EP1460895A1

EP1460895A1 - Aqueous plant-protection formulations

Info

Publication number: EP1460895A1
Application number: EP02796652A
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: 2004-09-29
Also published as: CA2471240A1; US20050085391A1; DE10163887A1; WO2003055305A1; BR0215298A; MXPA04006130A

Abstract

The invention relates to aqueous plant-protection formulations, comprising water-soluble pesticides, agrochemical salts and polymers based on acrylamidopropylmethylenesulphonic acids (AMPS) and so-called macromonomers. The formulations exhibit a high solubility for the pesticides and the agrochemical salts and an excellent shelf-life. The addition of the polymers improves the compatibility and the water-solubility of the pesticides and the agrochemical salts. Salting-out effects are prevented or minimised. The formulations are preferably concentrated formulations, preferably soluble liquids (SL) and soluble concentrates.

Description

description

Aqueous crop protection formulations

The present invention relates to aqueous crop protection formulations comprising water-soluble pesticides, agrochemical salts and polymers based on acrylamidopropylmethylene sulfonic acid (AMPS) and so-called macromonomers. The polymers improve the compatibility and water solubility of the pesticides and the agrochemical salts. Salt-out effects are suppressed.

Plant protection formulations with a broad spectrum of activity, which contain pesticides and fertilizers in a single formulation, are becoming increasingly important. The different physico-chemical properties of pesticides and fertilizers often cause incompatibilities

Components, which is particularly noticeable at high concentrations. Such incompatibilities cause phase separations, crystallization and sedimentation processes. In addition, the high electrolyte content of the formulations causes a strong salting-out effect, which de facto reduces the solubility of the components.

However, the solubility of pesticides and agrochemical salts is the determining factor in the production of highly concentrated aqueous plant formulations. Highly concentrated solutions without organic solvents are desired, which are not subject to phase separation, crystallization and sedimentation even after a long storage period and large temperature fluctuations.

Surprisingly, it has now been found that aqueous crop protection formulations containing water-soluble pesticides, agrochemical salts and polymers based on acrylamidopropylmethylene sulfonic acid (AMPS) and so-called

Macromonomers, a high solubility of the pesticides and agrochemical salts, as well as and show excellent storage stability. The polymers improve the compatibility and water solubility of the pesticides and agrochemical salts and act as solubilizers. Salt-out effects are suppressed or minimized. The formulations are preferably concentrated formulations, preferably solvent liquids (SL) and solvent concentrates.

The invention accordingly relates to aqueous crop protection formulations comprising i) at least one polymer which can be prepared by radical copolymerization of A) acrylamidopropylmethylene sulfonic acid (AMPS) and / or their

Salt;

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, ii) at least one pesticide and iii) at least one agrochemical salt.

The agrochemical salts iii) are not pesticides ii).

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, trialkylammonium or tetraalkylammonium salts, the alkyl substituents of the ammonium ions independently of one another (-CC ₂₂ ) alkyl radicals represent, which can be occupied by 0 to 3 hydroxyalkyl groups, the alkyl chain length can vary in a range from C ₂ to C-io. 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) _x (R ⁴ - 0) ₂ - R ³ (1) wherein

R ^{1 is} 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) 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 (C ₁ -C ₁₀₀ ) -

Hydrocarbon residue, preferably (-C-C ₃ o) hydrocarbon residue.

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. In particular, 5 <x + z <50 applies. R ³ particularly preferably represents an aliphatic (C4-C ₂ 2) alkyl or

Alkenyl radical, preferably (C ₁ O-C2 ₂ ) alkyl or alkenyl radical; a phenyl radical; a (CrC ₂₂ ) alkylphenyl radical, preferably (Cι-Cg) alkylphenyl radical, particularly preferably (Cι-C ₄ ) alkylphenyl radical, particularly preferably sec-butyl or n-

Butyl-alkylphenyl; a poly ((-CC ₂₂ ) alkyl) phenyl radical, preferably poly ((-CC ₈ ) alkyl) phenyl radical, particularly preferably poly ((-CC ₄ ) alkyl) phenyl radical, particularly preferably

Poly ((sec-butyl) phenyl group, most preferably tris (sec-butyl) phenyl group or tris (n-butyl) phenyl group; or a polystyrylphenyl group [i.e. poly (phenylethyl) phenyl group], particularly preferred

Tristyrylphenyl residue [i.e. Tris (phenylethyl) phenyl group].

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 styrene sulfonic acid, vinyl sulfonic acid, vinyl phosphonic acid, allylsulfonic acid, methallylsulfonic acid, acrylic acid, methacrylic acid and / or maleic acid or maleic anhydride, fumaric acid, crotonic acid, itaconic acid or 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, wherein the substituents of the amines are independent from each other represent (CC ₂₂ ) -alkyl radicals which are 0 to 3 Hydroxyalkyl groups may be occupied, which may vary in alkyl chain length in the range C ₂ to C ₁ 0th 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, styrene sulfonic acid, maleic acid, fumaric acid, crotonic acid and senecioic acid, with aliphatic, aromatic or cycloaliphatic alcohols with a carbon number of 1 to 30.

Likewise suitable comonomers C) are open-chain and cyclic N-vinylamides (N-vinyllactams) with a ring size of 4 to 9 atoms, preferably N-vinylformamide (NVF), N-vinylmethylformamide, N-vinylmethyl acetamide (VIMA), N-vinyl acetamide , N-vinyl pyrrolidone (NVP), N-vinyl caprolactam; Amides of acrylic and methacrylic acid, particularly preferably acrylamide, N, N-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- (methacryloy! Oxy) ethyl ester]; N, N-dimethylaminomethacrylate; Diethylamino-methyl; Acrylic and

methacrylamidoglycolic; [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, triallyl amine, tetraallyl ethylenediamine, allyl ester of phosphoric acid; and / or vinylphosphonic acid derivatives. Polymers that can be produced by 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 represents a number between 0 and 50, preferably 1 and 50, particularly preferably 5 and 30, and R ^{3 represents} a (Cιo-C 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, styrene sulfonic 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

(Cι ₀ -C ₁₈ ) fatty alcohol polyglycol ether with 8 EO units (Genapol ^® C-080);

Cn-oxo alcohol polyglycol ether with 8 EO units (Genapol ^® UD-080);

(C ₂ -C ₁₄ ) fatty alcohol polyglycol ether with 7 EO units (Genapol ^® LA-070);

(Cι ₂ -C ₁₄ ) fatty alcohol polyglycol ether with 11 EO units (Genapol ^® LA-110); (C ₁₆ -C ₈ ) fatty alcohol polyglycol ether with 8 EO units (Genapol ^® T-080);

(-C ₆ -C ₁₈ ) fatty alcohol polyglycol ether with 15 EO units (Genapol ^® T-150);

(Cι ₆ -C ₁₈ ) fatty alcohol polyglycol ether with 11 EO units (Genapol ^® T-110); (Ci6-Cι ₈ ) fatty alcohol polyglycol ether with 20 EO units (Genapol ^® T-200); (C ₁₆ -C ₈ ) fatty alcohol polyglycol ether with 25 EO units (Genapol ^® T-250); (Ci8-C ₂₂ ) fatty alcohol polyglycol ether with 25 EO units; iso- (C ₁₆ -C ₈ ) fatty alcohol polyglycol ether with 25 EO units; and C ₂ 2 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 for use

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 ₁ -C 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 acrylamide, vinylformamide, N-vinylmethylacetamide, sodium methallyl sulfonate, hydroxyethyl methacrylate, acrylic acid, methacrylic acid,

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

The proportions 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, i.e. 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 be low hydrophobic, i.e. 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 trimethyiolpropane triacrylate, allyl compounds, preferably allyl (meth) acrylate,

Triallyl cyanurate, maleic acid diallyl ester, polyallyl ester, tetraallyloxyethane,

Triallylamine, tetraallylethylenediamine, allyl ester of phosphoric acid; and or

Vinylphosphonic.

The polymers can be obtained by radical copolymerization, e.g. Precipitation polymerization, emulsion polymerization, solution polymerization or

Suspension polymerization produced.

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% less than 423 micrometers, 52.0% less than 212 micrometers, 26.6% less than 106 micrometers, 2.6% less than 45 micrometers and 26 .6% greater than 850 microns. 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 energy electromagnetic rays or the customary 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, Azobisdimethylvalerionitril, as well as inorganic peroxy compounds, such as (NH ₄₎ ₂ S2θ ₈ , K ₂ S ₂ 0 ₈ or H ₂ O2, optionally in combination with reducing agents, such as sodium hydrogen sulfite and iron (II) sulfate, or redox systems which, as the reducing component, are 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 with their functional groups, the monomer distribution and the degree of crosslinking, the salting-out effects of the salt components can be minimized and the theological properties of the solutions can be adjusted.

The polymer content of the formulations, based on the finished formulations, 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. The water content of the formulations, based on the finished formulations, is preferably 5 to 60% by weight, particularly preferably 5 to 50% by weight.

The invention is particularly suitable for highly concentrated solutions with a water content of 5 to 30% by weight.

Suitable pesticides are herbicides, insecticides, fungicides, acaricides, bactericides,

Molluscids, nematicides and / or rodenticides.

The pesticides are preferably water-soluble pesticides. Water-soluble pesticides are understood to mean those which have a water solubility, based on the pure aqueous solution, of greater than 800 g / l, preferably greater

1000 g / l.

Ionic pesticides are preferably used, particularly preferably

Glyphosate, sulphosate and glufosinate, particularly preferably glyphosate in the form of its mono (isopropylammonium salt) or mono (trimethylsulfonium) salt.

The pesticide content of the formulations is based on the finished product

Formulations, preferably 5-85% by weight, particularly preferably 25 to

60% by weight, particularly preferably 25 to 50% by weight.

The agrochemical salts are preferably inorganic

Fertilizers, preferably ammonium salts, particularly preferably ammonium sulfate, nitrates, preferably ammonium nitrate, and / or phosphates. The proportion of agrochemical salts, based on the finished formulations, is preferably 5 to 85% by weight, particularly preferably 25 to 60% by weight, particularly preferably 25 to 50% by weight.

As auxiliaries / additives, the formulations can contain, inter alia, surface-active substances (adjuvants), foam inhibitors, thickeners, antifreeze, evaporation inhibitors, preservatives, anti-gel agents and neutralizing agents.

The proportion of surface-active substances, based on the finished formulations, is preferably 5 to 50% by weight, particularly preferably 15 to 40% by weight.

Suitable surface-active substances are preferably adducts 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 and 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 monoesters and diesters and sorbitan / sorbitol monoesters and diesters of saturated and unsaturated fatty acids having 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) alkyl sulfonic acids and (Ci ₂ -C ₈ ) alkylarylsulfonic acids;

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

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, for example sodium. Potassium, aluminum, magnesium and titanium stearates or the sodium and / or potassium salts of 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 formulations are preferably adjusted to a pH in the range from 2 to 12, particularly preferably 3 to 8, particularly preferably 6.5 to 7.5.

Surprisingly, it has also been found that the formulations can be free of organic solvents, such as, for example, xylene or (C ₆ -C ₆ ) aromatics mixtures (for example ^® Solvesso types).

The formulations are preferably solvent liquids (SL) or solvent concentrates.

The use of the polymers gives the user extensive freedom in the choice of their components. The formulations show a high compatibility of the components with each other (pesticides, salts, adjuvants etc.), a high solubility of the pesticides and agrochemical salts as well as an excellent storage stability. The polymers act as solubilizers. Salt-out effects are suppressed or minimized.

Example 1: Preparation of polymer 1

500 g of toluene were placed in a 1 L Quickfit flask equipped with a stirrer, internal thermometer, gas inlet tubes for nitrogen and ammonia gas and a reflux condenser. In addition, 3.0 g of 2-acrylamido-2-methy (propanesulfonic acid (AMPS) was charged and neutralized with the equivalent amount of ammonia. Then 60.0 g of an ester formed from acrylic acid and (Ci ₂ -Cι) fatty alcohol polyglycol ether with 7 ethylene oxide units (Genapol ^® LA-070) and 30.0 g of isopropanol 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.degree. The mixture was 4 hours at the specified

Temperature stirred under reflux. After completion of the reaction, the product was transferred to a rotary evaporator and the solvent was removed by vacuum distillation at approx. 50 ° C.

Example 2: Preparation of polymer 2

Procedure analogous to example 1; Furthermore, 1.0 g of trimethylolpropane triacrylate (TMPTA) was added for crosslinking.

Example 3: Soluble Liquid Formulation (SL) without polymer composition:

Ammonium sulfate, techn. 40% by weight

Arkopal ^® N 100 (nonylphenol ethoxylate with 10 EO units) 30% by weight

Glyphosate IPA (aq. Sol 62% by weight) 30% by weight

When the components were mixed together, the phases separated spontaneously.

Example 4: Soluble Liquid Formulation (SL) with polymer composition: ammonium sulfate, techn. 40% by weight

Arkopal ^® N 100 (nonylphenol ethoxylate with 10 EO units) 28% by weight

Glyphosate IPA (aq. Sol 62% by weight) 30% by weight

Polymer 1 from Example 1 2% by weight

Mixing them together resulted in a homogeneous, clear solution that remained stable over a longer period of time.

Claims

claims:

1. Aqueous crop protection formulations comprising i) 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 which is based on

Based on polyalkylene oxides, and

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) R ¹ - Y - (R ² - 0) _x (R ⁴ - 0) _z - R ³ (1)

is what

R ¹ for a vinyl, allyl, acrylic, methacrylic, senecioyl or Crotonylrest; R ² and R ⁴ independently of one another for (C ₂ -C) 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 for hydrogen or a saturated or unsaturated linear or branched aliphatic, cycloaliphatic or aromatic (-C-Cιoo) hydrocarbon radical, preferably (Cι-C ₃₀ ) -

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 or 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 that 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 represents a number between 0 and 50, preferably 1 and 50, particularly preferably 5 and 30, and R ^{3 represents} a (Cιo-C 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-vinylpyrrolidone, vinylphosphonic acid, styrene, styrene sulfonic 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 of

(Cιo-Ci ₈ ) fatty alcohol polyglycol ether with 8 EO units;

Cιι-Oxoalkoholpolyglykolether with 8 EO units,

(Ci ₂ -Cι) -Fetta! Alcohol polyglycol ether with 7 EO units,

(Ci ₂ -Cι) fatty alcohol polyglycol ether with 11 EO units, (Ci ₆ -Cι ₈ ) fatty alcohol polyglycol ether with 8 EO units,

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

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

(Cι ₆ -Ci _δ ) fatty alcohol polyglycol ether with 20 EO units,

(Cι ₆ -Cιs) fatty alcohol polyglycol ether with 25 EO units, (Cι ₈ -C ₂₂ ) fatty alcohol polyglycol ether with 25 EO units, iso- (C ₁₆ -Cι ₈ ) fatty alcohol polyglycol ether with 25 EO units and / or

C2 ₂ 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

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 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 ₁ -C ₂₂ ) all yl) phenyl radical, preferably tris (sec-butyl) phenyl radical or tris (n-butyl) phenyl radical, particularly 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,

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

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 contains, based on the finished formulation, 0.01 to 10% by weight, preferably 0.01 to 5% by weight, of polymers.

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

14, characterized in that the water content, based on the finished formulation, is 5 to 60% by weight, preferably 5 to 50% by weight, particularly preferably 5 to 30% by weight.

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

15, characterized in that the water solubility of the pesticides is greater than 800 g / l, preferably greater than 1000 g / l.

17. Plant protection formulation according to at least one of claims 1 to 16, characterized in that the pesticides are ionic pesticides.

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

17, characterized in that the pesticides are glyphosate, sulphosate and / or glufosinate.

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

18, characterized in that the proportion of pesticides, based on the finished formulation, is 5 to 85% by weight, preferably 25 to 60% by weight.

20. Plant protection formulation according to at least one of claims 1 to 19, characterized in that the agrochemical salts are inorganic fertilizers, preferably ammonium salts and / or phosphates.

21. Plant protection formulation according to at least one of claims 1 to 20, characterized in that the proportion of agrochemical salts, based on the finished formulation, is 5 to 85% by weight, preferably 25 to 60% by weight.

22. Plant protection formulation according to at least one of claims 1 to 21, characterized in that it is free of organic solvents.

23. Plant protection formulation according to at least one of claims 1 to 22, characterized in that it is a Soluble Liquid (SL) or a Soluble Concentrate.