WO2001008481A1

WO2001008481A1 - Pesticide preparations containing polyglycerin or polyglycerin derivatives

Info

Publication number: WO2001008481A1
Application number: PCT/EP2000/006771
Authority: WO
Inventors: Ralf Zerrer; Gerd Roland Meyer; Franz Xaver Scherl
Original assignee: Clariant Gmbh
Priority date: 1999-07-30
Filing date: 2000-07-15
Publication date: 2001-02-08

Abstract

The invention relates to pesticide preparations containing polyglycerin and/or polyglycerin derivatives of formula (I) as adjuvant, wherein R?1, R2 and R3¿ represent hydrogen or the radicals cited in the description and n has a value ranging between 4 and 40. Said preparations are preferably herbicidal preparations.

Description

Pesticide preparations containing polyglycerols or polyglycerol derivatives

The invention relates to pesticide preparations containing polyglycerols and / or polyglycerol derivatives with improved biological activity of the pesticides (herbicides, insecticides, fungicides, bactericides, molluscids, nematicides and rodenticides).

Plant protection products are chemical or natural substances that are found in

Plant cells, tissues or parasitic organisms enter or damage the plant and / or destroy it.

The majority of pesticides are herbicides, followed by insecticides and fungicides.

The most important herbicides are chemical substances which act on the transport system of plants, for example by inhibiting photosynthesis, fatty acid biosynthesis or amino acid biosynthesis, and which inhibit nucleation and growth or cause the plant to die.

The biological activity of a pesticide can be determined on the basis of the growth of the plant or the damage to the plants by the action of the active compound on the leaf, depending on the action time and the action concentration. In order to optimally develop the pesticidal effect, the pesticide must wet the leaf green and remain there for a sufficient time or penetrate the

Active substance can be reached through the leaf surface. A general problem is that only a fraction of the active ingredient develops the desired activity, i.e. applied to harmful plants and grasses and can adhere there long enough to penetrate the plant cells. The vast majority is lost unused.

In order to remedy this ecological and economic disadvantage, as is described in a large number of patents, the mostly aqueous pesticide Formulations are added to auxiliaries which improve the wetting ability, the solubility, the emulsifying power or the adsorption behavior of the active substance. Furthermore, additives can facilitate and accelerate the penetration of the active substances through the leaf surface into the plant.

WO 98/06259 describes a method for supporting the biological activity of crop protection agents, according to which an aqueous surfactant solution is sprayed onto the plants as a co-formulation with or after the application of the active substance. Aqueous organosilicon and / or organofluorine compounds are used as the wetting agent.

In EP 379 852 and US 4,853,026, the herbicide N-phosphonomethylglycine (glyphosate) oils are added as water-in-oil emulsions in order to improve the contact of the hydrophilic active substance with the lipophilic epidermis of the plants. The disadvantage is the insufficient stability of the emulsions. According to WO 99/05914, the action of anionic pesticides can be improved by formulating the anionic active substance together with protonated polyamines or their derivatives as an aqueous colloidal dispersion.

US 5,858,921 teaches that one can reduce the concentration of glyphosate without reducing the biological activity by using the

Formulation of water-soluble, long-chain alkyldimethylamine oxides and water-soluble quaternary ammonium halides.

US 5 750468 describes glyphosate formulations which contain tertiary or quaternary ether amines as adjuvant.

All of the methods described so far for improving the biological activity of pesticides have met with limited success. It was therefore the task of developing new compositions or formulations of pesticides, in particular herbicides of the substance class N-phosphonomethylglycine (glyphosate), with improved effectiveness, which at the same time are economical, easy to handle and are well tolerated by humans and the environment. Glyphosate is used as a very environmentally friendly and at the same time highly effective and widely usable herbicide in agriculture in large quantities. It is preferably applied as a water-soluble salt, for example as an alkali metal, ammonium, alkylamine, alkylsulfonium, alkylphosphonium, sulfonylamine or aminoguanidine salt or as a free acid in aqueous formulations, but also in solid form with wetting agents on leaves and grasses, where it affects the plant's transport system and destroys it.

Surprisingly, it was found that the pesticidal activity of crop protection agents can be significantly improved by adding polyglycerols or polyglycerol derivatives.

The invention relates to pesticide preparations containing polyglycerols and / or polyglycerol derivatives of the formula (I)

R ¹ - O - (CH ₂ CH ₂ O) _n - R ² (I)

OR ³

wherein the radicals R ¹ , R ² and R ^{3 are,} independently of one another, the same or different and a radical, or in the case of R ³ optionally a combination of radicals selected from the group

Hydrogen; (-C ₃₀ ) alkyl, optionally substituted by 1 to 3 (CrC ₄ ) alkyl or (-C ₄ ) alkoxy groups; (C ₂ -C ₃₉ ) alkenyl, optionally sulfonated and optionally substituted by 1 to 3 (-C ₄ ) alkyl or (-C ₄ ) alkoxy groups;

Phenyl, optionally substituted by 1 to 3 (CC ₄ ) alkyl or (-C-C ₄ ) alkoxy groups; Naphthyl, optionally by 1 to 3 (-CC ₄ ) -alkyl- or (C1-C4) -

Alkoxy groups substituted; R ⁴ R ⁵ N- (CHι) y-; HO- (CH ₂ ) y-; - (AO) _z H; -SO ₃ H; -SO ₃ ^" X ⁺ ; -PO ₃ H ₂ ; -PO ₃ ^{2 '} X ⁺ ; -CR ₂ -COOH; -CR ₂ -COO-χ ⁺ ; -CO-R ⁷ -COOH; -CO-R ⁷ - COO ^" X ⁺ ;

-C- (R) ₂ C (R) ₂ C (R) ₂ -N (R ² ) ₂ , where R is H and / or CH ₃ ;

-C (R) ₂ C (R) ₂ C (R) ₂ -N ((AO) _z ) ₂ H, where R is H and / or CH ₃ ;

- (- CH ₂ CHCH ₂ O) _n -R ²

O (AO) _z H or R ^a -CO-, where R ^{a is} hydrogen, (CrC ₃₀ ) -alkyl, optionally substituted by 1 to 3 (CrC ₄ ) -alkyl or (C-ι-C ₄ ) -alkoxy groups, (C ₂ -C ₃₀ ) alkenyl, optionally sulfonated and optionally substituted by 1 to 3 (CrC ₄ ) alkyl or (-C-C) alkoxy groups, phenyl, optionally by 1 to 3 (dC ₄ ) - alkyl or (-C-C ₄ ) -Alkoxy groups substituted, naphthyl, optionally substituted by 1 to 3 (CrC) -alkyl or (CrC ₄ ) -alkoxy groups, or R ^a for a group selected from the formulas

I

RR ⁵ N-CH- (CH ₂ ) _X R ⁶ ; RR ^{5 is} N- (CH ₂ ) _y - or HO- (CH ₂ ) _y -, where n is a number from 4 to 40, preferably 5 to 20, in particular 5 to 20; R ⁴ and R ⁵ , which may be the same or different, for hydrogen, (C 1 -C 8) alkyl, (C ₂ -C ₃₀ ) alkenyl, optionally sulfonated, or for a group of the formula - (AO) zH; R ^{6 is} hydrogen, -CONH ₂ , -COOH, -SCH ₃ or -NH ₂ ; R ⁷ for (d-do-alkylene), (C ₂ -C ₃₀ ) alkenyl, optionally sulfonated; X ^{+ is} Na ⁺ , K ⁺ , Ca ²⁺ or N (R ⁸ ) ₄ ⁺ , where R ^{8 is} H or (CrCιo) alkyl, preferably (Cι-C ₄ ) alkyl; x for a number from 0 to 15; y for a number from 4 to 6; z for a number from 0 to 30, preferably 0 to 5; and A represents a group -C ₂ H - or -C ₃ H ₆ .

Pesticide preparations according to the invention are also to be regarded as those which contain polyglycerol mixtures, polyglycerol / polyglycerol derivative mixtures and / or polyglycerol derivative mixtures.

If the description below refers to polyglycerol derivatives, it should also be understood to mean polyglycerols.

Surprisingly, highly concentrated aqueous formulations of anionic pesticides, in particular glyphosate in salt form, and polyglycerol derivatives are phase stable. Crystallization of the ionic components when polyglycerol derivatives are added does not take place even after a long storage period. In addition to the high stability of the electrolyte, the adjuvant polyglycerol derivative used according to the invention shows an improvement in the compatibility and the contact ability of the hydrophilic active substance with the lipophilic epidermis Plants. A good wetting and absorption capacity of the pesticide formulation according to the invention supports the biological activity of the active ingredient in the plants.

The used according to the invention as adjuvants in pesticide formulations

Polyglycerol derivatives are obtained by polycondensation of glycerol under alkaline conditions, if appropriate in the presence of alcohols, and subsequent reaction with fatty acids, fatty acid alkyl esters or also fatty acid chlorides or fatty acid anhydrides, or by reaction with amino acids, lactams or lactones after ring opening. For this purpose, glycerin and possibly fatty alcohol are heated to 200 - 280 ° C. With the discharge of condensation water, the polyglycerol derivative is formed within 24 to 72 hours. The hydroxyl number (OH number) of such a reaction mixture is 825-846 mg KOH / g.

If necessary, after cooling the reaction mixture to 60-100 ° C by adding acid, preferably phosphoric acid, the pH can be adjusted to 3-5 and by adding fatty acids, such as e.g. Coconut fatty acid, fatty acid alkyl esters or also fatty acid chlorides or fatty acid anhydrides or amino acids, lactams or lactones, the polyglycerol derivative are esterified. The reaction is complete after 4-8 h.

The reaction is controlled by determining the residual acid number, which should be <1 after the reaction has ended. After the reaction mixture has cooled to 60-100.degree. C., the mixture is diluted to an active substance content of 40-70% with demineralized water and a pH of 6-7 is established by adding alkali metal hydroxide.

As a result of this production process, the polyglycerol derivatives used according to the invention are mixtures of compounds of the above-mentioned formula with different values for n, including unreacted glycerol. The R ³ radicals are incorporated into the polyglycerol derivatives (sulfation, phosphation, amination, etc.) by the standard methods known to those skilled in the art. According to the invention, the polyglycerol derivatives are suitable as adjuvants in pesticide formulations for improving the biological activity of herbicides, insecticides, fungicides, acaricides, bactericides, molluscids, nematicides and rodenticides. In a preferred embodiment, the polyglycerol derivatives

Herbicide formulations added. Suitable herbicides are, without restricting the invention to these, in particular glyphosates, their salts and / or derivatives, but also acifluorfen, asulam, benazolin, bentazone, bilanafos, bromacil, bromoxynil, chloramben, clopyralide, 2,4-D, 2,4 -DB, Dalapon, Dicamba, Dichlorprop, Diclofop, Endothall, Fenac, Fenoxaprop, Flamprop, Fluazifop, Flumiclorac, Fluoroglycofen, Fornesafen, Fosamine, Glufosinate, Haloxyfop, Imazapic, Imazamethabenz, Imazamox, MazyrpCP, Imazamethazz , Mecoprop, Methylarsonic acid / MSMA, Naptalam, Picloram, Quinclorac, Quizalofop, 2,3,6-TBA and TCA.

The preparations according to the invention can contain the polyglycerol derivatives in almost any amount. The following preparations are preferred: Formulations as "tank mix" and "ready to use compositions" contain 0.001 to 10% by weight, preferably 0.05 to 2% by weight of pesticide and 0.01% by weight to 10% by weight .-%, preferably 0.1% to 2%, particularly preferably 0.2% to 1% polyglycerol derivative. The weight ratio of polyglycerol derivative to pesticide can be between 1:10 to 500: 1, in particular 1: 4 to 4: 1.

Concentrate formulations which are diluted before use can contain the pesticide in the amounts by weight of 5 to 60%, preferably 20 to 40% and the polyglycerol derivative in amounts of 3% by weight to 50% by weight. The weight ratio of polyglycerol derivative to pesticide can be between 1:20 to 1: 1, preferably 1:10 to 1: 2.

Alternatively, the formulations according to the invention can be prepared in solid form as powders, pellets, tablets or granules, which are dissolved in water before use. Solid preparations can the pesticide in the weight of 20% to 80%, preferably from 50% to 75%, particularly preferably from 60% to 70% and the polyglycerol derivative in weight amounts of 5% to 50%, preferably 10% to 30%.

The formulations according to the invention can furthermore contain the customary thickeners, anti-gel agents, freezing agents, solvents, dispersants, emulsifiers, preservatives, further adjuvants, binders, anti-foaming agents, thinners, disintegrants and wetting agents.

As a thickener, xanthan gum and / or cellulose, for example

Carboxy, methyl, ethyl or propyl cellulose in amounts by weight of 0.01 to 5% based on the finished agent can be used. Are suitable as solvents

Monopropylene glycol, animal and mineral oils.

Nonionic, amphoteric, cationic and anionic surfactants are suitable as dispersants and emulsifiers.

Organic acids and their esters, for example ascorbic acid, ascorbic palmitate, sorbate, benzoic acid, methyl- and propyl-4-, can be used as preservatives.

Hydroxybenzoate, propionates, phenol, for example 2-phenylphenate,

1, 2-Benzisothiazolin-3-one, formaldehyde, sulfurous acid and their salts are used.

Suitable defoamers are e.g. Polysilicone. Other adjuvants can e.g. Alcohol ethoxylates, alkyl polysaccharides,

Fatty amine ethoxylates, sorbitan and sorbitol ethoxylate derivatives and derivatives of

Alk (en) ylsuccinic anhydride. The mixing ratio of these adjuvants to the polyglycerol derivative can be in the range from 1:10 to 10: 1.

For solid formulations, polyvinyl pyrrolidone, polyvinyl alcohol, carboxymethyl cellulose, sugar, for example sucrose, sorbitol, or starch are suitable as binders.

Carbon black, tallow, kaolin, aluminum, calcium or magnesium stearate, sodium tripolyphosphate, sodium tetraborate, sodium sulphate, silicates and sodium benzoate are suitable as thinners, absorbers or carriers. Cellulose, for example carboxymethyl cellulose, polyvinylpyrrolidone, sodium or potassium acetate, carbonates, bicarbonates, sesquicarbonates, act as disintegrants. Ammonium sulphate or potassium hydrogen phosphate. Alcohol ethoxylates / propoxylates can be used as wetting agents.

A great technical advantage of the pesticide preparations according to the invention is their high salt stability, in particular that of the pesticide polyglyceryl alkyl ester preparations; in an aqueous medium even with a high pesticide concentration.

The formulations according to the invention can be used in accordance with the customary methods.

Aqueous concentrates and solid formulations are diluted with the appropriate amount of water before application. Pesticide amounts in the range of 0.1 to 5 kg, preferably 0.3 to 2.5 kg, are applied per hectare. The proportion of the adjuvant polyglycerol derivative according to the invention is in the range from 0.1 to 3.0 kg / ha. The volume of the pesticide formulation created for spraying is in the range from 50 to 1000 l / ha.

The invention also relates to a method for increasing the biological activity of pesticides, which is characterized in that the pesticides are used in the form of pesticide preparations containing polyglycerols and / or polyglycerol derivatives according to formula (I). The method is preferably suitable for herbicides, in particular for glyphosates, their salts and / or derivatives.

Examples:

The following examples show the influence of polyglycerol esters on the biological activity of the herbicide glyphosate. Glyphosate (N-phosphonomethylglycine) is used as a water-soluble salt, for example as an alkali metal, ammonium, alkylamine, alkylsulfonium, alkylphosphonium, sulfonylamine or aminoguanidine salt in aqueous

Formulations used. The aqueous composition according to the invention has a pH of 4 to 8, preferably 6 to 7. 1) Production of polyglycerols:

Preparation of a polyglycerol with n = 15:

5000 g of glycerol, 73 g of hypophosphorous acid (w = 50%) and 183 g of sodium hydroxide solution (w = 18%) are initially introduced with stirring and heated to 240 ° C. while introducing about 0.7 m ^{3 of} nitrogen / hour. After a reaction time of about 90 hours, a degree of condensation of n = 15 is reached. The water formed in the reaction is discharged into a separator. The other polyglycerols are prepared analogously to the above regulation. Table 1 lists the key figures for the polyglycerols produced.

Table 1: Key figures of the polyglycerols produced:

* different runtime due to changed nitrogen throughput

2) Preparation of polyglycerol esters of the formula (II)

R ^a - CO - O - (CH ₂ CHCH ₂ O) _n - R ²

(N) OR ³

from polyglycerols and fatty acids.

Producing a polyglycerol ester of polyglycerol (n = 15) and coconut fatty acid (C _{_8/1} δ):

500 g of polyglycerol (n = 15) are introduced with stirring and, while simultaneously introducing nitrogen at 80 ° C., the pH is adjusted to 5 with 5% phosphoric acid (aqueous). The pH is measured in a 1% aqueous solution. Then 87.4 g of coconut fatty acid (Cs) are added and one Nitrogen throughput heated from 0.1 m / h to 230 ° C. After reaching an acid number of <0.5 mg KOH / g in about 5 to 12 hours at 230 ° C, the experiment is ended. The other polyglycerol esters are prepared from polyglycerol and other fatty acids analogously to the above regulation. The key figures of the polyglycerol esters produced are listed in Table 2.

Table 2: Key figures of the polyglycerol esters produced:

** lower reaction temperature (170 - 200 ° C)

3) Preparation of test formulations containing the polyglycerol esters I-VI of the formula (II):

Table 3: Composition of the polyglycerol esters I - VI of the formula (II):

Test formulations are prepared, each containing 200 g, 300 g and 500 g of glyphosate and 600 g of the polyglycerol esters I-VI in 300 l of water. The weights are based on 100% active ingredient and 100% adjuvant. A formulation amount corresponding to the ratio of 300 l / ha is applied in a greenhouse to the plant species Abutilon theophrasti (ABUTH), Sesbania exaltata (SEBEX), Pharbitis purpurea (PHBPU), Galium aparine (GALAP), Amaranthus retroflexus (AMARE), Echinochloa crus (ECHCG) and after 21 days at 20 ° C the plant growth was assessed on a scale. 0% of the measurement scale stands for no effect, 100% for a complete death of all plant species mentioned above. The influence of the polyglycerol esters (adjuvants) I - VI on the herbicidal action of glyphosate is shown in Table 4.

Table 4: Influence of polyglycerol ester (adjuvant) on the herbicidal activity of glyphosates

Claims

claims

1) Pesticide preparations containing polyglycerols and / or polyglycerol derivatives of the formula (I)

R ¹ - O - (CH ₂ CH ₂ O) _n - R ² (I)

OR ³

wherein the radicals R ¹ , R ² and R ^{3 are,} independently of one another, the same or different and a radical, or in the case of R ³ optionally a combination of radicals selected from the group hydrogen; (CrC ₃₀ ) alkyl, optionally substituted by 1 to 3 (CrC ₄ ) alkyl or (CrC ₄ ) alkoxy groups; (C ₂ -C ₃₉ ) alkenyl, optionally sulfonated and optionally substituted by 1 to 3 (C 1 -C ₄ ) alkyl or (CrC ₄ ) alkoxy groups; Phenyl, optionally substituted by 1 to 3 (C 1 -C ₄ ) alkyl or (C 1 -C ₄ ) alkoxy groups; Naphthyl, optionally substituted by 1 to 3 (CC ₄ ) alkyl or (CC ₄ ) alkoxy groups; R ⁴ R ⁵ N- (CHι) y-; HO- (CH ₂ ) y-; - (AO) z H; -SO ₃ H; -SO ₃ ^" X ⁺ ; -PO ₃ H ₂ ; -PO ₃ ² -χ ⁺ ; -CR ₂ -COOH; -CR ₂ -COO-χ ⁺ ; -CO-R ⁷ - COOH; -CO-R ⁷ - COO ^" X ⁺ ; -C- (R) ₂ C (R) ₂ C (R) ₂ -N (R ² ) ₂ , where R is H and / or CH ₃ ; -C (R) ₂ C (R) ₂ C (R) ₂ -N ((AO) _z ) ₂ H, where R is H and / or CH ₃ ;

- CH ₂ CHCH ₂ O) _n -R ²

O (AO) _z H

or R ^a -CO-, where R ^{a is} hydrogen, (CrC ₃ o) -alkyl, optionally substituted by 1 to 3 (CrC) -alkyl or (C _r C ₄ ) -alkoxy groups, (C ₂ -C ₃₀ ) alkenyl optionally sulfonated and optionally substituted by 1 to 3 (CrC ₄₎ alkyl or (CrC) alkoxy groups, phenyl, optionally substituted by 1 to 3 (CC ₄₎ - alkyl or (Cι-C ₄₎ alkoxy groups , Naphthyl, optionally substituted by 1 to 3 (-C ₄ ) alkyl or (CrC) alkoxy groups, or R ^a for a group selected from the formulas R ⁴ R ⁵ N-CH- (CH ₂ ) _X R ⁶ ; R ⁴ R ⁵ N- (CH ₂ ) _y - or HO- (CH ₂ ) _y -,

is, where n is a number from 4 to 40, preferably 5 to 20, in particular 5 to 20; R ⁴ and R ⁵ , which may be the same or different, for hydrogen, (CrCιo) alkyl, (C ₂ -C ₃ o) alkenyl, optionally sulfonated, or for a group of the formula - (AO) _z H; R ^{6 is} hydrogen, -CONH ₂ , -COOH, -SCH ₃ or -NH ₂ ; R ⁷ for (C -C ₀ - alkylene), (C ₂ -C ₃₀ ) alkenyl, optionally sulfonated; X ^{+ is} Na ⁺ , K ⁺ , Ca ²⁺ or N (R ⁸ ) ₄ \ where R ^{8 is} H or (CrC ₁₀ ) alkyl, preferably (CC ₄ ) alkyl; x for a number from 0 to 15; y for a number from 4 to 6; z for a number from 0 to 30, preferably 0 to 5; and A represents a group -CH ₄ - or -C ₃ H ₆ .

2) Pesticide preparations according to claim 1, characterized in that the pesticide is a herbicide.

3) Pesticide preparations according to claim 2, characterized in that the herbicide is glyphosate, its salts and / or derivatives.

4) Process for increasing the biological activity of pesticides, which is characterized in that the pesticides are used in the form of pesticide preparations according to at least one of claims 1 to 3.