha 2. Monoammonium salt
go 2 880 g / Ha 3.2 kg / Ha 3. Monoammonium salt
90% 3 600 G / Ha 4 kg / Ha 4. MIPA salt 48% (2) 2 880 g / Ha 6 1 / Ha
T. Control (1) Ammonium glyphosate.

(2) Isopropyl salt of Glyphosate.

Evaluation: 38 days after treatment.

BLOCK
ABCDX treatment
01 65 60 60 62 61.75
02 62 65 70 65 65.50
03 70 70 68 70 69.50
04 70 65 65 65 66.25 49 days after treatment:
BLOCK
ABCDX treatment
01 85 80 85 85 83.75
02 85 88 80 88 85.25
03 82 90 90 85 86.75
04 88 85 87 85 86.25 110 days after treatment:
BLOCK
ABCD treatment
01 95 90 90 95 92.50
02 95 95 96 95 95.25
03 97 96 99 96 97.00
04 95 90 90 98 93.25
conclusions:
Monoammonium Glyphosate 90% behaved under the test conditions detailed above, as a herbicide acting on grasses.

 The test showed that this herbicide acts on weeds treated in a manner similar to that used with MIPA 48% salt herbicide, the dose being comparable to treatment No. 2, with 3.2 kg / ha of commercial product.

 That is, in treatments Nos. 2 and 4, identical amounts of active ingredient / Ha of each of the formulations compared were used.

Claims (11)

 1. Product intended to be applied as an agent  phytotoxic, characterized in that it comprises as  active agent of ammonium salts of N- (phosphonomethyl) glycine.  2. Product according to claim 1,  characterized in that the active agent is monosel  of ammonium of N- (phosphonomethyl) glycine.  3. Concentrated composition useful for preparing  on the site phytotoxic formulations by  dissolution in water, characterized in that  composition is a powdered or granular product of which  the active agent comprises ammonium salts of the N- (phosphonomethyl) glycine according to claim 1 or  2, and at least one of the adjuvants formed by the agents  wetting agents, surfactants and additives  powdery.  4. Concentrated composition according to  claim 3, characterized in that the salt  ammonium is the ammonium monosalt of the  N- (phosphonomethyl) glycine.  5. Concentrated composition according to  claim 3 or 4, characterized in that the  powdery additives are chosen from the group formed  by kaolin, attapulgite, silica and earth of  diatoms.  6. Concentrated composition according to one of the  Claims 3 to 5, characterized in that the adjuvant  is selected from nonylphenolpolyethoxylated and  sodium lanylsulfonate  7. Concentrated composition according to one of the  Claims 3 to 5, characterized in that the adjuvant  is a dispersing agent that is polyvinyl alcohol  or sodium naphthalenesulfonate.  8. Phytotoxic preparation, characterized in that it comprises as active agent at least one of the ammonium salts of N- (phosphonomethyl) glycine according to claim 1 or 2, in a vehicle acceptable in the agronomic field.  9. Phytotoxic preparation according to claim 8, characterized in that said active agent is the ammonium monosalt of N- (phosphonomethyl) glycine.  10. Phytotoxic preparation according to claim 8 or 9, characterized in that this preparation is an aqueous solution.  11. Phytotoxic preparation according to claim 8 or 9, characterized in that it is a powdered preparation which comprises one of said ammonium salts as active agent, and a powdered diluent.