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WO2003067981A1 - Produits phytosanitaires - Google Patents

Produits phytosanitaires Download PDF

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Publication number
WO2003067981A1
WO2003067981A1 PCT/EP2003/001272 EP0301272W WO03067981A1 WO 2003067981 A1 WO2003067981 A1 WO 2003067981A1 EP 0301272 W EP0301272 W EP 0301272W WO 03067981 A1 WO03067981 A1 WO 03067981A1
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WO
WIPO (PCT)
Prior art keywords
acid
optionally
chloride
copolymers
mol
Prior art date
Application number
PCT/EP2003/001272
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German (de)
English (en)
Inventor
Michael Marcus Walter
Roman MORSCHHÄUSER
Ralf Zerrer
Original Assignee
Clariant Gmbh
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Publication date
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Publication of WO2003067981A1 publication Critical patent/WO2003067981A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
    • A01N25/28—Microcapsules or nanocapsules

Definitions

  • the present invention relates to the use of comb-shaped copolymers containing acryloyldimethyltaurate in crop protection agents.
  • Pesticides are chemical or natural substances found in plant cells
  • Pesticides and mixtures can be used undiluted or preferably diluted in the form of solutions, emulsions, microemulsions, suspensions, dispersions, powders, foams, pastes, granules and aerosols.
  • certain additives are required to formulate the active ingredient in order to achieve the desired performance properties with regard to solubility, viscosity, dispersibility and emulsification capacity, inhibition of crystallization, adhesion and wetting capacity, anti-caking behavior, compatibility etc.
  • Acryloyldimethyltauric acid can serve both as a thickener, consistency agent, emulsifier, dispersant, and / or stabilizer, crystallization inhibitor, and adhesive and wetting agent, and is outstandingly suitable for the formulation of a large number of formulations containing pesticides.
  • This invention therefore relates to crop protection agents containing at least one copolymer obtainable by free-radical copolymerization of A) acryloyldimethyltauric acid and / or acryloyldimethyltaurates,
  • component A) is copolymerized with at least one component selected from one of groups D) to G).
  • the copolymers according to the invention preferably have a molecular weight of 10 3 g / mol to 10 9 g / mol, particularly preferably 10 4 to 10 7 g / mol, particularly preferably 5 * 10 4 to 5 * 10 6 g / mol.
  • Acryloyldimethyltaurates can be the inorganic or organic salts of acryloyldimethyltauric acid (acrylamidopropyl-2-methyl-2- act sulfonic acid).
  • the Li + , Na + , K + , Mg ++ , Ca ++ , A ++ and / or NH 4 + salts are preferred.
  • the monoalkylammonium, dialkylammonium, trialkylammonium and / or tetraalkylammonium salts are likewise preferred, it being possible for the alkyl substituents of the amines, independently of one another, to be (CrC 22 ) alkyl radicals or (C 2 -C 1 0 ) hydroxyalkyl radicals. Furthermore, one to three times ethoxylated ammonium compounds with different degrees of ethoxylation are preferred. It should be noted that mixtures of two or more of the above representatives are also within the meaning of the invention.
  • the degree of neutralization of acryloyldimethyltauric acid can be between 0 and 100%, a degree of neutralization of above 80% is particularly preferred.
  • the content of acryloyldimethyltauric acid or acryloyldimethyltaurates is at least 0.1% by weight, preferably 20 to 99.5% by weight, particularly preferably 50 to 98% by weight.
  • Monomers are used whose reaction parameters allow copolymerization with acryloyldimethyltauric acid and / or acryloyldimethyltaurates in the respective reaction media.
  • Preferred comonomers B) are unsaturated carboxylic acids and their anhydrides and salts, and also their esters with aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic alcohols with a carbon number of 1 to 30.
  • Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, styrene sulfonic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid and senecioic acid.
  • Preferred counterions are Li + , Na + , K + , Mg ++ , Ca ++ , Al +++ , NH 4 + , monoalkylammonium, dialkylammonium, trialkylammonium and / or tetraalkylammonium radicals, where the Alkyl substituents of the amines independently to (C ⁇ -C22) alkyl or (C 2 -C ⁇ 0) can act from one another -hydroxyalkyl.
  • comonomers B) are open-chain N-vinylamides, preferably N-vinylformamide (VIFA), N-vinylmethylformamide,
  • VIMA N-vinyl methylacetamide
  • N-vinylacetamide N-vinylacetamide
  • N-vinyl lactams with a ring size of 3 to 9, preferably N-vinyl pyrrolidone
  • NVP N-vinylcaprolactam
  • Amides of acrylic and methacrylic acid preferably acrylamide, methacrylamide, N, N-dimethyl-acrylamide, N, N-diethylacrylamide and
  • comonomers B are inorganic acids and their salts and esters.
  • Preferred acids are vinylphosphonic acid, vinylsulfonic acid,
  • the proportion by weight of comonomers B), based on the total mass of the copolymers, can be 0 to 99.8% by weight and is preferably 0.5 to 80% by weight, particularly preferably 2 to 50% by weight.
  • Suitable comonomers C) are all olefinically unsaturated monomers with a cationic charge which are capable of forming copolymers in the selected reaction media with acryloyldimethyltauric acid or its salts.
  • the resulting distribution of the cationic charges across the chains can be statistical, alternating, block-like or gradient-like.
  • the cationic comonomers C) are also to be understood as those which contain the cationic charge in the form of a betaine, wear zwitterionic, or amphoteric structure.
  • Comonomers C) in the sense of the invention are also amino-functionalized precursors which are converted into their corresponding quaternary (for example reaction with dimethyl sulfate, methyl chloride), zwitterionic (for example reaction with hydrogen peroxide), betaine (for example reaction with chloroacetic acid) or amphomeric derivatives by polymer-analogous reactions can.
  • DMAC Diallyldimethylammonium chloride
  • MATAC [2- (methacryloyloxy) ethyl] trimethylammonium chloride
  • the proportion by weight of the comonomers C), based on the total mass of the copolymers, can be 0.1 to 99.8% by weight, preferably 0.5 to 30% by weight and particularly preferably 1 to 20% by weight.
  • Suitable polymerizable, silicon-containing components D) are all at least mono-olefinically unsaturated compounds which are capable of radical copolymerization under the reaction conditions chosen in each case.
  • the distribution of the individual silicone-containing monomers across the resulting polymer chains does not necessarily have to be statistical.
  • Preferred silicone-containing components are those of the formula (I)
  • R 1 represents a polymerizable function from the group of vinylically unsaturated compounds, which is suitable for building polymer structures by radical means.
  • a suitable chemical bridge Z is required to bind the silicone-containing polymer chain to the reactive end group R 1 .
  • Preferred bridges Z are -O-, - ((CrC 5 o) alkylene) -, - ((C 6 -C 30 ) arylene) -, - ((C 5 -C 8 ) cycloalkylene) -, - ((CrC5o) Alkenylene) -, - (polypropylene oxide) n-, - (polyethylene oxide) 0 -,
  • n and o independently of one another are numbers from 0 to 200 and the distribution of the EO / PO units can be random or block-shaped. Also suitable as Z bridge groups
  • the polymer middle part is represented by silicone-containing repeat units.
  • radicals R 3 , R 4 , R 5 and R 6 independently of one another are -CH 3 , -0-CH,
  • indices w and x represent stoichiometric coefficients which, independently of one another, are 0 to 500, preferably 10 to 250.
  • the distribution of the repeating units over the chain can not only be purely statistical, but can also be block-like, alternating or gradient-like.
  • R 2 can symbolize an aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (C 1 -C 5 o) hydrocarbon radical
  • R 7 stands for further Si-containing groups. Preferred R 7 radicals are -0-Si (CH 3 ) 3 , -0-Si (Ph) 3 , -0-Si (0-Si (CH 3 ) 3) 2 CH 3 ) and -0-Si (0-Si (Ph) 3 ) 2 Ph). If R 2 represents an element of the group [-ZR 1 ], it is a matter of difunctional monomers which can be used for crosslinking the resulting polymer structures.
  • Formula (I) describes not only vinylically functionalized, silicone-containing polymer species with a typical polymer distribution, but also defined compounds with discrete molecular weights.
  • Particularly preferred silicone-containing components are the following acrylic or methacrylic modified silicone-containing components:
  • the content of silicon-containing components can be up to 99.9% by weight, preferably 0.5 to 30% by weight, particularly preferably 1 to 20% by weight.
  • Suitable polymerizable, fluorine-containing components E) are all at least mono-olefinically unsaturated compounds which are capable of radical copolymerization under the reaction conditions chosen in each case.
  • the distribution of the individual fluorine-containing monomers across the resulting polymer chains does not necessarily have to be statistical.
  • the formation of, for example, block (also multiblock) or gradient-like structures is also within the meaning of the invention.
  • Combinations of two or more different fluorine-containing components E) are also possible, monofunctional representatives leading to the formation of comb-shaped structures, whereas di-, tri- or polyfunctional components E) lead to at least partially crosslinked structures.
  • Preferred fluorine-containing components E) are those of the formula (II).
  • R 1 represents a polymerizable function from the group of vinylically unsaturated compounds, which is suitable for building polymer structures by radical means.
  • a suitable chemical bridge Y is required to bond the fluorine-containing group to the reactive end group R 1 .
  • Preferred bridges Y are -O-, -0 (0) -, -C (0) -0-, -S-, -0-CH 2 -CH (0 -) - CH 2 OH, -0-CH 2 - CH (OH) -CH 2 -0-, -0-SOz-O-, -0-S (0) -0-, -PH-, -P (CH 3 ) -, -PO3-, -NH-, -N (CH 3 ) -, -O- CrC ⁇ oJ alkyl-O-, -O-phenyl-O-, -O-benzyl-O-, -0- (C 5 -C 8 ) cycloalkyl-0-, - 0- (C r C 5 o) alkenyl-0-, -0- (CH (CH 3 ) -CH 2 -0) n-, -0- (CH 2 -CH 2 -0) n - and
  • n, m and o independently of one another are numbers from 0 to 200 and the distribution of the EO and PO units can be statistical or block-shaped.
  • R and s are stoichiometric coefficients that independently represent numbers from 0 to 200.
  • Preferred fluorine-containing components E) according to formula (II) are perfluorohexylethanol methacrylate, perfluorohexoylpropanol methacrylate, perfluorooctyethanol methacrylate, perfluorooctylpropanol methacrylate, perfluorhexylethanolylpolygycolether methacrylate, perfluorhexoyl propanolcol polyglycol [ethyl glycol]
  • Perfluorooctylethanolyl poly [ethyl glycol block co-propylene glycol ether] methacrylate, perfluorooctyl propanolyl polypropylene glycol ether methacrylate.
  • the content of fluorine-containing components can be up to 99.9% by weight, preferably 0.5 to 30% by weight, particularly preferably 1 to 20% by weight.
  • the macromonomers F) are at least simple olefinically functionalized polymers with one or more discrete repeating units and a number average molecular weight greater than or equal to 200 g / mol. Mixtures of chemically different macromonomers F) can also be used in the copolymerization.
  • the macromonomers are polymeric structures which are composed of one or more repeating unit (s) and have a molecular weight distribution which is characteristic of polymers.
  • Preferred macromonomers F) are compounds of the formula (III).
  • R 1 represents a polymerizable function from the group of vinylically unsaturated compounds which are suitable for building polymeric structures by radical means.
  • a suitable bridging group Y is required to connect the polymer chain to the reactive end group.
  • Preferred bridges Y are -O-, rC (O) -, -0 (O) -O-, -S-, -0-CH 2 -CH (0 -) - CH 2 OH, -0-CH 2 -CH (OH) -CH 2 0-, -0-S0 2 -0-,
  • Repeat units A, B, C and D represent.
  • Preferred repeating units A, B, C and D are derived from acrylamide, methacrylamide,
  • Methyl methacrylate acrylonitrile, maleic acid, vinyl acetate, styrene, 1, 3-butadiene,
  • Isoprene isobutene, diethylacrylamide and diisopropylacrylamide.
  • indices v, w, x and z in formula (III) represent the stoichiometric coefficients relating to the repeating units A, B, C and D.
  • v, w, x and z are independently 0 to 500, preferably 1 to 30, the
  • R 2 denotes a linear or branched aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (Ci-CsoJ hydrocarbon residue, OH, -NH 2 , -N (CH 3 ) 2 or is equal to the structural unit [-YR 1 ].
  • Particularly preferred macromonomers F) are acrylic or methacrylic monofunctionalized alkyl ethoxylates of the formula (IV).
  • R 3 , R 4 , R 5 and R ⁇ independently of one another are hydrogen or n-aliphatic, iso-aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (CrC3o) hydrocarbon radicals.
  • R 3 and R 4 are preferably H or -CH3, particularly preferably H; R5 is the same
  • R 6 is an n-aliphatic, iso-aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (C1-C30) -
  • Ethylene oxide units (EO) and propylene oxide units (PO), v and w are independently 0 to 500, preferably 1 to 30, the sum of v and w having to be> 1 on average.
  • Macromonomer chains can be statistical, block-like, alternating or gradient-like.
  • Y stands for the bridges mentioned above.
  • Also particularly suitable as macromonomers F) are esters of (meth) acrylic acid with
  • Genapo .1l® types are products from Clariant GmbH.
  • the molecular weight of the macromonomers F) is preferably 200 g / mol to 10 6 g / mol, particularly preferably 150 to 10 4 g / mol and particularly preferably 200 to 5000 g / mol.
  • suitable macromonomers up to 99.9% by weight can be used.
  • Fractions of 1 to 20% by weight and 75 to 95% by weight are particularly preferred.
  • Preferred copolymers are those which can be obtained by copolymerizing at least components A), B) and F). Also preferred as copolymers are those which can be obtained by copolymerizing at least components A), C) and F).
  • copolymers are those which can be obtained by copolymerizing at least components A), F) and G).
  • copolymers are those which can be obtained by copolymerizing at least components A), B) and G).
  • the copolymerization is carried out in the presence of at least one polymeric additive G), the additive G) being added to the polymerization medium in whole or in part in solution before the actual copolymerization.
  • the use of several additives G) is also according to the invention.
  • Crosslinked additives G) can also be used.
  • additives G) or their mixtures only have to be wholly or partly soluble in the chosen polymerization medium.
  • additive G) has several functions. On the one hand, it prevents the formation of over-crosslinked polymer fractions in the copolymer being formed in the actual polymerization step and, on the other hand, the additive G) is statistically attacked by active radicals in accordance with the generally known mechanism of graft copolymerization. As a result, depending on the additive G), more or less large amounts of it are incorporated into the copolymers.
  • suitable additives G) have the property of changing the solution parameters of the copolymers which form during the radical polymerization reaction in such a way that the average molecular weights are shifted to higher values.
  • those which were produced with the addition of additives G) advantageously show a significantly higher viscosity in aqueous solution.
  • Preferred additives G) are homo- and copolymers soluble in water and / or alcohols, preferably in t-butanol. Copolymers are also to be understood as meaning those with more than two different types of monomers. Particularly preferred additives G) are homopolymers and copolymers of N-vinylformamide, N-vinyl acetamide, N-vinyl pyrrolidone, ethylene oxide, propylene oxide, acryloyldimethyltauric acid, N-vinyl caprolactam, N-vinyl methylacetamide, acrylamide, acrylic acid, methacrylic acid, N-vinyl morpholide, hydroxyethyl methacrylate, Diallyldimethylammonium chloride (DADMAC) and / or [2- (methacryloyloxy) ethyl] trimethylammonium chloride (MAPTAC); Polyalkylene glycols and / or alkyl polyglycols.
  • Particularly preferred additives G) are polyvinylpyrrolidones (such as Luviskol K15 ®, K20 ® and K30 ® from BASF), poly (N-vinylformamides), poly (N-vinylcaprolactams) and copolymers of N-vinylpyrrolidone, N-vinylformamide and / or acrylic acid which can also be partially or completely saponified.
  • polyvinylpyrrolidones such as Luviskol K15 ®, K20 ® and K30 ® from BASF
  • poly (N-vinylformamides) poly (N-vinylcaprolactams)
  • copolymers of N-vinylpyrrolidone, N-vinylformamide and / or acrylic acid which can also be partially or completely saponified.
  • the molecular weight of the additives G) is preferably 10 2 to 10 7 g / mol, particularly preferably 0.5 * 10 4 to 10 6 g / mol.
  • the amount of polymeric additive G) used is based on
  • Total mass of the monomers to be polymerized in the copolymerization preferably 0.1 to 90% by weight, particularly preferably 1 to 20% by weight and particularly preferably 1.5 to 10% by weight.
  • the copolymers according to the invention are crosslinked, i.e. they contain comonomers with at least two polymerizable vinyl groups.
  • Preferred crosslinkers are methylene bisacrylamide; methylenebismethacrylamide; Esters of unsaturated mono- and polycarboxylic acids with polyols, preferably diacrylates and triacrylates or methacrylates, particularly preferably butanediol and ethylene glycol diacrylate or methacrylate, trimethylolpropane triacrylate (TMPTA) and trimethylolpropane trimethacrylate (TMPTMA); Allyl compounds, preferably allyl (meth) acrylate, triallyl cyanurate, maleic acid diallyl ester, polyallyl ester, tetraallyloxyethane, triallylamine, tetraallylethylene diamine; Allyl esters of phosphoric acid; and / or vinylphosphonic acid derivatives.
  • TMPTA trimethylolpropane triacrylate
  • TMPTMA trimethylolpropane trimethacrylate
  • Allyl compounds preferably allyl (meth) acryl
  • Trimethylolpropane triacrylate is particularly preferred as the crosslinking agent.
  • the weight fraction of crosslinking comonomers, based on the total mass of the copolymers, is preferably up to 20% by weight, particularly preferably 0.05 to 10% by weight and particularly preferably 0.1 to 7% by weight.
  • All organic or inorganic solvents can be used as the polymerization medium which are largely inert with respect to radical polymerization reactions and which advantageously permit the formation of medium or high molecular weights.
  • Water is preferred; lower alcohols; preferably methanol, ethanol, propanols, iso-, sec- and t-butanol, particularly preferably t-butanol; Hydrocarbons with 1 to 30 carbon atoms and mixtures of the aforementioned compounds.
  • the polymerization reaction is preferably carried out in the temperature range between 0 and 150 ° C., particularly preferably between 10 and 100 ° C., both under normal pressure and under elevated or reduced pressure. If necessary, the polymerization can also be carried out under a protective gas atmosphere, preferably under nitrogen.
  • High energy electromagnetic radiation, mechanical energy or the usual chemical polymerization initiators such as organic peroxides, e.g. Benzoyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide, cumene hydroperoxide, dilauroyl peroxide or azo initiators, such as e.g. Azodiisobutyronitrile (AIBN) can be used.
  • organic peroxides e.g. Benzoyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide, cumene hydroperoxide, dilauroyl peroxide or azo initiators, such as e.g. Azodiisobutyronitrile (AIBN)
  • AIBN Azodiisobutyronitrile
  • inorganic peroxy compounds such as (NH 4 ) 2S 2 ⁇ 8 , K 2 S 2 0 8 or H 2 O2, optionally in combination with reducing agents (e.g. sodium bisulfite, ascorbic acid, iron (II) sulfate etc.) or redox systems , which contain an aliphatic or aromatic sulfonic acid (eg benzenesulfonic acid, toluenesulfonic acid etc.) as reducing component.
  • reducing agents e.g. sodium bisulfite, ascorbic acid, iron (II) sulfate etc.
  • redox systems which contain an aliphatic or aromatic sulfonic acid (eg benzenesulfonic acid, toluenesulfonic acid etc.) as reducing component.
  • All solvents can be used as the polymerization medium which are largely inert with respect to radical polymerization reactions and which permit the formation of high molecular weights.
  • Water and lower, tertiary alcohols or hydrocarbons having 3 to 30 carbon atoms are preferably used.
  • t-butanol is used as the reaction medium.
  • Mixtures of two or more representatives of the potential solvents described are of course also according to the invention. This also includes emulsions of immiscible solvents (e.g. water / hydrocarbons).
  • reaction control which lead to the polymer structures according to the invention are suitable (solution polymerization, emulsion process, precipitation process, high-pressure process, suspension process, bulk polymerization, gel polymerization, etc.).
  • Precipitation polymerization is particularly suitable, particularly preferably precipitation polymerization in tert-butanol.
  • AMPS 2-acrylamido-2-methylpropane sulfonic acid
  • the contents of the flask were rendered inert with nitrogen while stirring and heated to 60 ° C. using a heating bath.
  • AMPS 2-acrylamido-2-methylpropane sulfonic acid
  • 20.0 g of an ester formed from methacrylic acid and (C 22 ) - fatty alcohol polyglycol ether with 25 EO units were added.
  • the contents of the flask were rendered inert with nitrogen while stirring and heated to 60 ° C. using a heating bath. After the temperature had been reached, 1.5 g of dilauroyl peroxide were added as an initiator and the mixture was heated to 80 ° C. while purging with nitrogen. The mixture was stirred under reflux at the specified temperature for 4 hours. After the reaction had ended, the polymer was isolated by suction removal of the solvent and subsequent vacuum drying.
  • the following list shows 93 copolymers which are particularly suitable for the formulation of the agents according to the invention.
  • the various copolymers No. 1 to No. 93 can be obtained according to the following production processes 1, 2, 3 and 4.
  • Butanol can be produced.
  • the monomers were initially introduced into t-butanol, the reaction mixture was rendered inert, and the reaction was then started after heating to 60 ° C. by adding the corresponding t-butanol-soluble initiator (preferably dilauroyl peroxide). After the reaction has ended (2 hours), the polymers are isolated by suction extraction of the solvent and subsequent vacuum drying.
  • polymers are after the gel polymerization process in water produced.
  • the monomers are dissolved in water, the reaction mixture is rendered inert, and the reaction is then started after heating to 65 ° C. by adding suitable initiator or initiator systems (preferably Na 2 S 2 0 8 ).
  • suitable initiator or initiator systems preferably Na 2 S 2 0 8 .
  • the polymer gels are then crushed and the polymers isolated after drying.
  • These polymers can be prepared in water using the emulsion process.
  • the monomers are mixed in a water / organ mixture.
  • Solvent preferably cyclohexane
  • emulsifier emulsifier
  • the reaction mixture is rendered inert using N 2 and the reaction is then started after heating to 80 ° C. by adding suitable initiator or initiator systems (preferably Na2S 2 0 8 ).
  • suitable initiator or initiator systems preferably Na2S 2 0 8 .
  • the polymer emulsions are then evaporated (cyclohexane acts as a tug for water), thereby isolating the polymers.
  • Monomers are initially introduced in the solvent, the reaction mixture is rendered inert, and the reaction is then heated to 70 ° C. by adding suitable ones
  • Initiator or initiator systems (preferably dilauroyl peroxide) started.
  • the reaction mixture is by customary methods and according to the particular
  • Copolymers containing acryloyldimethyltaurate both in crosslinked and in uncrosslinked form While networked systems e.g. Outstanding property profiles with regard to emulsion stabilization showed, especially with the help of the uncrosslinked variants that electrolyte-containing systems could be thickened, which are known to be very difficult or impossible to thicken with polyelectrolytes.
  • the polymers according to the invention are also suitable as thickeners and dispersants, as emulsifiers, suspending agents with thickening action and as consistency agents for emulsions and suspensions, and as, adhesives,
  • the emulsifying, stabilizing and / or consistency effect of the polymers according to the invention in emulsions is caused or enhanced by an association of the polymer side chains with one another, and by an interaction of the polymer side chains with the hydrophobic oil components.
  • Polymers with a high proportion of hydrophobic side chains have a high dispersing or emulsifying capacity and a high susceptibility to the agents.
  • the polymers according to the invention are suitable for use in solvent concentrates (SL), water-soluble granules (SG), soluble powders (SP), suspension concentrates (SC), emulsifiable concentrates (EC), oil-in-water emulsions (EW) , water-in-oil emulsion (EO), emulsifiable oil suspension (ES), microemulsions (ME), multible emulsions (O / W / O), suspoemulsions (SE), capsule suspensions (CS), granules (GR), tablets (TB), wettable poders (WP), water-dispersible granules (WG).
  • solvent concentrates SL
  • SG water-soluble granules
  • SP soluble powders
  • SC suspension concentrates
  • EC emulsifiable concentrates
  • EW oil-in-water emulsions
  • EO water-in-oil emulsion
  • ES emulsifiable oil suspension
  • the crop protection agents according to the invention can contain pesticides from the group of the herbicides, insecticides, fungicides, acaricides, bactericides, molluscids, nematicides and / or rodenticides.
  • Suitable herbicides are, without restricting the invention to these, in particular glyphosates, their salts and / or derivatives, but also acifluorfen, asulam, benazolin, bentazone, bilanafos, bromacil, bromoxynil, chloramben, clopyralide, 2,4-D, 2,4 -DB, Dalapon, Dicamba, Dichlorprop, Diciofop, Endothall, Fenac, Fenoxaprop, Flamprop, Fluazifop, Flumiclorac, Fluoroglycofen, Fomesafen, Fosamine, Glufosinate, Haloxyfop, Imazapic, Imazamethabenz, Imazamox, MazyrpCP, Imazamethazz , Mecoprop, Methylarsonic acid / MSMA, Naptalam, Picioram, Quinclorac, Quizalofop, 2,3,6-TBA and TCA.
  • Preferred fungicidal active ingredients are amino derivatives, such as 8- (1,1-dimethylethyl) -nethyl-N-propyl-1,4-dioxaspiro [4,5] decane-2-methamine (spiroxamines) and fenpropidine, and also morpholine derivatives such as aldimorph, dodemorph and fenpropimorph.
  • compositions according to the invention can be used in almost the AMPS copolymers any amount included.
  • formulations as "tank mix” and “ready to use compositions” contain 0.001 to 10% by weight, preferably 0.05 to 2% by weight of pesticide and 0.01 to 10% by weight, preferably 0.1 to 2% by weight, particularly preferably 0.2 to 1% by weight of AMPS copolymer.
  • the weight ratio of AMPS copolymer to pesticide can be between 1:10 to 500: 1, in particular 1: 4 to 4: 1.
  • Concentrate formulations which are diluted before use, can contain the pesticide in amounts by weight of 5 to 60%, preferably 20 to 40%, and the AMPS copolymer in amounts of 3% by weight to 50% by weight.
  • Weight ratio of AMPS copolymer to pesticide can be between 1:20 to 1: 1, preferably 1:10 to 1: 2.
  • the formulations according to the invention can be prepared in solid form as powders, pellets, tablets or granules, which are dissolved in water before use.
  • Solid preparations can contain the pesticide in the amounts by weight from 20% to 80%, preferably from 50% to 75%, particularly preferably from 60% to 70% and the AMPS copolymer in the amount by weight from 5% to 50%, preferably 10% to 30 %, contain.
  • the formulations according to the invention can moreover include the customary thickeners, anti-gel agents, freezing agents, solvents, dispersants, emulsifiers, preservatives, further adjuvants, diluents, binders, anti-foaming agents, evaporation inhibitors, buffers, neutralizing agents, cold stabilizers, disintegrants and wetting agents, but also agrochemical salts, preferably ammonium salts , particularly preferably ammonium sulfate, ammonium nitrate, and / or phosphate.
  • Xanthan gum and / or cellulose for example carboxy-, methyl-, ethyl- or propyl cellulose, silicas and attapulgite in weight amounts of 0.01 to 5% based on the finished agent can be used as thickeners.
  • Suitable organic solvents are all customary organic solvents which, on the one hand, are not very miscible with water, but on the other hand dissolve the active ingredients well or form a suitable continuous phase.
  • Aliphatic and aromatic hydrocarbons such as toluene, xylene, carbon tetrachloride, chloroform, methylene chloride, dichloroethane, ester and ethyl acetate may be mentioned as preferred.
  • halogenated hydrocarbons such as toluene, xylene, carbon tetrachloride, chloroform, methylene chloride, dichloroethane, ester and ethyl acetate may be mentioned as preferred.
  • Organic acids and their esters for example ascorbic acid, ascorbic palmitate, sorbate, benzoic acid, methyl and propyl 4-hydroxybenzoate, propionates, phenol, for example 2-phenylphenate, 1, 2-benzisothiazolin-3-one, formaldehyde, sulfuric acid can be used as preservatives and their salts, Preventol and Proxel are used.
  • Fatty acid alkyl ester alkoxylates are suitable as defoamers; Organopolysiloxanes such as polydimethylsiloxanes and their mixtures with microfine, optionally signed silica; paraffins; Waxes and microcrystalline waxes and their mixtures with signed silica. Mixtures of different foam inhibitors, e.g. those made of silicone oil, paraffin oil and / or waxes.
  • 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.
  • Nonionic, amphoteric, cationic and anionic surfactants are suitable as dispersants and emulsifiers.
  • Suitable surface-active substances are preferably adducts of 2 to 30 mol of ethylene oxide and / or 0 to 5 mol of propylene oxide with linear fatty alcohols with 8 to 22 C atoms, with fatty acids with 12 to 22 C atoms, with mono-, di- and / or trialkylphenols with 8 to 15 carbon atoms in the alkyl group and at (C 8 -C 8 ) - alkylamines; secondary ether amines and alkoxylated secondary ether amine derivatives; (C ⁇ 2 -C ⁇ 8 ) fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol; Glycerol mono- and diesters and sorbitan / sorbitol mono- and diesters of saturated and unsaturated fatty acids with 6 to 22 carbon atoms and their ethylene oxide addition products; Addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hard
  • anionic surfactants for example alkali and ammonium salts of linear or branched alkyl (en) sulfates with 8 to 22 carbon atoms, (Ci 2 -C 8 ) alkyl sulfonic acids and (Ci 2 -C 8 ) alkylarylsulfonic acids;
  • polyvinylpyrrolidone for solid formulations, polyvinylpyrrolidone, polyvinyl alcohol, carboxymethyl cellulose, sugar, for example sucrose, sorbitol, or starch are suitable as binders.
  • Carbon black, tallow, kaolin, aluminum, calcium or magnesium stearate, sodium tripolyphosphate, sodium tetraborate, sodium sulphate, silicates and sodium benzoate are suitable as thinners, absorbers or carriers.
  • Cellulose for example carboxymethyl cellulose, polyvinylpyrrolidone, sodium or potassium acetate, carbonates, bicarbonates, sesquicarbonates, ammonium sulfate or potassium hydrogen phosphate act as disintegrants.
  • Alcohol ethoxylates / propoxylates can be used as wetting agents.
  • formulations according to the invention can be used according to the customary methods.
  • Aqueous concentrates and solid formulations are diluted with the appropriate amount of water before application.
  • Pesticide amounts in the range of 0.1 to 5 kg, preferably 0.3 to 2.5 kg, are applied per hectare.
  • the proportion of the adjuvant AMPS copolymer according to the invention is in the range from 0.1 to 3.0 kg / ha.
  • the volume of the pesticide formulation created for spraying is in the range from 50 to 1000 l / ha.
  • the use of the polymers gives the user extensive freedom in the choice of their components.
  • the formulations show a high compatibility of the components with each other (pesticides, salts, adjuvants etc.), a high solubility of the pesticides and agrochemical salts as well as an excellent storage stability.
  • the polymers act as solubilizers. Salt-out effects are suppressed or minimized.
  • the formulations are usually adjusted to a pH in the range 2 to 12, preferably pH 3 to 8.
  • Emulsion concentrates (EC) (comparative example) (according to the invention)
  • Emulsion concentrates (EC) (comparative example) (according to the invention)
  • Plant protection agent using a high-speed stirrer e.g. Ultra-Turrax
  • a high-speed stirrer e.g. Ultra-Turrax
  • Solvesso 150 (Exxon Chemicals) aromatic hydrocarbon mixture dispersant LFS (Clariant GmbH) poly (arylalkyl) phenol polyethylene glycol phosphoric acid salt
  • Phenylsulfonate CA (Clariant GmbH) calcium alkylbenzenesulfonate Emulsogen EL (Clariant GmbH) ethoxylated vegetable oil Defoamer SE 57 (Wacker) polydimethylsiloxane + filler

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  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Toxicology (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne des produits phytosanitaires, contenant au moins un copolymère pouvant être obtenu par copolymérisation radicalaire A) d'acryloyldiméthyltaurine et/ou d'acryloyldiméthyltaurates, B) éventuellement d'un ou de plusieurs autres comonomères non cationiques, oléfiniquement insaturés, C) éventuellement d'un ou de plusieurs comonomères cationiques, oléfiniquement insaturés, D) éventuellement d'un ou de plusieurs composants renfermant du silicium, E) éventuellement d'un ou de plusieurs composants fluorés, F) éventuellement d'un ou de plusieurs macromonomères, G) la copolymérisation s'effectuant éventuellement en présence d'au moins un additif polymère, H) à condition que le composant A) soit copolymérisé avec au moins un composant sélectionné dans un des groupes D) à G).
PCT/EP2003/001272 2002-02-16 2003-02-10 Produits phytosanitaires WO2003067981A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008046075A1 (de) * 2008-09-08 2010-03-11 Evonik Röhm Gmbh (Meth)acrylatmonomer, Polymer sowie Beschichtungsmittel

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996000251A1 (fr) * 1994-06-24 1996-01-04 The Dow Chemical Company Nouveau copolymers greffes amphipatiques, leur preparation, compositions et procedes d'utilisation
WO1999066004A1 (fr) * 1998-06-15 1999-12-23 The Lubrizol Corporation Procede d'utilisation d'une composition aqueuse contenant un polymere synthetique hydrosoluble ou dispersable dans l'eau
EP1069142A1 (fr) * 1999-07-15 2001-01-17 Clariant GmbH Polymères solubles dans l'eau et leur utilisation dans des produits cosmétiques et pharmaceutiques
WO2001060877A1 (fr) * 2000-02-16 2001-08-23 Clariant Gmbh Copolymeres et leur utilisation en tant qu'agents anti-derive

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996000251A1 (fr) * 1994-06-24 1996-01-04 The Dow Chemical Company Nouveau copolymers greffes amphipatiques, leur preparation, compositions et procedes d'utilisation
WO1999066004A1 (fr) * 1998-06-15 1999-12-23 The Lubrizol Corporation Procede d'utilisation d'une composition aqueuse contenant un polymere synthetique hydrosoluble ou dispersable dans l'eau
EP1069142A1 (fr) * 1999-07-15 2001-01-17 Clariant GmbH Polymères solubles dans l'eau et leur utilisation dans des produits cosmétiques et pharmaceutiques
WO2001060877A1 (fr) * 2000-02-16 2001-08-23 Clariant Gmbh Copolymeres et leur utilisation en tant qu'agents anti-derive

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008046075A1 (de) * 2008-09-08 2010-03-11 Evonik Röhm Gmbh (Meth)acrylatmonomer, Polymer sowie Beschichtungsmittel

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