Classifications

• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
  • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
  • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels

Definitions

• 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.
• AMPS acrylamidopropylmethylene sulfonic acid
• macromonomers By adding the polymers, the individual components (pesticides, adjuvants, etc.) are highly susceptible.
• Pesticides with predominantly hydrophobic groups hardly soluble in water and poorly compatible with other pesticides or adjuvants, dispersants and electrolytes.
• 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
• AMPS acrylamidopropylmethylene sulfonic acid
• 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
• 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) -
• Chlorine and / or fluorine-containing comonomers 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 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 is preferably 70 to 100 mol%.
• the comonomer A) is preferably the sodium and / or
• AMPS acrylamidopropylmethylene sulfonic acid
• the macromonomers B) are preferably those of the formula (1)
• 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;
• 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
• 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 (C ⁇ -C 22) alkylphenyl group, preferably (CrCgVAlkylphenylrest, particularly preferably (C ⁇ -C4) alkylphenyl group, particularly preferably sec-butyl or n-butyl-alkylphenyl; a poly ((C ⁇ -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].
• R 3 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.
• 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.
• 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.
• the degree of neutralization of the optional olefinically unsaturated acids C) can be 0% to 100%, preferably 70 and 100 mol%.
• 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.
• N-vinyllactams N-vinyllactams
• NVF N- Vinyl formamide
• VIMA N-vinyl methylacetamide
• NP N-vinyl pyrrolidone
• 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.
• 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.
• AMPS acrylamidopropylmethylene sulfonic acid
• AMPS the sodium salt of acrylamidopropylmethylene sulfonic acid
• Ammonium salt of acrylamidopropylmethylene sulfonic acid preferably the ammonium salt of acrylamidopropylmethylene sulfonic acid (AMPS);
• 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
• 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
• esters formed from acrylic or methacrylic acid and alkyl ethoxylates selected from the group (C ⁇ o-C ⁇ 8 ) fatty alcohol polyglycol ether with 8 EO units (Genapol ® C-080); Cn-oxo alcohol polyglycol ether with 8 EO units (Genapol ® UD-080);
• R 3 is a poly ((-C 22 ) alkyl) phenyl radical, preferably tris (sec-butyl) phenyl radical, and tris (n-butyl) phenyl radical, particularly preferably
• the proportion by weight of the macromonomers B) in the polymer can vary between 0.1 and 99.9% by weight.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• Polymerization can also be carried out in a protective gas atmosphere, preferably under nitrogen.
• 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 ⁇ 8, 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
• 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.
• 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 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.
• the suspensions / suspension concentrates additionally contain at least one dispersant.
• 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.
• 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 /
• 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
• clofentezine (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-
• 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.
• at least one sparingly soluble pesticide preferably selected from glyphosate, sulphosate and glufosinate.
• readily soluble pesticide preferably selected from glyphosate, sulphosate and glufosinate.
• 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 -C ⁇ 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
• 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;
• 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 can be measured according to the CIPAC method MT161
• the invention also relates to the use of polymers which can be prepared by radical copolymerization of
• AMPS acrylamidopropylmethylene sulfonic acid
• 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.
• 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
• the suspensions are preferably suspension concentrates.
• composition (% by weight) (9)
• 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).
• composition (% by weight) (g)
• 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).
• composition (% by weight) (g)
• 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.
• composition (% by weight) (g)

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• Life Sciences & Earth Sciences (AREA)
• General Health & Medical Sciences (AREA)
• Health & Medical Sciences (AREA)
• Pest Control & Pesticides (AREA)
• Agronomy & Crop Science (AREA)
• Dispersion Chemistry (AREA)
• Chemical & Material Sciences (AREA)
• Plant Pathology (AREA)
• Toxicology (AREA)
• Engineering & Computer Science (AREA)
• Dentistry (AREA)
• Wood Science & Technology (AREA)
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• Environmental Sciences (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)

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• 2001
  • 2001-12-22 DE DE10163888A patent/DE10163888A1/de not_active Withdrawn
• 2002
  • 2002-12-17 CA CA002471239A patent/CA2471239A1/en not_active Abandoned
  • 2002-12-17 MX MXPA04006131A patent/MXPA04006131A/es unknown
  • 2002-12-17 US US10/500,026 patent/US20060142159A1/en not_active Abandoned
  • 2002-12-17 BR BR0215299-1A patent/BR0215299A/pt not_active IP Right Cessation
  • 2002-12-17 EP EP20020805758 patent/EP1469727A1/de not_active Withdrawn
  • 2002-12-17 WO PCT/EP2002/014365 patent/WO2003055304A1/de not_active Application Discontinuation

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