HU206606B - Process for producing solide growth controlling or herbicide compositions containing n-/phosphono-methyl/-glycine and/or derivatives and solide composition for applying the process - Google Patents

Abstract

Water soluble plant-growth controlling solid active agents, N-(phosphono-methyl)-glycine and its derivs. are mixed with carbonate and hydrogen carbonate salts and with customary plant protection additives. Sufficient initiating water is added to govern the extent of a double decompsn. - reaction between these cpds. The solid obtd. is converted by colloid-chemical means into foams, creams, moist pastes and wet feel powders packaged as powders, granules or compressed briquettes.

Description

The present invention also relates to a solid composition prepared without the use of water in the above process.

FIELD OF THE INVENTION The present invention relates to a process for the preparation of water-soluble solid plant growth regulating or herbicidal compositions containing N-phosphonomethylglycine and / or N-phosphonomethylglycine derivatives as active ingredient and a solid composition for carrying out the process.

Compounds of formula (I) wherein Z is hydrogen (C 1 -C 4) -alkylcarbonyl, perhalogenated (C 1 -C 4) -alkylcarbonyl, (C 2 -C 6) -alkenyloxycarbonyl, C 4 -C 4 alkylphenylsulfonyl,

M ¹ and M ² are independently hydrogen, alkali metal, ammonium or guanidine N-phosphonomethylglycine derivatives as new compounds since 1964. The parent compound, N-phosphonomethylglycine, was first disclosed in U.S. Patent No. 3,988,142. U.S. Pat. More derivatives eg. The preparation of esters, amides, salts, and their use as phytotoxic agents is known in U.S. Patent No. 3,799,758. U.S. Patents. According to the process described herein, a simple physical mixture of N-phosphonomethylglycine derivatives of formula (I) as active ingredients and auxiliaries commonly used in the manufacture of a plant protection product is prepared and used as a formulation. The description only outlines the preparation of particularly important salts, which are widely used in practice, in crystalline form, and does not address either the difficulty of crystallization or the high hygroscopicity of the salts which may be obtained. Due to the above reasons, a solid formulation with a high active ingredient content and a high solubility in water is not practicable.

In several patents, e.g. U.S. Pat. No. 4,147,719. and

EP 0098034; Aqueous concentrates of the desired N-phosphonomethylglycine salts are prepared by catalytic oxidation of the corresponding N-phosphonomethyliminodiacetic acid salt solution for use in herbicidal compositions. There are several factors limiting the concentration of active ingredient in the liquid agents that can be prepared in practice. For example, cold tolerance, partial crystallization, excipient precipitation, etc.

The use of liquid pesticides is, moreover, disadvantaged by the high cost of packaging, storage and transport, the vulnerability of the containers used for packaging and the resulting risk of spillage and environmental contamination.

The salts of the N-phosphonomethylglycine derivatives are in most cases prepared by the neutralization of the corresponding acid with an organic base in an aqueous medium, with an alkali metal hydroxide, and possibly with the corresponding carbonate or bicarbonate salts.

It is noteworthy in this respect that U.S. Pat. U.S. Pat. No. 4,123,125, which discloses 1-aminoguanidine bicarbonate for neutralization. Primarily, an aqueous solution is obtained from which the corresponding mono-1-aminoquanidine salt is obtained by evaporation under vacuum and treatment with isopropanol. This process is difficult to implement on an industrial scale and is energy intensive. The specification does not mention that it would advantageously utilize any form of carbon dioxide formed as a by-product.

Although the simple salts of N-phosphonomethylglycine are most commonly used as herbicides in crop production, numerous publications and patents refer to other applications. An example of this is disclosed in U.S. Pat. U.S. Pat. No. 4,600,123, which uses the sodium salt of N-phenylsulfonamido-N-phosphonomethylglycine to increase sugar production in sugar cane.

The importance of active ingredient formulation is emphasized in most patents. A variety of pesticidal formulations containing the active compounds represented by the general formula (I) are known.

SUMMARY OF THE INVENTION The present invention relates to water-soluble solid compositions of high active ingredient content and to processes for their preparation which outperform the serogroups known from prior art sources in every respect.

Since most of the compounds of formula I, including the most important N-phosphonomethylglycine, are poorly soluble in water, only a suitable water-soluble salt can be used to formulate a spray composition of optimal composition.

In our development work, we have sought to formulate a composition which contains the appropriate salt or compounds which, during the first stage of use, during the preparation of the spray, by chemical reactions, form the salt which functions as the appropriate active ingredient. Of course, no harmful by-products (such as toxic, corrosive substances) of this reaction should be present.

The best experience was obtained with the carbonate and bicarbonate salts. During our experiments, we came to the surprising conclusion that the formula II -

Z has the meaning given above,

R is hydrogen, (C1-C8) alkylglymorpholinocarboxylic acids and compounds of formula (III) wherein

HU 206 606 Β

A ¹ and A ² are independently hydrogen, alkali metal, ammonium or guanidine, with the proviso that A ¹ and A ² cannot be hydrogen carbonates at the same time, and mixtures of auxiliaries commonly used in the manufacture of pesticides retain their composition for long periods. If water is added to these mixtures, partial dissolution will trigger a decomposition reaction to form the compound of formula (I), water, and carbon dioxide. (Drawing 2/1)

The resulting compound of formula I is immediately soluble in water. During the reaction, the addition of water as the initiator and the reaction water will continuously dissolve the target compound (s) of formula (I). Once the saturation concentration has been reached, the reaction is carried out in a quasi-solid phase to the extent of the auxiliaries between the unreacted (Π) and (III) forming the true solid phase and the crystalline particles of the resulting compound (I) and For compounds of formula I, the diffusion resistance of a dispersion of a saturated aqueous solution. Conveniently, the ratio of water used as initiator to excipients can be controlled within arbitrary ranges. In the process, the mixture is converted to the desired product through colloidal chemical processes through solid powder, foam, cream, wet paste, and finally wet-feel powder states. By-product carbon dioxide ensures maximum dispersion of components and perfect spatial homogeneity of the composition.

This invention relates to (I) and (Π) of the formula: - wherein Z, Μ ^1, M ² and R is as defined above and N- (phosphonomethyl) glycine and / or regulatory or herbicidal solid plant growth derivatives for preparing by mixing the acid derivatives of formula (Π) and formula (III), wherein A ¹ and A ² represent the above carbonates and ionic, nonionic and briquetting excipients commonly used in the preparation of a plant protection product, and (II) and (ΠΙ). ), the resulting solid product is formulated as a powder, granule or briquette serum, depending on the application.

The present invention also relates to a solid composition which contains as an active ingredient ionic, non-ionic, acid derivatives of formula (Π) and carbonates of formula (III) wherein Z, R, A ¹ and A ² are as defined above. and briquetting aids. This solid composition (powder, granule or briquette) can be used to produce plant growth regulating or herbicidal pine broths such that the salt of Formula I, wherein Z, M * and M ² are as defined above, is formed by the user. situ when preparing the spray.

Advantageous effects of the invention may be summarized as follows:

- the solubility of the additives in the formulation of the invention is not a limiting factor,

- the preparation has a high tolerance to cold,

- reducing packaging costs, simplifying, storing and transporting less costs,

- loss of discharge and environmental damage,

- the carbon dioxide evolved during dissolution facilitates the mixing of the spray liquid and, in the case of briquettes, its rapid disintegration.

The details of the invention are illustrated by the following examples.

/. example

169 g (1 mol) of N-phosphonomethylglycine (II), 48 g (0.5 mol) of ammonium carbonate (III) 15.5 g Ci / Ctf Alkylamine ethoxylate and 6.5 g of octaethylene glycolmononylphenyl ether are thoroughly homogenized and 25 ml of water are added in several portions with vigorous stirring. The water starts the decomposition reaction, liberates the carbon dioxide foam and then creates a creamy form. Finally, after mixing, after the carbon dioxide evolution has ceased, the substance decomposes into a powder.

This powder was dried in a vacuum desiccator over phosphorus pentoxide. 210 g of dry powder product are obtained with the following composition:

83.0% by weight of N-phosphonomethylglycine monoammonium salt (I) by weight of N- (phosphonomethyl) glycine (II)

1.5% by weight of ammonium carbonate (ΠΙ)

3.1% by weight of octaethylene glycol mononylonyl phenyl ether

7.4% by weight C3 ₃ / C15 alkylamine ethoxylate

The product dissolves rapidly in water, without any residue. The appropriate concentration of solution can be applied directly by spraying.

Example 2

Example 1 except that 84 g (1 mol) of sodium bicarbonate was used as the compound of formula III and 68 ml of water were used to initiate the decomposition reaction and no drying was carried out.

The product is a slightly sticky powder weighing 303 g and having the following composition:

55.8% by weight of monosodium salt of N-phosphonomethylglycine (I)

6.4% by weight of N-phosphonomethylglycine (II)

3.2% by weight of sodium bicarbonate (III)

2.3% by weight of C13 / C15 alkylamine ethoxylate

5.2% by weight of octaethylene glycol mononylonyl phenyl ether

27.1% water

Example 3

169 g (1 mol) of N-phosphonomethylglycine (II), 37 g (0.5 mol) of lithium carbonate

After thoroughly homogenizing, 3.5 g of sodium dioctylsulfosuccinate are added and 25 ml of water are added in several portions with vigorous stirring. The water starts the decomposition reaction, liberates the carbon dioxide foam, and then creates a cream-like form.

Finally, after mixing, after the carbon dioxide evolution has ceased, the substance decomposes into a powder. The material was dried in a dry air stream at 110-130 ° C.

178.5 g of anhydrous powder product having the following composition were obtained:

wt.% N-phosphonomethylglycine monolithium salt (I) wt.% sodium dioctylsulfosuccinate

Example 4

The process described in Example 3 except that compound (III) of the formula 180 g (1 mole) of guanidine carbonate, 15.7 g of excipient _{C] 3} / C ₁₅ alkyl ethoxylate and 6.8 g octaethylporphyrin a mixture of -glycol mononylonyl phenyl ether is used.

We do not dry, the product weighs 371 g and has the following composition:

57.5% by weight of N-phosphonomethylglycine quanidine salt (I)

3.0% by weight of N-phosphonomethylglycine (II)

25.5% by weight of guanidine carbonate (III)

1.8% by weight of octaethylene glycol mononylonyl phenyl ether

4.2% by weight C3 / C15 alkylamine ethoxylate

8.0% by weight water

Example 5

The process described in Example 3 except that compound (III) is selected from sodium carbonate and potassium carbonate (69 g, 0.5 mol) in a mixture of excipients 5g C _l3 / C ₁₅ 53 g (0.5 mole) of the formula - of alkylamine ethoxylate and 1.5 g of octaethylene glycol mononylonyl phenyl ether and 51 ml of water as the initiator. The wet mixture was dried in a vacuum desiccator over phosphorus pentoxide.

242 g of powder product are obtained having the following composition:

94.6% by weight of sodium potassium salt of N-phosphonomethylglycine (I)

2.1% by weight of C13 / C15 alkylamine ethoxylate

0.6% by weight of octaethylene glycol mononylonyl phenyl ether

2.7% water

Example 6

72.7 parts of N- (phosphonomethyl) glycine monooktil ester [compound (II) of the formula], 23.3 parts by weight of guanidine carbonate [(III) compound] and 4 parts of C. _I3 / C ₁₅ - alkylamine ethoxylate to form a homogeneous powder mixture having the following composition:

72.7% by weight of N-phosphonomethylglycine monooctyl ester (II)

23.3% by weight of guanidine carbonate (III)

4.0% by weight of C 1 -C 4 -alkylamine ethoxylate

This mixture is dissolved in the amount of water depending on the intended use to give a directly usable spray liquid.

Example 7.

Example 6 is followed. 66.1 parts by weight of N- [N- (phosphonomethyl) glycine] -morpholide (II), 26.7 parts by weight of ammonium carbonate and 7.2 parts by weight of sodium dioctylsulfosuccinate as an excipient. .

The composition of the powder mixture is as follows:

66.1% by weight of N-phosphonomethylglycine morpholide (II)

26.7% by weight of ammonium carbonate (II)

7.2% by weight of sodium dioctylsulfosuccinate

Example 8

6-7. examples. 32.3 parts by weight of 4-methylphenylsulfonyl-N- (phosphonomethyl) glycine as a compound of the formula II, 3.7 parts by weight of lithium carbonate as the compound of the formula III and 2 parts by weight of sodium dioctylsulfosuccinate as an excipient employed. The composition of the powder mixture is as follows:

% by weight (4 methylphenylsulfonyl) -N-phosphonomethylglycine (II)

9.7% by weight of lithium carbonate (III)

5.3% by weight of sodium dioctylsulfosuccinate

Example 9

6-8. In the same manner as in Examples 1 to 4, 22.5 parts by weight of N-formyl-N-phosphonomethylglycine ethyl ester (II), 8.4 parts by weight of sodium hydrogen carbonate as a compound of formula (III) and parts used in C ₃ / _C-I5 alkyl amine ethoxylate and 1 part by weight of octaethylene glycol monononyl phenyl ether mixture.

The composition of the powder mixture is as follows:

66.4% by weight of N-formyl-N- (phosphonomethyl) glycine ethyl ether (II)

24.8% by weight of sodium bicarbonate (III)

5.9% w / w C 1 / C 15 alkylamine ethoxylate

2.9% by weight of octaethylene glycol nonylphenyl ether

Example 10

174 g (0.68 mole) of N-allyloxycarbonyl-N- (phosphonomethyl) glycine (II), 32 g (0.34 mole) of ammonium carbonate [(III) ) compound], a uniform mixture is prepared of 10.4 g of C _I3 / _C-I5 alkyl amine ethoxylate and 4.6 g octaethylene glycol monononyl feniléterbó'l, then during continuous mixing-kneading, several portions of 10 ml of water to initiate exchange degradation.

The resulting material is dried in a desiccator over phosphorus pentoxide and then powdered.

217 g of product are obtained having the following composition:

by weight N- (allyloxycarbonyl) -N- (phosphonomethyl) glycine (III)

64.2% by weight of monoammonium salt of N-allyloxycarbonyl-N- (phosphonomethyl) glycine (I)

11.9% by weight of ammonium carbonate (HI)

4.8% by weight of C [3 / C 15] alkylamine ethoxylate

2.1% by weight of octaethylene glycol mononylonyl phenyl ether

HU 206606 Β

Example 11

6-9. In the same manner as in Examples 1 to 4, 29.3 parts by weight of N-trifluoroacetyl-N-phosphonomethylglycine ethyl ester (Π), 18 parts by weight of guanidine carbonate as compound (H1), by weight of sodium dioctylsulfosuccinate.

The composition of the powder mixture is as follows:

58.2% by weight of N-trifluoroacetyl, N- (phosphonomethyl) glycine ethyl ester (Π)

35.8% by weight guanidine carbonate (1H)

6.0% by weight of dioctyl sulfosuccinate

Example 12

169 g (1 mole) of N- (phosphonomethyl) glycine (Π), the compound (300 g, 3 mole) of potassium bicarbonate, 50 g of soluble starch, 9 g of C _l3 / C ₁₅ alkyl ethoxylate and 10 g of water are added in small portions to a mixture of 3 g of octaethylene glycol mononylonyl phenyl ether in a continuous small amount of stirring. Swap degradation occurs only partially. The resulting slightly sticky powder is compressed into briquettes or tablets of appropriate size.

524 g of product are obtained having the following composition:

14.9% by weight of N-phosphonomethylglycine (II)

20.0% by weight of N-phosphonomethylglycine monopotassium salt (I)

50.0% by weight of potassium bicarbonate (III)

9.5% by weight of starch

1.7 wt% C13 / C15 alkylamine ethoxylate

0.6% by weight of octaethylene glycol mononylonyl phenyl ether

3.3% by weight water

Briquettes dissolve rapidly in water because the carbon dioxide released by the reactivation of unreacted components is accelerated by decomposition.

The concentration of the spray juice can be easily adjusted by the number of briquettes depending on the application.

Claims (5)

PATENT CLAIMS A process for the preparation of compounds of formula (I) and (Π) wherein Z is hydrogen, boiling, perhalogenated (C 1-4) alkylcarbonyl, (C 2-6) alkenyloxycarbonyl, (1-) (C 4) alkylphenylsulfonyl, M ¹ and M ² independently represent hydrogen, an alkali metal ion, an ammonium ion or a guanidine ion, R is hydrogen, C 1-8 alkyl or morpholino for the preparation of a solid plant growth regulator or herbicidal composition comprising N-phosphonomethylglycine and / or derivatives thereof, wherein Z and R are as defined above -N- ( phosphonomethyl) glycine derivative and a compound of formula (ΙΠ) A ¹ and A ² are each independently hydrogen, an alkali metal ion, ammonium ion or guanidine ion, provided that A ¹ and A ² are not simultaneously hydrogen atoms, characterized in that the compound of formula II wherein Z and R is 0.5 to 3.0 moles, calculated as above, of the compound of formula III, wherein A ¹ and A ² are as defined above, ionic wetting agents and optionally nonionic wetting agents and optionally briquetting auxiliaries commonly used in the manufacture of pesticides. mixed, and then (II) and (ΙΠ) compounds of the formula: - wherein: Z, R, A ¹ and A ² represents water was added to initiate and adjust the rate of interconversion of the above metathesis of the mixture an amount of 1-40% by weight, subsequently the solid product obtained is known in the art to be in powder, granule or briquette form let's get it out. 2. The process of claim 1, wherein the ionic wetting agent is present in an amount of 0.5 to 10% by weight. The process of claim 1, wherein the nonionic wetting agent is optionally used in an amount of 0.510% by weight. A process according to claim 1, wherein the briquetting aid is optionally used in an amount of 5 to 15% by weight. 5. A solid composition for the preparation of a plant growth regulator or herbicidal spray containing N-phosphonomethylglycine derivative of the formula (I), wherein Z, M ¹ and M ² are as defined above, characterized in that: H) of formula: - wherein Z and R are as defined above - 1,585% by weight, (III) carbonate of the formula: - wherein A ¹ and A ² represents a proportion of the above -1-50% wt 0.5 10% by weight ionic, optionally 0.5-10% by weight nonionic wetting agent and optionally 5-15% by weight briquetting aid.