PL172415B1 - Permanent herbicidal or plant growth regulating composition PL - Google Patents

Abstract

Constant fungicidal composition or plant growth regulating composition based on glyphosate / glyphosine salt, characterised in that as an active agent it contains 0.1-99.9 percent non-hygroscopic monoammmonium, especially mono-isopropylammonium, salts of a compound with formula 1, in which R1 is hydroxyl or alkyl group, A is (C1-4) alkylamine or (C1-4) aminalkyl group, containing primary or secondary amine groups, preferably -CH2-NH- or -CH(NH2)-CH2-B groups, B is ammonium or alkylammonium ion in a form free of diammonium salts with formula 2, whereby R1, A and B have the above meaning and it contains potential carriers or supporting substances.

Description

The present invention relates to a herbicidal or plant growth regulating composition which comprises glyphosate / glyphosinate salts as an active ingredient.

The most important representative derivatives are the (alkyl / ammonium) salts of N- (phosphonomethylglycine called glyphosate and (3-amino-3-carboxypropyl) -methanophosphinic acid called glyophosinate.

Such salts are known as active ingredients of pesticides and their production and properties are described in the literature, e.g. in U.S. Patent Nos. 3,315,675, 3,405,531, 3,868,407, 4,140,513, 4,315,765.4 387,676. and Hungarian Patent No. 184,601, as well as United States Patent No. 3,288,846.4 507 250, 4147 719, 4,487,742, German Patent No. 3,312,165, European Patent No. 249,188, 265,412, 301 391 and Japanese Patent Nos. 60 248 190, 02 190 196, 59 181 288.

However, these salts are known only in their hygroscopic form, which binds atmospheric moisture and were therefore sold in aqueous solutions. This was a great inconvenience, because it required special packaging, which after use was a troublesome waste, difficult to manage due to the residue of toxic substances. Transport of toxic liquids is also more difficult and dangerous than solids.

More attempts have been made to solve this problem.

Various additives have been proposed as auxiliaries, e.g. to obtain compositions in the form of a wettable powder (European Patent Nos. 256 942,

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352 508; Japanese Patent Specifications No. 0142 409.5818 31162 175 407.62 175 408 and U.S. Patent No. 4,405,531). In practice, however, it was necessary to protect these powders from moisture, use the entire packaging immediately after opening, so that there would be no hygroscopic residues, store the products in proper conditions, etc., but it did not give the expected results. Another approach to solving this problem was to propose that the product be spray dried (Japanese Patent 63 10 701) and another suggestion to mix the salt with a solvent and molten surfactant to obtain a mixture from which the solvent had to be removed and the surfactant cooled to a solidification, and then formulate a solid product (European Patent No. 0 206 537). Although salt formation is carried out by reacting an acidic reagent with a basic reagent in an aqueous medium (e.g. Hungarian Patent No. 185,003, Swiss Patent No. 620,812 and German Patent No. 2,717,440), there are publications in the literature on reacting an acid with a basic reagent without solvents. The molten surfactant is added to the reaction mixture, and the agent form is formed after cooling the mixture. (See also Spanish Patent No. 530,743, which uses benzene or water as a solvent in a similar method).

In all publications one can find statements that the obtained products are hygroscopic (e.g. German patent no. 2717 440, Swiss patent no. 620 812 in relation to the ammonium salt of glufosinate), and in some it is stated that the products are solidified in the form of glassy materials, which can be ground in a mortar but which are still hygroscopic during storage.

Hungarian patent application No. 1322/90 describes new formulations of N- (phosphonomethyl) -glycine in water-soluble bags containing sodium or potassium salt of N- (phosphonomethyl) -glycine in the form of a wettable powder that is easy to apply. According to this publication, the authors have not been able to produce similar formulations with the mono-isopropylammonium salt of N- (iosphonomethyl) -glycine due to its extremely hygroscopic nature. Also, according to this publication, aqueous solutions of the mono-isopropylammonium salt were not suitable because the solution dissolves the pouch material before use.

Tests of the products obtained according to some known methods (e.g. European Patent No. 02 56 608 and Spanish Patent No. 530 743) have been undertaken to show that the products obtained were not strictly a mono-isopropylammonium salt.

The basis to the present invention is the recognition that the known processes always result obtained the mono-isopropylammonium shown in the accompanying drawings by formula 1 wherein R ¹ is hydroxy or alkyl, A is a group Cn4alkiloaminowe or aminoalkyl containing primary or secondary amino groups, preferably the group - CH2-NH- or -CH (NH2) -CH2-, B is an ammonium ion or an alkyl substituted ammonium ion which, however, contains some amounts of the diammonium salts represented by formula 2.

It has been found that di-ammonium salts differ significantly from mono-ammonium salts in their hygroscopicity such that small amounts of di-ammonium salts drastically affect the hygroscopic properties of such salts.

The results of the analyzes carried out by classical analysis methods do not always indicate the presence of the di-ammonium salt of formula II in the mono-ammonium salt of formula I due to the simultaneous presence of free acids of formula III which masks the presence of the di-ammonium salt.

When examining N- (phosphonomethyl) -glycine, obtained by known methods, using FT-IR spectroscopy, it was found that the products always contained oscillation bonds for the carbonyl group of free N- (phosphonomethyl) -glycine at wavelengths of 1717 and 1733 cm ⁴ and oscillations for the free carboxylate group in diisopropylammonium salt of N- (phosphonomethyl) glycine at 1561 and 1633 cm ^-1 . A change in the proportion between these bonds shows a change in the ratio of components. This was demonstrated by preparing standard samples of mono-di-isopropylammonium salts and obtaining calibration spectra.

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It can be seen from the IR spectroscopic data that glufosinate also exists in two different forms of twin ionic structure. Thus, a carboxyl group may appear both in dissociated form with an absorption band of 1640 and 1600 cm ⁴ and in undissociated form with an absorption band of 1733 and 1728 cm ¹ .

Very careful when preparing samples, sometimes mono-ammonium salts, which are contaminated with di-ammonium salts as well as free acid, undergo additional reaction steps as the samples dissolve prior to making their spectra with results that are not typical of the product before measuring.

Figures 1-6 show the results of the tests carried out.

Fig. 1 shows the X-ray diffraction spectrum of the α-crystals of the mono-isoproylammonium salt of N- (phosphonomethyl) -glycine in the intensity versus angle. In Fig. 2 X-ray diffraction spectrum of the β-type crystals of the mono-isopropylammonium salt of N- (phosphonomethyl) -glycine in the intensity versus angle system. Figure 3 shows the result of DSC testing for α-crystals of mono-isopropylammonium salt of N- (phosphonomethyl) -glycine, in the heat flow vs. temperature system in ° C; Fig. 4 DSC study of the β-type crystals of N- (phosphonomethyl) -glycine mono-isopropylammonium salt, heat flow versus temperature in ° C; 5 Fig. 5 DsC study of α and β crystals of the mono-isopropylammonium salt of N- (phosphonomethyl) -glycine, heat flow versus temperature in ° C; Fig. 6 shows the spectrum of α-crystals of the mono-isopropylammonium salt of N- (phosphonomethyl) -glycine in the absorbance system versus wavenumber.

When comparing the spectra obtained with our assay, it is clear that in the products thus obtained, an absorption band disappears for the undissociated carbonyl group at -1730 cm-1 and multiply the baseband dissociated carboxyl group characteristic for the salts at 1640 and 1600 cm ^-1.

With the above spectroscopic data in hand, HPLC methods and analytical methods of automatic melting point measurement can be used to completely determine the properties of the new salts.

The term non-hygroscopic used according to the invention means that when exposed to a temperature of 25 ° C in an environment with a humidity of 60%, there is no appreciable water uptake within 3 weeks or an uptake of less than 0.1%. The salts are crystalline, have melting point ranges other than those published heretofore, and their water solubility is somewhat higher compared to salts prepared by known methods.

According to the invention, a solid herbicidal or plant growth regulating composition based on a glyphosate / glyphosate salt as active ingredient comprises 0.1-99.9% of non-hygroscopic mono-ammonium, especially mono-isopropylammonium, salts of a compound of formula I in which R1 is hydroxy or alkyl, A is (C1-4) alkylamino or (C1-4) aminoalkyl containing primary or secondary amino groups, preferably -CH2-NH- or -CH (NH2) -CH2- groups, B is ammonium or alkylammonium ion, free of diammonium salts of formula II, wherein R, A and B are as defined, and includes optional excipients.

The preferred active ingredients of the compositions according to the invention are solid, crystalline non-hygroscopic mono-isopropylammonium N- (phosphonomethyl) -glycines of the α and / or β crystal type.

The mono-isopropylammonium salt of N- (phosphonomethyl) -glycine (glyphosate), crystal type a, has a melting point of 158-163 ° C and the following lattice values measured by X-ray diffraction: 110, 90.6, 59.4, 41, 3 and 37.1 nm and the following absorption bands obtained by FT-IR spectroscopy: 1660, 1553, 1545, 1075, 515 and 475 cm'-.

The mono-isopropylammonium salt of N- (phosphonomethyl) -glycine (glyphosate), crystal type β has a melting point of 143-155 ° C and the following lattice values measured by X-ray diffraction: 70.0, 48.3, 44.7, 33.5 and 28.15 nm and

172 415 the following absorption bands obtained by FT-IR spectroscopy: 1645,1594,1561, 1066, 500 and 455 cm1

3-Amino-3-carboxypropyl-methanophosphinic acid mono-isopropylammonium salt (glyphosates) has a melting point of 199-203 ° C and the following absorption bands obtained by FT-IR spectroscopy: 1640,1601,1530,1138,1037, 750 and 471 cm ' ¹ .

The compositions according to the invention contain, in addition to the active ingredient, adjuvants and additives that are customary in the pesticide industry and / or products which favorably modify the properties of the composition for agricultural purposes.

Auxiliary substances in the compositions are inert carriers such as diatomaceous earth, kaolin, attapulgite, fuller's earth, montmorillonite, bentonite, synthetic silicic acids, thiosulphates and other agents.

Surfactants, surface tension reducing agents, cationic, anionic, nonionic or amphoteric agents can be used as additives and auxiliaries. Other additives include adjuvants, adhesion promoters or reducing agents, dust and foam inhibitors, dissolution promoters, solid and liquid carriers, dispersing and coloring agents, products to increase resistance to rain or corrosion, activators, etc.

The preferred auxiliaries are: water-soluble alkyl sulfates and phosphates, alkyl benzene sulfonates, naphthyl and alkyl naphthyl sulfonates, sulfated fatty alcohols, amines, acid amides; sulphated or sulphonated fatty acid esters, sulphonated vegetable oils, alkylphenols, polyoxyethylene derivatives, polyoxyethylene alkyl, alkylene, alkynyl and alkylaryl ethers, polyoxyethylene alkylaryl ether and formaldehyde condensates, polyalkoxyalkylene sorbitalenes, sorbitan blockers, polyoxyolylene glycers, and polyalkylene glycers and mixtures thereof, polyoxyalkylene alkylamines, e.g. ethoxylated tallow amine, cocoa, etc., phospholipids, alkyl polyglycoside derivatives, methyl, hydroxyethyl and hydroxymethyl cellulose and other cellulose derivatives, lignosulfonates, quaternary ammonium salts, silicone wetting agents, silicone fluoroaliphatic agents surfactants, tetraethoxysilane derivatives etc.

The compositions may advantageously contain as special additives inorganic or organic nitrogen-containing products such as urea, urea derivatives or inorganic salts such as chloride, sulphate, phosphate, calcium borate, sodium ammonium etc. They may also contain paraffinic hydrocarbons, mineral oil fractions, natural oils vegetable, organic solvents.

In addition to the above ingredients, the compositions according to the invention may contain other products which are themselves pesticidal or biologically active. These can be insecticides, fungicides, herbicides, plant growth regulators or chemical fertilizers, trace elements, etc.

The compositions according to the invention are prepared by mixing the active ingredient of general formula I as defined above in an amount of 0.1-99.0% together with adjuvants used in pesticides and / or products which favorably modify the properties of the active ingredients, including products which they have biological properties or are known as components of pesticides.

Depending on the intended use, solid compositions are prepared in the form of granules, lozenges, tablets, and powders.

Due to the fact that the active ingredient in the composition according to the invention is solid, non-hygroscopic, the composition can be supplied in bags made of a water-soluble polymer, very convenient to use, with a size of 0.1-10 kg, e.g. 0.5-5 kg. kg. Preferably, these bags are completely filled with the agent of the invention, but some space may be left in them to facilitate the addition of other desired substances before use. Such bags are solid and flexible at ambient temperature and humidity. The wall thickness of the pouch is usually 20-100, preferably 30-60 micrometers, and the walls are welded together from at least one side.

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Water-soluble pouches are known per se. They can be made of water-soluble polymers of vinyl alcohol, especially vinyl alcohol plasticized with polyols, including methyl cellulose, ethylene oxide copolymers, vinylpyrrolidone or vinyl acetate polymers, gelatin, carboxymethylcellulose, dextrose, hydroxyethyl cellulose or methyl cellulose in combination with polyhydric alcohols. ethylene, propylene glycol, glycerin, sorbitol and others.

Plastic bags, in addition to the composition according to the invention, may also contain additional products such as protective colloids, thixotropic products, stabilizers, etc. These bags are thrown into the required amount of water and mixed intensively. The polymeric material disappears in about 2 minutes, the herbicide dissolves or disperses in the water and the liquid thus obtained is applied to the field as required.

A method of destroying undesirable plants or influencing plant growth consists in treating the plants with an effective amount of the herbicide or plant growth regulating agent of the invention by dispersing the agent over the plants as a solution, dispersion or suspension in water or in a mixture of water and an organic solvent.

The active ingredient, i.e. the solid non-hygroscopic monoisopropylammonium salt of the compound of formula I, in which R, A and B are as defined above, free of the diisopropylammonium salt, is obtained by a conventional salt formation method, avoiding foreign impurities, and then removed from the resulting salt. of the product, the diammonium salt of the formula 2 or the reaction is carried out so that the formation of the diammonium salt of the formula 2 is inhibited.

Preferred methods include using the following processes alone or in combination with each other:

a) the reaction of an acid of general formula III with a basic reagent capable of forming the B + ion in an organic polar solvent or in a solvent mixture containing a polar organic solvent in which the salt and acid of general formulas 1 and 3 are insoluble or poorly soluble, while the basic reagent and the diammonium salt of general formula 2 formed as a by-product are readily soluble and, if appropriate, subsequent heating of the reaction mixture or

b) reacting a diammonium salt of general formula 2 with an acid of general formula 3 under reaction conditions according to method a) or

c) the reaction of an acid of general formula 3 with a salt capable of generating the B + ion under the reaction conditions of method (a) or

d) extracting the hygroscopic salt of general formula 1 with an organic, preferably polar solvent or solvent mixture containing an organic polar solvent, in which the mono-ammonium salt of general formula 1 is insoluble, while the di-ammonium salt of general formula 2 is readily soluble or

e) removing, at room temperature under vacuum or with heating, from the di-ammonium salt of general formula 2 or the mono-ammonium salt contaminated with such di-ammonium salt, that amount of the amine containing the B + ion that is greater than the molar equivalent, or

f) reacting the salt of the acid of general formula 3 under the reaction conditions of method a) with a reagent capable of forming the B + ion, and optionally isolating the salt of general formula 1 thus formed, preferably by filtration.

The method of obtaining mono-isopropylammonium salt of glyphosate / glyphosate is described in detail in Polish patent description No. 169 534.

The following examples illustrate the compositions of the invention and methods of making them.

Example I.

To a mixture of 0.5 g of ethoxylated nonylphenol and 2.84 g of ethoxylated alkylamine dissolved in 40 ml of ethanol at room temperature, the mono-isopropylammonium salt of N- (phosphonomethyl) -glycine prepared as described in example 1.2 of Patent Specification 169 534 was added. The solution was homogenized and the ethanol was evaporated. 172,415 were obtained, 63.3 g of non-hygroscopic product, readily soluble in water, containing 69.6% N- (phosphonomethyl) -glycine.

Example II.

In 30 ml of ethanol, the excipients were suspended containing 1.1 g of ethoxylated nonylphenol, 6.39 g of ethoxylated alkylamine, 12.69 g of ethoxylated fatty amine and 9.28 g of fatty alcohol polyglycol ether, 60 g of N- mono-isopropylammonium salt ( phosphonomethyl) glycine and the suspension are homogenized, after adding 4.4 g of urea. After ethanol evaporation, 93 g of a non-hygroscopic product containing 47.4% of N- (phosphonomethyl) -glycine, easily soluble in water, was obtained.

Example III.

In 30 ml of methanol, the excipients were suspended containing 1.53 g of ethoxylated nonylphenol, 3.89 g of ethoxylated alkylamine, 7.92 g of ethoxylated fatty amine and 5.97 g of polyglycol iso-tridecanol ether, 60 g of N- mono-isopropylammonium salt were added. (phosphonomethyl) -g. glycine, and the mixture is homogenized after the addition of a mixture of 2.78 g of potassium chloride, 0.03 g of 1-naphthylacetic acid and 0.08 g of boric acid. After evaporation of the alcohol, 82 g of a product containing 53.8% N- (phosphonomethyl) -giicine, non-hygroscopic and easily soluble in water, were obtained.

Example IV.

g of N- (phosphonomethyl) glycine mono-isopropylammonium salt was homogenized with a solution of 40 g of Hyspray excipient (ethoxylated fatty amine from FAL FINE Agrochemicals Ltd.) in 60 ml of ethanol. After evaporation of the alcohol, 125 g of a non-hygroscopic product, readily soluble in water, containing 50.4 g of N- (phospho-nomethyl) -glycine was obtained.

Example V.

181 g (1 mol) of (3-amino-3-carboxy-propyl) -methanophosphonic acid were reacted at room temperature with 17 g (1.0 mol) of ammonia previously dissolved in methanol. The mixture spontaneously warmed to 35 ° C, then refluxed at 65 ° C for 30 minutes, cooled, filtered to give 193 g of (3-amino-3-carboxy-propyl) -methanophosphinic acid ammonium salt crystals. to which 10 g of auxiliary product lauropal-x (polyalkoxylated fatty alcohol from WITCO SA) was added.

Example VI.

50 g of ammonium bicarbonate and 50 g of Hyspray were added to the product obtained from 1 mole of 100% N- (phosphonomethyl) glycine and 1 mole of 100% pure isopropylamine in absolute ethanol. Thus, 195 g of a non-hygroscopic product, readily soluble in water, containing 32% N- (phosphonomethyl) -glycine was obtained.

Example VII.

The procedure was as in Example 4, except that 80 g of Hyspray and 10 g of lauropal-x were used in 100 ml of ethanol with 85 g of the mono-isopropylammonium salt of N- (phosphonomethyl) -glycine and 70 g of ammonium bicarbonate and 50 g of ammonium sulfate. 295 g of a non-hygroscopic product, easily soluble in water, containing 21.3% N- (phosphonomethyl) -glycine was obtained.

Example VIII.

The procedure of Example 7 was followed except that 50 g of Hyspray auxiliary, 100 ml of ethanol, 50 g of ammonium bicarbonate and 500 g of ammonium sulfate were used. 695 g of a non-hygroscopic product, readily soluble in water, containing 9% N- (phosphonomethyl) -glycine was obtained.

Example IX.

Excipients: 0.2 g of ethoxylated nonylphenol and 1.2 g of ethoxylated alkylamine were dissolved in 10 ml of ethanol at room temperature. The solution was homogenized with 24 g (0.1 mol) of (3-amino-3-carboxypropyl) -methanophosphinic acid mono-isopropylammonium salt and the ethanol was evaporated. 25.3 g of a non-hygroscopic product, readily soluble in water, containing 71% of the mono-isopropylammonium salt of (3-amino-3-carboxypropyl) methanophosphinic acid was obtained.

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Example X.

Excipients: 0.2 g of ethoxylated nonylphenol and 7.3 g of ethoxylated fatty acid were mixed with 5 ml of ethanol to obtain a suspension, which was homogenized with 24 g (0.1 mol) of the mono-isopropylammonium salt of (3-amino-3-carboxypropyl) acid. methane phosphine and ethanol was evaporated. The obtained 31.4 g of a non-hygroscopic product, readily soluble in water, containing 57.6% of the mono-isopropylammonium salt of (3-amino-3-carboxypropyl) methane-phosphoric acid.

Example XI.

0.2 g of ethoxylated nonylphenol and 1.2 g of ethoxylated alkylamine were mixed with 8 ml of ethanol to give a suspension, which was homogenized with 19.8 g (0.1 mol) of (3-amino-3-carboxypropyl) methanophosphinic acid ammonium salt and evaporated. alcohol. 21.1 g of a non-hygroscopic product, readily soluble in water, was obtained, which contained 85% of the mono-isopropylammonium salt of (3-amino-3-carboxypropyl) methanophosphinic acid.

Example XII.

0.2 g of ethoxylated nonylphenol, 1.2 g of ethoxylated alkylamine and 6 g of ethoxylated fatty amine were mixed with 8 ml of ethanol to obtain a suspension which was homogenized with 20 g (0.1 mol) of the ammonium salt of (3-amino-3-carboxypropyl) ) methane phosphine. After working up, 26.1 g of a similar product as above, containing 65% (3-amino-3-carboxypropyl) -methanophosphinic acid, hereinafter abbreviated acmpa, were obtained.

By proceeding as above, the following funds were obtained:

Example salt acmpa % content acmpa Ethoxylated nonylphenol Ethoxylated amine fatty Sulfate ammonium Polyalkoxy. alcohol fatty XIII i. -prop *) 98 2 XIV i. -prop 84 1 15 XV ammonium 98 2 XVI ammonium 80 2 18 XVII i. -prop 84 1 10 5 XVIII ammonium 68 1 10 twenty 1

i. prop = isopropylammonium

The water-soluble, suspended, water-dispersible solid products can optionally be ground in a mill or other suitable grinding equipment.

Example XIX.

(3-Amino-3-carboxypropyl) -methanophosphinic acid isopropylammonium salt 33%

N- (phosphonomethyl) glycine isopropylammonium salt 65%

Nonylphenol ethoxylate 1%

Polyalkoxylated fatty alcohol 1%

Example XX.

(3-Amino-3-carboxypropyl) -methanophosphinic acid, ammonium salt 33%

N- (phosphonomethyl) glycine ammonium salt 65%

Nonylphenol ethoxylate 1%

Polyalkoxylated fatty alcohol 1%

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Example XXI.

(3-Amino-3-carboxypropyl) -methanophosphinic acid isopropylammonium salt 26%

N- (phosphonomethyl) glycine isopropylammonium salt 53%

Nonylphenol ethoxylate 1%

Ammonium sulfate 20%

Example XXII.

(3-Amino-3-carboxypropyl) -methanophosphinic acid ammonium salt 26%

N- (phosphonomethyl) glycine ammonium salt 53%

Nonylphenol ethoxylate 1%

Ammonium sulfate 20%

Example XXIII.

(3-Amino-3-carboxypropyl) -methanophosphinic acid isopropylammonium salt 55%

Fatty amine ethoxylate 18%

Imazapril-isopropylamine 27%

Example XXIV.

(3-Amino-3-carboxypropyl) -methanophosphinic acid ammonium salt 55%

Ethoxylated alkylphenol 18%

Imazaprylammon 27%

Example XXV.

(3-Amino-3-carboxypropyl) -methanophosphinic acid ammonium salt 54% Fatty amine ethoxylate 19%

Imazaprylammon 27 *%

Example XXVI.

(3-Amino-3-carboxypropyl) -methanophosphinic acid isopropylammonium salt 32%

Ethoxylated alkylamine 4%

2,2-D isopropylammonium salt 64%

Nonylphenol ethoxylate 1%

Example XXVII.

(3-Amino-3-carboxypropyl) -methanophosphinic acid isopropylammonium salt 30%

Polyalkoxylated fatty alcohol 20%

Triazine 30%

Silica 5 ¹ %

Ammonium sulfate 15%

Example XXVIII.

(3-Amino-3-carboxypropyl) -methanophosphinic acid, ammonium salt 30%

Polyoxylated fatty alcohol 15%

Triazine 30 *%

Ammonium sulfate 25%

Example XXIX.

(3-Amino-3-carboxypropyl) -methanophosphinic acid ammonium salt 68%

Oxyfluorophen 14%

Nonylphenol ethoxylate 1%

Polyoxyethylene fatty acid 5%

Ammonium sulfate 5%

Silica 5 *%

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A suitably sized bag was filled with 1 kg of the compositions prepared according to the above examples. The bag was made of polyvinyl alcohol plasticized with polyhydric alcohol. The bag was in the shape of a square closed on three sides. In the above examples, powders have been obtained with properties that they can be easily poured into bags and the bags then sealed by welding.

After storage and transport, these bags are thrown into the water at the point of use and mixed intensively. The polymer disappears within 2 minutes and the herbicide dissolves completely or is dispersed in the water to give a field-ready composition.

The following examples show further water-soluble or suspendable solid compositions. In these examples the active ingredient, the non-hygroscopic mono-isopropylammonium salt of N- (phosphonomethyl) glycine, was abbreviated as the solid salt of mono-ipa glyphosate.

Example XXXI. Solid glyphosate mono-ip salt 99% Nonylphenol ethoxylate 22% Example XXXII. Solid glyphosate mono-ip salt 955% Nonylphenol ethoxylate 11% Ethoxylated alkylamine 44% Example XXXIII. Solid glyphosate mono-ip salt 802% Nonylphenol ethoxylate 22% Fatty amine ethoxylated 11% Example XXXIV. Solid glyphosate mono-ip salt 772% Nonylphenol ethoxylate 11% Ethoxylated alkylamine 72% Fatty amine ethoxylated 10% Urea 52% Example XXXV. Solid glyphosate mono-ip salt 60% Nonylphenol ethoxylate 11% Ethoxylated alkylamine 72% Fatty amine ethoxylated 102% Polyalkoxylated fatty alcohol 22% Ammonium sulfate 20% Example XXXVI. Solid glyphosate mono-ip salt 70% Nonylphenol ethoxylate 11% Ethoxylated alkylamine 4% Ammonium sulfate twenty% Silica 52% Example XXXVII. Solid glyphosate mono-ip salt 68.00% Nonylphenol ethoxylate 2.00% Ethoxylated alkylamine 4, ^ 2 ^^ Fatty amine ethoxylated Ether of isotridecyl alcohol and polyglycol 7.30% KCl 3.45% 1-naphthylacetic acid 0.052% Boric acid 0.10% Example XXXVIII. Solid glyphosate mono-ip salt 50% 2,4-D isopropylammonium salt 32%

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Nonylphenol ethoxylate 1% Ethoxylated alkylamine 4% Ammonium sulfate 8% Silica 5% Example XXXIX. Solid glyphosate mono-ip salt 40% Mono-ipa glufosinate salt 7% Nonylphenol ethoxylate 2% Sodium lignosulfonate 3% Ammonium sulfate 33% Silica 5% Kaolin 10% Example XL. Solid glyphosate mono-ip salt 40% Dimetipine 7% Nonylphenol ethoxylate 2% Sodium lignosulfonate 3% Ammonium sulfate 33% Silica 5% Kaolin 10% Example XLI. Solid glyphosate mono-ip salt 50% Oxyfluorfen 4% Nonylphenol ethoxylate 2% Sodium lignosulfonate 3% Silica 16% Kaolin twenty% Example XLII. Solid glyphosate mono-ip salt 40% Nonylphenol ethoxylate 1% Ethoxylated alkylamine 4% Fatty amine ethoxylated 15% Ammonium sulfate thirty% Kaolin 10% Example XLIII. Solid glyphosate mono-ip salt 80% ATPLUS 411 19% Polyalkoxylated fatty alcohol 1% Example XLIV. Solid glyphosate mono-ip salt 40% Glufosinate ammonium salt twenty% Nonylphenol ethoxylate 1% Ethoxylated alkylamine 4% Ammonium sulfate 35% Example XLV. Solid glyphosate mono-ip salt 0.05% Ammonium sulfate 80.00% Nonylphenol ethoxylate 1.00% Fatty amine ethoxylated 18.95% Example XLVI. Solid glyphosate mono-ip salt 99% Nonylphenol ethoxylate 1%

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Example XLVII.

Solid mono-ip glyphosate salt 1%

Dissovet S 99%

Example XLVIII.

Solid Monoipa Glyphosate Salt 19%

Ammonium sulfate 77%

Ammonium nitrate 28%

Polyalkoxylated fatty alcohol 11%

Example of IL.

Solid mono-ip glyphosate salt 99 ,,%

Polyalkoxylated fatty alcohol 0.11%

Example L.

g of monolisopropylammonium salt of Nl (phosphono.methyl) glycine, 3 g of 3,6-dichloro-1-pyridine-carbonic acid, 10 g of potassium ligninsulfonic acid, 1 g of sodium oleyl-methyl tauric acid, 4 g of polyoxylated nonylphenol, 4 g of polyethane of the alkylamide and 10 g of synthetic silica are ground to a size of 7-10 microns. A wettable powder containing 50% N- (phosphonomethyl) glycine and 17.5% metribezin was obtained for use in a known manner.

Example LI.

g of N- (phosphonomethyl) glycine mono-isopropylammonium salt, 2,3-dihydro-5,6-dimethylOl1,4-lithium 1,1,4,4-tetroxide, 3 g polyethoxylated nonylphenol, 7 g polyethoxylated fatty amine, 7 g salt Potassium ligninsulfonic acid and 5 g of synthetic silica were ground to the desired size to obtain a non-hygroscopic product for use in agriculture.

Example LII.

g of N-phosphonomethyljglycine mono-isopropylammonium salt, 8.75 g of 4laminOl3methylmercapto-6lt-butyl-1,2,4-triazine, 5 g of lignosulfonic acid potassium, 5 g of polyethoxylated nonylphenol, 1 g of sodium oleylmethyltauric acid and 12, 25 g of Aerosil was ground to a size of 5-15 microns. A non-hygroscopic powder containing 50% N- (phosphonomethyl) -giicine was obtained, which could be used for the preparation of suspensions intended for agricultural use.

Analytical tests

A. Flowability tests

When the compositions according to the invention are to be used in water-soluble bags, it is necessary to check their suitability for this purpose by means of a flow test which can be carried out as follows:

100 g of non-hygroscopic salt is poured into a 2 cm diameter funnel at the outlet and the time required for the product to pour out is measured. For loose powders or those considered to meet the flow criterion, this time is in the range up to 10 seconds. Table 1 shows the times for some compositions according to the invention.

Example Flow time (seconds)

XXXI 4.0 XXXII 2.0 XXXIII 4.0 XXXIV 2.0 XXXV 1.5 XXXVI 2.0 XXXVII 7.0 XXXVIII 5.0 XXXIX 5.0 XL 9.5 XLI 7.2 XLII 4.5 XLIII 4.0

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XLIV 3.0

XII 5.0

XIII 5.0

B. X-ray diffraction testing

Four different samples of the mono-isopropylamine salt of N- (phosphonomethyl) -glycine obtained by the method described in Polish patent description No. 169 534 in examples 1.12, 1.1 and 1.13, respectively, were tested.

Table 2

Salt from the example Solvent Crystal type 112 (169 534) absolute ethanol and 1.1 ethanol 96% and 113 water β - methanol / diethyl ether (freshly prepared) β

Method: The test was carried out on an X-ray diffractometer of the HZG-4 / C type. Radiation source: CoK 1 = 17.9 nm (Co tube 30 keV 12 mA Fe filter). Goniometric sensor, speed 1 / mm. The lampholder was made of Al.

The method of sample preparation and testing was always the same. On the basis of X-ray diffraction it wyh ^part d of the plane of the network and their relative intensity was determined as shown in Table 3. Some of the diffraction patterns as also shown in FIG. 4 and 5.

From the results presented, it can be seen that the samples have two different structures, which are designated α and β crystal types as indicated in Table 3.

Table 3

Abs. ethanol 96% ethanol Methanol-diethyl ether Water dA ° I / Io dA ° I / Io dA ° I / Io dA ° I / Io 1 2 3 4 5 6 7 8 11.0 100 11.0 100 7.03 100 7.00 100 9.06 47 9.09 45 4.83 16 4.83 13 7.41 13 7.39 14 4.56 19 4.54 29 5.94 42 5.96 43 4.48 46 4.47 43 5.54 38 5.56 46 4.27 23 4.26 29 5.38 9 4.17 46 4.17 33 4.98 12 5.0 15 4.06 37 4.05 40 4.85 33 4.86 37 3.937 48 3.937 49 4.55 9 4.56 10 3.831 65 3.820 76 4.37 11 3.621 6 3.62 7 4,298 9 4.30 9 3.527 55 3.515 48 4.13 83 4.13 94 3.358 21 3.351 twenty 4.08 31 3.297 18 3.30 19 4.01 58 4.01 48 3.198 10 3.195 9 3.82 14 3.83 15 3.140 39 3.136 34 3.782 15 3.79 12 2.917 37 2.912 28

172 415

Table 3 (continued):

1 2 3 4 5 6 7 8 3.710 51 3.71 56 2.821 4 2.815 6 3.59 6 2.739 11 2.737 8 3.48 10 3.488 11 2.654 6 2,650 6 3.403 29 3.403 24 2.547 7 2.545 10 3.295 9 3.293 9 2.502 6 2.502 8 3.257 17 3.259 16 2.421 12 2,420 18 3.189 29 3.191 34 2.35 21 2.405 11 3.035 7 3.037 6 2.34 15 2.985 6 2.983 6 2.929 7 2.932 7 2.909 6 2,790 10 2,789 10 2.688 2.502 18 2.502 24

C. Dissolution Test

Table 4 below shows some solubility values of N- (phosphonomethyl) glycine mono-isopropylammonium and di-isopropylammonium salts, on the basis of which the process of the invention can be carried out. All solvents and solvent mixtures which show a sufficient difference in solubility between the salts and the separate products can be used.

Table 4

Solubility (g / liter)

Solvent Mono-IPA salt * Di-IPA salt * Glyphosate ** water 1470 1980 12 methanol 56 570 <0.3 ethanol 0.2 n-propanol 0.7 170 <0.5 i.propanol <0.5 n-butanol 0.1 35 benzyl alcohol 0.5 420 <0.2 propylene glycol 184.0 244 <0.2 dimethylformamide 1.8 22 <0.2 benzene <0.1 <0.1 <0.1 i.propylamine <0.1 <0.1

* = isopropylamine ** = N- (phosphonomethyl) -glycine

The values given below can be used to evaluate the best solvent to be used with (3-amino-3-carboxy-propyl) -methanophosphinic acid.

172 415

Table 5

Solubility (g / liter, temp. 25 ° C)

Solvent Mono-ammonium salt Mono-IPA salt Glufosinate water 2000 1150 99 methanol 14 260 23 ethanol 4 5 9 n-propanol 6 5 9 i.propanol 10 4 12 benzyl alcohol 9 300 9 propylene glycol 9 280 21 dimethylformamide 10 8 12 benzene - - 7

D. Moisture uptake

The samples were tested in open containers at 60% humidity and 25 ° C. The results are shown in Table 6 below.

Table 6

Salt days 1 2 7 14 thirty 90 Salt monoisoprepyleamenewa N- (phonemethyl) glycine * 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% Salt di- isoprepyleamonewa Nl (phosphenomethyl) - glycine ** 13.0% 14.0% 16.1% 18.8% 19.2% 30.9%

Appearance * - The mono-isopropylammonium salt remained unchanged after 30 days ** - The di-isopropylammonium salt became viscous and hygroscopic in 1 day and became completely liquid in 14 days.

Biological examples

A. Compositions prepared according to Example XXXIV or CCGCI were dispersed in water to give 3 g active ingredient / liter liquid. 6 mg of active ingredient was withdrawn from each sample and sprayed on 15-day-old barley plants kept in pots in the greenhouse. After 4 days, the amount of chlorophyll per plant dry weight was determined. The results are presented in Table 7.

Table 7

Control sample 9.26 mg / g Composition of Example IX 3.42 mg / g Composition from Example XI 3.43 mg / g

Growth inhibition was also determined. The results are presented in Table 8.

172 415

Table 0

Control sample 0 Composition of Example IX 0.72 cm Composition from Example XI 0.0 cm

B. By the method described in paragraph A above, 12-day-old bean plants were sprayed with 4.2 mg of active ingredient / pot (1.2 ml of liquid) and the photosynthetic activity was determined on the third day.

The results are presented in Table 9.

Table 9

Control sample Example IX Example XI Photosynthesis 602 340 322 Photosynthesis 226 09 116 0.217 0.062 0.134 2.402 0.404 0 (525

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Publishing Department of the Polish Patent Office of the Republic of Poland Circulation 90 copies

Price PLN 4.00

Claims (4)

Patent claims A solid herbicidal or plant growth regulating composition based on a glyphosate / glyphosate salt, characterized in that the active ingredient is 0.1-99.9% of non-hygroscopic mono-ammonium, especially mono-isopropylammonium, salts of a compound of the formula I, wherein R ¹ is hydroxy or alkyl, A is (C 1-4 alkylamino or (C 1-4 aminoalkyl containing primary or secondary amino groups, preferably -CH2-NH- or -CH (NH2) -CH2- groups, B is ammonium ion) or alkylammonium, in the form free of the diammonium salts of formula II, wherein R 1, A and B are as defined above, and contains optional carriers or auxiliaries. 2. A composition according to claim 1 The method of claim 1, wherein the mono-isopropylammonium salt of N- (phosphonomethyl) -glycine having a-type crystals with a melting point of 158-163 ° C, the following lattice values measured by X-ray diffraction 11.0, 9.06, 5.94, 4.13 and 3.71 A and the following absorption bands obtained by FT-IR spectroscopy 1660,1553,1545,1075, 515 and 475 cm ⁴ . 3. A composition according to p. The method of claim 1, wherein the mono-isopropylammonium salt of N- (phosphonomethyl) -glycine having δ-type crystals with a melting point of 143-155 ° C, the following lattice values measured by X-ray diffraction of 7.00,4.83, 4.47, 3.35 and 2.815 A and the following absorption bands obtained by FT-Ir spectroscopy 1645,1594,1561,1066, 500 and 455 cm ⁴ . 4. A composition according to p. 1, characterized in that it contains mono-isopropylammonium salt of 3-amino-3-carboxypropylmethanophosphinic acid with a melting point of 199-203 ° C and the following absorption bands obtained by FT-IR spectroscopy: 1640,1601,1530,1138,1037, 750 and 471 cm ⁴ .