EP1469727A1

EP1469727A1 - Plant-protective agents in the form of suspensions

Info

Publication number: EP1469727A1
Application number: EP20020805758
Authority: EP
Inventors: Gerd Roland Meyer; Roman MORSCHHÄUSER; Ralf Zerrer
Original assignee: Clariant GmbH
Current assignee: Clariant Produkte Deutschland GmbH
Priority date: 2001-12-22
Filing date: 2002-12-17
Publication date: 2004-10-27
Also published as: BR0215299A; WO2003055304A1; MXPA04006131A; US20060142159A1; DE10163888A1; CA2471239A1

Abstract

The invention relates to aqueous plant-protective agents on the form of suspensions, comprising polymers based on acrylamidopropylmethylenesulphonic acids (AMPS) and so-called macromonomers. Said suspensions have a high compatibility and suspension-suitability for the components (pesticides, adjuvants, dispersants, electrolytes etc.). The invention is particularly suitable for suspension concentrates. Said suspension concentrates exhibit a long shelf-life.

Description

description

Plant protection formulations in the form of suspensions

The present invention relates to crop protection formulations in the form of suspensions containing polymers based on acrylamidopropylmethylene sulfonic acid (AMPS) and so-called macromonomers. By adding the polymers, the individual components (pesticides, adjuvants, etc.) are highly susceptible.

In crop protection formulations in the form of suspensions, it is often observed that the susceptibility, i.e. the ability to suspend, the individual components (pesticides, adjuvants, etc.) is insufficient. This deficiency is observed in particular in the case of suspension concentrates, which often only show insufficient storage stability. When diluting suspension concentrates to the desired spray concentration, it is also frequently observed that gel formation, phase separation, crystallization or sedimentation of the individual components occur. This results in restricted variety of formulations, loss of efficiency of the active substances, risk of clogging for filter and nozzle systems and a high level of cleaning.

One of the reasons for the problems mentioned above is that the individual components are usually poorly compatible with one another, which is particularly noticeable at high concentrations. For example, Pesticides with predominantly hydrophobic groups hardly soluble in water and poorly compatible with other pesticides or adjuvants, dispersants and electrolytes.

Surprisingly, it has now been found that aqueous crop protection formulations in the form of suspensions which contain at least one polymer based on acrylamidopropylmethylene sulfonic acid (AMPS) and so-called macromonomers are highly compatible with the components

(Pesticides, adjuvants, dispersants, electrolytes etc.) with each other and a high susceptibility (suspension) of the components. In addition, suspension concentrates show high storage stability. The invention accordingly relates to aqueous crop protection formulations in the form of suspensions containing at least one polymer which can be prepared by radical copolymerization of

A) acrylamidopropylmethylene sulfonic acid (AMPS) and / or its salts; B) one or more macromonomers containing i) an end group capable of polymerization, which in

Reaction medium is at least partially soluble, ii) a hydrophobic part which is hydrogen or a saturated or unsaturated, linear or branched, aliphatic, cycloaliphatic or aromatic (C1-C100) -

Represents hydrocarbon radical, and iii) optionally a hydrophilic part based on polyalkylene oxides; and C) optionally one or more further at least mono- or poly-olefinically unsaturated oxygen, nitrogen, sulfur, phosphorus,

Chlorine and / or fluorine-containing comonomers.

The macromonomers B) preferably contain a hydrophilic part which is based on polyalkoxides, preferably polyethylene oxides and / or polypropylene oxides.

Suitable salts of acrylamidopropylmethylene sulfonic acid (AMPS) are preferably the lithium, sodium, potassium, magnesium, calcium, ammonium, monoalkylammonium, dialkylammonium, T alkylammonium or tetraalkylammonium salts, the alkyl substituents of the ammonium ions independently represent (-C ₂₂ ) alkyl radicals which can be occupied by 0 to 3 hydroxyalkyl groups, the alkyl chain length of which can vary in a range from C ₂ to C-10. One to three times ethoxylated ammonium compounds with different degrees of ethoxylation are also suitable. The sodium and ammonium salts are particularly preferred as salts.

The degree of neutralization of acrylamidopropylmethylene sulfonic acid (AMPS) is preferably 70 to 100 mol%. The comonomer A) is preferably the sodium and / or

Ammonium salts of acrylamidopropylmethylene sulfonic acid (AMPS).

The macromonomers B) are preferably those of the formula (1)

R ¹ - Y- (R ² - 0) χ (R ⁴ - 0) ₂ - R ³ (1) wherein

R ¹ for a vinyl, allyl, acrylic (ie CH ₂ = CH-CO-), methacrylic (ie

CH ₂ = C (CH ₃ ) -CO-) ₍ senecioyl or crotonyl radical;

R ² and R ⁴ independently of one another are for (C ₂ -C ₄ ) alkylene; x and z independently of one another for an integer between 0 and 500, preferably with x + z greater than or equal to 1;

Y is O, S, PH or NH, preferably O; and

R ^{3 represents} hydrogen or a saturated or unsaturated linear or branched aliphatic, cycloaliphatic or aromatic (CrC-ioo) hydrocarbon radical, preferably (-C-C ₃₀ ) hydrocarbon radical.

R ¹ particularly preferably represents an acrylic or methacrylic radical.

R ² and R ⁴ are particularly preferably a C ₂ or C ₃ alkylene radical. x and z are particularly preferably, independently of one another, a number between 0 and 50, preferably with x + z greater than or equal to 1. Particularly preferred applies

5 <x + z <50.

R ³ particularly preferably represents an aliphatic (C ₄ -C ₂₂ ) alkyl or

Alkenyl radical, preferably (C ₁₀ -C ₂₂ ) alkyl or alkenyl radical; a phenyl radical; a (Cι-C ₂₂₎ alkylphenyl group, preferably (CrCgVAlkylphenylrest, particularly preferably _(Cι-C4) alkylphenyl group, particularly preferably sec-butyl or n-butyl-alkylphenyl; a poly _((Cι-C22) alkyl ) phenyl radical, preferably poly ((C 1 -C ₉ ) alkyl) phenyl radical, particularly preferably poly ((C 1 -C 8) alkyl) phenyl radical, particularly preferably

Poly ((sec-butyl) phenyl radical, very particularly preferably tris (sec-butyl) phenyl radical or tris (n-butyl) phenyl radical; or a polystyrylphenyl radical [ie poly (phenylethyl) phenyl radical], particularly preferably tristyrylphenyl radical [ie tris (phenylethyl) phenyl radical].

Particularly preferred as R ³ are 2,4,6-tris (1-phenylethyl) phenyl and 2,4,6-tris (sec-butyl) phenyl.

The macromonomers B) are preferably prepared by reacting reactive derivatives of unsaturated carboxylic acids, preferably methacrylic or acrylic acid, with the corresponding hydroxyl-containing, optionally alkoxylated, alkyl or aryl radicals. Ring-opening addition to the respective carboxylic acid glycidyl ester is also possible.

In a preferred embodiment, the polymers also contain further olefinically unsaturated oxygen, nitrogen, sulfur, phosphorus, chlorine and / or fluorine-containing comonomers C).

Preferred comonomers C) are olefinically unsaturated acids or their salts, preferably with mono- and divalent counterions, particularly preferably styrofisulfonic acid, vinylsulfonic acid, vinylphosphonic acid, allylsulfonic acid, methallylsulfonic acid, acrylic acid, methacrylic acid and / or maleic acid or maleic anhydride, fumaric acid, crotonic acid or itaconic acid Senecioic acid or its salts. Preferred counterions are Li ⁺ , Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , Al ³⁺ , NH ₄ ⁺ , monoalkylammonium, dialkylammonium, dialkylammonium, trialkylammonium and tetraalkylammonium ions, where the substituents of the amines are independent represent (C ₁ -C 2) -alkyl radicals which can be occupied by 0 to 3 hydroxyalkyl groups, the alkyl chain length of which can vary in the range C ₂ to C ₁ 0. In addition, one to three times ethoxylated ammonium compounds with different degrees of ethoxylation, as well as corresponding acid anhydrides (also mixed) can be used. The degree of neutralization of the optional olefinically unsaturated acids C) can be 0% to 100%, preferably 70 and 100 mol%.

Also suitable as comonomers C) are esters of unsaturated carboxylic acids, preferably acrylic and methacrylic acid, styroisulfonic acid, maleic acid, Fumaric acid, crotonic acid and senecioic acid, with aliphatic, aromatic or cycloaliphatic alcohols with a carbon number of 1 to 30. Also suitable comonomers C) are open-chain and cyclic N-vinylamides (N-vinyllactams) with a ring size of 4 to 9 atoms, preferably N- Vinyl formamide (NVF), N-vinyl methyl formamide, N-vinyl methylacetamide (VIMA), N-vinyl acetamide, N-vinyl pyrrolidone (NVP), N-vinyl caprolactam; Amides of acrylic and methacrylic acid, particularly preferably acrylamide, NN-dimethylacrylamide, N, N-diethylacrylamide, N, N-diisopropylacrylamide; alkoxylated acrylic and methacrylamides, preferably hydroxymethyl methacrylamide, hydroxyethyl methacrylamide and hydroxypropyl methacrylamide.

Also suitable are succinic acid mono- [2- (methacryloyloxy) ethyl ester]; N, N-dimethylaminomethacrylate; Diethylamino-methyl; Acrylic and methacrylamidoglycolic acid; [2- (methacryloyloxy) ethyl] trimethylammonium chloride (MAPTAC) and [(2-acryolyloxy) ethyl)] trimethylammonium chloride (APTAC); 2-vinylpyridine; 4-vinylpyridine; vinyl acetate; methacrylate; acrylonitrile; Vinyl chloride; vinylidene chloride; Tetrafluoroethylene; Diallyldimethyldimethylammonium chloride (DADMAC); stearyl; lauryl; and / or tetrafluoroethylene. Methylene bisacrylic and methacrylamide are also suitable; Esters of unsaturated mono- and polycarboxylic acids with polyols, e.g. Diacrylates or triacrylates such as butanediol and ethylene glycol diacrylate or methacrylate and trimethylolpropane triacrylate; Allyl compounds, e.g. Allyl (meth) acrylate, triallyl cyanurate, maleic acid diallyl ester, polyallyl ester, tetraallyloxyethane, triallylamine, tetraallylethylene diamine, allyl ester of phosphoric acid; and / or vinylphosphonic acid derivatives.

Polymers which can be prepared by free-radical copolymerization of are particularly preferred for use

A) acrylamidopropylmethylene sulfonic acid (AMPS), the sodium salt of acrylamidopropylmethylene sulfonic acid (AMPS) and / or the

Ammonium salt of acrylamidopropylmethylene sulfonic acid, preferably the ammonium salt of acrylamidopropylmethylene sulfonic acid (AMPS); B) one or more macromonomers selected from the group of the esters formed from methacrylic or acrylic acid, preferably methacrylic acid, and compounds of the formula (2)

HO- (CH ₂ -CH ₂ - 0) _x - R ³ (2)

wherein x is a number between 0 and 50, preferably 1 and 50, particularly preferably 5 and 30, and

R ^{3 represents} a (-CC ₂₂ , -alkyl radical; and C) optionally one or more comonomers selected from the group

Acrylamide, vinylformamide, N-vinylmethylacetamide,

Sodium methallyl sulfonate, hydroxyethyl methacrylate, acrylic acid,

Methacrylic acid, maleic anhydride, methacrylamide, vinyl acetate,

N-vinylpyrrolidone, vinylphosphonic acid, styrene, styroisulfonic acid (Na salt), t-butyl acrylate and methyl methacrylate, preferably methacrylic acid and / or

Methacrylamide.

Particularly suitable as macromonomers B) are esters formed from acrylic or methacrylic acid and alkyl ethoxylates selected from the group (Cιo-Cι ₈ ) fatty alcohol polyglycol ether with 8 EO units (Genapol ^® C-080); Cn-oxo alcohol polyglycol ether with 8 EO units (Genapol ^® UD-080);

(Ci ₂ -Cι ₄ ) fatty alcohol polyglycol ether m 1 7 EO units (Genapol ^® LA-070); (Ci ₂ -Cι ₄ ) fatty alcohol polyglycol ether m 1 11 EO units (Genapol ^® LA-110); (Ci ₆ -Ci ₈ ) fatty alcohol polyglycol ether m 1 8 EO units (Genapol ^® T-080); (Ci ₆ -Cι ₈ ) fatty alcohol polyglycol ether m 1 15 EO units (Genapol ^® T-150); (Ci ₆ -Ci ₈ ) fatty alcohol polyglycol ether m 1 11 EO units (Genapol ^® T-110); (Ci6-Cι ₈ ) fatty alcohol polyglycol ether m 1 20 EO units (Genapol ^® T-200); (Ci ₆ -Ci ₈ ) fatty alcohol polyglycol ether m 1 25 EO units (Genapol ^® T-250); (Cι ₈ -C22) fatty alcohol polyglycol ether m 1 25 EO units; iso- (Ci ₆ -Cι ₈ ) fatty alcohol polyglycol ether with 25 EO units; and C ₂₂ fatty alcohol polyglycol ether with 25 EO units (Mergital ^® B 25) The EO units stand for ethylene oxide units. The Genapol ^® types are products from Clariant, while Mergital ^® B25 is a product from Cognis.

Polymers which can be prepared by free-radical copolymerization of are also particularly preferred

A) acrylamidopropylmethylene sulfonic acid (AMPS), the sodium salt of acrylamidopropylmethylene sulfonic acid (AMPS) and / or the ammonium salt of acrylamidopropylmethylene sulfonic acid, preferably the ammonium salt of acrylamidopropylmethylene sulfonic acid (AMPS);

B) one or more macromonomers selected from the group of the esters formed from acrylic acid or methacrylic acid, preferably methacrylic acid, and compounds of the formula (3)

HO- (CH ₂ -CH ₂ - 0) _x - R ³ (3) where x is a number between 0 and 50, preferably 1 and 50, particularly preferably 5 and 30, and

R ^{3 is} a poly ((-C ₂₂ ) alkyl) phenyl radical, preferably tris (sec-butyl) phenyl radical, and tris (n-butyl) phenyl radical, particularly preferably

2,4,6-Tris (sec-butyl) phenyl, a tris (styryl) phenyl, is preferred

2,4,6-tris (1-phenylethyl) phenyl group; and

C) optionally one or more comonomers selected from acrylamide, vinylformamide, N-vinylmethylacetamide and sodium methallyl sulfonate, hydroxyethyl methacrylate, acrylic acid, methacrylic acid,

Maleic anhydride, methacrylamide, vinyl acetate, N-vinylpyrrolidone, vinylphosphonic acid, styrene, styroisulfonic acid (Na salt), t-butyl acrylate, methyl methacrylate, preferably methacrylic acid and / or methacrylamide.

The proportion by weight of the macromonomers B) in the polymer can vary between 0.1 and 99.9% by weight. In a preferred embodiment, the polymers are highly hydrophobically modified, ie the proportion of macromonomers B) is 50.1 to 99.9% by weight, preferably 70 to 95% by weight, particularly preferably 80 to 94% by weight. In a further preferred embodiment, the polymers are modified to have a low hydrophobicity, ie the proportion of macromonomers B) is 0.1 to 50% by weight, preferably 5 to 25% by weight, particularly preferably 6 to 20% by weight.

The monomer distribution of the monomers A), B) and C) in the polymers can be alternating, statistical, gradient-like or block-like (also multiblock). The number average molecular weight of the polymers is preferably 1000 to 20,000,000 g / mol, preferably 20,000 to 5,000,000 g / mol, particularly preferably 50,000 to 1,500,000 g / mol.

In a preferred embodiment, the polymers are cross-linked, i.e. at least one crosslinker having at least two double bonds is polymerized into the polymer. Preferred crosslinkers are methylenebisacryl and methacrylamide; Esters of unsaturated mono- or polycarboxylic acids with polyols, preferably diacrylates and triacrylates, e.g. Butanediol and ethylene glycol diacrylate or methacrylate and trimethylolpropane triacrylate, allyl compounds, preferably allyl (meth) acrylate, triallyl cyanurate, maleic acid diallyl ester, polyallyl ester, tetraallyloxyethane, triallyl amine, tetraallyl ethylenediamine, allyl ester of phosphoric acid; and / or vinylphosphonic acid derivatives.

The polymers can be obtained by radical copolymerization, e.g. Precipitation polymerization, emulsion polymerization, solution polymerization or suspension polymerization. Polymers which have been prepared by precipitation polymerization, preferably in tert-butanol, are particularly suitable.

With the help of precipitation polymerization in tert-butanol, a specific particle size distribution of the polymers can be achieved compared to other solvents. The size distribution of the polymer particles can be determined, for example, by laser diffraction or sieve analysis. The following grain size distribution, as determined by sieve analysis, is representative of a favorable size distribution: 60.2% smaller than 423 micrometers, 52.0% smaller 212 microns, 26.6% smaller than 106 micrometers, 2.6% smaller than 45 micrometers and 26.6% larger than 850 micrometers.

The polymerization reaction can be carried out in the temperature range between 0 and 150.degree. C., preferably between 10 and 100.degree. C., both under normal pressure and under elevated or reduced pressure. As usual, the

Polymerization can also be carried out in a protective gas atmosphere, preferably under nitrogen.

To initiate the polymerization, high-energy electromagnetic radiation or the usual chemical polymerization initiators can be used, for example organic peroxides, such as benzoyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide, cumene hydroperoxide, azo compounds, such as azobisisobutyronitrile, azobisdimethylvalerionium nitrate (NH), _4- peroxide nitrate, as well as inorganic peroxide nitrates, as well as inorganic ₂ S ₂ θ8, K ₂ S ₂ 0 ₈ or H ₂ 0 ₂ , optionally in combination with reducing agents, such as sodium bisulfite and iron (II) sulfate, or redox systems which, as a reducing component, contain an aliphatic or aromatic sulfonic acid, such as, for example, benzenesulfonic acid , Toluenesulfonic acid or derivatives of these acids, such as Mannich adducts of sulfinic acid, aldehydes and amino compounds.

The polymers are readily water-soluble and thermostable. By choosing the monomers, the monomer distribution and the degree of crosslinking, in particular the adsorption behavior of the polymers with respect to the water-insoluble active substances can be adjusted. In addition, the rheological properties of the suspensions can be adjusted.

It has surprisingly been found that the use of the polymers has a particularly advantageous effect on suspension concentrates. Suspension concentrates are highly concentrated suspensions that are diluted with water to the desired spray concentration when applied. The dilution factor is preferably in the range from 10 to 1000, particularly preferably from 20 to 200. The use of the polymers significantly increases the compatibility and suspensibility of the components despite the high concentrations. Furthermore, gel formation, phase separation, crystallization and / or sedimentation of the individual components is strongly suppressed when diluted. In addition, the storage stability of the suspension concentrates is increased.

The water content of the suspension concentrates, based on the finished concentrates, is preferably 10 to 50% by weight, particularly preferably 10 to 45% by weight, particularly preferably 25 to 45% by weight.

The proportion of polymers in the suspension concentrates, based on the finished concentrates, is preferably 0.01 to 10% by weight, particularly preferably

0.01 to 5% by weight, particularly preferably 0.01 to 2.5% by weight, very particularly preferably 0.025 to 2.5% by weight.

In a preferred embodiment, the suspensions / suspension concentrates additionally contain at least one dispersant.

Surprisingly, it was found that a synergistic effect occurs between the dispersants and the polymers, which manifests itself in the fact that, in the presence of the dispersants, a small amount of polymers is sufficient to significantly increase the susceptibility. The proportion of the dispersant is based on the finished product

Suspension concentrates, preferably 0.5 to 10% by weight, particularly preferably 0.5 to 5% by weight, and the proportion of the polymers, based on the finished suspension concentrates, is preferably 0.01 to 2.5% by weight , particularly preferably 0.025 to 1 wt .-%. All common dispersants are suitable as dispersants.

Preferred are phosphoric acid esters and their salts (eg potassium, sodium or triethanolamine salts) of fatty alcohols and their alkoxylates, preferably poly (arylalkyl) phenol polyethylene glycol phosphoric acid esters and tristyryl polyglycol ether phosphates; carbomethoxy; Methyl cellulose; Strength; alginates; sulfonated naphthalene-formaldehyde condensates; lignosulfonates; Polyvinyl pyrrolidone and / or polyvinyl alcohol. By definition, the suspensions / suspension concentrates contain at least one pesticide. Herbicides, insecticides, fungicides, acaricides, bactericides, molluscids, nematicides and / or rodenticides are preferred as pesticides.

The proportion of pesticides, based on the finished suspension concentrates, is preferably 10-90% by weight, particularly preferably 30 to 60% by weight, particularly preferably 40 to 50% by weight.

The invention is particularly advantageous for suspensions /

Suspension concentrates containing water-soluble, hydrophobic pesticides. Such pesticides are particularly prone to agglomeration. Pesticides whose water solubility is less than 10 grams / liter, preferably less than 1 gram / liter, are poorly soluble. Pesticides whose solubility in water is preferably greater are readily soluble

100 grams / liter, particularly preferably greater than 500 grams / liter, particularly preferably greater than 800 grams / liter.

Preferred sparingly soluble pesticides are those from the azole class, for example propiconazole (1 - [2- (2,4-dichlorophenyl) -4-propyl-1, 3-dioxolan-2-yl-methyl-1 H-1 , 2,4-triazole and tebuconazole ((RS) -1-p-chlorophenyl-4,4-dimethyl-3- (1 H-1, 2,4-triazol-1 - ylmethyl) pentan-3-ol) , the sulfonates, for example ethofumesate and benfuresate, the anilides, for example propanil, the phenylurea derivatives, for example monuron, diuron (N '- (3,4-dichlorophenyl) -N, N-dimethylurea) and amitrole, the triazines, for example simazine and atrazine (6-chloro-N-ethyl-N ^, - (1-methylethyl) -1, 3,5-triazine-2,4-diamine), the tetrazines, e.g. clofentezine (3,6-bis (2-chlorophenyl) - 1,2,4,5-tetrazine, the propionic acid derivatives, e.g. Dalapon, the carbamates, e.g. pyrazolinates, tebuconazole, hexaconazole, phenmedipham (3-

[(Methoxycarbonyl) amino] phenyl (3-methylphenyl) carbamate) and Desmedipham, the thiocarbamates, the alkylenebis (dithiocarbamate), e.g. Maneb ([1,2-ethanediylbis- [carbamodithiato] (2 -)] manganese), Mancozeb ([ [1,2-ethanediylbis [carbamodithiato]] (2 -)] manganese and [[1,2-ethanediylbis- [carbamodithiato]] (2 -)] zinc, carbaryl (1-naphthylmethylcarbamate), azoxystrobin (methyl (E) - 2 - [[6- (2-cyanophenoxy) -4-pyrimidinyl] oxy] -a- (methoxymethylene) - benzyl acetate), linuron, trifluralin, metsulfuron-methyl (2 - [[[[(4-methoxy-6-methyl-1, 3,5-triazin-2-yl) amino] carbonyl] amino] -sulfonyl] benzoate), Triasulfuron (2- (2-chloroethoxy) -N - [[(4-methoxy-6-methyl-1,3,5-triazin-2-yl) aminol-carbonyl] benzylsulfonamide), tribenuron-methyl (methyl 2- [ [[[(4-methoxy-6-methyl-1, 3,5-triazin-2-yl) methylamino] carbonyl] amino] sulfonyl] benzoate) and chlorosulfone (2-chloro-N - [[(4-methoxy -6-methyl-1, 3,5-triazin-2-yl) amino] carbonyl] - benzylsulfonamide), the halophthalonitrile, for example chlorothalonil (2,4,5,6-tetrachloro-1,3-dicyanobenzyl, copper hydroxide and difluorobenzuron (N - [[(4-chlorophenyl) amino] carbonyl] -2,6-difluorobenzamide)).

In a preferred embodiment, the suspensions / suspension concentrates contain mixtures of at least one sparingly soluble pesticide and at least one readily soluble pesticide, preferably selected from glyphosate, sulphosate and glufosinate. The presence of the copolymers makes the sparingly soluble and the readily soluble pesticides compatible with one another.

The suspensions / suspension concentrates may contain, among other things, surface-active substances (adjuvants), solid carriers, foam inhibitors, thickeners, antifreezes, evaporation inhibitors, preservatives, anti-gel agents and neutralizing agents as auxiliary substances / additives.

The proportion of surface-active substances, based on the finished suspension concentrates, is preferably 10 to 50% by weight, particularly preferably 20 to 40% by weight.

Suitable surface-active substances are preferably addition products of 2 to 30 mol of ethylene oxide and / or 0 to 5 mol of propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms, with mono-, di- and / or trialkylphenols with 8 to 15 carbon atoms in the alkyl group, at (C ₈ -C ₈ ) - alkylamines; secondary ether amines and alkoxylated secondary ether amine derivatives; (Ci ₂ -Cι ₈ ) fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol; Glycerol mono- and diesters and sorbitan / sorbitol mono- and diesters of saturated and unsaturated fatty acids with 6 to 22 carbon atoms and their ethylene oxide addition products; Addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil; Polyol and in particular polyglycerol esters, for example polyglycerol polyricinoleate and polyglycerol poly-12-hydroxystearate; Carboxamides, for example decanecarboxylic acid dimethyl amide; high molecular weight silicone compounds, for example dimethylpolysiloxanes with an average molecular weight of 10,000 to 50,000 g / mol. Also suitable are anionic surfactants, for example alkali and ammonium salts of linear or branched alkyl (en) sulfates with 8 to 22 carbon atoms, (Ci ₂ -Ci8) alkylsulfonic acids and (Ci ₂ -Ci8) alkylarylsulfonic acids;

Bis (phenolsulfonic acid) ether and its alkali metal or ammonium salts, isethionates, preferably cocoyl isethionate; Naphthalenesulfonic acid and / or sulphosuccinates.

Suitable solid carriers are preferably clays, natural and synthetic bentonites, silica gels, calcium and magnesium silicates, titanium dioxide, aluminum, calcium or magnesium carbonate, ammonium, sodium, potassium, calcium or barium sulfate, carbon, Starch, modified starch, cellulose or cellulose derivatives, and mixtures thereof.

Preferred foam inhibitors are fatty acid alkyl ester alkoxylates; Organopolysiloxanes and their mixtures with microfine, optionally signed silica; paraffins; Waxes and microcrystalline waxes and their mixtures with signed silica. Mixtures of different foam inhibitors, e.g. those made of silicone oil, paraffin oil and / or waxes. The foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.

Hardened castor oil is preferred as the thickener; Salts of long chain fatty acids, preferably in amounts of up to 5% by weight, particularly preferably in amounts of 0.5 to 2% by weight, e.g. Sodium-. Potassium, aluminum, magnesium and titanium stearates or the sodium and / or potassium salts of the

behenic acid; Polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses; Carboxymethyl cellulose and hydroxyethyl cellulose; higher molecular weight polyethylene glycol mono- and diesters of fatty acids; polyacrylates; Polyvinyl alcohol and / or polyvinyl pyrrolidone used.

Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid.

The suspension concentrates are usually adjusted to a pH in the range 2 to 12, preferably 3 to 8, particularly preferably 6.5 to 7.5.

The use of the polymers gives the user extensive freedom in the choice of his. Components. The suspensions show a high compatibility of the components with each other (pesticides, adjuvants, dispersants, electrolytes, etc.) and a high susceptibility (suspension) of the components. When diluted, the suspension concentrates show a clearly reduced tendency towards gel formation, phase separation, crystallization and / or sedimentation. In addition, the suspension concentrates show a significantly increased storage stability.

The suspensibility of the suspensions is preferably greater than 85%, particularly preferably greater than 95%, particularly preferably greater than 95%.

Suspensibility is defined as the percentage

Weight share of suspended substances in the total amount of all substances.

Suspensibility (suspension) can be measured according to the CIPAC method MT161

(SC) can be determined.

The invention also relates to the use of polymers which can be prepared by radical copolymerization of

A) acrylamidopropylmethylene sulfonic acid (AMPS) and / or its salts;

B) one or more macromonomers containing i) an end group capable of polymerization, which in

Reaction medium is at least partially soluble, ii) a hydrophobic part which is hydrogen or a saturated or unsaturated, linear or branched, aliphatic, cycloaliphatic or aromatic (C1-C ₁ 00) - represents hydrocarbon radical, and iii) optionally a hydrophilic part, which is based on polyalkylene oxides; and C) optionally one or more further at least mono- or poly-olefinically unsaturated oxygen, nitrogen, sulfur, phosphorus, chlorine and / or fluorine-containing comonomers, to increase the susceptibility of crop protection formulations which are in the form of suspensions.

The suspensions are preferably suspension concentrates.

The following examples are intended to explain the subject matter of the invention in more detail, but without restricting it thereto.

Example 1 :

Preparation of polymer 1:

500 g of toluene were placed in a 1 liter Quickfit flask equipped with a stirrer, internal thermometer, gas inlet tubes for nitrogen and ammonia gas and a reflux condenser. Furthermore, 3.0 g of 2-acrylamido-2-methylpropane sulfonic acid (AMPS) were introduced and neutralized with the equivalent amount of ammonia. 60.0 g of stearyl acrylate and 30.0 g of isopropanol were then added. The contents of the flask were rendered inert with nitrogen while stirring and heated to 70 ° C. using a heating bath. After the temperature had been reached, 3.0 g of AIBN were added as an initiator and the mixture was heated to 80 ° C. while purging with nitrogen. The mixture was stirred under reflux at the specified temperature for 4 h. After the reaction had ended, the product was transferred to a rotary evaporator and the solvent was removed by vacuum distillation at about 50.degree. Preparation of polymer 2:

As described under 1, but using 60.0 g of an ester, formed from acrylic acid, and (C12-14) -fatty alcohol polyglycol ethers with 7 EO units (Genapol ^® LA-070) instead of the Stearylacrylats.

Production of atrazine suspension concentrates with and without polymer:

a) suspension concentrate with dispersant and without polymer

Composition: (% by weight) (9)

Atrazine (99%) 43.60 510.0

Dispersing Agent LFS ^® 2.10 25.0

Defoamer SE 57 ^® 1, 50 17.0

Kelzan ^® S (2% aq) 7.20 85.0

Ethylene glycol 4.30 50.0

Deionized Water 41, 30 484.0

The suspension was susceptible to 84%. The suspensibility was the total suspensibility of all components, which was determined according to the CIPAC method MT 161 (SC).

b) suspension concentrate with polymer 1 and without dispersant

Composition: (% by weight) (g)

Atrazine (99%) 43.60 510.0

Defoamer SE 57 ^® 1.50 17.0

Kelzan ^® S (2% aq) 7.20 85.0

Polymer 1 2.10 1.17 ethylene glycol 4.30 50.0

Deionized water 41.30 484.0 The suspension was susceptible to 88%. The suspensibility was the total suspensibility of all components, which was determined according to the CIPAC method MT 161 (SC).

c) suspension concentrate with polymer 1 and with dispersant

Composition: (% by weight) (g)

Atrazine (99%) 43.60 510.0

Dispersing Agent LFS ^® 2.00 23.80

Defoamer SE 57 ^® 1, 50 17.0

Kelzan ^® S (2% aq) 7.20 85.0

Polymer 1 0.10 1.17

Ethylene glycol 4.30 50.0

Deionized Water 41, 30 484.0

The suspension was susceptible to 96%. The suspensibility was the total suspensibility of all components, which was determined according to the CIPAC method MT 161 (SC). This result demonstrates the synergistic effect between polymer and dispersant. It can be seen that with the addition of only 0.1% by weight of polymer, the susceptibility increased sharply.

d) suspension concentrate with polymer 2 and with dispersant

Composition: (% by weight) (g)

Atrazine (99%) 43.60 510.0

Dispersing Agent LFS ^® 2.00 23.80

Defoamer SE 57 ^® 1, 50 17.0

Kelzan ^® S (2% aq) 7.20 85.0

Polymer 2 0.10 1.17

Ethylene glycol 4.30 50.0

Deionized Water 41, 30 484.0 The suspension was susceptible to 98%. The suspensibility was the total suspensibility of all components, which was determined according to the CIPAC method MT 161 (SC). This result demonstrates the synergistic effect between polymer and dispersant. It can be seen that with the addition of only 0.1% by weight of polymer, the susceptibility increased sharply.

Chemical name of the commercial products used:

Dispersing Agent LFS ^® poly (arylalkyl) phenol-polyethylene glycol-phosphoric acid ester

Defoamer SE 57 ^® silicone defoamer from Wacker

Kelzan S ^ (2% aq) thickener "Xanthangum"

Claims

claims:

1. Aqueous crop protection formulation in the form of a suspension containing at least one polymer which can be prepared by radical copolymerization of

A) acrylamidopropylmethylene sulfonic acid (AMPS) and / or its salts;

B) one or more macromonomers containing i) an end group capable of polymerization which is at least partially soluble in the reaction medium, ii) a hydrophobic part which is hydrogen or a saturated or unsaturated, linear or branched, aliphatic, cycloaliphatic or aromatic (C1- C100) represents hydrocarbon radical, and iii) optionally a hydrophilic part based on polyalkylene oxides; and

C) optionally one or more further at least mono- or poly-olefinically unsaturated oxygen, nitrogen, sulfur, phosphorus, chlorine and / or fluorine-containing comonomers.

2. Plant protection formulation according to claim 1, characterized in that the comonomer A) is the sodium and / or ammonium salts of acrylamidopropylmethylene sulfonic acid (AMPS).

3. Plant protection formulation according to claim 1 and / or 2, characterized in that the macromonomers B) are those of the formula (1)

R1 _ Y_ (R2 _ ₀ ) _X (R ⁴ - 0) Z - R ³ (1)

is where R ^{1 is} a vinyl, allyl, acrylic, methacrylic, senecioyl or

Crotonylrest; R ² and R ⁴ independently of one another for (C2-C ₄ ) alkylene, x and z independently of one another for an integer between 0 and 500, preferably with x + z greater than or equal to 1; Y is O, S, PH or NH, preferably O; and

R ^{3 is} hydrogen or a saturated or unsaturated linear or branched aliphatic, cycloaliphatic or aromatic

(Cι-Cιoo) hydrocarbon residue, preferably (C1-C30) -

Hydrocarbon residue.

4. Plant protection formulation according to claim 3, characterized in that

R ¹ for an acrylic or methacrylic radical;

R ² and R ⁴ independently of one another are C ₂ alkylene or C ₃ alkylene; x and z independently of one another for an integer between 0 and 50, preferably with x + z greater than or equal to 1;

R ³ for an aliphatic (C ₄ -C ₂₂ ) alkyl or alkenyl radical is preferred

(Cιo-C ₂₂ ) alkyl or alkenyl radical; a phenyl radical; a (-C ₂₂ ) alkylphenyl radical, preferably (sec-butyl) - or (n-butyl) - alkylphenyl radical; a poly ((-C ₂₂ ) alkyl) phenyl radical, preferably tris (sec-butyl) phenyl radical and tris (n-butyl) phenyl radical; or a polystyrylphenyl radical, preferably tristyrylphenyl radical.

5. Plant protection formulation according to claim 4, characterized in that the radical R ³ is a 2,4,6-tris (sec-butyl) phenyl radical or 2,4,6-tris (1-phenylethyl) phenyl radical.

6. Plant protection formulation according to claim 1, characterized in that the polymers can be prepared by radical copolymerization of A) acrylamidopropylmethylene sulfonic acid (AMPS), the sodium salt of acrylamidopropylmethylene sulfonic acid (AMPS) and / or the Ammonium salt of acrylamidopropylmethylene sulfonic acid, preferably the ammonium salt of acrylamidopropylmethylene sulfonic acid (AMPS);

B) one or more macromonomers selected from the group of the esters formed from methacrylic or acrylic acid, preferably methacrylic acid, and compounds of the formula (2)

HO- (CH ₂ -CH ₂ - 0) _x - R ³ (2)

R ^{3 represents} a (C oC ₂₂ ) alkyl radical; and

C) optionally one or more comonomers selected from the group consisting of acrylamide, vinylformamide, N-vinylmethylacetamide, sodium methallylsulfonate, hydroxyethyl methacrylate, acrylic acid, methacrylic acid, maleic anhydride, methacrylamide, vinyl acetate,

N-vinyl pyrrolidone, vinyl phosphonic acid, styrene, styroisulfonic acid (Na salt), t-butyl acrylate and methyl methacrylate.

7. Plant protection formulation according to at least one of claims 1 to 6, characterized in that the macromonomers B) are esters formed from acrylic or methacrylic acid and alkyl ethoxylates selected from the group

Group of (Cιo-Ci _δ ) fatty alcohol polyglycol ethers with 8 EO units;

Cn-oxo alcohol polyglycol ether with 8 EO units, (Ci ₂ -Cu) fatty alcohol polyglycol ether with 7 EO units, (Cι ₂ -Ci ₄ ) fatty alcohol polyglycol ether with 11 EO units, (Ci ₆ -Ci8) fatty alcohol polyglycol ether with 8 EO units,

(Cι ₆ -Ci ₈ ) fatty alcohol polyglycol ether with 15 EO units, (Cι ₆ -Cι ₈ ) -

Fatty alcohol polyglycol ether with 11 EO units, (Cι ₆ -Cι ₈ ) -

Fatty alcohol polyglycol ether with 20 EO units, (Cι ₆ -Cι ₈ ) -

Fatty alcohol polyglycol ether with 25 EO units, (C18-C22) - Fatty alcohol polyglycol ether with 25 EO units, iso- (Cι ₆ -C-i8) -

Fatty alcohol polyglycol ether with 25 EO units and / or Q ₂₂ fatty alcohol polyglycol ether with 25 EO units.

8. Plant protection formulation according to claim 1, characterized in that the polymers can be prepared by radical copolymerization of

A) acrylamidopropylmethylene sulfonic acid (AMPS), the sodium salt of acrylamidopropylmethylene sulfonic acid (AMPS) and / or the ammonium salt of acrylamidopropylmethylene sulfonic acid, preferably the ammonium salt of acrylic amidopropylmethylene sulfonic acid (AMPS);

B) one or more macromonomers selected from the group of the esters formed from methacrylic or acrylic acid, preferably methacrylic acid, and compounds of the formula (3)

HO- (CH -CH ₂ - 0) _x - R ³ (3) where x is a number between 0 and 50, preferably 1 and 50, particularly preferably 5 and 30, and R ^{3 is} a poly ((CrC ₂₂ ) alkyl) - phenyl radical, preferably tris (sec-butyl) phenyl radical or tris (n-butyl) phenyl radical, particularly preferably 2,4,6-

Tris (sec-butyl) phenyl radical, a tris (styryl) phenyl radical, preferably 2,4,6-

Tris (1-phenylethyl) phenyl group; and C) optionally one or more comonomers selected from the group consisting of acrylamide, vinylformamide, N-vinylmethylacetamide,

Sodium methallyl sulfonate, hydroxyethyl methacrylate, acrylic acid,

Methacrylic acid, maleic anhydride, methacrylamide, vinyl acetate,

9. crop protection formulation according to at least one of claims 1 to 8, characterized in that the proportion of macromonomers B) in the polymers 50.1 to 99.9 wt .-%, preferably 70 to 95 wt .-%, particularly preferably 80 to 94% by weight.

10. Plant protection formulation according to at least one of claims 1 to 8, characterized in that the proportion of macromonomers B) in the Polymers is 0.1 to 50% by weight, preferably 5 to 25% by weight, particularly preferably 6 to 20% by weight.

11. Plant protection formulation according to at least one of claims 1 to 9, characterized in that the number average molecular weight of the polymers

1000 to 20,000,000 g / mol, preferably 20,000 to 5,000,000 g / mol, particularly preferably 50,000 to 1,500,000 g / mol.

12. Plant protection formulation according to at least one of claims 1 to 11, characterized in that the polymers are crosslinked.

13. Plant protection formulation according to at least one of claims 1 to

12, characterized in that the copolymerization is a precipitation polymerization, preferably in tert-butanol.

14. Plant protection formulation according to at least one of claims 1 to

13, characterized in that it is a suspension concentrate.

15. Suspension concentrate according to claim 14, characterized in that the water content, based on the finished formulation, is 10 to 50% by weight, preferably 10 to 45% by weight, particularly preferably 25 to 45% by weight.

16. Suspension concentrate according to claim 14 and / or 15, characterized in that the proportion of the polymers, based on the finished

Formulation, 0.01 to 10 wt .-%, preferably 0.01 to 5 wt .-%, is.

17. Suspension concentrate according to at least one of claims 1 to 16, characterized in that it additionally contains at least one dispersant.

18. Suspension concentrate according to claim 17, characterized in that it is as a dispersant phosphoric acid esters and salts of fatty alcohols and Fatty alcohol alkoxylates, preferably poly (arylalkyl) phenol polyethyleneglycol phosphoric acid esters and tristyryl polyglycol ether phosphates; carbomethoxy; Methyl cellulose; Strength; alginates; sulfonated naphthalene-formaldehyde condensates; lignosulfonates; Contains polyvinyl pyrrolidone and / or polyvinyl alcohol.

19. Suspension concentrate according to at least one of claims 14 to 18, characterized in that, based on the finished suspension concentrate, 0.5 to 10% by weight, particularly preferably 0.5 to 5% by weight, of dispersants and 0 , 01 to 2.5 wt .-%, preferably 0.025 to 1 wt .-%, of polymers.

20. Suspension concentrate according to at least one of claims 14 to 19, characterized in that the proportion of pesticides, based on the finished suspension concentrate, 10 - 90 wt .-%, preferably 30 to 60 wt .-%, particularly preferably 40 to 50 wt .-%.

21. Plant protection formulation according to at least one of claims 1 to

20, characterized in that it contains at least one water-insoluble pesticide.

22. Plant protection formulation according to at least one of claims 1 to

21, characterized in that it contains at least one water-insoluble pesticide and at least one water-soluble pesticide.

23. Use of polymers which can be prepared by radical copolymerization of

A) acrylamidopropylmethylene sulfonic acid (AMPS) and / or its salts;

Reaction medium is at least partially soluble, ii) a hydrophobic part which is hydrogen or a saturated or unsaturated, linear or branched, aliphatic, represents cycloaliphatic or aromatic (C1-C100) hydrocarbon radical, and iii) optionally a hydrophilic part based on polyalkylene oxides; and C) optionally one or more further at least mono- or poly-olefinically unsaturated oxygen, nitrogen, sulfur, phosphorus, chlorine and / or fluorine-containing comonomers, to increase the susceptibility of crop protection formulations which are in the form of suspensions.

24. Use according to claim 23, characterized in that the crop protection formulations are suspension concentrates.