EP1461389A1 - Inhibiteur de cristallisation pour preparations de phytoprotection - Google Patents

Inhibiteur de cristallisation pour preparations de phytoprotection

Info

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Withdrawn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)
English (en)
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/fr
Withdrawn legal-status Critical Current

Links

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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

La présente invention concerne l'utilisation de polymères à base d'acide acrylamidopropylméthylènesulfonique (AMPS) et de macromonomères en tant qu'inhibiteur de cristallisation dans des préparations de phytoprotection. Ces polymères empêchent la recristallisation des substances actives pesticides (herbicides, insecticides, acaricides, bactéricides, molluscicides, nématicides et rodenticides) qui sont contenues dans les préparations de phytoprotection. L'utilisation est notamment avantageuse en cas de concentrés émulsifiables et de concentrés pouvant être mis en suspension.
EP02793036A 2001-12-22 2002-12-17 Inhibiteur de cristallisation pour preparations de phytoprotection Withdrawn EP1461389A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10163902A DE10163902A1 (de) 2001-12-22 2001-12-22 Kristallisationsinhibitor für Pflanzenschutz-Formulierungen
DE10163902 2001-12-22
PCT/EP2002/014367 WO2003055944A1 (fr) 2001-12-22 2002-12-17 Inhibiteur de cristallisation pour preparations de phytoprotection

Publications (1)

Publication Number Publication Date
EP1461389A1 true EP1461389A1 (fr) 2004-09-29

Family

ID=7710829

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02793036A Withdrawn EP1461389A1 (fr) 2001-12-22 2002-12-17 Inhibiteur de cristallisation pour preparations de phytoprotection

Country Status (7)

Country Link
US (2) US20050182219A1 (fr)
EP (1) EP1461389A1 (fr)
BR (1) BR0215300A (fr)
CA (1) CA2471243A1 (fr)
DE (1) DE10163902A1 (fr)
MX (1) MXPA04006134A (fr)
WO (1) WO2003055944A1 (fr)

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10351004A1 (de) 2003-10-30 2005-05-25 Basf Ag Nanopartikuläre Wirkstoffformulierungen
DE602006003643D1 (de) * 2005-03-29 2008-12-24 Canon Kk Ladungsüberwachungsharz und toner
EP2363421B1 (fr) 2005-04-18 2013-09-18 Basf Se Copolymères CP pour la préparation de compositions comprenant au moins un fongicide du groupe des conazoles
MX2009002889A (es) * 2006-09-22 2009-04-01 Huntsman Spec Chem Corp Inhibicion de maduracion de ostwald en formulaciones quimicas.
CN101522736B (zh) 2006-10-05 2012-03-28 巴斯夫欧洲公司 梳型聚合物及其在制备活性或有效成分配制剂中的用途
PE20090529A1 (es) * 2007-07-06 2009-06-04 Basf Se Uso de homo y copolimeros para la estabilizacion de formulaciones de principios activos
BRPI1006658B1 (pt) * 2009-04-22 2018-02-06 Akzo Nobel Chemicals International B.V. Agrochemical formulation, and method for producing an agrochemical formulation
WO2012069514A1 (fr) * 2010-11-25 2012-05-31 Basf Se Composition anhydre comprenant un pesticide et des copolymères présentant des groupes acide sulfonique
BR112013029907A2 (pt) * 2011-06-01 2016-08-09 Basf Se “método de controle de vegetação indesejada e uso de uma base”
US9145340B2 (en) 2012-08-13 2015-09-29 Verdesian Life Sciences, Llc Method of reducing atmospheric ammonia in livestock and poultry containment facilities
ES2718662T3 (es) * 2012-09-04 2019-07-03 Dow Agrosciences Llc Composiciones y métodos para mejorar la compatibilidad de las sales de herbicidas solubles en agua
US9961922B2 (en) 2012-10-15 2018-05-08 Verdesian Life Sciences, Llc Animal feed and/or water amendments for lowering ammonia concentrations in animal excrement
US11254620B2 (en) 2013-08-05 2022-02-22 Verdesian Life Sciences U.S., Llc Micronutrient-enhanced polymeric seed coatings
TW201522390A (zh) 2013-08-27 2015-06-16 特級肥料產品公司 聚陰離子聚合物
WO2015035031A1 (fr) 2013-09-05 2015-03-12 Verdesian Life Sciences, Llc Compositions d'acide borique
CA2945823C (fr) 2014-05-21 2022-04-26 Verdesian Life Sciences, Llc Compositions de traitement de sol polymeres comprenant des acides humiques
US10822487B2 (en) 2014-05-22 2020-11-03 Verdesian Life Sciences Llc Polymeric compositions
US11304955B2 (en) 2017-06-09 2022-04-19 Isp Investments Llc Small-molecule povidone analogs in coamorphous pharmaceutical phases
CN112822943A (zh) * 2018-09-04 2021-05-18 维乌作物保护有限公司 农业制剂中的结晶抑制剂
EA202192571A1 (ru) * 2019-03-27 2022-01-20 Сингента Кроп Протекшн Аг Составы на основе фунгицидов с пониженной скоростью роста кристаллов
JP7305232B1 (ja) 2022-12-14 2023-07-10 竹本油脂株式会社 結晶成長抑制剤、及びそれを含有する農薬組成物

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4859458A (en) * 1981-09-15 1989-08-22 Morton Thiokol, Inc. Hair conditioning polymers containing alkoxylated nitrogen salts of sulfonic acid
US4521578A (en) * 1983-09-26 1985-06-04 Dresser Industries, Inc. Composition and method of preparation of novel aqueous drilling fluid additives
US5639841A (en) * 1995-02-28 1997-06-17 Union Carbide Chemicals & Plastics Technology Corporation Polymers containing macromonomer mixtures
DE19646484C2 (de) * 1995-11-21 2000-10-19 Stockhausen Chem Fab Gmbh Flüssigkeitsabsorbierende Polymere, Verfahren zu deren Herstellung und deren Verwendung
DE59814329D1 (de) * 1997-07-23 2009-02-05 Basf Se Verwendung von polysiloxanhaltigen polymeren für kosmetische formulierungen
DE19805121A1 (de) * 1998-02-09 1999-08-12 Basf Ag Verfahren zur Herstellung farbstoffenthaltender, wässriger Polymerisatdispersionen
DE19907587A1 (de) * 1999-02-22 2000-08-24 Basf Ag Haarkosmetische Formulierungen
DE19926355A1 (de) * 1999-06-10 2000-12-14 Clariant Gmbh Wasserlösliche Mischpolymere und ihre Verwendung für Exploration und Förderung von Erdöl und Erdgas
DE50015912D1 (de) * 1999-07-15 2010-06-10 Clariant Produkte Deutschland Wasserlösliche Polymere und ihre Verwendung in kosmetischen und pharmazeutischen Mitteln
DE10059830A1 (de) * 2000-12-01 2002-06-13 Clariant Gmbh Kationisch modifizierte Kammpolymere auf Basis von Acryloyldimethyltaurinsäure
JP2002327102A (ja) * 2000-12-01 2002-11-15 Clariant Gmbh アクリロイルジメチルタウリン酸をベースとするコポリマーおよび相乗作用添加物を含有する組成物
DE10119338A1 (de) * 2001-04-20 2002-10-24 Clariant Gmbh Verwendung von Copolymerisaten auf Basis von Acrylamidoalkylsulfonsäuren als Verdicker in Zubereitungen enthaltend organische Lösemittel
GB0116945D0 (en) * 2001-07-11 2001-09-05 Unilever Plc Antiperspirant formulations
JP2003131502A (ja) * 2001-08-10 2003-05-09 Canon Inc イミド系摺動層を有するヒータ及びこのヒータを用いた像加熱装置

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03055944A1 *

Also Published As

Publication number Publication date
BR0215300A (pt) 2004-12-21
MXPA04006134A (es) 2004-11-01
CA2471243A1 (fr) 2003-07-10
US20050182219A1 (en) 2005-08-18
US20060030486A1 (en) 2006-02-09
WO2003055944A1 (fr) 2003-07-10
DE10163902A1 (de) 2003-07-03

Similar Documents

Publication Publication Date Title
EP1461389A1 (fr) Inhibiteur de cristallisation pour preparations de phytoprotection
EP3324738B1 (fr) Formulations agrochimiques avec copolymères comprenant un éther d'hydroxybutylvinyle en tant qu'épaississant associatif
DE3782865T2 (de) Pfropfcopolymer mit einem stabilisationseffekt fuer dispersionen, dessen herstellungsverfahren und verfahren fuer eine emulsionspolymerisation mit diesem stabilisiermittel.
EP1339791B1 (fr) Copolymere greffe a base d'acide acryloyldimethyletaurine
DE69815748T2 (de) Pestizid-Zusammensetzungen
EP1354001A2 (fr) Compositions renfermant des copolymeres a base d'acide acryloyldimethyl-amino-ethylsulfonique et des additifs synergiques
EP2429286B1 (fr) Polymères permettant d'augmenter la mobilité dans le sol d'insecticides peu solubles
DE69410296T2 (de) Herstellung von amphipatischen pfropfcopolymeren, zusammensetzung davon und deren verwendung
EP1931197A2 (fr) Preparation contenant au moins un fongicide du groupe des conazoles, un autre fongicide et un copolymere stabilisant
DE10059829A1 (de) Gepfropfte Kammpolymere auf Basis von Acryloyldimethyltaurinsäure
WO2009007328A2 (fr) Utilisation d'homo- et de copolymères pour la stabilisation de formulations de substances actives
DE10059830A1 (de) Kationisch modifizierte Kammpolymere auf Basis von Acryloyldimethyltaurinsäure
EP1278787A1 (fr) Copolymeres et leur utilisation en tant qu'agents anti-derive
EP1778736A2 (fr) Dispersions aqueuses de polymerisats anioniques solubles dans l'eau et/ou expansibles dans l'eau, procede de fabrication et utilisation
WO2011069931A1 (fr) Formulation de pesticides sensibles à la lumière et de polymères en peigne à teneur en absorbeur d'uv
EP1460895A1 (fr) Formulations phytosanitaires aqueuses
EP1469727A1 (fr) Formulations phytosanitaires se presentant sous forme de suspensions
DE102005025739A1 (de) Copolymerisierbare Polyalkylenglykol-Makromonomere, deren Herstellung und Verwendung
DE3590744C2 (de) Dispersionsstabilisator, sowie dessen Verwendung
WO2003055306A1 (fr) Preparations solides de phytoprotection
DE10029462A1 (de) Wasserlösliche Polymere und ihre Verwendung in kosmetischen und pharmazeutischen Mitteln
DE10127876A1 (de) Zusammensetzungen, enthaltend Copolymere auf Basis von Acryloyldimethyltaurinsäure und synergistische Additive
EP1022940A1 (fr) Auxiliaires de dispersion pour granulats contenant des principes actifs agrochimiques insolubles dans l'eau
DE10206468A1 (de) Pflanzenschutzmittel
WO2002058471A1 (fr) Melanges liquides contenant du metazachlore

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20040722

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LI LU MC NL PT SE SI SK TR

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: CLARIANT PRODUKTE (DEUTSCHLAND) GMBH

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20061211