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EP1461389A1 - Crystallization inhibitor for plant-protective formulations - Google Patents

Crystallization inhibitor for plant-protective formulations

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Publication number
EP1461389A1
EP1461389A1 EP02793036A EP02793036A EP1461389A1 EP 1461389 A1 EP1461389 A1 EP 1461389A1 EP 02793036 A EP02793036 A EP 02793036A EP 02793036 A EP02793036 A EP 02793036A EP 1461389 A1 EP1461389 A1 EP 1461389A1
Authority
EP
European Patent Office
Prior art keywords
use according
radical
acid
units
sulfonic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP02793036A
Other languages
German (de)
French (fr)
Inventor
Gerd Roland Meyer
Roman MORSCHHÄUSER
Ralf Zerrer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant Produkte Deutschland GmbH
Original Assignee
Clariant GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Clariant GmbH filed Critical Clariant GmbH
Publication of EP1461389A1 publication Critical patent/EP1461389A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/10—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of amides or imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to the use of water-soluble
  • Copolymers based on acrylamidopropylmethylene sulfonic acid (AMPS) or their salts and macromonomers as crystallization inhibitors in crop protection formulations.
  • AMPS acrylamidopropylmethylene sulfonic acid
  • Pesticides with predominantly hydrophobic groups and low polarity are hardly soluble compounds in water.
  • the formulation options are essentially restricted to emulsifiable concentrates (EC) and suspension concentrates (SC). These are diluted with water to the desired spray concentration and applied by the user. Important for the necessary storage stability of the concentrated aqueous
  • Suspension is a fine-particle, constant particle size of the solid active ingredients. Crystallization leads to the formation of larger particles and thus to sedimentation and sedimentation, which prevent the required uniform dilutability of the concentrate and possibly also clog the filter and nozzle system. A somewhat different difficulty due to crystallization occurs with emulsifiable concentrates. These normally water-free concentrates are also diluted with water to the desired spray concentration by the user. Solubility in water of the organic solvent used can then lead to severe crystallization of the active substances in the spray mixture. Loss of efficiency of the active substances, risk of clogging for filter and nozzle systems and a high cleaning effort are the result.
  • polymers based on acrylamidopropylmethylsulfonic acid (AMPS) and macromonomers are outstandingly suitable as crystallization inhibitors in crop protection agents.
  • the polymers prevent the crop protection Formulations contain pesticidal active ingredients (herbicides, insecticides, fungicides, acaricides, bactericides, molluscids, nematicides and rodenticides).
  • the invention accordingly relates to the use of polymers which can be prepared by radical copolymerization of A) acrylamidopropylmethylene sulfonic acid (AMPS) and / or salts thereof; 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) 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, as a crystallization inhibitor in crop protection formulations.
  • a hydrophobic part which is hydrogen or a saturated or unsaturated, linear or branched, aliphatic, cycloaliphatic or aromatic (C1-C100) 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
  • the macromonomers B) preferably contain a hydrophilic part which is based on polyalkoxides, preferably polyethylene oxides and / or polypropylene oxides.
  • Suitable salts of acrylamidopropylmethylsulfonic acid are preferably the lithium, sodium, potassium, magnesium, calcium, ammonium, monoalkylammonium, dialkylammonium, trialkylammonium or tetraalkylammonium salts, the alkyl substituents of the ammonium ions being independent represent (C 2 -C 2) alkyl radicals which may be occupied by 0 to 3 hydroxyalkyl groups, the length of the alkyl chain of which may vary in the range from C 2 to C 10 . Single to triple ethoxylated are also suitable
  • Ammonium compounds with different degrees of ethoxylation 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).
  • AMPS acrylamidopropylmethylene sulfonic acid
  • the macromonomers B) are preferably those of the formula (1)
  • 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 is hydrogen or a saturated or unsaturated linear or branched aliphatic, cycloaliphatic or aromatic (C1-C100) -
  • Hydrocarbon residue preferably (CrC 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 ⁇ -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 (C -C 22 ) - alkyl or
  • Alkenyl radical preferably (C 10 -C 2 2) alkyl or alkenyl radical; a phenyl radical; a (-CC 22 ) alkylphenyl radical, preferably (Ci-CgJ-alkylphenyl radical, particularly preferably (CrC) -alkylphenyl radical, particularly preferably sec-butyl or n-butyl-alkylphenyl radical; a poly ((-C-C 22 ) alkyl) phenyl radical, preferably poly ((C-Cg) alkyl) phenyl radical, particularly preferably poly ((C-C) 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
  • 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 ones. 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 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.
  • 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, where the substituents of the amines are independent represent (CrC 22 ) alkyl radicals from one another, which can be occupied by 0 to 3 hydroxyalkyl groups, the alkyl chain length of which can vary in the range from C2 to C 10 .
  • one to three times ethoxylated ammonium compounds with different degrees of ethoxylation, as well as corresponding acid anhydrides (also mixed) can be used.
  • the substituents of the amines are independent represent (CrC 22 ) alkyl radicals from one another, which can be occupied by 0 to 3 hydroxyalkyl groups, the alkyl chain length of which can vary in the range from C2
  • 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, styrene sulfonic acid, maleic acid, fumaric acid, crotonic acid and senecioic acid, with aliphatic, aromatic or cyclo-aliphatic alcohols with a carbon number of 1 to 30.
  • N-vinyllactams open-chain and cyclic N-vinylamides
  • NVF N-vinylformamide
  • VIMA N-vinyl methylacetamide
  • NP N-vinyl pyrrolidone
  • 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.
  • 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.
  • x is a number between 0 and 50, preferably 1 and 50, particularly preferably 5 and 30, and
  • R 3 represents a (-C 0 -C 22 ) alkyl radical; and C) optionally one or more comonomers selected from the group
  • N-vinyl pyrrolidone vinyl phosphonic acid, styrene, styrene sulfonic acid (Na salt), t-butyl acrylate and methyl methacrylate, preferably methacrylic acid and / or
  • suitable as macromonomers B) are esters formed from acrylic or methacrylic acid and alkyl ethoxylates selected from the group (C ⁇ o-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);
  • the EO units stand for ethylene oxide units.
  • Genapol ® types are products from Clariant, while Mergital ® B25 is a product from Cognis.
  • 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);
  • R 3 is a poly ((-CC 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, or a tris (styryl) phenyl radical, preferably 2,4,6-tris (1-phenylethyl) phenyl radical; 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, styrene sulfonic acid (sodium salt), sodium salt Butyl acrylate, methyl methacrylate
  • the proportion by weight of comonomers C) and 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 comonomers 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 methylene, isacryl- and methacrylamide; Esters of unsaturated mono- or polycarboxylic acids with polyols, preferably diacrylates and triacrylates. e.g. Butandio! - u ⁇ d . Ethyl glycol diacrylate or methacrylate and trimethylolpropane triacrylate, allyl compounds, preferably 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.
  • the polymers are preferably produced by radical copolymerization, for example 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 become. 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
  • 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 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 to initiate the polymerization, e.g. organic peroxides such as benzoyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide, cumene hydroperoxide, azo compounds such as e.g. Azobisisobutyronitrile, Azobisdimethylvalerionitril, as well as inorganic peroxides such as benzoyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide, cumene hydroperoxide, azo compounds such as e.g. Azobisisobutyronitrile, Azobisdimethylvalerionitril, as well as inorganic peroxides, tert-butyl hydroperoxide, methyl ethyl ketone peroxide, cumene hydroperoxide, azo compounds such as e.g
  • Peroxy compounds such as (NH 4 ) 2S 2 ⁇ 8 , K 2 S2 ⁇ 8 or H2O2, optionally in combination with reducing agents, such as sodium hydrogen sulfite and iron (II) sulfate, or redox systems which, as the reducing component, contain an aliphatic or aromatic sulfonic acid, such as, for example, benzenesulfonic acid, toluenesulfonic acid or derivatives of these acids, such as, for example, Mannich adducts of sulfinic acid, aldehydes and amino compounds.
  • reducing agents such as sodium hydrogen sulfite and iron (II) sulfate
  • redox systems which, as the reducing component, contain an aliphatic or aromatic sulfonic acid, such as, for example, benzenesulfonic acid, toluenesulfonic acid or derivatives of these acids, such as, for example, Mannich adducts of sul
  • the polymers When used as a crystallization inhibitor, the polymers are preferably used in amounts, based on the finished crop protection formulations, of from 0.01 to 10% by weight, particularly preferably 0.1 to 7% by weight, particularly preferably 0.5 to 5 % By weight.
  • the crop protection formulations can comprise one or more pesticidal active compounds from the group of the herbicides, insecticides, fungicides, acaricides, bactericides, molluscids, nematicides and rodenticides.
  • the use of the polymers as crystallization inhibitors is particularly advantageous when the active ingredients are poorly soluble in water due to their low polarity or high hydrophobicity and are particularly strong for crystallization tend.
  • the active ingredients from the sulfonate class for example ethofumesate and benfuresate; Anilides, for example propanil; Phenylurea derivatives, for example monuron, diuron; Azoles, for example amitrole; Triazines, for example simazine and atrazine; Propionic acid derivatives, for example dalapon; carbamates; Pyrazolinate; tebuconazole; hexaconazole; phenmedipham; desmedipham; linuron; and to call trifluralin.
  • the crop protection formulations can be a wide variety of means. Preferred are emulsifiable concentrates (EC), oil-in-water emulsions (EW), water-in-oil emulsions, suspension concentrates (SC), suspoemulsions (SE), suspensions, microemulsions (ME), dispersions and agents derived from the aforementioned Agents are available by dilution with water and / or solvents, preferably water.
  • EC emulsifiable concentrates
  • EW oil-in-water emulsions
  • SC suspension concentrates
  • SE suspoemulsions
  • ME microemulsions
  • dispersions and agents derived from the aforementioned Agents are available by dilution with water and / or solvents, preferably water.
  • the emulsifiable concentrates (EC) can be prepared in a simple manner by metering the active substance (s), the polymer (s) and the other formulation components into the solvent (s) and dissolving with stirring. When using the emulsifiable concentrates (EC), the required volumes are measured, stirred in water and sprayed in the field in the form of their diluted emulsions.
  • the crop protection formulations can contain further additives and auxiliaries, for example emulsifiers, dispersants, solvents, thickeners, antifreeze agents,
  • Non-ionic, amphoteric and anionic surfactants are suitable as emulsifiers and dispersants.
  • Alkylarylethoxylates (Arkopale ®, Clariant GmbH), nonylphenol (Synperonic ® NP-4, Uniquema), Alkanoylethoxylate (Genapol® ®, Clariant GmbH) and polyethylene oxide polypropylene oxide block copolymers are preferred.
  • Preferred ampholytic emulsifiers are di-Na-N-lauryl- ⁇ -imidodipropionate and lecithin.
  • Suitable anionic surfactants are preferably alkyl sulfates, preferably having (C 1 0-C 24) - alkyl moieties or-Hydroxyalkylkomponenten such Alkylglycerinsiilfate,
  • Fatty acid amide (ether) sulfates, oleyl glycerol sulfates and alkylaryl sulfates e.g.
  • alkylphenol alkyl sulfonates, preferably with (-C 0 -C 24 ) alkyl components or hydroxyalkyl components; alkyl ether; Glycerol ether sulfonates and alkylbenzenesulfonates.
  • Suitable solvents are preferably aliphatic and aromatic hydrocarbons, for example mineral oils, paraffins, alkylbenzenes, for example toluene, xylene, naphthalene derivatives, in particular 1-methylnaphthalene, 2-methylnaphthalene, (C 6 -Ci 6 ) aromatic mixtures, for example Solvesso series (ESSO) with the types Soivesso ® 100 (bp. 162-177 ° C), Soivesso ® 150 (bp. 187-207 ° C) and Soivesso ® 200 (bp. 219-282 ° C), (C 6 -C 2 o) aliphatics, which can be linear or cyclic, for example the Shellsol series, types T and K or BP-n- Paraffins, also halogenated
  • Hydrocarbons for example carbon tetrachloride, chloroform, chlorobenzene, chlorotoluene, methylene chloride, dichloroethane, esters, for example triacetin (acetic acid triglyceride), butyrolactone, propylene carbonate, triethyl citrate and phthalic acid (-C-C 22 ) alkyl esters, especially phthalic acid (C 4 -C 8 -alkyl) ), Esters of polyalcohols, ethers, such as diethyl ether, tetrahydrofuran, dioxane,
  • Alkylene monoalkyl ethers and dialkyl ethers such as e.g. Propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether or monoethyl ether, diglyme and tetraglyme, amides such as dimethylformamide, dimethylacetamide, di-n-butylformamide, dimethylcapryl / caprin fatty acid amide and N-alkylpyrrolidone, ketone, acetone, such as acetone, such as acetone, such as acetone, such as acetone, such as acetone, such as acetone, such as acetone, such as acetone, such as acetone, such as acetone, Sulfoxides and sulfones such as dimethyl sulfoxide and sulfolane, polyglycols, animal, vegetable and mineral oils.
  • amides such as dimethylformamide, dimethylacetamide, di
  • cellulose ethers and other cellulose derivatives eg carboxymethyl cellulose, hydroxyethyl cellulose
  • gelatin starch and starch derivatives
  • sodium alginates e.g., sodium alginates, fatty acid polyethylene glycol esters, agar-agar, tragacanth or dextrins are known.
  • polymers such as polyvinyl alcohols, polyacrylamides, polyvinylamides, polysulfonic acids, polyacrylic acid, polyacrylic acid esters, polyvinylpyrrolidone, polyvinyl methyl ether, polyethylene oxides, copolymers of maleic anhydride and vinyl methyl ether, as well as various mixtures and copolymers of the above compounds, including their various salts and ester.
  • These polymers can optionally be cross-linked or uncross-linked.
  • Preventol and Proxel are suitable as preservatives, for example silane derivatives such as poly-dimethylsiloxanes and magnesium stearate or perfluorinated phosphone or phosphine derivatives are suitable as defoamers.
  • All conventional substances that can be used for this purpose can act as cold stabilizers.
  • Examples include urea, glycerin and propylene glycol.
  • buffers All common acids and their salts can be used as buffers. Phosphate buffers, carbonate buffers and citrate buffers may preferably be mentioned.
  • the crop protection formulations preferably have a pH in the range from 2 to 12, particularly preferably from 3 to 8.
  • Example 2 Polymer 2 Analogous procedure as in Example 1; Furthermore, 1.0 g of trimethylolpropane triacrylate (TMPTA) was added for crosslinking.
  • TMPTA trimethylolpropane triacrylate
  • the SC was produced in the manner known to the person skilled in the art. When the formulation was stored at room temperature and 54 ° C., there was no crystallization of the active ingredient and the associated sedimentation, even after a long period of time, which was not the case with a corresponding formulation without polymer 1.
  • Example 5 Application example Preparation of an emulsifiable concentrate (EC) from 42.00 g of dimethoate
  • the EC was produced in the manner known to the person skilled in the art. When the EC was diluted with water, the active ingredient did not crystallize out over a period of several days even at storage temperatures of 10 ° C., which occurred within 30 minutes when the above-mentioned EC was produced without the use of polymer 2.
  • the EC was produced in the manner known to the person skilled in the art. When the EC was diluted with water, the active ingredient did not crystallize out over several periods of time, even at storage temperatures of 10 ° C., which occurred within 30 minutes when the above-mentioned EC was produced without the use of polymer 2.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention relates to the use of polymers on the basis of acrylamide propyl methylene sulfonic acid (AMPS) and macromonomers as crystallization inhibitors for plant-protective formulations. The polymers prevent the pesticides (herbicides, insecticides, fungicides, acaricides, bactericides, molluscides, nematicides, and rodenticides) contained in the plant-protective formulations from crystallizing. Said polymers are particularly useful in emulsifiable concentrates (EC) and suspension concentrates (SC).

Description

Beschreibungdescription

Kristallisationsinhibitor für Pflanzenschutz-FormulierungenCrystallization inhibitor for crop protection formulations

Die vorliegende Erfindung betrifft die Verwendung von wasserlöslichenThe present invention relates to the use of water-soluble

Copolymeren auf Basis von Acrylamidopropylmethylensulfonsäure (AMPS) bzw. deren Salzen und Makromonomeren als Kristallisationsinhibitor in Pflanzenschutz- Formulierungen.Copolymers based on acrylamidopropylmethylene sulfonic acid (AMPS) or their salts and macromonomers as crystallization inhibitors in crop protection formulations.

Pestizide Wirkstoffe mit überwiegend hydrophoben Gruppen und geringer Polarität sind in Wasser kaum lösliche Verbindungen. Die Formulierungsmöglichkeiten sind im wesentlichen auf emulgierbare Konzentrate (EC) und Suspensionskonzentrate (SC) eingeschränkt. Diese werden vom Anwender mit Wasser auf die gewünschte Spritzkonzentration verdünnt und ausgebracht. Wichtig für die notwendige Lagerstabilität der konzentrierten wässrigenPesticides with predominantly hydrophobic groups and low polarity are hardly soluble compounds in water. The formulation options are essentially restricted to emulsifiable concentrates (EC) and suspension concentrates (SC). These are diluted with water to the desired spray concentration and applied by the user. Important for the necessary storage stability of the concentrated aqueous

Suspension ist eine feinteilige, konstante Partikelgröße der festen Wirkstoffe. Kristallisation führt zur Bildung größerer Partikel und damit zu Sedimentation und Bodensatzbildung, die die erforderliche gleichmäßige Verdünnbarkeit des Konzentrates verhindern und evtl. auch das Filter und Düsensystem verstopfen. Eine etwas andere durch Kristallisation bedingte Schwierigkeit tritt mit emulgierbaren Konzentraten auf. Diese normalerweise wasserfreien Konzentrate werden ebenfalls vom Anwender mit Wasser auf die gewünschte Spritzkonzentration verdünnt. Durch Wasserlöslichkeit des verwendeten organischen Lösemittels kann es dann zu starker Kristallisation der Wirksubstanzen in der Spritzbrühe kommen. Effizienzverlust der Wirksubstanzen, Verstopfungsgefahr für Filter- und Düsensysteme und ein hoher Reinigungsaufwand sind die Folge.Suspension is a fine-particle, constant particle size of the solid active ingredients. Crystallization leads to the formation of larger particles and thus to sedimentation and sedimentation, which prevent the required uniform dilutability of the concentrate and possibly also clog the filter and nozzle system. A somewhat different difficulty due to crystallization occurs with emulsifiable concentrates. These normally water-free concentrates are also diluted with water to the desired spray concentration by the user. Solubility in water of the organic solvent used can then lead to severe crystallization of the active substances in the spray mixture. Loss of efficiency of the active substances, risk of clogging for filter and nozzle systems and a high cleaning effort are the result.

Überraschenderweise wurde nun gefunden, dass Polymere auf Basis von Acrylamidopropylmethylensulfonsäure (AMPS) und Makromonomeren hervorragend als Kristallisationsinhibitor in Pflanzenschutzmittel geeignet sind. Dabei verhindern die Polymere ein Auskristallisieren der in den Pflanzenschutz- Formulierungen enthaltenen pestiziden Wirkstoffe (Herbizide, Insektizide, Fungizide, Akarizide, Bakterizide, Molluskide, Nematizide und Rodentizide). Gegenstand der Erfindung ist demnach die Verwendung von Polymeren, herstellbar durch radikalische Copolymerisation von A) Acrylamidopropylmethylensulfonsäure (AMPS) und/oder deren Salzen; B) einem oder mehreren Makromonomeren, enthaltend i) eine zur Polymerisation befähigte Endgruppe, die imSurprisingly, it has now been found that polymers based on acrylamidopropylmethylsulfonic acid (AMPS) and macromonomers are outstandingly suitable as crystallization inhibitors in crop protection agents. The polymers prevent the crop protection Formulations contain pesticidal active ingredients (herbicides, insecticides, fungicides, acaricides, bactericides, molluscids, nematicides and rodenticides). The invention accordingly relates to the use of polymers which can be prepared by radical copolymerization of A) acrylamidopropylmethylene sulfonic acid (AMPS) and / or salts thereof; B) one or more macromonomers containing i) an end group capable of polymerization, which in

Reaktionsmedium zumindest teilweise löslich ist, ii) einen hydrophoben Teil, der Wasserstoff oder einen gesättigten oder ungesättigten, linearen oder verzweigten, aliphatischen, cycloaliphatischen oder aromatischen (C1-C100)- Kohlenwasserstoffrest darstellt, und iii) gegebenenfalls einen hydrophilen Teil, der auf Polyalkylenoxiden basiert; und C) optional einem oder mehreren weiteren mindestens einfach oder mehrfach olefinisch ungesättigten Sauerstoff-, Stickstoff-, Schwefel-, Phosphor-, Chlor- und/oder Fluor-haltigen Comonomeren, als Kristallisationsinhibitor in Pflanzenschutz-Formulierungen.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) 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, as a crystallization inhibitor in crop protection formulations.

Bevorzugt enthalten die Makromonomeren B) einen hydrophilen Teil der auf Polyalkoxiden, bevorzugt Polyethylenoxiden und /oder Polypropylenoxiden, basiert.The macromonomers B) preferably contain a hydrophilic part which is based on polyalkoxides, preferably polyethylene oxides and / or polypropylene oxides.

Als Salze der Acrylamidopropylmethylensulfonsäure (AMPS) eignen sich bevorzugt die Lithium-, Natrium-, Kalium-, Magnesium-, Caicium-, Ammonium-, Monoalkylammonium-, Dialkylammonium-, Trialkylammonium- oder Tetraalkyl- ammonium-Salze, wobei die Alkylsubstituenten der Ammoniumionen unabhängig voneinander (Cι-C22)-Alkylreste darstellen, die mit 0 bis 3 Hydroxyalkylgruppen besetzt sein können, deren Alkylkettenlänge im Bereich von C2 bis C10 variieren kann. Ebenfalls geeignet sind ein- bis dreifach ethoxylierteSuitable salts of acrylamidopropylmethylsulfonic acid (AMPS) are preferably the lithium, sodium, potassium, magnesium, calcium, ammonium, monoalkylammonium, dialkylammonium, trialkylammonium or tetraalkylammonium salts, the alkyl substituents of the ammonium ions being independent represent (C 2 -C 2) alkyl radicals which may be occupied by 0 to 3 hydroxyalkyl groups, the length of the alkyl chain of which may vary in the range from C 2 to C 10 . Single to triple ethoxylated are also suitable

Ammoniumverbindungen mit unterschiedlichem Ethoxylierungsgrad. Als Salze besonders bevorzugt sind die Natrium- und Ammonium-Salze. Der Neutralisationsgrad der Acrylamidopropylmethylensulfonsäure (AMPS) beträgt bevorzugt 70 bis 100 Mol-%.Ammonium compounds with different degrees of ethoxylation. 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%.

Bevorzugt handelt es sich beim Comonomeren A) um die Natrium- und/oder Ammoniumsalze der Acrylamidopropylmethylensulfonsäure (AMPS).The comonomer A) is preferably the sodium and / or ammonium salts of acrylamidopropylmethylene sulfonic acid (AMPS).

Bevorzugt handelt es sich bei den Makromonomeren B) um solche der Formel (1 )The macromonomers B) are preferably those of the formula (1)

i _ γ_ (R2 _ 0)x (R4 - O)z - R3 (1 ) worin R1 für einen Vinyl-, Allyl-, Acryl- [d.h. CH2=CH-CO-], i _ γ_ (R 2 _ 0) x (R 4 - O) z - R 3 (1) where R 1 is a vinyl, allyl, acrylic [ie CH 2 = CH-CO-],

Methacryl- [d.h. CH2=C(CH3)-CO-], Senecioyl- oder Crotonylrest;Methacrylic [ie CH 2 = C (CH 3 ) -CO-], senecioyl or crotonyl radical;

R2 und R4 unabhängig voneinander für (C2-C4)-Alkylen; x und z unabhängig voneinander für eine ganze Zahl zwischen 0 und 500, bevorzugt mit x+z größer oder gleich 1 ; Y für O, S, PH oder NH, bevorzugt O; undR 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

R3 für Wasserstoff oder einen gesättigten oder ungesättigten linearen oder verzweigten aliphatischen, cycloaliphatischen oder aromatischen (C1-C100)-R 3 is hydrogen or a saturated or unsaturated linear or branched aliphatic, cycloaliphatic or aromatic (C1-C100) -

Kohlenwasserstoffrest, bevorzugt (CrC3o)-Kohlenwasserstoffrest, steht.Hydrocarbon residue, preferably (CrC 3 o) hydrocarbon residue.

R1 steht besonders bevorzugt für einen Acryl- oder Methacrylrest.R 1 particularly preferably represents an acrylic or methacrylic radical.

R2 und R4 stehen besonders bevorzugt für einen C2-oder Cß-Alkylen-Rest. x und z stehen besonders bevorzugt unabhängig voneinander für eine Zahl zwischen 0 und 50, bevorzugt mit x+z größer oder gleich 1. Insbesondere bevorzugt gilt 5 < x+z < 50. R3 steht besonders bevorzugt für einen aliphatischen (C -C22)- Alkyl- oderR 2 and R 4 are particularly preferably a C 2 or C β -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 (C -C 22 ) - alkyl or

Alkenylrest, bevorzugt (C10- C22)-Alkyl- oder Alkenylrest; einen Phenylrest; einen (Cι-C22)-Alkylphenylrest, bevorzugt (Ci-CgJ-Alkylphenylrest, besonders bevorzugt (CrC )-Alkylphenylrest, insbesondere bevorzugt sec-Butyl- oder n-Butyl-Alkylphenylrest; einen PoIy((Cι-C22)alkyl)phenylrest, bevorzugt Poly((C-ι-Cg)alkyl)phenylrest, besonders bevorzugt Poly((Cι-C )alkyl)phenylrest, insbesondere bevorzugt Poly((sec-Butyl)phenylrest, ganz besonders bevorzugt Tris(sec-Butyl)phenylrest oder Tris(n-Butyl)phenylrest; oder einen Polystyrylphenylrest [d.h. Poly(phenylethyl)phenylrest], besonders bevorzugt Tristyrylphenylrest [d.h. Tris(phenylethyl)phenylrest].Alkenyl radical, preferably (C 10 -C 2 2) alkyl or alkenyl radical; a phenyl radical; a (-CC 22 ) alkylphenyl radical, preferably (Ci-CgJ-alkylphenyl radical, particularly preferably (CrC) -alkylphenyl radical, particularly preferably sec-butyl or n-butyl-alkylphenyl radical; a poly ((-C-C 22 ) alkyl) phenyl radical, preferably poly ((C-Cg) alkyl) phenyl radical, particularly preferably poly ((C-C) 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 ].

Insbesondere bevorzugt als Reste R3 sind 2,4,6-Tris(1-phenylethyl)-phenylreste und 2,4,6-Tris(sec-butyl)-phenylreste.Particularly preferred as R 3 are 2,4,6-tris (1-phenylethyl) phenyl and 2,4,6-tris (sec-butyl) phenyl.

Die Herstellung der Makromonomeren B) erfolgt bevorzugt durch Umsetzung reaktiver Derivate ungesättigter Carbonsäuren, bevorzugt der Methacryl- oder Acrylsäure, mit den entsprechenden hydroxylgruppenhaltigen, gegebenenfalls alkoxylierten. Alkyl- oder Arylresten. Auch die ringöffnende Addition an die jeweiligen Carbonsäureglycidylester ist möglich.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 ones. Alkyl or aryl radicals. Ring-opening addition to the respective carboxylic acid glycidyl ester is also possible.

In einer bevorzugten Ausführungsform enthalten die Polymere noch weitere olefinisch ungesättigte Sauerstoff-, Stickstoff-, Schwefel-, Phosphor-, Chlor- und/oder Fluor-haltige Comonomere C).In a preferred embodiment, the polymers also contain further olefinically unsaturated oxygen, nitrogen, sulfur, phosphorus, chlorine and / or fluorine-containing comonomers C).

Bevorzugt als Comonomere C) sind olefinisch ungesättigte Säuren oder deren Salze, bevorzugt mit ein- und zweiwertigen Gegenionen, besonders bevorzugt Styrolsulfonsäure, Vinylsulfonsäure, Vinylphosphonsäure, Allylsulfonsäure, Methallylsulfonsäure, Acrylsäure, Methacrylsäure und/oder Maleinsäure bzw. Maleinsäureanhydrid, Fumarsäure, Crotonsäure, Itaconsäure oder Seneciosäure bzw. deren Salze. Bevorzugte Gegenionen sind Li+, Na+, K+, Mg2+, Ca2+, Al3+, NH4 +, Monoalkylammonium-, Dialkylammonium-, Dialkylammonium-, Trialkylammonium- und Tetraalkylammonium-Ionen, worin die Substituenten der Amine unabhängig voneinander (CrC22)-Alkylreste darstellen, die mit 0 bis 3 Hydroxyalkylgruppen besetzt sein können, deren Alkylkettenlänge im Bereich C2 bis C10 variieren kann. Zusätzlich können auch ein bis dreifach ethoxylierte Ammoniumverbindungen mit unterschiedlichem Ethoxylierungsgrad, sowie entsprechende Säureanhydride (auch gemischte) eingesetzt werden. DerPreferred 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, where the substituents of the amines are independent represent (CrC 22 ) alkyl radicals from one another, which can be occupied by 0 to 3 hydroxyalkyl groups, the alkyl chain length of which can vary in the range from C2 to C 10 . 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

Neutralisationsgrad der optionalen olefinisch ungesättigten Säuren C) kann 0 bis 100 %, bevorzugt 70 und 100 Mol-% betragen. Weiterhin geeignet als Comonomere C) sind Ester ungesättigter Carbonsäuren, bevorzugt Acryl- und Methacrylsäure, Styrolsulfonsäure, Maleinsäure, Fumarsäure, Crotonsäure und Seneciosäure, mit aliphatischen, aromatischen oder cyclo-aliphatischen Alkoholen mit einer Kohlenstoffzahl von 1 bis 30. Ebenfalls geeignete Comonomere C) sind offenkettige und cyclische N-Vinylamide (N-Vinyllactame) mit einer Ringgröße von 4 bis 9 Atomen, bevorzugt N-Vinylformamid (NVF); N-Vinylmethylformamid; N-Vinyl-methylacetamid (VIMA); N-Vinylacetamid; N-Vinylpyrrolidon (NVP); N-Vinylcaprolactam; Amide der Acryl- und der Methacrylsäure, besonders bevorzugt Acrylamid, N,N-Dimethylacrylamid, N,N-Diethylacrylamid, N,N-Diisopropylacrylamid; alkoxylierte Acryl- und Methacrylamide, bevorzugt Hydroxymethylmethacrylamid, Hydroxyethylmethacrylamid und Hydroxypropylmethacrylamid. Ebenfalls geeignet sind Bemsteinsäuremono-[2-(methacryloyloxy)-ethylester]; N,N-Dimethylaminomethacrylat; Diethylamino-methylmethacrylat; Acryl- und Methacrylamidoglykolsäure; [2-(Methacryloyloxy)ethyl]trimethylammoniumchlorid (MAPTAC) und [(2-Acryolyloxy)ethyl)]trimethylammoniumchlortid (APTAC); 2-Vinylpyridin; 4-Vinylpyridin; Vinylacetat; Methacrylsäureglycidylester; Acrylnitril; Vinylchlorid; Vinylidenchlorid; Tetrafluorethylen; Diallyldimethyldimethylammoniumchlorid (DADMAC); Stearylacrylat; Laury|methacrylat; und/oder Tetrafluorethylen.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 cyclo-aliphatic alcohols with a carbon number of 1 to 30. Also suitable are comonomers C) open-chain and cyclic N-vinylamides (N-vinyllactams) with a ring size of 4 to 9 atoms, preferably N-vinylformamide (NVF); N-vinyl methyl formamide; N-vinyl methylacetamide (VIMA); N-vinylacetamide; N-vinyl pyrrolidone (NVP); N-vinylcaprolactam; 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- (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; Laury | methacrylate; and / or tetrafluoroethylene.

Auch geeignet sind Methylenbisacryl- und -methacrylamid; Ester ungesättigter Mono- und Polycarbonsäuren mit Polyolen, z.B. Diacrylate oder Triacrylate wie Butandiol- und Ethylenglykoldiacrylat bzw. -methacrylat und Trimethylolpropantriacrylat; Allylverbindungen, z.B. Allyl(meth)acrylat, Triallylcyanurat, Maleinsäurediallylester, Polyallylester, Tetraallyloxyethan, Triallylamin, Tetraallylethylendiamin, Allylester der Phosphorsäure und/oder Vinylphosphonsäurederivate.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.

Besonders bevorzugt für die Verwendung sind Polymere, herstellbar durch radikalische Copolymerisation vonPolymers which can be prepared by free-radical copolymerization of are particularly preferred for use

A) Acrylamidopropylmethylensulfonsäure (AMPS), dem Natriumsalz der Acrylamidopropylmethylensulfonsäure (AMPS) und/oder dem Ammoniumsalz der Acrylamidopropylmethylensulfonsäure, bevorzugt dem Ammoniumsalz der Acrylamidopropylmethylensulfonsäure (AMPS); B) einem oder mehreren Makromonomeren, ausgewählt aus der Gruppe der Ester gebildet aus Methacryl- oder Acrylsäure, bevorzugt Methacrylsäure, und Verbindungen der Formel (2)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-(CH2-CH2- O)x - R3 (2)HO- (CH 2 -CH 2 - O) x - R 3 (2)

worin x eine Zahl zwischen 0 und 50, bevorzugt 1 und 50, besonders bevorzugt 5 und 30, undwherein x is a number between 0 and 50, preferably 1 and 50, particularly preferably 5 and 30, and

R3 einen (Cι0-C22)-Alkylrest darstellen; und C) optional einem oder mehreren Comonomeren ausgewählt aus der GruppeR 3 represents a (-C 0 -C 22 ) alkyl radical; and C) optionally one or more comonomers selected from the group

Acrylamid, Vinylformamid, N-Vinylmethylacetamid undAcrylamide, vinylformamide, N-vinylmethylacetamide and

Natriummethallylsulfonat, Hydroxyethylmethacrylat, Acrylsäure, Methacrylsäure, Maleinsäureanhydrid, Methacrylamid, Vinylacetat,Sodium methallyl sulfonate, hydroxyethyl methacrylate, acrylic acid, methacrylic acid, maleic anhydride, methacrylamide, vinyl acetate,

N-Vinylpyrrolidon, Vinylphosphonsäure, Styrol, Styrolsulfonsäure (Na-Salz), t-Butylacrylat und Methylmethacrylat, bevorzugt Methacrylsäure und/oderN-vinyl pyrrolidone, vinyl phosphonic acid, styrene, styrene sulfonic acid (Na salt), t-butyl acrylate and methyl methacrylate, preferably methacrylic acid and / or

Methacrylamid.Methacrylamide.

Insbesondere.geeignet als Makromonomere B) sind Ester gebildet aus Acryl- oder Methacrylsäure und Alkylethoxylaten ausgewählt aus der Gruppe (Cιo-C18)-Fettalkoholpolyglykolether mit 8 EO-Einheiten (Genapol® C-080); Cn-Oxoalkoholpolyglykolether mit 8 EO-Einheiten (Genapol® UD-080);In particular, suitable as macromonomers B) are esters formed from acrylic or methacrylic acid and alkyl ethoxylates selected from the group (Cιo-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);

(Ci2-Cι )-Fettalkoholpolyglykolether m 1 7 EO-Einheiten (Genapol® LA-070); (Ci2-Cι4)-Fettalkoholpolyglykolether m 1 11 EO-Einheiten (Genapol® LA-110); (Ci6-C 8)-Fettalkoholpolyglykolether m t 8 EO-Einheiten (Genapol® T-080); (Ci6-Cι8)-Fettalkoholpolyglykolether m 1 15 EO-Einheiten (Genapol® T-150); (Ci6-Cι8)-Fettalkoholpolyglykolether m 1 11 EO-Einheiten (Genapol® T-110); (Cιe-C18)-Fettalkoholpolyglykolether m 120 EO-Einheiten (Genapol® T-200); (Ci6-Cι8)-Fettalkoholpolyglykolether m 1 25 EO-Einheiten (Genapol® T-250); (Cι8-C22)-Fettalkoholpolyglykolether m 125 EO-Einheiten; iso-(C 6-Cι8)-Fettalkoholpolyglykolether mit 25 EO-Einheiten; und C22-Fettalkoholpolyglykolether mit 25 EO-Einheiten (Mergital® B 25)(Ci 2 -Cι) fatty alcohol polyglycol ether m 1 7 EO units (Genapol ® LA-070); (Ci2-Cι 4 ) fatty alcohol polyglycol ether m 1 11 EO units (Genapol ® LA-110); (Ci6-C 8) fatty alcohol polyglycol ethers mt 8 EO units (Genapol ® T-080); (Ci6-Cι 8 ) fatty alcohol polyglycol ether m 1 15 EO units (Genapol ® T-150); (Ci6-Cι 8 ) fatty alcohol polyglycol ether m 1 11 EO units (Genapol ® T-110); (Cιe-C 18 ) fatty alcohol polyglycol ether m 120 EO units (Genapol ® T-200); (Ci 6 -Cι 8 ) fatty alcohol polyglycol ether m 1 25 EO units (Genapol ® T-250); (-C 8 -C 2 2) fatty alcohol polyglycol ether m 125 EO units; iso- (C 6 -C 8 ) fatty alcohol polyglycol ether with 25 EO units; and C 22 fatty alcohol polyglycol ether with 25 EO units (Mergital ® B 25)

Hierbei stehen die EO-Einheiten für Ethylenoxid-Einheiten. Bei den Genapol®- Typen handelt es sich um Produkte der Firma Clariant, bei Mergital® B25 um ein Produkt der Firma Cognis.The EO units stand for ethylene oxide units. The Genapol ® types are products from Clariant, while Mergital ® B25 is a product from Cognis.

Ebenfalls besonders bevorzugt für die Verwendung sind Polymere, herstellbar durch radikalische Copolymerisation vonPolymers which can be prepared by free-radical copolymerization of are also particularly preferred for use

A) Acrylamidopropylmethylensulfonsäure (AMPS), dem Natriumsalz der Acrylamidopropylmethylensulfonsäure (AMPS) und/oder demA) acrylamidopropylmethylene sulfonic acid (AMPS), the sodium salt of acrylamidopropylmethylene sulfonic acid (AMPS) and / or the

Ammoniumsalz der Acrylamidopropylmethylensulfonsäure, bevorzugt dem Ammoniumsalz der Acrylamidopropylmethylensulfonsäure (AMPS);Ammonium salt of acrylamidopropylmethylene sulfonic acid, preferably the ammonium salt of acrylamidopropylmethylene sulfonic acid (AMPS);

B) einem oder mehreren Makromonomeren, ausgewählt aus der Gruppe der Ester gebildet aus Acrylsäure oder Methacrylsäure, bevorzugt Methacrylsäure, und Verbindungen der Formel (3)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-(CH2-CH2- O)χ- R3 (3) worin x eine Zahl zwischen 0 und 50, bevorzugt 1 und 50, besonders bevorzugt 5 und 30, undHO- (CH 2 -CH 2 - O) χ- R 3 (3) where x is a number between 0 and 50, preferably 1 and 50, particularly preferably 5 and 30, and

R3 einen Poly((Cι-C22)alkyl)-phenylrest, bevorzugt Tris(sec-butyl)- phenylrest oder Tris(n-butyl)-phenylrest, besonders bevorzugt 2,4,6- Tris(sec-butyl)-phenylrest, oder einen Tris(styryl)phenylrest, bevorzugt 2,4,6-Tris(1-phenylethyl)-phenylrest, darstellt; und C) optional einem oder mehreren Comonomeren ausgewählt aus Acrylamid, -Vinylformamid, N-Vinylmethylacetamid und Natriummethallylsulfonat, Hydroxyethylmethacrylat, Acrylsäure, Methacrylsäure, Maleinsäureanhydrid, Methacrylamid, Vinylacetat, N-Vinylpyrrolidon, Vinylphosphonsäure, Styrol, Styrolsulfonsäure (Na-Salz), t-Butylacrylat, Methylmethacrylat, bevorzugt Methacrylsäure und/oder Methacrylamid.R 3 is a poly ((-CC 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, or a tris (styryl) phenyl radical, preferably 2,4,6-tris (1-phenylethyl) phenyl radical; 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, styrene sulfonic acid (sodium salt), sodium salt Butyl acrylate, methyl methacrylate, preferably methacrylic acid and / or methacrylamide.

Der Gewichtsanteil der Comonomeren C) und Makromonomeren B) im Polymer kann zwischen 0,1 und 99,9 Gew.-% variieren. In einer bevorzugten Ausführungsform sind die Polymere hoch hydrophob modifiziert, d.h. der trägt der Anteil an Makromonomeren B) beträgt 50,1 bis 99,9 Gew.-%, bevorzugt 70 bis 95 Gew.-%, besonders bevorzugt 80 bis 94 Gew.-%. In einer weiteren bevorzugten Ausführungsform sind die Polymere niedrig hydrophob modifiziert, d.h. der Anteil an Makromonomeren B) beträgt 0,1 bis 50 Gew.-%, bevorzugt 5 bis 25 Gew.-%, besonders bevorzugt 6 bis 20 Gew.-%.The proportion by weight of comonomers C) and 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.

Die Monomerenverteilung der Comonomere A), B) und C) in den Polymeren kann alternierend, statistisch, gradientenartig oder blockartig (auch Multiblock) sein. Das zahlenmittlere Molekulargewicht der Polymere beträgt bevorzugt 1000 bis 20 000 000 g/mol, bevorzugt 20 000 bis 5 000 000 g/mol, insbesondere bevorzugt 50 000 bis 1 500 000 g/mol.The monomer distribution of the comonomers 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 einer bevorzugten Ausführungsform sind die Polymere vernetzt, d.h. in das Polymer ist mindestens ein Vernetzer mit mindestens zwei Doppelbindungen einpolymerisiert.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.

Bevorzugte Vernetzer sind Methylen isacryl- und -methacrylamid; Ester ungesättigter Mono- oder Polycarbonsäuren mit Polyolen, bevorzugt Diacrylate und Triacrylate. z.B. Butandio!- uηd.Ethyle glykoldiacrylat bzw. -methacrylat und Trimethylolpropantriacrylat, Allylverbindungen, bevorzugt Allyl(meth)acrylat, Triallylcyanurat, Maleinsäurediallylester, Polyallylester, Tetraallyloxyethan, Triallylamin, Tetraallylethylendiamin, Allylester der Phosphorsäure; und/oder Vinylphosphonsäurederivate.Preferred crosslinkers are methylene, isacryl- and methacrylamide; Esters of unsaturated mono- or polycarboxylic acids with polyols, preferably diacrylates and triacrylates. e.g. Butandio! - uηd . Ethyl glycol diacrylate or methacrylate and trimethylolpropane triacrylate, allyl compounds, preferably 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.

Die Herstellung der Polymere erfolgt bevorzugt durch radikalische Copolymerisation, z.B. Fällungspolymerisation, Emulsionspolymerisation, Lösungspolymerisation oder Suspensionspolymerisation. Besonders geeignet sind Polymere die durch Fällungspolymerisation, bevorzugt in tert.-Butanol, hergestellt wurden. Mit Hilfe der Fällungspolymerisation in tert.- Butanol lässt sich im Vergleich zu anderen Lösungsmittel eine spezifische Partikelgrößen-verteilung der Polymere erreichen. Die Größenverteilung der Polymerpartikel kann z.B. durch Laserbeugung oder Siebanalyse bestimmt werden. Repräsentativ für eine günstige Größenverteilung ist die folgende Korngrößenverteilung, wie sie durch Siebanalyse bestimmt wurde: 60,2 % kleiner 423 Mikrometer, 52,0 % kleinerThe polymers are preferably produced by radical copolymerization, for example 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 become. 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 Mikrometer, 26,6 % kleiner 106 Mikrometer, 2,6 % kleiner 45 Mikrometer und 26,6 % größer 850 Mikrometer.212 microns, 26.6% smaller than 106 micrometers, 2.6% smaller than 45 micrometers and 26.6% larger than 850 micrometers.

Die Polymerisationsreaktion kann im Temperaturbereich zwischen 0 und 150°C, vorzugsweise zwischen 10 und 100°C, sowohl bei Normaldruck als auch unter erhöhtem oder erniedrigtem Druck durchgeführt werden. Wie üblich kann die Polymerisation auch in einer Schutzgasatmosphäre, vorzugsweise unter Stickstoff, ausgeführt werden.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.

Zur Auslösung der Polymerisation können energiereiche elektromagnetische Strahlen oder die üblichen chemischen Polymerisationsinitiatoren herangezogen werden, z.B. organische Peroxide, wie Benzoylperoxid, tert.-Butylhydroperoxid, Methylethylketonperoxid, Cumolhydroperoxid, Azoverbindungen, wie z.B. Azobisisobutyronitril, Azobisdimethylvalerionitril, sowie anorganischeHigh-energy electromagnetic radiation or the usual chemical polymerization initiators can be used to initiate the polymerization, e.g. organic peroxides such as benzoyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide, cumene hydroperoxide, azo compounds such as e.g. Azobisisobutyronitrile, Azobisdimethylvalerionitril, as well as inorganic

Peroxyverbindungen, wie z.B. (NH4)2S2θ8, K2S2θ8 oder H2O2, gegebenenfalls in Kombination mit Reduktionsmitteln, wie z.B. Natriumhydrogensulfit und Eisen(ll)- sulfat, oder Redoxsystemen, welche als reduzierende Komponente eine aliphatische oder aromatische Sulfonsäure, wie z.B. Benzolsulfonsäure, Toluolsulfonsäure-oder Derivate, dieser Säuren, wie z.B. Mannichaddukte aus Sulfinsäure, Aldehyden und Aminoverbindungen, enthalten.Peroxy compounds, such as (NH 4 ) 2S 2 θ 8 , K 2 S2θ 8 or H2O2, optionally in combination with reducing agents, such as sodium hydrogen sulfite and iron (II) sulfate, or redox systems which, as the reducing component, contain an aliphatic or aromatic sulfonic acid, such as, for example, benzenesulfonic acid, toluenesulfonic acid or derivatives of these acids, such as, for example, Mannich adducts of sulfinic acid, aldehydes and amino compounds.

Bei der Verwendung als Kristallisationsinhibitor werden die Polymere bevorzugt in Mengen, bezogen auf die fertigen Pflanzenschutz-Formulierungen, von 0,01 bis 10 Gew.-%, besonders bevorzugt 0,1 bis 7 Gew.-%, besonders bevorzugt 0,5 bis 5 Gew.-%, eingesetzt.When used as a crystallization inhibitor, the polymers are preferably used in amounts, based on the finished crop protection formulations, of from 0.01 to 10% by weight, particularly preferably 0.1 to 7% by weight, particularly preferably 0.5 to 5 % By weight.

Bei der erfindungsgemäßen Verwendung der Polymere können die Pflanzenschutz-Formulierungen einen oder mehrere pestizide Wirkstoffe aus der Gruppe der Herbizide, Insektizide, Fungizide, Akarizide, Bakterizide, Molluskide, Nematizide und Rodentizide enthalten.When the polymers are used according to the invention, the crop protection formulations can comprise one or more pesticidal active compounds from the group of the herbicides, insecticides, fungicides, acaricides, bactericides, molluscids, nematicides and rodenticides.

Die Verwendung der Polymere als Kristallisationsinhibitoren ist dann besonders vorteilhaft, wenn die Wirkstoffe aufgrund ihrer geringen Polarität bzw. hohen Hydrophobie in Wasser schwerlöslich sind und besonders stark zur Kristallisation neigen. Hier sind insbesondere die Wirkstoffe aus der Klasse der Sulfonate, beispielsweise Ethofumesat und Benfuresat; Anilide, beispielsweise Propanil; Phenylharnstoffderivate, z.B. Monuron, Diuron; Azole, z.B. Amitrol; Triazine z.B. Simazin und Atrazin; Propionsäurederivate, z.B. Dalapon; Carbamate; Pyrazolinate; Tebuconazole; Hexaconazole; Phenmedipham; Desmedipham; Linuron; und Trifluralin zu nennen.The use of the polymers as crystallization inhibitors is particularly advantageous when the active ingredients are poorly soluble in water due to their low polarity or high hydrophobicity and are particularly strong for crystallization tend. Here, in particular, are the active ingredients from the sulfonate class, for example ethofumesate and benfuresate; Anilides, for example propanil; Phenylurea derivatives, for example monuron, diuron; Azoles, for example amitrole; Triazines, for example simazine and atrazine; Propionic acid derivatives, for example dalapon; carbamates; Pyrazolinate; tebuconazole; hexaconazole; phenmedipham; desmedipham; linuron; and to call trifluralin.

Bei den Pflanzenschutz-Formulierungen kann es sich um die verschiedensten Mittel handeln. Bevorzugt sind emulgierbare Konzentrate (EC), Öl-in-Wasser Emulsionen (EW), Wasser-in-ÖI Emulsionen, Suspensionskonzentrate (SC), Suspoemulsionen (SE), Suspensionen, Mikroemulsionen (ME), Dispersionen und Mittel, die aus den vorgenannten Mitteln durch Verdünnen mit Wasser und/oder Lösungsmitteln, bevorzugt Wasser, erhältlich sind.The crop protection formulations can be a wide variety of means. Preferred are emulsifiable concentrates (EC), oil-in-water emulsions (EW), water-in-oil emulsions, suspension concentrates (SC), suspoemulsions (SE), suspensions, microemulsions (ME), dispersions and agents derived from the aforementioned Agents are available by dilution with water and / or solvents, preferably water.

Es hat sich gezeigt, dass die erfindungsgemäße Verwendung insbesondere vorteilhaft ist bei emulgierbaren Konzentraten (EC) und Suspensionskonzentraten (SC).It has been shown that the use according to the invention is particularly advantageous in the case of emulsifiable concentrates (EC) and suspension concentrates (SC).

Die emulgierbaren Konzentrate (EC) lassen sich auf einfache Weise dadurch herstellen, dass man in das oder die vorgelegte(n) Lösungsmittel die Wirksubstanz(en), das oder die Polymere und die übrigen Formulierungskomponenten eindosiert und unter Rühren löst. Bei der Anwendung der emulgierbaren Konzentrate (EC) werden die jeweils erforderlichen Volumina abgemessen, in Wasser verrührt und in Form ihrer verdünnten Emulsionen auf dem Feld ausgespritzt.The emulsifiable concentrates (EC) can be prepared in a simple manner by metering the active substance (s), the polymer (s) and the other formulation components into the solvent (s) and dissolving with stirring. When using the emulsifiable concentrates (EC), the required volumes are measured, stirred in water and sprayed in the field in the form of their diluted emulsions.

Die Pflanzenschutz-Formulierungen können neben den pestiziden Wirkstoffen und den Polymeren weitere Zusatz- und Hilfsstoffe, beispielsweise Emulgatoren, Dispergiermittel, Lösungsmittel, Verdicker, Frostschutzmittel,In addition to the pesticidal active ingredients and the polymers, the crop protection formulations can contain further additives and auxiliaries, for example emulsifiers, dispersants, solvents, thickeners, antifreeze agents,

Verdunstungshemmer, Konservierungsmittel, Riechstoffe, Farbstoffe, Antigelmittel, Netzmittel, Schutzkolloide, Dispergiermittel, Entschäumer und/oder Neutralisationsmittel enthalten. Als Emulgatoren und Dispergiermittel eignen sich nichtionische, amphotere und anionische Tenside.Contain evaporation inhibitors, preservatives, fragrances, dyes, anti-gel agents, wetting agents, protective colloids, dispersants, defoamers and / or neutralizing agents. Non-ionic, amphoteric and anionic surfactants are suitable as emulsifiers and dispersants.

Als nichtionogene Emulgatoren bzw. Dispergiermittel sind bevorzugt Anlagerungsprodukte von 2 bis 80 Mol Ethylenoxid und/oder bis 5 MolAddition products of 2 to 80 moles of ethylene oxide and / or up to 5 moles are preferred as nonionic emulsifiers or dispersants

Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C Atomen und an Mono-, Di- und/oder Trialkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe; (Ci2-Cι8)-Fettsäuremono- und -diester von Anlagerungsprodukten von 5 bis 50 Mol Ethylenoxid an Glycerin; Glycerinmono- und -diester und Sorbitan/Sorbitolmono- und diester von gesättigten und ungesättigten Fettsäuren mit 6 bis 22 Kohlenstoffatomen und deren Ethylenoxidanlagerungsprodukte. Bevorzugt sind Alkylarylethoxylate (Arkopale®, Clariant GmbH), Nonylphenolethoxylate (Synperonic® NP-4, Uniquema), Alkanoylethoxylate (Genapole®, Clariant GmbH) und Polyethylenoxid- Polypropylenoxid Blockcopolymere.Propylene oxide on linear fatty alcohols with 8 to 22 carbon atoms, on fatty acids with 12 to 22 carbon atoms and on mono-, di- and / or trialkylphenols with 8 to 15 carbon atoms in the alkyl group; (Ci2-Cι 8 ) fatty acid monoesters and diesters of adducts of 5 to 50 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. Alkylarylethoxylates (Arkopale ®, Clariant GmbH), nonylphenol (Synperonic ® NP-4, Uniquema), Alkanoylethoxylate (Genapol® ®, Clariant GmbH) and polyethylene oxide polypropylene oxide block copolymers are preferred.

Als ampholytische Emulgatoren bevorzugt sind Di-Na-N-Lauryl-ß-imidodipropionat und Lecithin.Preferred ampholytic emulsifiers are di-Na-N-lauryl-β-imidodipropionate and lecithin.

Als anionische Tenside bevorzugt sind Alkylsulfate, bevorzugt mit (C10-C24)- Alkylkomponenten oder-Hydroxyalkylkomponenten, z.B. Alkylglycerinsiilfate,Suitable anionic surfactants are preferably alkyl sulfates, preferably having (C 1 0-C 24) - alkyl moieties or-Hydroxyalkylkomponenten such Alkylglycerinsiilfate,

Fettalkoholethersulfate, Glycerinethersulfate, Hydroxymischethersulfate,Fatty alcohol ether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates,

Fettsäureamid-(ether)sulfate, Oleylglycerinsulfate und Alkylarylsulfate, z.B.Fatty acid amide (ether) sulfates, oleyl glycerol sulfates and alkylaryl sulfates, e.g.

Alkylphenolethersulfate; Alkylsulfonate, bevorzugt mit (Cι0-C24)-Alkylkomponenten oder -Hydroxyalkylkomponenten; Alkylethersulfonate; Glycerinethersulfonate und Alkylbenzolsulfonate.alkylphenol; Alkyl sulfonates, preferably with (-C 0 -C 24 ) alkyl components or hydroxyalkyl components; alkyl ether; Glycerol ether sulfonates and alkylbenzenesulfonates.

Als Dispergiermittel besonders geeignet sind Lignin-Sulfitablaugen undLignin sulfite liquors and are particularly suitable as dispersants

Ethylcellulose.Ethyl cellulose.

Als Lösungsmittel eignen sich bevorzugt aliphatische und aromatische Kohlenwasserstoffe, beispielsweise Mineralöle, Paraffine, Alkylbenzole, beispielsweise Toluol, Xylol, Naphthalinderivate, insbesondere 1 -Methylnaphthalin, 2-Methylnaphthalin, (C6-Ci6)-Aromatengemische, beispielsweise Solvesso-Reihe (ESSO) mit den Typen Soivesso® 100 (Kp. 162- 177°C), Soivesso® 150 (Kp. 187-207°C) und Soivesso® 200 (Kp. 219-282°C), (C6-C2o)-Aliphaten, die linear oder cyclisch sein können, beispielsweise die Shellsol-Reihen, Typen T und K oder BP-n-Paraffine, ebenso halogenierteSuitable solvents are preferably aliphatic and aromatic hydrocarbons, for example mineral oils, paraffins, alkylbenzenes, for example toluene, xylene, naphthalene derivatives, in particular 1-methylnaphthalene, 2-methylnaphthalene, (C 6 -Ci 6 ) aromatic mixtures, for example Solvesso series (ESSO) with the types Soivesso ® 100 (bp. 162-177 ° C), Soivesso ® 150 (bp. 187-207 ° C) and Soivesso ® 200 (bp. 219-282 ° C), (C 6 -C 2 o) aliphatics, which can be linear or cyclic, for example the Shellsol series, types T and K or BP-n- Paraffins, also halogenated

Kohlenwasserstoffe, beispielsweise Tetrachlormethan, Chloroform, Chlorbenzol, Chlortoluol, Methylenchlorid, Dichlorethan, Ester, beispielsweise Triacetin (Essigsäuretriglycerid), Butyrolacton, Propylencarbonat, Triethylzitrat und Phthalsäure(Cι-C22)-alkylester, insbesondere Phthalsäure-(C4-C8-alkylester), Ester von Polyalkoholen, Ether, wie Diethylether, Tetrahydrofuran, Dioxan,Hydrocarbons, for example carbon tetrachloride, chloroform, chlorobenzene, chlorotoluene, methylene chloride, dichloroethane, esters, for example triacetin (acetic acid triglyceride), butyrolactone, propylene carbonate, triethyl citrate and phthalic acid (-C-C 22 ) alkyl esters, especially phthalic acid (C 4 -C 8 -alkyl) ), Esters of polyalcohols, ethers, such as diethyl ether, tetrahydrofuran, dioxane,

Alkylenmonoalkylether und -dialkylether wie z.B. Propylenglykolmonomethylether, Propylenglykolmonoethylether, Ethylenglycol-monomethylether oder -monoethylether, Diglyme und Tetraglyme, Amide wie Dimethylformamid, Dimethylacetamid, Di-n-butylformamid, Dimethylcapryl/caprin-fettsäureamid und N-Alkylpyrrolidon, Ketone, wie Aceton, Cyclohexanon, Isophoron, Acetophenon, Methylethylketon, Sulfoxide und Sulfone wie Dimethylsulfoxid und Sulfolan, Polyglykole, tierische, pflanzliche und mineralische Öle.Alkylene monoalkyl ethers and dialkyl ethers such as e.g. Propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether or monoethyl ether, diglyme and tetraglyme, amides such as dimethylformamide, dimethylacetamide, di-n-butylformamide, dimethylcapryl / caprin fatty acid amide and N-alkylpyrrolidone, ketone, acetone, such as acetone, such as acetone, such as acetone, such as acetone, such as acetone, such as acetone, such as acetone, such as acetone, Sulfoxides and sulfones such as dimethyl sulfoxide and sulfolane, polyglycols, animal, vegetable and mineral oils.

Um die Theologischen Eigenschaften von wässrigen oder lösungsmittelhaltigen Emulsionen oder Suspensionen einzustellen, werden in-der Fachliteratur eineIn order to adjust the theological properties of aqueous or solvent-based emulsions or suspensions, the technical literature contains a

Vielzahl von unterschiedlichen Systemen angegeben. Bekannt sind beispielsweise Celluloseether und andere Cellulosederivate (z.B. Carboxymethylcellulose, Hydroxyethylcellulose), Gelatine, Stärke und Stärkederivate, Natriumalginate, Fettsäurepolyethylenglykolester, Agar-Agar, Traganth oder Dextrine. Als synthetische Polymere kommen verschiedene Materialien zum Einsatz, wie z.B. Polyvinylalkohole, Polyacrylamide, Polyvinylamide, Polysulfonsäuren, Polyacrylsäure, Polyacrylsäureester, Polyvinylpyrrolidon, Polyvinylmethylether, Polyethylenoxide, Copolymere aus Maleinsäureanhydrid und Vinylmethylether, sowie diverse Mischungen und Copolymerisate aus den o.a. Verbindungen, einschließlich ihrer verschiedenen Salze und Ester. Diese Polymere können wahlweise vernetzt oder unvemetzt sein. Als Konservierungsmittel eignen sich beispielsweise Preventol und Proxel, als Entschäumer beispielsweise Silan-Derivate, wie Poly-dimethylsiloxane und Magnesiumstearat oder perfluorierte Phosphon- oder Phosphinderivate.Variety of different systems specified. For example, cellulose ethers and other cellulose derivatives (eg carboxymethyl cellulose, hydroxyethyl cellulose), gelatin, starch and starch derivatives, sodium alginates, fatty acid polyethylene glycol esters, agar-agar, tragacanth or dextrins are known. Various materials are used as synthetic polymers, such as polyvinyl alcohols, polyacrylamides, polyvinylamides, polysulfonic acids, polyacrylic acid, polyacrylic acid esters, polyvinylpyrrolidone, polyvinyl methyl ether, polyethylene oxides, copolymers of maleic anhydride and vinyl methyl ether, as well as various mixtures and copolymers of the above compounds, including their various salts and ester. These polymers can optionally be cross-linked or uncross-linked. Preventol and Proxel are suitable as preservatives, for example silane derivatives such as poly-dimethylsiloxanes and magnesium stearate or perfluorinated phosphone or phosphine derivatives are suitable as defoamers.

Als Kältestabilisatoren können alle üblichen für diesen Zweck einsetzbaren Stoffe fungieren. Beispielhaft seien Harnstoff, Glycerin und Propylenglykol genannt.All conventional substances that can be used for this purpose can act as cold stabilizers. Examples include urea, glycerin and propylene glycol.

Als Puffer kommen alle üblichen Säuren und deren Salze in Frage. Vorzugsweise genannt seien Phosphatpuffer, Carbonatpuffer, Zitratpuffer.All common acids and their salts can be used as buffers. Phosphate buffers, carbonate buffers and citrate buffers may preferably be mentioned.

Die Pflanzenschutz-Formulierungen besitzen bevorzugt einen pH-Wert im Bereich 2 bis 12, besonders bevorzugt 3 bis 8.The crop protection formulations preferably have a pH in the range from 2 to 12, particularly preferably from 3 to 8.

Die erfindungsgemäße Verwendung der Polymere als Kristallisationsinhibitor hemmend stabilisierten Pflanzenschutzmittel sind chemisch, physikalisch und sowie anwendungstechnisch ausgezeichnet lagerstabil.The use of the polymers according to the invention as crystallization inhibitor-stabilized crop protection agents are chemically, physically and application-technically extremely stable in storage.

Die nachfolgenden Beispiele dienen der Erläuterung der Erfindung ohne sie jedoch darauf einzuschränken.The following examples serve to illustrate the invention, but without restricting it.

BeispieleExamples

Beispiel 1 : Polymer 1Example 1: Polymer 1

In einem 1 I Quickfitkolben der mit Rührer, Innenthermometer, Gaseinleitrohre für Stickstoff und Ammoniakgas sowie Rückflusskühler versehen war wurden 500 g Toluol vorgelegt. Des weiteren wurden 3,0 g 2-Acrylamido-2-methylpropan- sulfonsäure (AMPS) vorgelegt und mit der äquivalenten Menge Ammoniak neutralisiert. Anschließend wurden 60,0 g Stearylacrylat und 30,0 g Isopropanol hinzugefügt. Der Kolbeninhalt wird unter Rühren mit Stickstoff inertisiert und mittels Heizbad auf 70°C erwärmt. Nach Erreichen der Temperatur wurden 3,0 g AIBN als Initiator zugegeben und unter weiterem Stickstoffspülen wurde auf 80°C erhitzt. Die Mischung wurde 4 h bei der angegebenen Temperatur unter Rückfluss gerührt. Nach beendeter Reaktionsführung wurde das Produkt in einen Rotationsverdampfer überführt und das Lösemittel wurde durch Vakuumdestillation bei ca. 50°C entfernt.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 are 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 temperature indicated for 4 h. After completion of the reaction, the product was in a Transferred to a rotary evaporator and the solvent was removed by vacuum distillation at about 50 ° C.

Beispiel 2: Polymer 2 Analoges Vorgehen wie in Beispiel 1 ; des Weiteren wurden zur Vernetzung 1 ,0 g Trimethylolpropantriacrylat (TMPTA) hinzugegeben.Example 2: Polymer 2 Analogous procedure as in Example 1; Furthermore, 1.0 g of trimethylolpropane triacrylate (TMPTA) was added for crosslinking.

Beispiel 3: Polymer 3Example 3: Polymer 3

Analoges Vorgehen wie in Beispiel 1 ; anstelle von Stearylacrylat wurden jedoch 28,0 g eines Esters aus Acrylsäure und einem (Cι2-Cι4)-Fettsäurepolyglykolether mit 7 EO-Einheiten eingesetzt.Analogous procedure as in Example 1; instead of stearyl acrylate, however, 28.0 g of an ester of acrylic acid and a (-C 2 -C 4 ) fatty acid polyglycol ether with 7 EO units were used.

Beispiel 4: AnwendungsbeispielExample 4: Application example

Herstellung eines kristallisationsstabilisierten Suspensionskonzentrates (SC) aus 43,60 g Atrazin (99 %)Preparation of a crystallization-stabilized suspension concentrate (SC) from 43.60 g of atrazine (99%)

40,30 g Demineralisiertes Wasser40.30 g demineralized water

2,10 g ®Dispergiermittel LFS2.10 g ® LFS dispersant

1 ,00 g Polymer 1 aus Beispiel 11.00 g of polymer 1 from Example 1

1 ,50 g ®Defoamer SE 57 7,20 g ® Kelzan S (2 %ige wässrige Lösung)1.50 g ® Defoamer SE 57 7.20 g ® Kelzan S (2% aqueous solution)

4,30 g Ethylenglykol4.30 g ethylene glycol

Die Herstellung des SC erfolgte in der dem Fachmann bekannten Weise. Bei Lagerung der Formulierung bei Raumtemperatur und 54°C kam es auch nach längerer Zeit zu keinerlei Kristallisation des Wirkstoffes und der damit verbundenen Sedimentation, was bei einer entsprechenden Formulierung ohne Polymer 1 nicht der Fall war.The SC was produced in the manner known to the person skilled in the art. When the formulation was stored at room temperature and 54 ° C., there was no crystallization of the active ingredient and the associated sedimentation, even after a long period of time, which was not the case with a corresponding formulation without polymer 1.

Beispiel 5: Anwendungsbeispiel Herstellung eines emulgierbaren Konzentrates (EC) aus 42,00 g DimethoatExample 5: Application example Preparation of an emulsifiable concentrate (EC) from 42.00 g of dimethoate

45,00 g Cyclohexanon45.00 g cyclohexanone

6,00 g ®Emulsogen EL 360 6,00 g Xyiol6.00 g ® Emulsogen EL 360 6.00 g xyiol

1 ,00 g Polymer 2 aus Beispiel 21.00 g of polymer 2 from example 2

Die Herstellung des EC erfolgte in der dem Fachmann bekannten Weise. Bei Verdünnung des EC mittels Wasser unterblieb selbst bei Lagertemperaturen von 10°C über einen Zeitraum von mehreren Tagen ein Auskristallisieren des Wirkstoffes, was bei Herstellung des oben genannten EC ohne Verwendung des Polymers 2 innerhalb von 30 min eintrat.The EC was produced in the manner known to the person skilled in the art. When the EC was diluted with water, the active ingredient did not crystallize out over a period of several days even at storage temperatures of 10 ° C., which occurred within 30 minutes when the above-mentioned EC was produced without the use of polymer 2.

Beispiel e: AnwendungsbeispielExample e: application example

Herstellung eines emulgierbaren Konzentrates (EC) aus 42,00 g DimethoatPreparation of an emulsifiable concentrate (EC) from 42.00 g of dimethoate

45,00 g Cyclohexanon45.00 g cyclohexanone

6,00 g ® Emulsogen EL 3606.00 g ® Emulsogen EL 360

6,00 g Xylol6.00 g xylene

1 ,00 g Polymer 3 aus Beispiel 31.00 g of polymer 3 from Example 3

Die Herstellung des EC erfolgte in der dem Fachmann bekannten Weise. Bei Verdünnung des EC mittels Wasser unterblieb selbst bei Lagertemperaturen von 10°C über einen Zeitraum, von mehreren Jagen ein Auskristallisieren des Wirkstoffes, was bei Herstellung des oben genannten EC ohne Verwendung des Polymers 2 innerhalb von 30 min eintrat. The EC was produced in the manner known to the person skilled in the art. When the EC was diluted with water, the active ingredient did not crystallize out over several periods of time, even at storage temperatures of 10 ° C., which occurred within 30 minutes when the above-mentioned EC was produced without the use of polymer 2.

Claims

Patentansprüche: claims: 1. Verwendung von Polymeren, herstellbar durch radikalische Copolymerisation von A) Acrylamidopropylmethylensulfonsäure (AMPS) und/oder deren Salzen; B) einem oder mehreren Makromonomeren, enthaltend i) eine zur Polymerisation befähigte Endgruppe, die im1. Use of polymers which can be prepared by radical copolymerization of A) acrylamidopropylmethylene sulfonic acid (AMPS) and / or their salts; B) one or more macromonomers containing i) an end group capable of polymerization, which in Reaktionsmedium zumindest teilweise löslich ist, ii) einen hydrophoben Teil, der Wasserstoff oder einen gesättigten oder ungesättigten, linearen oder verzweigten, aliphatischen, cyclo- aliphatischen oder aromatischen (C-ι-Cιoo)-KohΙenwasserstoffrest darstellt, und iii) gegebenenfalls einen hydrophilen Teil, der auf Polyalkylenoxiden basiert; und D) optional einem oder mehreren weiteren mindestens einfach oder mehrfach olefinisch ungesättigten Sauerstoff-, Stickstoff-, Schwefel-, Phosphor-, Chlor- und/oder Fluor-haltigen Comonomeren, als Kristallisationsinhibitor in Pflanzenschutz-Formulierungen.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 (C-ι-Cιoo) hydrocarbon radical, and iii) optionally a hydrophilic part, based on polyalkylene oxides; and D) optionally one or more further at least mono- or poly-olefinically unsaturated oxygen, nitrogen, sulfur, phosphorus, chlorine and / or fluorine-containing comonomers, as a crystallization inhibitor in crop protection formulations. 2. Verwendung nach Anspruch 1 , dadurch gekennzeichnet, dass es sich beim Comonomeren A) um die Natrium- und/oder Ammoniumsalze der Acrylamidopropylmethylensulfonsäure (AMPS) handelt.2. Use according to claim 1, characterized in that the comonomer A) is the sodium and / or ammonium salts of acrylamidopropylmethylene sulfonic acid (AMPS). 3. Verwendung nach Anspruch 1 und/oder 2, dadurch gekennzeichnet, dass es sich bei den Makromonomeren B) um solche gemäß Formel (1)3. Use according to claim 1 and / or 2, characterized in that the macromonomers B) are those of the formula (1) R1 - Y- (R2 - 0)x (R4 - O)z - R3 (1 )R 1 - Y- (R 2 - 0) x (R 4 - O) z - R 3 (1) handelt, worin R1 für einen Vinyl-, Allyl-, Acryl-, Methacryl-, Senecioyl- oderis where R 1 is a vinyl, allyl, acrylic, methacrylic, senecioyl or Crotonylrest; R2 und R4 unabhängig voneinander für (C2-C4)-Alkylen, x und z unabhängig voneinander für eine ganze Zahl zwischen 0 und 500, bevorzugt mit x+z größer oder gleich 1 ; Y für O, S, PH oder NH, bevorzugt O; undCrotonylrest; R 2 and R 4 independently of one another 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 R3 für Wasserstoff oder einen gesättigten oder ungesättigten linearen oder verzweigten aliphatischen, cycloaliphatischen oder aromatischen (Cι-Cιoo)-Kohlenwasserstoffrest, bevorzugt (C1-C30)-R 3 for hydrogen or a saturated or unsaturated linear or branched aliphatic, cycloaliphatic or aromatic (-C-Cιoo) hydrocarbon radical, preferably (C1-C30) - Kohlenwasserstoffrest, steht.Hydrocarbon residue. 4. Verwendung nach Anspruch 3, dadurch gekennzeichnet, dass R1 für einen Acryl- oder Methacryl-Rest;4. Use according to claim 3, characterized in that R 1 for an acrylic or methacrylic radical; R2 und R4 unabhängig voneinander für C2-Alkylen oder C3-Alkylen; x und z unabhängig voneinander für eine ganze Zahl zwischen 0 und 50, bevorzugt mit x + z größer oder gleich 1 ; R3 für einen aliphatischen (C4-C22)- Alkyl- oder Alkenylrest, bevorzugt (C10- C22)- Alkyl- oder Alkenylrest; einen Phenylrest; einen (Cι-C22)-Alkylphenylrest, bevorzugt (sec-Butyl)- und (n-Butyl)- Alkylphenylrest; einen Poly((Cι-C22)alkyl)phenylrest, bevorzugt Tris(sec- butyl)phenylrest und Tris(n-Butyl)phenylrest; oder einen Polystyrylphenylrest, bevorzugt Tristyrylphenylrest, stehen.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 is an aliphatic (C4-C22) alkyl or alkenyl radical, preferably (C10-C22) alkyl or alkenyl radical; a phenyl radical; a (-CC 22 ) alkylphenyl, preferably (sec-butyl) - and (n-butyl) - alkylphenyl; 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. Verwendung nach Anspruch 4, dadurch gekennzeichnet, dass es sich beim R Reesstt RR33 uumm eeiinneenn 22,4,6-Tris(sec-butyl)-phenylrest oder 2,4,6-Tris(1-phenylethyl)- phenylrest handelt.5. Use according to claim 4, characterized in that the R Reesstt RR 33 uumm eeiinneenn 22,4,6-tris (sec-butyl) phenyl radical or 2,4,6-tris (1-phenylethyl) phenyl radical , 6. Verwendung nach Anspruch 1 , dadurch gekennzeichnet, dass die Polymere herstellbar sind durch radikalische Copolymerisation von A) Acrylamidopropylmethylensulfonsäure (AMPS), dem Natriumsalz der Acrylamidopropylmethylensulfonsäure (AMPS) und/oder dem6. Use 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 Ammoniumsalz der Acrylamidopropylmethylensulfonsäure, bevorzugt dem Ammoniumsalz der Acrylamidopropylmethylensulfonsäure (AMPS); B) einem oder mehreren Makromonomeren, ausgewählt aus der Gruppe der Ester gebildet aus Methacryl- oder Acrylsäure, bevorzugt Methacrylsäure, und Verbindungen der Formel (2)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-(CH2-CH2- O)x - R3 (2)HO- (CH 2 -CH 2 - O) x - R 3 (2) worin x eine Zahl zwischen 0 und 50, bevorzugt 1 und 50, besonders bevorzugt 5 und 30, undwherein x is a number between 0 and 50, preferably 1 and 50, particularly preferably 5 and 30, and R3 einen (Cιo-C22)-Alkylrest darstellen; und C) optional einem oder mehreren Comonomeren ausgewählt aus der Gruppe Acrylamid, Vinylformamid, N-Vinylmethylacetamid, Natriummethallylsulfonat, Hydroxyethylmethacrylat, Acrylsäure, Methacrylsäure, Maleinsäureanhydrid, Methacrylamid, Vinylacetat, N-Vinylpyrrolidon, Vinylphosphonsäure, Styrol, Styrolsulfonsäure (Na-Salz), t-Butylacrylat und Methylmethacrylat.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. Verwendung nach mindestens einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass es sich bei den Makromonomeren B) um Ester gebildet aus Acryl- oder Methacrylsäure und Alkylethoxylaten ausgewählt aus der Gruppe der (Cιo-Cιs)-Fettalkoholpolyglykolether mit 8 EO-Einheiten; Cn-Oxoalkoholpolyglykolether mit 8 EO-Einheiten,7. Use 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-Cιs) fatty alcohol polyglycol ethers with 8 EO units ; Cn-oxo alcohol polyglycol ether with 8 EO units, (Ci2-Cι4)-Fettalkoholpolyglykolether mϊ 1 7 EO-Einheiten,(Ci 2 -Cι 4 ) fatty alcohol polyglycol ether mϊ 1 7 EO units, (Ci2-Cι )-Fettalkoholpolyglykolether mϊ 1 11 EO-Einheiten,(Ci 2 -Cι) fatty alcohol polyglycol ether mϊ 1 11 EO units, (Ci6-Cι8)-Fettalkoholpolyglykolether mϊ 1 8 EO-Einheiten, (Cι6-Cιa)-Fettalkoholpolyglykolether mi 1 15 EO-Einheiten,(Ci 6 -Cι 8 ) fatty alcohol polyglycol ether mether 1 8 EO units, (Cι 6 -Cιa) fatty alcohol polyglycol ether mi 1 15 EO units, (Ci6-Cι8)-Fettalkoholpolyglykolether mi it 11 EO-Einheiten,(Ci6-Cι 8 ) fatty alcohol polyglycol ether with 11 EO units, (Ci6-Cι8)-Fettalkoholpolyglykolether mϊ 120 EO-Einheiten,(Ci 6 -Cι 8 ) fatty alcohol polyglycol ether with 120 EO units, (Ci6-Cι8)-Fettalkoholpolyglykolether mϊ 1 25 EO-Einheiten,(Ci 6 -Cι 8 ) fatty alcohol polyglycol ether with 1 25 EO units, (Cι8-C22)-Fettalkoholpolyglykolether mϊ 125 EO-Einheiten, iso-(Ci6-Cι8)-Fettalkoholpolyglykolether mit 25 EO-Einheiten und/oder(Cι 8 -C2 2 ) fatty alcohol polyglycol ether with 125 EO units, iso- (Ci 6 -Cι 8 ) fatty alcohol polyglycol ether with 25 EO units and / or C22-Fettalkoholpolyglykolether mit 25 EO-Einheiten handelt. C22 fatty alcohol polyglycol ether with 25 EO units. 8. Verwendung nach Anspruch 1 , dadurch gekennzeichnet, dass die Polymere herstellbar sind durch radikalische Copolymerisation von8. Use according to claim 1, characterized in that the polymers can be prepared by radical copolymerization of A) Acrylamidopropylmethylensulfonsäure (AMPS), dem Natriumsalz der Acrylamidopropylmethylensulfonsäure (AMPS) und/oder dem Ammoniumsalz der Acrylamidopropylmethylensulfonsäure, bevorzugt dem Ammoniumsalz der Acrylamidopropylmethylensulfonsäure (AMPS);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) einem oder mehreren Makromonomeren, ausgewählt aus der Gruppe der Ester gebildet aus Methacryl- oder Acrylsäure, bevorzugt Methacrylsäure, und Verbindungen der Formel (3)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-(CH2-CH2- O)x- R3 (3) worin x eine Zahl zwischen 0 und 50, bevorzugt 1 und 50, besonders bevorzugt 5 und 30, und R3 einen Poly((CrC22)alkyl)-phenylrest, bevorzugt Tris(sec-butyl)- phenylrest, und Tris(n-butyl)-phenylrest, besonders bevorzugt 2,4,6-HO- (CH 2 -CH 2 - O) 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, and tris (n-butyl) phenyl radical, particularly preferably 2,4,6 Tris(sec-butyl)-phenylrest, einen Tris(styryl)-phenylrest, bevorzugt 2,4,6-Tris (sec-butyl) phenyl radical, a tris (styryl) phenyl radical, preferably 2,4,6- Tris(1-phenylethyl)-phenylrest, darstellt; und C) optional einem oder mehreren Comonomeren ausgewählt aus der Gruppe Acrylamid, Vinylformamid, N-Vinylmethylacetamid,Tris (1-phenylethyl) phenyl group; and C) optionally one or more comonomers selected from the group consisting of acrylamide, vinylformamide, N-vinylmethylacetamide, Natriummethallylsulfonat, Hydroxyethylmethacrylat, Acrylsäure,Sodium methallyl sulfonate, hydroxyethyl methacrylate, acrylic acid, Methacrylsäure, Maleinsäureanhydrid, Methacrylamid, Vinylacetat,Methacrylic acid, maleic anhydride, methacrylamide, vinyl acetate, N-Vinylpyrrolidon, Vinylphosphonsäure, Styrol, Styrolsulfonsäure (Na-Salz), t-Butylacrylat und Methylmethacrylat.N-vinyl pyrrolidone, vinyl phosphonic acid, styrene, styrene sulfonic acid (Na salt), t-butyl acrylate and methyl methacrylate. 9. Verwendung nach mindestens einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass der Anteil an Makromonomeren B) in den Polymeren 50,1 bis 99,9 Gew.-%, bevorzugt 70 bis 95 Gew.-%, besonders bevorzugt 80 bis9. Use 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 Gew.-%, beträgt.94% by weight. 10. Verwendung nach mindestens einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass der Anteil an Makromonomeren B) in den Polymeren 0,1 bis 50 Gew.-%, bevorzugt 5 bis 25 Gew.-%, besonders bevorzugt 6 bis 20 Gew.-%, beträgt.10. Use according to at least one of claims 1 to 8, characterized in that the proportion of macromonomers B) in the polymers 0.1 to 50% by weight, preferably 5 to 25% by weight, particularly preferably 6 to 20% by weight. 11. Verwendung nach mindestens einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass das zahlenmittlere Molekulargewicht der Polymere 1000 bis 20 000 000 g/mol, bevorzugt 20 000 bis 5 000 000 g/mol, insbesondere bevorzugt 50 000 bis 1 500 000 g/mol, beträgt.11. Use 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. Verwendung nach mindestens einem der Ansprüche 1 bis 11 , dadurch gekennzeichnet, dass die Polymere vernetzt sind.12. Use according to at least one of claims 1 to 11, characterized in that the polymers are crosslinked. 13. Verwendung nach mindestens einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, dass es sich bei der Copolymerisation um eine Fällungspolymerisation, bevorzugt in tert.-Butanol, handelt.13. Use according to at least one of claims 1 to 12, characterized in that the copolymerization is a precipitation polymerization, preferably in tert-butanol. 14. Verwendung nach mindestens einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, dass die Pflanzenschutz-Formulierungen, bezogen auf die fertigen Formulierungen, 0,01 bis 10 Gew.-%, bevorzugt 0,1 bis 7 Gew.-%, besonders bevorzugt 0,5 bis 5 Gew.-%, Polymere enthalten.14. Use according to at least one of claims 1 to 13, characterized in that the crop protection formulations, based on the finished formulations, 0.01 to 10 wt .-%, preferably 0.1 to 7 wt .-%, particularly preferably 0.5 to 5 wt .-%, contain polymers. 15. Verwendung nach mindestens einem der Ansprüche 1 bis 14, dadurch gekennzeichnet, dass die Pflanzenschutz-Formulierungen als pestizide Wirkstoffe einen oder mehrere Stoffe ausgewählt aus Herbiziden, Insektiziden, Fungiziden, Akariziden, Bakteriziden, Molluskiden, Nematiziden und Rodentiziden enthalten.15. Use according to at least one of claims 1 to 14, characterized in that the crop protection formulations contain one or more substances selected from herbicides, insecticides, fungicides, acaricides, bactericides, molluscids, nematicides and rodenticides as pesticidal active ingredients. 16. Verwendung nach Anspruch 15, dadurch gekennzeichnet, dass es sich bei den pestiziden Wirkstoffen um Sulfonate, Anilide, Phenylhamstoffderivate, Azole, Triazine, Propionsäurederivate, Carbamate, Pyrazolinate, Tebuconazole, Hexaconazole, Phenmedipham, Desmedipham, Linuron und/oder Trifluralin handelt.16. Use according to claim 15, characterized in that the pesticidal active ingredients are sulfonates, anilides, phenylurea derivatives, azoles, triazines, propionic acid derivatives, carbamates, pyrazolinates, tebuconazoles, hexaconazoles, phenmedipham, desmedipham, linuron and / or trifluralin. 17. Verwendung nach mindestens einem der Ansprüche 1 bis 16, dadurch gekennzeichnet, dass es sich bei den Pflanzenschutz-Formulierungen um emulgierbare Konzentrate (EC), Öl-in-Wasser Emulsionen (EW), Wasser-in-ÖI Emulsionen, Suspensionskonzentrate (SC), Suspoemulsionen (SE), Suspensionen, Mikroemulsionen (ME), Dispersionen handelt.17. Use according to at least one of claims 1 to 16, characterized in that it is the crop protection formulations emulsifiable concentrates (EC), oil-in-water emulsions (EW), water-in-oil emulsions, suspension concentrates (SC), suspoemulsions (SE), suspensions, microemulsions (ME), dispersions. 18. Verwendung nach Anspruch 17, dadurch gekennzeichnet, dass es sich bei den Pflanzenschutz-Formulierungen um emulgierbare Konzentrate (EC) oder Suspensionskonzentrate (SC) handelt.18. Use according to claim 17, characterized in that the crop protection formulations are emulsifiable concentrates (EC) or suspension concentrates (SC). 19. Verwendung nach mindestens einem der Ansprüche 1 bis 16, dadurch gekennzeichnet, dass es sich bei den Pflanzenschutz-Formulierungen um solche handelt, die dadurch erhältlich sind, dass man emulgierbare Konzentrate (EC), Öl- in-Wasser Emulsionen (EW), Wasser-in-ÖI Emulsionen, Suspensionskonzentrate (SC), Suspoemulsionen (SE), Suspensionen, Mikroemulsionen (ME) oder Dispersionen mit Wasser und/oder Lösungsmitteln, bevorzugt Wasser, verdünnt.19. Use according to at least one of claims 1 to 16, characterized in that the crop protection formulations are those which are obtainable by emulsifiable concentrates (EC), oil-in-water emulsions (EW), Water-in-oil emulsions, suspension concentrates (SC), suspoemulsions (SE), suspensions, microemulsions (ME) or dispersions diluted with water and / or solvents, preferably water. 20. Verwendung nach Anspruch 19, dadurch gekennzeichnet, dass es sich bei den Pflanzenschutz-Formulierungen um solche handelt, die dadurch erhältlich sind, dass man emulgierbare Konzentrate (EC) oder Suspensionskonzentrate (SC), mit Wasser und/oder Lösungsmitteln, bevorzugt Wasser, verdünnt. 20. Use according to claim 19, characterized in that the crop protection formulations are those which are obtainable by emulsifiable concentrates (EC) or suspension concentrates (SC), with water and / or solvents, preferably water, diluted.
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US20060030486A1 (en) 2006-02-09
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DE10163902A1 (en) 2003-07-03
BR0215300A (en) 2004-12-21
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