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WO2003067981A1 - Plant protecting agents - Google Patents

Plant protecting agents 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
Other languages
German (de)
French (fr)
Inventor
Michael Marcus Walter
Roman MORSCHHÄUSER
Ralf Zerrer
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Clariant Gmbh
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Filing date
Publication date
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Publication of WO2003067981A1 publication Critical patent/WO2003067981A1/en

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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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Abstract

The invention relates to plant protecting agents containing at least one copolymer, obtained by radical copolymerisation of A) acryloyldimethyltaurine acid and/or acryloyldimethyltaurates, B) optionally, one or more other olefinically unsaturated, non cationic comonomers, C) optionally one or more olefinically unsaturated, cationic comonomers, D) optionally one or more components containing silicon, E) optionally one or more components containing fluorine, F) optionally one or more macromonomers, G) whereby the copolymerisation occurs optionally in the presence of at least one polymer additive, H) under the proviso that component A) is copolymerised with at least one component selected from one of the groups D) - G).

Description

Beschreibung description
PflanzenschutzmittelPesticides
Die vorliegende Erfindung betrifft die Verwendung von kammförmigen, Acryloyldimethyltaurat enthaltenden Copolymeren in Pflanzenschutzmitteln.The present invention relates to the use of comb-shaped copolymers containing acryloyldimethyltaurate in crop protection agents.
Pestizide (Herbizide, Insektizide, Fungizide, Bakterizide, Molluskide, Nematizide und Rodentizide) sind chemische oder natürliche Substanzen, die in Pflanzenzellen,Pesticides (herbicides, insecticides, fungicides, bactericides, molluscides, nematicides and rodenticides) are chemical or natural substances found in plant cells,
-geweben oder parasitäre Organismen in oder auf der Pflanze eindringen und- tissue or parasitic organisms penetrate into or on the plant and
Unkraut und Pflanzenschädlinge schädigen und/oder zerstören.Damage and / or destroy weeds and plant pests.
Den größten Anteil an Pestiziden stellen Herbizide, gefolgt von Insektiziden undThe largest proportion of pesticides are herbicides, followed by insecticides and
Fungiziden. Pestizide Mittel und Mischungen lassen sich unverdünnt oder vorzugsweise verdünnt einsetzen in Form von Lösungen, Emulsionen, Mikroemulsionen, Suspensionen, Dispersionen, Pulver, Schäume, Pasten, Granulate, sowie Aerosole. Je nach Art und Eigenschaften der biozid wirksamen Substanzen sind zur Formulierung des Wirkstoffes bestimmte Zusätze erforderlich, um die gewünschten anwendungstechnischen Eigenschaften bezüglich Löslichkeit, Viskosität, Dispergier- und Emulgiervermögen, Kristallisationsinhibierung, Haft- und Netzvermögen, Antibackverhalten, Kompatibilität etc. zu bewerkstelligen.Fungicides. 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. Depending on the type and properties of the biocidally active substances, 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.
Es wurde nun gefunden, dass eine neue Polymerfamilie auf der Basis vonIt has now been found that a new family of polymers based on
Acryloyldimethyltaurinsäure sowohl als Verdicker, Konsistenzgeber, Emulgator, Dispergator, und/oder Stabilisator, Kristallisationsinhibitor, sowie Haft- und Netzmittel dienen kann und sich zur Formulierung einer Vielzahl von pestizidhaltigen Formulierungen hervorragend eignet.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.
Gegenstand dieser Erfindung sind daher Pflanzenschutzmittel, enthaltend mindestens ein Copolymer, erhältlich durch radikalische Copolymerisation von A) Acryloyldimethyltaurinsäure und/oder Acryloyldimethyltauraten,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,
B) gegebenenfalls einem oder mehreren weiteren olefinisch ungesättigten, nicht kationischen, gegebenenfalls vernetzenden, Comonomeren, die wenigstens ein Sauerstoff-, Stickstoff-, Schwefel- oder Phosphoratom aufweisen und ein Molekulargewicht kleiner 500 g/mol besitzen,B) optionally one or more further olefinically unsaturated, non-cationic, optionally crosslinking, comonomers which have at least one oxygen, nitrogen, sulfur or phosphorus atom and have a molecular weight of less than 500 g / mol,
C) gegebenenfalls einem oder mehreren olefinisch ungesättigten, kationischen Comonomeren, die wenigstens ein Sauerstoff-, Stickstoff-, Schwefel- oder Phosphoratom aufweisen und ein Molekulargewicht kleiner 500 g/mol besitzen, D) gegebenenfalls einer oder mehreren mindestens monofunktionellen, zur radikalischen Polymerisation befähigten, siliziumhaltigen Komponente(n),C) optionally one or more olefinically unsaturated, cationic comonomers which have at least one oxygen, nitrogen, sulfur or phosphorus atom and have a molecular weight of less than 500 g / mol, D) optionally one or more at least monofunctional radicals capable of free-radical polymerization, silicon-containing component (s),
E) gegebenenfalls einer oder mehreren mindestens monofunktionellen, zur radikalischen Polymerisation befähigten, fluorhaltigen Komponente(n),E) optionally one or more at least monofunctional fluorine-containing component (s) capable of radical polymerization,
F) gegebenenfalls einem oder mehreren einfach oder mehrfach olefinisch ungesättigten, gegebenenfalls vernetzenden, Makromonomeren, die jeweils mindestens ein Sauerstoff-, Stickstoff-, Schwefel- oder Phosphoratom besitzen und ein zahlenmittleres Molekulargewicht größer oder gleich 200 g/mol aufweisen, wobei es sich bei den Makromonomeren nicht um eine siliziumhaltige Komponente D) oder fluorhaltige Komponente E) handelt,F) optionally one or more mono- or poly-olefinically unsaturated, optionally crosslinking, macromonomers, each having at least one oxygen, nitrogen, sulfur or phosphorus atom and having a number-average molecular weight greater than or equal to 200 g / mol, where it is in the Macromonomers are not silicon-containing component D) or fluorine-containing component E),
G) wobei die Copolymerisation gegebenenfalls in Gegenwart mindestens eines polymeren Additivs mit zahlenmittleren Molekulargewichten von 200 g/mol bis 109 g/mol erfolgt,G) the copolymerization optionally taking place in the presence of at least one polymeric additive with number-average molecular weights of 200 g / mol to 10 9 g / mol,
H) mit der Maßgabe, dass die Komponente A) mit mindestens einer Komponente ausgewählt aus einer der Gruppen D) bis G) copolymerisiert wird.H) with the proviso that component A) is copolymerized with at least one component selected from one of groups D) to G).
Die erfindungsgemäßen Copolymere besitzen bevorzugt ein Molekulargewicht von 103 g/mol bis 109 g/mol, besonders bevorzugt von 104 bis 107 g/mol, insbesondere bevorzugt 5*104 bis 5*106 g/mol.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.
Bei den Acryloyldimethyltauraten kann es sich um die anorganischen oder organischen Salze der Acryloyldimethyltaurinsäure (Acrylamidopropyl-2-methyl-2- sulfonsäure) handeln. Bevorzugt werden die Li+-, Na+-, K+-, Mg++-, Ca++-, A ++- und/oder NH4 +-Salze. Ebenfalls bevorzugt sind die Monoalkylammonium-, Dialkylammonium-, Trialkylammonium- und/oder Tetraalkylammoniumsalze, wobei es sich bei den Alkylsubstituenten der Amine unabhängig voneinander um (CrC22)-Alkylreste oder (C2-Cι0)-Hydroxyalkylreste handeln kann. Weiterhin sind auch ein bis dreifach ethoxylierte Ammoniumverbindungen mit unterschiedlichem Ethoxylierungsgrad bevorzugt. Es sollte angemerkt werden, dass auch Mischungen von zwei- oder mehreren der oben genannten Vertreter im Sinne der Erfindung sind.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.
Der Neutralisationsgrad der Acryloyldimethyltaurinsäure kann zwischen 0 und 100 % betragen, besonders bevorzugt ist ein Neutralisationsgrad von oberhalb 80 %.The degree of neutralization of acryloyldimethyltauric acid can be between 0 and 100%, a degree of neutralization of above 80% is particularly preferred.
Bezogen auf die Gesamtmasse der Copolymere beträgt der Gehalt an Acryloyldimethyltaurinsäure bzw. Acryloyldimethyltauraten mindestens 0,1 Gew.-%, bevorzugt 20 bis 99,5 Gew.-%, besonders bevorzugt 50 bis 98 Gew.-%.Based on the total mass of the copolymers, 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.
Als Comonomere B) können alle olefinisch ungesättigten, nicht kationischenAll olefinically unsaturated, non-cationic ones can be used as comonomers B)
Monomere eingesetzt werden, deren Reaktionsparameter eine Copolymerisation mit Acryloyldimethyltaurinsäure und/oder Acryloyldimethyltauraten in den jeweiligen Reaktionsmedien erlauben. Als Comonomere B) bevorzugt sind ungesättigte Carbonsäuren und deren Anhydride und Salze, sowie deren Ester mit aliphatischen, olefinischen, cycloaliphatischen, arylaliphatischen oder aromatischen Alkoholen mit einer Kohlenstoffzahl von 1 bis 30.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.
Als ungesättigte Carbonsäuren besonders bevorzugt sind Acrylsäure, Methacrylsäure, Styrolsulfonsäure, Maleinsäure, Fumarsäure, Crotonsäure, Itaconsäure und Seneciosäure.Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, styrene sulfonic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid and senecioic acid.
Als Gegenionen bevorzugt sind Li+, Na+, K+, Mg++, Ca++, Al+++, NH4 +, Monoalkylammonium-, Dialkylammonium-, Trialkylammonium- und/oder Tetraalkyl- ammoniumreste, wobei es sich bei den Alkylsubstituenten der Amine unabhängig voneinander um (Cι-C22)-Alkylreste oder (C2-Cι0)-Hydroxyalkylreste handeln kann.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 (Cι-C22) alkyl or (C 2 -Cι 0) can act from one another -hydroxyalkyl.
Zusätzlich können auch ein bis dreifach ethoxylierte Ammoniumverbindungen mit unterschiedlichem Ethoxylierungsgrad Anwendung finden. Der Neutralisationsgrad der Carbonsäuren kann zwischen 0 und 100 % betragen. Als Comonomere B) weiterhin bevorzugt sind offenkettige N-Vinylamide, bevorzugt N-Vinylformamid (VIFA), N-Vinylmethylformamid,In addition, one to three times ethoxylated ammonium compounds with different degrees of ethoxylation can also be used. The degree of neutralization of the carboxylic acids can be between 0 and 100%. Also preferred as comonomers B) are open-chain N-vinylamides, preferably N-vinylformamide (VIFA), N-vinylmethylformamide,
N-Vinylmethylacetamid (VIMA) und N-Vinylacetamid; cyclische N-VinylamideN-vinyl methylacetamide (VIMA) and N-vinylacetamide; cyclic N-vinyl amides
(N-Vinyllactame) mit einer Ringgröße von 3 bis 9, bevorzugt N-Vinylpyrrolidon(N-vinyl lactams) with a ring size of 3 to 9, preferably N-vinyl pyrrolidone
(NVP) und N-Vinylcaprolactam; Amide der Acryl- und Methacrylsäure, bevorzugt Acrylamid, Methacrylamid, N,N-Dimethyl-acrylamid, N,N-Diethylacrylamid und(NVP) and N-vinylcaprolactam; Amides of acrylic and methacrylic acid, preferably acrylamide, methacrylamide, N, N-dimethyl-acrylamide, N, N-diethylacrylamide and
N,N-Diisopropylacrylamid; alkoxylierte Acryl- und Methacrylamide, bevorzugtN, N-diisopropylacrylamide; alkoxylated acrylic and methacrylamides, preferred
Hydroxyethylmethacrylat, Hydroxymethylmethacrylamid,Hydroxyethyl methacrylate, hydroxymethyl methacrylamide,
Hydroxyethylmethacrylamid, Hydroxypropylmethacrylamid undHydroxyethyl methacrylamide, hydroxypropyl methacrylamide and
Bemsteinsäuremono-[2-(methacryloyloxy)-ethylester]; N,N- Dimethylaminomethacrylat; Diethylamino-methylmethacrylat; Acryl- undBemsteinsäuremono- [2- (methacryloyloxy) ethyl ester]; N, N-dimethylaminomethacrylate; Diethylamino-methyl; Acrylic and
Methacrylamidoglykolsäure; 2- und 4-Vinylpyridin; Vinylacetat;methacrylamidoglycolic; 2- and 4-vinyl pyridine; vinyl acetate;
Methacrylsäureglycidylester; Styrol; Acrylnitril; Vinylchlorid; Stearylacrylat;methacrylate; styrene; acrylonitrile; Vinyl chloride; stearyl;
Laurylmethacrylat; Vinylidenchlorid; und/oder Tetrafluorethylen.lauryl; vinylidene chloride; and / or tetrafluoroethylene.
Als Comonomere B) ebenfalls geeignet sind anorganische Säuren und deren Salze und Ester. Bevorzugte Säuren sind Vinylphosphonsäure, Vinylsulfonsäure,Also suitable as comonomers B) are inorganic acids and their salts and esters. Preferred acids are vinylphosphonic acid, vinylsulfonic acid,
Allylphosphonsäure und Methallylsulfonsäure und deren Salze und Ester.Allylphosphonic acid and methallylsulfonic acid and their salts and esters.
Der Gewichtsanteil der Comonomere B), bezogen auf die Gesamtmasse der Copolymere, kann 0 bis 99,8 Gew.-% betragen und beträgt bevorzugt 0,5 bis 80 Gew.-%, besonders bevorzugt 2 bis 50 Gew.-%.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.
Als Comonomere C) kommen alle olefinisch ungesättigten Monomere mit kationischer Ladung in Frage, die in der Lage sind, in den gewählten Reaktionsmedien mit Acryloyldimethyltaurinsäure oder deren Salze Copolymere zu bilden. Die dabei resultierende Verteilung der kationischen Ladungen über die Ketten hinweg kann statistisch, alternierend, block- oder gradientenartig sein. Es sei darauf hingewiesen, dass unter den kationischen Comonomeren C) auch solche zu verstehen sind, die die kationische Ladung in Form einer betainischen, zwitterionischen, oder amphoteren Struktur tragen. Comonomere C) im Sinne der Erfindung sind auch aminofunktionalisierte Precursor, die durch polymeranaloge Reaktionen in Ihre entsprechenden quaternären (z.B. Reaktion mit Dimethylsulfat, Methylchlorid), zwitterionischen (z.B. Reaktion mit Wasserstoffperoxid), betainischen (z.B. Reaktion mit Chloressigsäure), oder amphomeren Derivate überführt werden können.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. It should be pointed out that 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.
Besonders bevorzugt als Comonomere C) sindAre particularly preferred as comonomers C)
Diallyldimethylammoniumchlorid (DADMAC), [2-(Methacryloyloxy)ethyl]trimethylammoniumchlorid (MAPTAC),Diallyldimethylammonium chloride (DADMAC), [2- (methacryloyloxy) ethyl] trimethylammonium chloride (MAPTAC),
[2-(Acryloyloxy)ethyl]trimethylammoniumchlorid,[2- (acryloyloxy) ethyl] trimethylammonium chloride,
[2-Methacrylamidoethyl]trimethylammoniumchlorid,[2-methacrylamidoethyl] trimethyl ammonium chloride,
[2-(Acrylamido)ethyl]trimethylammoniumchlorid,[2- (acrylamido) ethyl] trimethylammonium chloride,
N-Methyl-2-vinylpyridiniumchlorid N-Methyl-4-vinylpyridiniumchloridN-methyl-2-vinylpyridinium chloride N-methyl-4-vinylpyridinium chloride
Dimethylaminoethylmethacrylat,dimethylaminoethyl
Dimethylaminopropylmethacrylamid,dimethylaminopropylmethacrylamide,
Methacryloylethyl-N-oxid und/oderMethacryloylethyl-N-oxide and / or
Methacryloylethyl-betain.Methacryloylethyl betaine.
Der Gewichtsanteil der Comonomeren C) kann, bezogen auf die Gesamtmasse der Copolymere, 0,1 bis 99,8 Gew.-%, bevorzugt 0,5 bis 30 Gew.-% und besonders bevorzugt 1 bis 20 Gew.-% betragen.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.
Als polymerisationsfähige, siliziumhaltige Komponenten D) sind alle mindestens einfach olefinisch ungesättigten Verbindungen geeignet, die unter den jeweils gewählten Reaktionsbedingungen zur radikalischen Copolymerisation befähigt sind. Dabei muss die Verteilung der einzelnen silikonhaltigen Monomere über die entstehenden Polymerketten hinweg nicht notwendigerweise statistisch erfolgen.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.
Auch die Ausbildung von beispielsweise block- (auch multiblock-) oder gradientenartigen Strukturen ist im Sinne der Erfindung. Kombinationen von zwei oder mehreren unterschiedlichen silikonhaltigen Vertretern sind auch möglich. Die Verwendung von silikonhaltigen Komponenten mit zwei oder mehr polymerisationsaktiven Gruppen führt zum Aufbau verzweigter oder vernetzter Strukturen.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 silicone-containing representatives are also possible. The use of silicone-containing components with two or more polymerization-active groups leads to the formation of branched or cross-linked Structures.
Bevorzugte silikonhaltige Komponenten sind solche gemäß Formel (I)Preferred silicone-containing components are those of the formula (I)
R1 - Z- [(Si(R3R4)-0-)w-(Si(R5R6)-0)x-]- R2 (I).R 1 - Z- [(Si (R 3 R 4 ) -0-) w - (Si (R 5 R 6 ) -0) x -] - R 2 (I).
Dabei stellt R1 eine polymerisationsfähige Funktion aus der Gruppe der vinylisch ungesättigten Verbindungen dar, die zum Aufbau polymerer Strukturen auf radikalischem Wege geeignet ist. Bevorzugt stellt R1 einen Vinyl-, Allyl-, Methallyl-, Methylvinyl-, Acryl- (CH2=CH-CO-), Methacryl- (CH2=C[CH3]-CO-), Crotonyl-, Senecionyl-, Itaconyl-, Maleinyl-, Fumaryl- oder Styrylrest dar. Zur Anbindung der silikonhaltigen Polymerkette an die reaktive Endgruppe R1 ist eine geeignete chemische Brücke Z erforderlich. Bevorzugte Brücken Z sind -O-, -((CrC5o)Alkylen)-, -((C6-C30) Arylen)-, -((C5-C8) Cycloalkylen)-, -((CrC5o)Alkenylen)-, -(Polypropylenoxid)n-, -(Polyethylenoxid)0-,R 1 represents a polymerizable function from the group of vinylically unsaturated compounds, which is suitable for building polymer structures by radical means. R 1 preferably represents a vinyl, allyl, methallyl, methylvinyl, acrylic (CH 2 = CH-CO-), methacrylic (CH 2 = C [CH 3 ] -CO-), crotonyl, senecionyl , Itaconyl, maleinyl, fumaryl or styryl radical. 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 -,
-(Polypropylenoxid)n(Polyethylenoxid)o-, wobei n und o unabhängig voneinander Zahlen von 0 bis 200 bedeuten und die Verteilung der EO/PO-Einheiten statistisch oder blockförmig sein kann. Weiterhin geeignet als Brückegruppierungen Z sind- (Polypropylene oxide) n (polyethylene oxide) o-, where 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
-((Cι-C10)Alkyl)-(Si(OCH3)2)- und -(Si(OCH3)2)-. Der polymere Mittelteil wird durch silikonhaltige Wiederholungseinheiten repräsentiert.- ((-C-C 10 ) alkyl) - (Si (OCH 3 ) 2) - and - (Si (OCH 3 ) 2 ) -. The polymer middle part is represented by silicone-containing repeat units.
Die Reste R3, R4, R5 und R6 bedeuten unabhängig voneinander -CH3, -0-CH ,The radicals R 3 , R 4 , R 5 and R 6 independently of one another are -CH 3 , -0-CH,
-C6H5 oder -0-C6H5.-C 6 H 5 or -0-C 6 H 5 .
Die Indizes w und x repräsentieren stöchiometrische Koeffizienten, die unabhängig voneinander 0 bis 500, bevorzugt 10 bis 250, betragen.The indices w and x represent stoichiometric coefficients which, independently of one another, are 0 to 500, preferably 10 to 250.
Die Verteilung der Wiederholungseinheiten über die Kette hinweg kann nicht nur rein statistisch, sondern auch blockartig, alternierend oder gradientenartig sein kann.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.
R2 kann einerseits einen aliphatischen, olefinischen, cycloaliphatischen, arylaliphatischen oder aromatischen (Cι-C5o)-Kohlenwasserstoffrest symbolisierenOn the one hand, R 2 can symbolize an aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (C 1 -C 5 o) hydrocarbon radical
(linear oder verzweigt) oder -OH, -NH2, -N(CH3)2, -R7 oder für die Struktureinheit(linear or branched) or -OH, -NH 2 , -N (CH 3 ) 2 , -R 7 or for the structural unit
[-Z-R1] stehen. Die Bedeutung der beiden Variablen Z und R1 wurde bereits erklärt. R7 steht für weitere Si-haltige Gruppierungen. Bevorzugte R7-Reste sind -0-Si(CH3)3, -0-Si(Ph)3, -0-Si(0-Si(CH3)3)2CH3) und -0-Si(0-Si(Ph)3)2Ph). Wenn R2 ein Element der Gruppe [-Z-R1] darstellt, handelt es sich um difunktionelle, Monomere, die zur Vernetzung der entstehenden Polymerstrukturen herangezogen werden können.[-ZR 1 ] are available. The meaning of the two variables Z and R 1 has already been explained. 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.
Formel (I) beschreibt nicht nur vinylisch funktionalisierte, silikonhaltige Polymerspezies mit einer polymertypischen Verteilung, sondern auch definierte Verbindungen mit diskreten Molekulargewichten.Formula (I) describes not only vinylically functionalized, silicone-containing polymer species with a typical polymer distribution, but also defined compounds with discrete molecular weights.
Besonders bevorzugte silikonhaltige Komponenten sind die folgenden acrylisch- oder methacrylisch modifizierten silikonhaltigen Komponenten:Particularly preferred silicone-containing components are the following acrylic or methacrylic modified silicone-containing components:
Figure imgf000008_0001
Figure imgf000008_0001
Methacryloxypropyldimethylsilyl endgeblockte Polydimethylsiloxane (f = 2 bis 500)Methacryloxypropyldimethylsilyl endblocked polydimethylsiloxanes (f = 2 to 500)
Figure imgf000008_0002
Figure imgf000008_0002
Methacryloxypropyl endgeblockte Polydimethylsiloxane (f = 2 bis 500)Methacryloxypropyl endblocked polydimethylsiloxanes (f = 2 to 500)
Figure imgf000008_0003
Figure imgf000008_0003
Vinyldimethoxysilyl endgeblockte Polydimethylsiloxane (f = 2 bis 500)Vinyldimethoxysilyl endblocked polydimethylsiloxanes (f = 2 to 500)
Bezogen auf die Gesamtmasse der Copolymere kann der Gehalt an siliziumhaltigen Komponenten bis 99,9 Gew.-%, bevorzugt 0,5 bis 30 Gew.-%, insbesondere bevorzugt 1 bis 20 Gew.-%, betragen.Based on the total mass of the copolymers, 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.
Als polymerisationsfähige, fluorhaltige Komponenten E) sind alle mindestens einfach olefinisch ungesättigten Verbindungen geeignet, die unter den jeweils gewählten Reaktionsbedingungen zur radikalischen Copolymerisation befähigt sind. Dabei muss die Verteilung der einzelnen fluorhaltigen Monomere über die entstehenden Polymerketten hinweg nicht notwendigerweise statistisch erfolgen. Auch die Ausbildung von beispielsweise block- (auch multiblock-) oder gradientenartigen Strukturen ist im Sinne der Erfindung. Kombinationen von zwei oder mehreren unterschiedlichen, fluorhaltigen Komponenten E) ist auch möglich, wobei monofunktionelle Vertreter zur Bildung kammförmiger Strukturen führen, wohingegen di-, tri-, oder polyfunktionelle Komponenten E) zu zumindest teilvernetzten Strukturen führen.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.
Bevorzugte fluorhaltige Komponenten E) sind solche gemäß Formel (II).Preferred fluorine-containing components E) are those of the formula (II).
R1-Y-CrH2rCsF2sCF3 (II)R 1 -YC r H 2 rC s F 2s CF 3 (II)
Dabei stellt R1 eine polymerisationsfähige Funktion aus der Gruppe der vinylisch ungesättigten Verbindungen dar, die zum Aufbau polymerer Strukturen auf radikalischem Wege geeignet ist. Bevorzugt stellt R1 ein Vinyl-, Allyl-, Methallyl-, Methylvinyl-, Acryl- (CH2=CH-CO-), Methacryl- (CH2=C[CH3]-C0-), Crotonyl-, Senecionyl-, Itaconyl-, Maleinyl-, Fumaryl- oder Styrylrest, besonders bevorzugt einen Acryl- und Methacrylrest, dar. Zur Anbindung der fluorhaltigen Gruppierung an die reaktive Endgruppe R1 ist eine geeignete chemische Brücke Y erforderlich. Bevorzugte Brücken Y sind -O-, -0(0)-, -C(0)-0-, -S-, -0-CH2-CH(0-)-CH2OH, -0-CH2-CH(OH)-CH2-0-, -0-SOz-O-, -0-S(0)-0-, -PH-, -P(CH3)-, -PO3-, -NH-, -N(CH3)-, -O- CrCδoJAlkyl-O-, -O-Phenyl-O-, -O-Benzyl-O-, -0-(C5-C8)Cycloalkyl-0-, -0-(CrC5o)Alkenyl-0-, -0-(CH(CH3)-CH2-0)n-, -0-(CH2-CH2-0)n- undR 1 represents a polymerizable function from the group of vinylically unsaturated compounds, which is suitable for building polymer structures by radical means. R 1 is preferably vinyl, allyl, methallyl, methylvinyl, acrylic (CH 2 = CH-CO-), methacrylic (CH 2 = C [CH 3 ] -C0-), crotonyl, senecionyl , Itaconyl, maleinyl, fumaryl or styryl radical, particularly preferably an acrylic and methacrylic radical. 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 δ 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
-0-([CH-CH2-0]n-[CH2-CH2-0]m)0-, wobei n, m und o unabhängig voneinander Zahlen von 0 bis 200 bedeuten und die Verteilung der EO- und PO-Einheiten statistisch oder blockförmig sein kann. Bei r und s handelt es sich um stöchiometrische Koeffizienten, die unabhängig voneinander Zahlen von 0 bis 200 bedeuten.-0 - ([CH-CH 2 -0] n - [CH2-CH2-0] m ) 0 -, where 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.
Bevorzugte fluorhaltige Komponenten E) gemäß Formel (II) sind Perfluorhexylethanol-methacrylat, Perfluorhexoylpropanol-methacrylat, Perfluoroctyethanol-methacrylat, Perfluoroctylpropanol-methacrylat, Perfluorhexylethanolylpolygycolether-methacrylat, Perfluorhexoyl-propanolyl-poly-[ethylglykol-co-propylenglycolether]-acrylat,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]
Perfluoroctylethanolyl-poly-[ethylglykol-blockco-propyienglycolether]-methacrylat, Perfluoroctylpropanolyl-polypropylen-glycolether-methacrylat.Perfluorooctylethanolyl poly [ethyl glycol block co-propylene glycol ether] methacrylate, perfluorooctyl propanolyl polypropylene glycol ether methacrylate.
Bezogen auf die Gesamtmasse des Copolymeren kann der Gehalt an fluorhaltigen Komponenten bis 99,9 Gew.-%, bevorzugt 0,5 bis 30 Gew.-%, insbesondere bevorzugt 1 bis 20 Gew.-%, betragen.Based on the total mass of the copolymer, 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.
Bei den Makromonomeren F) handelt sich um mindestens einfach olefinisch funktionalisierte Polymere mit einer oder mehreren diskreten Wiederholungs- einheiten und einem zahlenmittleren Molekulargewicht größer oder gleich 200 g/mol. Bei der Copolymerisation können auch Mischungen chemisch unterschiedlicher Makromonomere F) eingesetzt werden. Bei den Makromonomeren handelt es sich um polymere Strukturen, die aus einer oder mehreren Wiederholungseinheit(en) aufgebaut sind und eine für Polymere charakteristische Molekulargewichtsverteilung aufweisen.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.
Bevorzugt als Makromonomere F) sind Verbindungen gemäß Formel (III).Preferred macromonomers F) are compounds of the formula (III).
R »1 -
Figure imgf000010_0001
- ( /Drv)πJ - D F 2 (III)R »1 -
Figure imgf000010_0001
- (/ Drv) πJ - DF 2 (III)
R1 stellt eine polymerisationsfähige Funktion aus der Gruppe der vinylisch ungesättigten Verbindungen dar, die zum Aufbau polymerer Strukturen auf radikalischem Wege geeignet sind. Bevorzugt stellt R1 einen Vinyl-, Allyl-, Methallyl-, Methylvinyl-, Acryl- (CH2=CH-CO-), Methacryl- (CH2=C[CH3]-CO-),R 1 represents a polymerizable function from the group of vinylically unsaturated compounds which are suitable for building polymeric structures by radical means. R 1 preferably represents a vinyl, allyl, Methallyl, methyl vinyl, acrylic (CH 2 = CH-CO-), methacrylic (CH 2 = C [CH 3 ] -CO-),
Crotonyl-, Senecionyl-, Itaconyl-, Maleinyl-, Fumaryl- oder Styrylrest dar.Crotonyl, senecionyl, itaconyl, maleinyl, fumaryl or styryl radical.
Zur Anbindung der Polymerkette an die reaktive Endgruppe ist eine geeignete verbrückende Gruppe Y erforderlich. Bevorzugte Brücken Y sind -O-, rC(O)-, -0(O)-O-, -S-, -0-CH2-CH(0-)-CH2OH, -0-CH2-CH(OH)-CH20-, -0-S02-0-,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-,
-O-SO2-O-, -O-SO-O-, -PH-, -P(CH3)-, -PO3-, -NH- und -N(CH3)-, besonders bevorzugt -0-.-O-SO 2 -O-, -O-SO-O-, -PH-, -P (CH 3 ) -, -PO3-, -NH- and -N (CH 3 ) -, particularly preferably -0- ,
Der polymere Mittelteil des Makromonomeren wird durch die diskretenThe polymeric middle part of the macromonomer is characterized by the discrete
Wiederholungseinheiten A, B, C und D repräsentiert. Bevorzugte Wiederholungseinheiten A,B,C und D leiten sich ab von Acrylamid, Methacrylamid,Repeat units A, B, C and D represent. Preferred repeating units A, B, C and D are derived from acrylamide, methacrylamide,
Ethylenoxid, Propylen-oxid, AMPS, Acrylsäure, Methacrylsäure,Ethylene oxide, propylene oxide, AMPS, acrylic acid, methacrylic acid,
Methylmethacrylat, Acrylnitril, Maleinsäure, Vinylacetat, Styrol, 1 ,3-Butadien,Methyl methacrylate, acrylonitrile, maleic acid, vinyl acetate, styrene, 1, 3-butadiene,
Isopren, Isobuten, Diethylacrylamid und Diisopropylacrylamid.Isoprene, isobutene, diethylacrylamide and diisopropylacrylamide.
Die Indizes v, w, x und z in Formel (III) repräsentieren die stöchiometrische Koeffizienten betreffend die Wiederholungseinheiten A, B, C und D. v, w, x und z betragen unabhängig voneinander 0 bis 500, bevorzugt 1 bis 30, wobei dieThe 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
Summe der vier Koeffizienten im Mittel >1 sein muss.The sum of the four coefficients must be> 1 on average.
Die Verteilung der Wiederholungseinheiten über die Makromonomerkette kann statistisch, blockartig, alternierend oder gradientenartig sein. R2 bedeutet einen linearen oder verzweigten aliphatischen, olefinischen, cycloaliphatischen, arylaliphatischen oder aromatischen (Ci-CsoJ-Kohlenwasser- stoffrest, OH, -NH2, -N(CH3)2 oder ist gleich der Struktureinheit [-Y-R1].The distribution of the repeating units over the macromonomer chain can be statistical, block-like, alternating or gradient-like. 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 ].
Im Falle von R2 gleich [-Y-R1] handelt es sich um difunktionelle Makromonomere, die zur Vernetzung der Copolymere geeignet sind.In the case of R 2 equal to [-YR 1 ], these are difunctional macromonomers which are suitable for crosslinking the copolymers.
Besonders bevorzugt als Makromonomere F) sind acrylisch- oder methacrylisch monofunktionalisierte Alkylethoxylate gemäß Formel (IV).Particularly preferred macromonomers F) are acrylic or methacrylic monofunctionalized alkyl ethoxylates of the formula (IV).
Figure imgf000011_0001
R3, R4, R5 und Rβ bedeuten unabhängig voneinander Wasserstoff oder n-aliphatische, iso-aliphatische, olefinische, cycloaliphatische, arylaliphatische oder aromatische (CrC3o)-Kohlenwasserstoffreste.
Figure imgf000011_0001
R 3 , R 4 , R 5 and Rβ independently of one another are hydrogen or n-aliphatic, iso-aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (CrC3o) hydrocarbon radicals.
Bevorzugt sind R3 und R4 gleich H oder -CH3, besonders bevorzugt H; R5 ist gleichR 3 and R 4 are preferably H or -CH3, particularly preferably H; R5 is the same
H oder -CH3; und R6 ist gleich einem n-aliphatischen, iso-aliphatischen, olefinischen, cycloaliphatischen, arylaliphatischen oder aromatischen (C1-C30)-H or -CH3; and R 6 is an n-aliphatic, iso-aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (C1-C30) -
Kohlenwasserstoffrest. v und w sind wiederum die stöchiometrischen Koeffizienten betreffend dieHydrocarbon radical. v and w are again the stoichiometric coefficients regarding the
Ethylenoxideinheiten (EO) und Propylenoxideinheiten (PO), v und w betragen unabhängig voneinander 0 bis 500, bevorzugt 1 bis 30, wobei die Summe aus v und w im Mittel >1 sein muss. Die Verteilung der EO- und PO-Einheiten über dieEthylene 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. The distribution of the EO and PO units over the
Makromonomerkette kann statistisch, blockartig, alternierend oder gradientenartig sein. Y steht für die obengenannten Brücken.Macromonomer chains can be statistical, block-like, alternating or gradient-like. Y stands for the bridges mentioned above.
Weiterhin insbesondere bevorzugte Makromonomeren F) haben die folgendeFurther particularly preferred macromonomers F) have the following
Struktur gemäß Formel (IV):Structure according to formula (IV):
Figure imgf000012_0001
Figure imgf000013_0001
Figure imgf000012_0001
Figure imgf000013_0001
Weiterhin als Makromonomere F) insbesondere geeignet sind Ester der (Meth)acrylsäure mitAlso particularly suitable as macromonomers F) are esters of (meth) acrylic acid with
(Cιo-Cι8)-Fettalkoholpolyglykolethern mit 8 EO-Einheiten (Genapol® C-080) Cn-Oxoalkoholpolyglykolethern mit 8 EO-Einheiten (Genapol® UD-080) (Ci2-Cι4)-Fettalkoholpolyglykolethem mit 7 EO-Einheiten (Genapol® LA-070) (Ci2-Cι4)-Fettalkoholpolyglykolethern mit 11 EO-Einheiten (Genapol® LA-110) (Ci6-Cι8)-Fettalkoholpolyglykolethem mit 8 EO-Einheiten (Genapol® T-080) (Ci6-Cι8)-Fettalkoholpolyglykolethern mit 15 EO-Einheiten (Genapol® T-150) (Ci6-C18)-Fettalkoholpolyglykolethem mit 11 EO-Einheiten (Genapol® T-110) (Ci6-Cι8)-Fettalkoholpolyglycolethem mit 20 EO-Einheiten (Genapol® T-200) (Ci6-Cι8)-Fettalkoholpolyglycolethem mit 25 EO-Einheiten (Genapol® T-250) (Ci8-C22)-Fettalkoholpolyglycolethern mit 25 EO-Einheiten und/oder iso-(Ci6-Cιs)-Fettalkoholpolyglycolethem mit 25 EO-Einheiten.(Cιo-Cι 8 ) fatty alcohol polyglycol ethers with 8 EO units (Genapol ® C-080) Cn-oxo alcohol polyglycol ethers with 8 EO units (Genapol ® UD-080) (Ci 2 -Cι 4 ) fatty alcohol polyglycol ethers with 7 EO units ( Genapol ® LA-070) (Ci 2 -Cι 4 ) fatty alcohol polyglycol ethers with 11 EO units (Genapol ® LA-110) (Ci 6 -Cι 8 ) fatty alcohol polyglycol ethers with 8 EO units (Genapol ® T-080) (Ci 6 -Cι 8 ) fatty alcohol polyglycol ethers with 15 EO units (Genapol ® T-150) (Ci 6 -C 18 ) fatty alcohol polyglycol ethers with 11 EO units (Genapol ® T-110) (Ci 6 -Cι 8 ) fatty alcohol polyglycol ethers 20 EO units (Genapol ® T-200) (Ci 6 -Cι 8 ) fatty alcohol polyglycol ether with 25 EO units (Genapol ® T-250) (Ci 8 -C 22 ) fatty alcohol polyglycol ethers with 25 EO units and / or iso - (Ci 6 -Cιs) fatty alcohol polyglycol ether with 25 EO units.
Bei den Genapo .1l®-Typen handelt es sich um Produkte der Firma Clariant GmbH.The Genapo .1l® types are products from Clariant GmbH.
Bevorzugt beträgt das Molekulargewicht der Makromonomeren F) 200 g/mol bis 106 g/mol, besonders bevorzugt 150 bis 104 g/mol und insbesondere bevorzugt 200 bis 5000 g/mol.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.
Bezogen auf die Gesamtmasse der Copolymere können geeignete Makromonomere bis zu 99,9 Gew.-% eingesetzt werden. Bevorzugt finden die Bereiche 0.5 bis 30 Gew.-% und 70 bis 99,5 Gew.-% Anwendung. Besonders bevorzugt sind Anteile von 1 bis 20 Gew.-% und 75 bis 95 Gew.-%.Based on the total mass of the copolymers, suitable macromonomers up to 99.9% by weight can be used. The ranges 0.5 to 30% by weight and 70 to 99.5% by weight are preferably used. Fractions of 1 to 20% by weight and 75 to 95% by weight are particularly preferred.
Bevorzugt als Copolymere sind solche, die durch Copolymerisation mindestens der Komponenten A), B) und F) erhältlich sind. Weiterhin bevorzugt als Copolymere sind solche, die durch Copolymerisation mindestens der Komponenten A), C) und F) erhältlich sind.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).
Weiterhin bevorzugt als Copolymere sind solche, die durch Copolymerisation mindestens der Komponenten A), F) und G) erhältlich sind.Also preferred as copolymers are those which can be obtained by copolymerizing at least components A), F) and G).
Weiterhin bevorzugt als Copolymere sind solche, die durch Copolymerisation mindestens der Komponenten A), B) und G) erhältlich sind.Also preferred as copolymers are those which can be obtained by copolymerizing at least components A), B) and G).
In einer bevorzugten Ausführungsform wird die Copolymerisation in Gegenwart mindestens eines polymeren Additivs G) durchgeführt, wobei das Additiv G) vor der eigentlichen Copolymerisation dem Polymerisationsmedium ganz- oder teilweise gelöst zugegeben wird. Die Verwendung von mehreren Additiven G) ist ebenfalls erfindungsgemäß. Vernetzte Additive G) können ebenfalls verwendet werden.In a preferred embodiment, 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.
Die Additive G) bzw. deren Mischungen müssen lediglich ganz oder teilweise im gewählten Polymerisationsmedium löslich sein. Während des eigentlichen Polymerisationsschrittes hat das Additiv G) mehrere Funktionen. Einerseits verhindert es im eigentlichen Polymerisationsschritt die Bildung übervernetzter Polymeranteile im sich bildenden Copolymerisat und andererseits wird das Additiv G) gemäß dem allgemein bekannten Mechanismus der Pfropf-Copolymerisation statistisch von aktiven Radikalen angegriffen. Dies führt dazu, dass je nach Additiv G) mehr oder weniger große Anteile davon in die Copolymere eingebaut werden. Zudem besitzen geeignete Additive G) die Eigenschaft, die Lösungsparameter der sich bildenden Copolymere während der radikalischen Polymerisationsreaktion derart zu verändern, dass die mittleren Molekulargewichte zu höheren Werten verschoben werden. Verglichen mit analogen Copolymeren, die ohne den Zusatz der Additive G) hergestellt wurden, zeigen solche, die unter Zusatz von Additiven G) hergestellt wurden, vorteilhafterweise eine signifikant höhere Viskosität in wässriger Lösung.The additives G) or their mixtures only have to be wholly or partly soluble in the chosen polymerization medium. During the actual polymerization step, 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. In addition, 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. Compared with analog copolymers which were produced without the addition of additives G), those which were produced with the addition of additives G) advantageously show a significantly higher viscosity in aqueous solution.
Bevorzugt als Additive G) sind in Wasser und/oder Alkoholen, bevorzugt in t- Butanol, lösliche Homo- und Copolymere. Unter Copolymeren sind dabei auch solche mit mehr als zwei verschiedenen Monomertypen zu verstehen. Besonders bevorzugt als Additive G) sind Homo- und Copolymere aus N-Vinylformamid, N-Vinylacetamid, N-Vinylpyrrolidon, Ethylenoxid, Propylenoxid, Acryloyldimethyltaurinsäure, N-Vinylcaprolactam, N-Vinylmethylacetamid, Acrylamid, Acrylsäure, Methacrylsäure, N-Vinylmorpholid, Hydroxyethylmethacrylat, Diallyldimethylammoniumchlorid (DADMAC) und/oder [2-(Methacryloyloxy)-ethyl]trimethylammoniumchlorid (MAPTAC); Polyalkylenglykole und/oder Alkylpolyglykole.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.
Insbesondere bevorzugt als Additive G) sind Polyvinylpyrrolidone (z.B. Luviskol K15®, K20®und K30® von BASF), Poly(N-Vinylformamide), Poly(N- Vinylcaprolactame) und Copolymere aus N-Vinylpyrrolidon, N-Vinylformamid und/oder Acrylsäure, die auch teilweise oder vollständig verseift sein können.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.
Das Molekulargewicht der Additive G) beträgt bevorzugt 102 bis 107 g/mol, besonders bevorzugt 0,5*104 bis 106 g/mol. Die Einsatzmenge des polymeren Additivs G) beträgt, bezogen auf dieThe 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
Gesamtmasse der bei der Copolymerisation zu polymerisierenden Monomere, bevorzugt 0,1 bis 90 Gew.-%, besonders bevorzugt 1 bis 20 Gew.-% und insbesondere bevorzugt 1,5 bis 10 Gew.-%.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.
In einer weiteren bevorzugten Ausführungsform sind die erfindungsgemäßen Copolymere vernetzt, d.h. sie enthalten Comonomere mit mindestens zwei polymerisationsfähigen Vinylgruppen.In a further preferred embodiment, the copolymers according to the invention are crosslinked, i.e. they contain comonomers with at least two polymerizable vinyl groups.
Bevorzugte Vernetzer sind Methylenbisacrylamid; Methylenbismethacrylamid; Ester ungesättigter Mono- und Polycarbonsäuren mit Polyolen, bevorzugt Diacrylate und Triacrylate bzw. -methacrylate, besonders bevorzugt Butandiol- und Ethylenglykoldiacrylat bzw. -methacrylat, Trimethylolpropantriacrylat (TMPTA) und Trimethylolpropantrimethacrylat (TMPTMA); Allylverbindungen, bevorzugt Allyl(meth)acrylat, Triallylcyanurat, Maleinsäurediallylester, Polyallylester, Tetraallyloxyethan, Triallylamin, Tetraallylethylendiamin; Allylester der Phosphorsäure; und/oder Vinylphosphonsäurederivate.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.
Insbesondere bevorzugt als Vernetzer ist Trimethylolpropantriacrylat (TMPTA). Der Gewichtsanteil an vernetzenden Comonomeren, bezogen auf die Gesamtmasse der Copolymere, beträgt bevorzugt bis 20 Gew.-%, besonders bevorzugt 0,05 bis 10 Gew.-% und insbesondere bevorzugt 0,1 bis 7 Gew.-%.Trimethylolpropane triacrylate (TMPTA) 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.
Als Polymerisationsmedium können alle organischen oder anorganischen Lösungsmittel dienen, die sich bezüglich radikalischer Polymerisationsreaktionen weitestgehend inert verhalten und vorteilhafterweise die Bildung mittlerer oder hoher Molekulargewichte zulassen. Bevorzugt Verwendung finden Wasser; niedere Alkohole; bevorzugt Methanol, Ethanol, Propanole, iso-, sec- und t-Butanol, insbesondere bevorzugt t-Butanol; Kohlenwasserstoffe mit 1 bis 30 Kohlenstoffatomen und Mischungen der vorgenannten Verbindungen.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.
Die Polymerisationsreaktion erfolgt bevorzugt im Temperaturbereich zwischen 0 und 150°C, besonders bevorzugt zwischen 10 und 100°C, sowohl bei Normaldruck als auch unter erhöhtem oder erniedrigtem Druck. Gegebenenfalls kann die Polymerisation auch unter einer Schutzgasatmosphäre, vorzugsweise unter Stickstoff, ausgeführt werden.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.
Zur Auslösung der Polymerisation können energiereiche elektromagnetische Strahlen, mechanische Energie oder die üblichen chemischen Polymerisationsinitiatoren, wie organische Peroxide, z.B. Benzoylperoxid, tert.- Butylhydroperoxid, Methylethylketonperoxid, Cumolhydroperoxid, Dilauroylperoxid oder Azoinitiatoren, wie z.B. Azodiisobutyronitril (AIBN), verwendet werden.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.
Ebenfalls geeignet sind anorganische Peroxyverbindungen, wie z.B. (NH4)2S2θ8, K2S208 oder H2O2, gegebenenfalls in Kombination mit Reduktionsmitteln (z.B. Natriumhydrogensulfit, Ascorbinsäure, Eisen(ll)-sulfat etc.) oder Redoxsystemen, welche als reduzierende Komponente eine aliphatische oder aromatische Sulfonsäure (z.B. Benzolsulfonsäure, Toluolsulfonsäure etc.) enthalten.Also suitable are inorganic peroxy compounds, such as (NH 4 ) 2S 2 θ 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.
Als Polymerisationsmedium können alle Lösungsmittel dienen, die sich bezüglich radikalischer Polymerisationsreaktionen weitestgehend inert verhalten und die Bildung hoher Molekulargewichte zulassen. Bevorzugt Verwendung finden Wasser und niedere, tertiäre Alkohole oder Kohlenwasserstoffe mit 3 bis 30 C-Atomen. In einer besonders bevorzugten Ausführungsweise wird t-Butanol als Reaktionsmedium verwendet. Mischungen aus zwei- oder mehreren Vertretern der beschriebenen potentiellen Lösungsmitteln sind selbstverständlich ebenfalls erfindungsgemäß. Dies schließt auch Emulsionen von nicht miteinander mischbaren Solventien ein (z.B. Wasser/Kohlenwasserstoffe). Grundsätzlich sind alle Arten der Reaktionsführung geeignet, die zu den erfindungsgemäßen Polymerstrukturen führen (Lösungspolymerisation, Emulsionsverfahren, Fällungsverfahren, Hochdruckverfahren, Suspensionsverfahren, Substanzpolymerisation, Gelpolymerisation usw.). Bevorzugt eignet sich die Fällungspolymerisation, besonders bevorzugt die Fällungspolymerisation in tert.-Butanol.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. In a particularly preferred embodiment, 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). In principle, all types of 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.
Die nachfolgenden Beispiele und Anwendungen sollen die Erfindung näher erläutern, ohne sie jedoch darauf zu beschränken.The following examples and applications are intended to explain the invention in more detail, but without restricting it thereto.
Beispiel 1example 1
In einem 1 I Vierhalskolben der mit Rührer, Innenthermometer, Gaseinleitrohre für Stickstoff und Ammoniak sowie Rückflusskühler versehen war, wurden 470 g tert.In a 1 liter four-necked flask equipped with a stirrer, internal thermometer, gas inlet tubes for nitrogen and ammonia and a reflux condenser, 470 g were tert.
Butanol vorgelegt.Submitted butanol.
Des weiteren wurden 5,0 g 2-Acrylamido-2-methylpropan-sulfonsäure (AMPS) vorgelegt und mit der äquivalenten Menge Ammoniak neutralisiert. Anschließend wurden 95,0 g eines Esters, gebildet aus Methacrylsäure und (C22)- Fettalkoholpolyglykolether mit 25 EO Einheiten, zugegeben.Furthermore, 5.0 g of 2-acrylamido-2-methylpropane sulfonic acid (AMPS) were initially charged and neutralized with the equivalent amount of ammonia. Then 95.0 g of an ester formed from methacrylic acid and (C 22 ) - fatty alcohol polyglycol ether with 25 EO units were added.
Der Kolbeninhalt wurde unter Rühren mit Stickstoff inertisiert und mittels Heizbad auf 60°C erwärmt.The contents of the flask were rendered inert with nitrogen while stirring and heated to 60 ° C. using a heating bath.
Nach Erreichen der Temperatur wurden 1 ,5 g Dilauroylperoxid als Initiator zugegeben und unter weiterem Stickstoffspülen auf 80°C erhitzt. Die Mischung wurde 4 Stunden bei angegebener Temperatur unter Rückfluss gerührt.After the temperature had been reached, 1.5 g of dilauroyl peroxide were added as the 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.
Beispiel 2Example 2
Wie unter 1 beschrieben, jedoch unter Verwendung von 95 g eines Esters, gebildet aus Methacrylsäure und (Cι2/i4)-Fettalkoholpolyglykolether mit 7 EO Einheiten (Genapol® LA-070), anstelle des (C22)-Fettalkoholpolyglykolethers mit 25 EO Einheiten. Beispiel 3As described under 1, but using 95 g of an ester formed from methacrylic acid and (Cι 2 / i 4 ) fatty alcohol polyglycol ether with 7 EO units (Genapol ® LA-070) instead of the (C 2 2) fatty alcohol polyglycol ether with 25 EO units. Example 3
In einem 1 I Quickfitkolben der mit Rührer, Innenthermometer, Gaseinleitrohre für Stickstoff und Ammoniak sowie Rückflusskühler versehen war, wurden 470 g tert. Butanol vorgelegt.In a 1 liter Quickfit flask equipped with a stirrer, internal thermometer, gas inlet tubes for nitrogen and ammonia and a reflux condenser, 470 g were tert. Submitted butanol.
Des weiteren wurden 80,0 g 2-Acrylamido-2-methylpropan-sulfonsäure (AMPS) vorgelegt und mit der äquivalenten Menge Ammoniak neutralisiert. Anschließend wurden 20,0 g eines Esters, gebildet aus Methacrylsäure und (C22)- Fettalkoholpolyglykolether mit 25 EO Einheiten, zugegeben. Der Kolbeninhalt wurde unter Rühren mit Stickstoff inertisiert und mittels Heizbad auf 60°C erwärmt. Nach Erreichen der Temperatur wurden 1 ,5 g Dilauroylperoxid als Initiator zugegeben und unter weiterem Stickstoffspülen auf 80°C erhitzt. Die Mischung wurde 4 Stunden bei angegebener Temperatur unter Rückfluss gerührt. Nach beendeter Reaktion wurde das Polymer durch Absaugen des Lösemittels und durch anschließende Vakuumtrocknung isoliert.Furthermore, 80.0 g of 2-acrylamido-2-methylpropane sulfonic acid (AMPS) were initially charged and neutralized with the equivalent amount of ammonia. Then 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.
Die nachfolgende Auflistung zeigt 93 Copolymere, die für die Formulierung der erfindungsgemäßen Mittel besonders geeignet sind. Die verschiedenen Copolymere Nr. 1 bis Nr. 93 sind gemäß den folgenden Herstellverfahren 1 , 2, 3 und 4 erhältlich.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.
Verfahren 1 :Procedure 1:
Diese Polymere sind nach dem Fällungsverfahren in tert. Butanol herstellbar. Dabei wurden die Monomere in t-Butanol vorgelegt, die Reaktionsmischung inertisiert und anschließend die Reaktion nach Anheizen auf 60°C durch Zugabe des entsprechenden t-Butanol löslichen Initiators (bevorzugt Dilauroylperoxid) gestartet. Die Polymere werden nach beendeter Reaktion (2 Stunden) durch Absaugen des Lösungsmittels und durch anschließende Vakuumtrocknung isoliert.These polymers are in tert after the precipitation process. 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.
Verfahren 2:Procedure 2:
Diese Polymere sind nach dem Gelpolymerisationsverfahren in Wasser herstellbar. Dabei werden die Monomere in Wasser gelöst, die Reaktionsmischung inertisiert und anschließend die Reaktion nach Anheizen auf 65°C durch Zugabe von geeigneten Initiatoren- oder Initiatorsystemen (bevorzugt Na2S208) gestartet. Die Polymergele werden anschließend zerkleinert und nach Trocknung die Polymere isoliert.These 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 ). The polymer gels are then crushed and the polymers isolated after drying.
Verfahren 3:Procedure 3:
Diese Polymere sind nach dem Emulsionsverfahren in Wasser herstellbar. Dabei werden die Monomere in einer Mischung aus Wasser/organ. Lösungsmittel (bevorzugt Cyclohexan) unter Verwendung eines Emulgators emulgiert, die Reaktionsmischung mittels N2 inertisiert und anschließend die Reaktion nach Anheizen auf 80°C durch Zugabe von geeigneten Initiatoren- oder Initiatorsystemen (bevorzugt Na2S208) gestartet. Die Polymeremulsionen werden anschließend eingedampft (Cyclohexan fungiert als Schlepper für Wasser) und dadurch die Polymere isoliert.These polymers can be prepared in water using the emulsion process. The monomers are mixed in a water / organ mixture. Solvent (preferably cyclohexane) is emulsified using an 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 ). The polymer emulsions are then evaporated (cyclohexane acts as a tug for water), thereby isolating the polymers.
Verfahren 4:Procedure 4:
Diese Polymere sind nach dem Lösungsverfahren in organischen LösungsmittelnThese polymers are after the solution process in organic solvents
(bevorzugt Toluol, z.B. auch tert. Alkohole) herstellbar. Dabei werden die(preferably toluene, e.g. also tertiary alcohols). The
Monomere im Lösungsmittel vorgelegt, die Reaktionsmischung inertisiert und anschließend die Reaktion nach Anheizen auf 70°C durch Zugabe von geeignetenMonomers 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
Initiatoren- oder Initiatorsystemen (bevorzugt Dilauroylperoxid) gestartet.Initiator or initiator systems (preferably dilauroyl peroxide) started.
Das Reaktionsgemisch wird nach üblichen Methoden und gemäß dem jeweiligenThe reaction mixture is by customary methods and according to the particular
Anforderungsprofil aufgearbeitet.Requirements profile worked up.
Polymere mit hydrophoben Seitenketten, unvemetztPolymers with hydrophobic side chains, uncrosslinked
Figure imgf000019_0001
Figure imgf000020_0001
Figure imgf000021_0001
Figure imgf000019_0001
Figure imgf000020_0001
Figure imgf000021_0001
Polymere mit hydrophoben Seitenketten, vernetztPolymers with hydrophobic side chains, cross-linked
Figure imgf000021_0002
Figure imgf000021_0002
Polymere mit hydrophoben Seitenketten, vernetzt, gepfropftPolymers with hydrophobic side chains, cross-linked, grafted
Figure imgf000021_0003
Figure imgf000021_0003
Polymere mit siliziumhaltigen Gruppen, unvernetzt Polymere mit siliziumhaltigen Gruppen, unvernetztPolymers with silicon-containing groups, uncrosslinked Polymers with silicon-containing groups, uncrosslinked
Figure imgf000022_0001
Figure imgf000022_0001
Polymere mit siliziumhaltigen Gruppen, vernetztPolymers with silicon-containing groups, cross-linked
Figure imgf000022_0002
Figure imgf000022_0002
Polymere mit hydrophoben Seitenketten und kationischen Gruppen, unvernetztPolymers with hydrophobic side chains and cationic groups, uncrosslinked
Figure imgf000022_0003
Polymere mit hydrophoben Seitenketten und kationischen Gruppen, vernetzt
Figure imgf000022_0003
Polymers with hydrophobic side chains and cationic groups, cross-linked
Figure imgf000023_0001
Figure imgf000023_0001
Polymere mit fluorhaltigen GruppenPolymers with fluorine-containing groups
Figure imgf000023_0002
Figure imgf000023_0002
Polymere mit fluorhaltigen Gruppen, gepfropftPolymers with fluorine-containing groups, grafted
Figure imgf000023_0003
Figure imgf000023_0003
Multifunktionelle PolymereMultifunctional polymers
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000024_0001
Figure imgf000025_0001
Chemische Bezeichnung der Reaktanden:Chemical name of the reactants:
AMPS Acryloyldimethyltaurat, wahlweise Na- oder NH4-SalzAMPS Acryloyldimethyltaurate, optionally Na or NH4 salt
Genapo Ir® ' T-080 Ci6-Ci8-Fettalkoholpolyglykolether mit 8 EO-Einheiten Genapol® T-110 Ci2-Cι -Fettalkoholpolyglykolether mit 11 EO-Einheiten Genapol® T-250 Ci6-C18-Fettalkoholpolyglycolether mit 25 EO-Einheiten Genapol® LA-040 Ci2-Ci4-Fettalkoholpolyglykolether mit 4 EO-Einheiten Genapol® LA-070 Ci2-C14-Fettalkoholpolyglykolether mit 7 EO-Einheiten Genapol® OX-100 Ci2-Ci5-Oxoalkoholpolyglykolether mit 10 EO-Einheiten Genapol® O-150 methacrylat Ci6-Cι8-Fettalkoholpolyglykolether methacrylat mit 15 EO-Einheiten,Genapo Ir® 'T-080 Ci6-Ci8 fatty alcohol polyglycol ether with 8 EO units Genapol ® T-110 Ci2-Cι fatty alcohol polyglycol ether with 11 EO units Genapol ® T-250 Ci6-C 18 fatty alcohol polyglycol ether with 25 EO units Genapol ® LA-040 Ci2-Ci 4 fatty alcohol polyglycol ether with 4 EO units Genapol ® LA-070 Ci2-C 14 fatty alcohol polyglycol ether with 7 EO units Genapol ® OX-100 Ci2-Ci5-oxo alcohol polyglycol ether with 10 EO units Genapol ® O-150 methacrylate Ci6-Cι 8 fatty alcohol polyglycol ether methacrylate with 15 EO units,
Genapol® LA-250 crotonat Ci2-Ci4-Fettalkoholpolyglykolether crotonat mitGenapol ® LA-250 crotonate Ci2-Ci4-fatty alcohol polyglycol ether crotonate with
25 EO-Einheiten25 EO units
Genapol® T-250 methacrylat Ci6-Ci8-Fettalkoholpolyglycolether methacrylat mit 25 EO-EinheitenGenapol ® T-250 methacrylate Ci6-Ci8 fatty alcohol polyglycol ether methacrylate with 25 EO units
Genapol® T-250 acrylat Ci6-Cιs-Fettalkoholpolyglycolether methacrylat mit 25 EO-EinheitenGenapol ® T-250 acrylate Ci6-Cιs fatty alcohol polyglycol ether methacrylate with 25 EO units
BB10® Polyoxyethylen(10)BehenyletherBB10 ® polyoxyethylene (10) behenyl ether
BB25® Polyoxyethylen(25)BehenyletherBB25 ® polyoxyethylene (25) behenyl ether
TMPTA TrimethylolpropantriacrylatTMPTA trimethylolpropane triacrylate
Poly-NVP Poly-N-VinylpyrrolidonPoly-NVP Poly-N-vinyl pyrrolidone
Silvet® 867 Siloxan Polyalkylenoxid CopolymerSilvet ® 867 siloxane polyalkylene oxide copolymer
MBA Methylen-bis-acrylamid AMA AllylmethacrylatMBA methylene bis-acrylamide AMA allyl methacrylate
®Y-12867 Siloxan Polyalkylenoxid Copolymer ® Y-12867 siloxane polyalkylene oxide copolymer
Silvet® 7608 Polyalkylenoxid-modifiziert.esSilvet ® 7608 polyalkylene oxide modified
Heptamethyltrisiloxanheptamethyltrisiloxane
Silvet® 7280 Polyalkylenoxid-modifiziertesSilvet ® 7280 polyalkylene oxide modified
Heptamethyltrisiloxanheptamethyltrisiloxane
DADMAC Diallyldimethyl-ammoniumchloridDADMAC diallyldimethyl ammonium chloride
HEMA 2-HydroxyethylmethacrylatHEMA 2-hydroxyethyl methacrylate
Quat 2-(Methacryloyloxy)ethyltrimethyl- ammoniumchloridQuat 2- (methacryloyloxy) ethyl trimethyl ammonium chloride
Fluowet® AC 600 PerfluoralkylethylacrylatFluowet ® AC 600 perfluoroalkyl ethyl acrylate
Span® 80 SorbitanesterSpan ® 80 sorbitan esters
Vorteilhafte Eigenschaften zeigen die beschriebenen kammförmigen,The described comb-shaped,
Acryloyldimethyltaurat enthaltenden Copolymeren sowohl in vernetzter als auch in unvemetzter Form. Während vernetzte Systeme z.B. hervorragende Eigenschaftsprofile im Hinblick auf Emulsionsstabilisierung zeigten, konnten insbesondere mit Hilfe der unvemetzten Varianten elektrolythaltige Systeme verdickt werden, die bekanntermaßen mit Polyelektrolyten nur sehr schwer oder gar nicht zu verdicken sind.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.
Die erfindungsgemäßen Polymere eignen sich ebenso als Verdicker und Dispergiermittel, als Emulgatoren, Suspendiermittel mit verdickender Wirkung und Konsistenzgeber für Emulsionen und Suspensionen, sowie als, Haftmittel,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,
Verdicker, Dispergier- und Emulgiermittel feststoffhaltiger Zubereitungen. Dabei können auch Mischungen der Polymere verwendet werden. Die emulgierende, stabilisierende und/ oder konsistenzgebende Wirkung der erfindungsgemäßen Polymere in Emulsionen wird durch eine Assoziation der Polymerseitenketten untereinander, sowie durch eine Wechselwirkung der Polymerseitenketten mit den hydrophoben Ölkomponenten verursacht bzw. verstärkt. Polymere mit hohem Anteil an hydrophoben Seitenketten bewirken ein hohes Dispergier- bzw. Emulgiervermögen gute eine hohe Suspensibilität der Mittel. Die erfindungsgemäßen Polymere eignen sich für den Einsatz in Soluble 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).Thickeners, dispersants and emulsifiers of preparations containing solids. Mixtures of the polymers can also be used. 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).
Die erfindungsgemäßen Pflanzenschutzmittel können Pestizide aus der Gruppe der Herbizide, Insektizide, Fungizide, Akarizide, Bakterizide, Molluskide, Nematizide und/oder Rodentizide enthalten.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.
Geeignete Herbizide sind, ohne die Erfindung auf diese einzuschränken, insbesondere Glyphosate, dessen Salze und/oder Derivate, aber auch Acifluorfen, Asulam, Benazolin, Bentazone, Bilanafos, Bromacil, Bromoxynil, Chloramben, Clopyralid, 2,4-D, 2,4-DB, Dalapon, Dicamba, Dichlorprop, Diciofop, Endothall, Fenac, Fenoxaprop, Flamprop, Fluazifop, Flumiclorac, Fluoroglycofen, Fomesafen, Fosamine, Glufosinate, Haloxyfop, Imazapic, Imazamethabenz, Imazamox, Imazapyr, Imazaquin, Imazethapyr, loxynil, MCPA, MCPB, Mecoprop, Methylarsonic acid/MSMA, Naptalam, Picioram, Quinclorac, Quizalofop, 2,3,6-TBA und TCA.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.
Bevorzugte fungizide Wirkstoffe sind Amino-Derivate, wie 8-(1,1-Dimethylethyl)- Nethyl-N-propyl-1 ,4-dioxaspiro[4,5]decan-2-methamin (Spiroxamine) und Fenpropidin, sowie Morpholin-Derivate, wie Aldimorph, Dodemorph und Fenpropimorph.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.
Als insektizide Wirkstoffe seien vorzugsweise genannt Azinphos-methyl, Azinphos-ethyl, Bromophos-A, Carbaryl, Chlorpyriphos, Chlorpyriphos M, Diazinon, Dichlorphos, Fenitrothion, Fonofos, Ediphenphos, Fenaminphos, Isofenphos, Malathion, Mesulfenphos, Methidathion, Parathion A, Parathion M, Permethrin, Pyrethrin, Pirimiphos, Profenofos, Pyraclophos, Tebupirimifos, Betacyfluthrin, Cyfluthrin, Cypermethrin, Transfluthrin, Lambda-cyhalothrin.Azinphos-methyl, Azinphos-ethyl, Bromophos-A, Carbaryl, Chlorpyriphos, Chlorpyriphos M, Diazinon, Dichlorphos, Fenitrothion, Fonofos, Ediphenphos, Fenaminphos, Isofenphos, Malathion, Mesulfenphos, Parion, Methidathion, Paran , Permethrin, Pyrethrin, Pirimiphos, Profenofos, Pyraclophos, Tebupirimifos, Betacyfluthrin, Cyfluthrin, Cypermethrin, Transfluthrin, Lambda-cyhalothrin.
Die erfindungsgemäßen Zubereitungen können die AMPS-Copolymere in nahezu beliebiger Menge enthalten. Bevorzugt sind folgende Zubereitungen: Formulierungen als "Tank-mix" und "ready to use compositions" enthalten 0,001 bis 10 Gew.-%, bevorzugt 0,05 bis 2 Gew.-% Pestizid und 0,01 bis 10 Gew.-%, bevorzugt 0,1 bis 2 Gew.-%, besonders bevorzugt 0,2 bis 1 Gew.-% AMPS- Copolymer. Das Gewichtsverhältnis von AMPS-Copolymer zu Pestizid kann hier zwischen 1:10 bis 500:1, insbesondere 1:4 bis 4:1, liegen.The preparations according to the invention can be used in almost the AMPS copolymers any amount included. The following preparations are preferred: 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.
Konzentrat-Formulierungen, die vor dem Gebrauch verdünnt werden, können das Pestizid in den Gewichtsmengen 5 bis 60 %, bevorzugt 20 bis 40 % und das AMPS-Copolymer in Mengen von 3 Gew.-% bis 50 Gew.-% enthalten. DasConcentrate 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. The
Gewichtsverhältnis AMPS-Copolymer zu Pestizid kann hier zwischen 1:20 bis 1 :1 , bevorzugt 1 :10 bis 1:2, liegen.Weight ratio of AMPS copolymer to pesticide can be between 1:20 to 1: 1, preferably 1:10 to 1: 2.
Alternativ können die ertϊndungsgemäßen Formulierungen in fester Form als Pulver, Pellets, Tabletten oder Granulate hergestellt werden, die vor dem Gebrauch in Wasser gelöst werden. Feste Zubereitungen können das Pestizid in den Gewichtsmengen von 20 % bis 80 %, bevorzugt von 50 % bis 75 %, besonders bevorzugt von 60 % bis 70 % und das AMPS-Copolymer in Gewichtsmengen von 5 % bis 50 %, bevorzugt 10 % bis 30 %, enthalten.Alternatively, 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.
Die erfindungsgemäßen Formulierungen können darüber hinaus die üblichen Verdickungsmittel, Antigelmittel, Frostmittel, Lösungsmittel, Dispergiermittel, Emulgatoren, Konservierungsmittel, weitere Adjuvants, Verdünnungsmittel, Bindemittel, Antischaummittel, Verdunstungshemmer, Puffer, Neutralisationsmittel, Kältestabilisatoren, Sprengmittel und Netzmittel, aber auch agrochemische Salze, bevorzugt Ammoniumsalze, besonders bevorzugt Ammoniumsulfat, Ammoniumnitrat, und/oder Phosphat, enthalten.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.
Als Verdickungsmittel können Xanthan gum und/oder Cellulose, beispielsweise Carboxy-, Methyl-, Ethyl-, oder Propylcellulose, Kieselsäuren und Attapulgit in Gewichtsmengen von 0,01 bis 5 % bezogen auf das fertige Mittel eingesetzt werden. Als organische Solventien eignen sich alle üblichen organischen Lösungsmittel, die einerseits mit Wasser wenig mischbar sind, andererseits aber die eingesetzten Wirkstoffe gut lösen bzw. eine geeignete kontinuierliche Phase bilden.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.
Vorzugsweise genannt seien aliphatische und aromatische Kohlenwasserstoffe, gegebenenfalls halogenierte Kohlenwasserstoffe, wie Toluol, Xylol, Tetrachlormethan, Chloroform, Methylenchlorid, Dichlorethan, Ester und Ethylacetat.Aliphatic and aromatic hydrocarbons, optionally halogenated hydrocarbons such as toluene, xylene, carbon tetrachloride, chloroform, methylene chloride, dichloroethane, ester and ethyl acetate may be mentioned as preferred.
Als Konservierungsmittel können organische Säuren und ihre Ester, beispielsweise Ascorbinsäure, Ascorbinpalmitat, Sorbat, Benzoesäure, Methyl- und Propyl-4-Hydroxybenzoat, Propionate, Phenol, beispielsweise 2-Phenylphenat, 1 ,2-Benzisothiazolin-3-on, Formaldehyd, schwefelige Säure und deren Salze, Preventol und Proxel eingesetzt werden.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.
Als Entschäumer eignen sich Fettsäurealkylesteralkoxylate; Organopolysiloxane wie Polydimethylsiloxane und deren Gemische mit mikrofeiner, gegebenenfalls signierter Kieselsäure; Paraffine; Wachse und Mikrokristallinwachse und deren Gemische mit signierter Kieselsäure. Vorteilhaft sind auch Gemische verschiedener Schauminhibitoren, z.B. solche aus Silikonöl, Paraffinöl und/oder oder Wachsen.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.
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.
Als Dispergiermittel und Emulgatoren eignen sich nichtionische, amphotere, kationische und anionische Tenside.Nonionic, amphoteric, cationic and anionic surfactants are suitable as dispersants and emulsifiers.
Als oberflächenaktive Stoffe eignen sich bevorzugt Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C-Atomen, an Mono-, Di- und/oder Trialkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe und an (C8-Cι8)- Alkylamine; sekundäre Etheraminen und alkoxylierte sekundäre Etheraminderivate; (Cι2-Cι8)-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 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; Anlagerungsprodukte von 15 bis 60 Mol Ethylenoxid an Rizinusöl und/oder gehärtetes Rizinusöl; Polyol- und insbesondere Polyglycerinester, z.B. Polyglycerinpolyricinoleat und Polyglycerinpoly-12- hydroxystearat; Carbonsäureamide, z.B. Decancarbonsäure-dimethyl-amid; hochmolekulare Siliconverbindungen, z.B. Dimethylpolysiloxane mit einem durchschnittlichen Molekulargewicht von 10.000 bis 50.000 g/mol. Weiterhin geeignet sind anionische Tenside, z.B. Alkali- und Ammoniumsalze von linearen oder verzweigten Alkyl(en)sulfaten mit 8 bis 22 Kohlenstoffatomen, (Ci2-Cι8)-Alkylsulfonsäuren und (Ci2-Cι8)-Alkylarylsulfonsäuren;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; (Cι 2 -Cι 8 ) fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol; Glycerol mono- and diesters and sorbitan / sorbitol mono- and diesters of saturated and unsaturated fatty acids with 6 to 22 carbon atoms and their ethylene oxide addition products; Addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil; Polyol and in particular polyglycerol esters, for example polyglycerol polyricinoleate and polyglycerol poly-12-hydroxystearate; Carboxamides, for example decanecarboxylic acid dimethyl amide; high molecular weight silicone compounds, for example dimethylpolysiloxanes with an average molecular weight of 10,000 to 50,000 g / mol. Also suitable are anionic surfactants, for example alkali and ammonium salts of linear or branched alkyl (en) sulfates with 8 to 22 carbon atoms, (Ci 2 -C 8 ) alkyl sulfonic acids and (Ci 2 -C 8 ) alkylarylsulfonic acids;
Bis(phenolsulfonsäure)ether und deren Alkali- oder Ammoniumsalze, Isethionate, bevorzugt Cocoylisethionat; Naphthalinsulfonsäure und/oder Sulphosuccinate.Bis (phenolsulfonic acid) ether and its alkali metal or ammonium salts, isethionates, preferably cocoyl isethionate; Naphthalenesulfonic acid and / or sulphosuccinates.
Für feste Formulierungen kommen als Bindemittel Polyvinylpyrrolidon, Polyvinylalkohol, Carboxymethylcellulose, Zucker, beispielsweise Sucrose, Sorbitol, oder Stärke in Betracht.For solid formulations, polyvinylpyrrolidone, polyvinyl alcohol, carboxymethyl cellulose, sugar, for example sucrose, sorbitol, or starch are suitable as binders.
Als Verdünner, Absorber oder Träger eignen sich Carbon Black, Talg, Kaolin, Aluminium-, Calcium- oder Magnesiumstearat, Natriumtripolyphosphat, Natriumtetraborat, Natriumsulphat, Silikate und Natriumbenzoat. Als Sprengmittel wirken Cellulose, beispielsweise Carboxymethylcellulose, Polyvinylpyrrolidon, Natrium- oder Kaliumacetat, Carbonate, Bicarbonate, Sesquicarbonate, Ammoniumsulfat oder Kaliumhydrogenphosphat. Als Netzmittel können Alkoholethoxylate/-propoxylate verwendet werden.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.
Die erfindungsgemäßen Formulierungen können gemäss den üblichen Methoden eingesetzt werden.The formulations according to the invention can be used according to the customary methods.
Wässrige Konzentrate und feste Formulierungen werden vor dem Ausbringen mit der entsprechenden Menge an Wasser verdünnt. Pro Hektar werden Pestizidmengen im Bereich von 0,1 bis 5 kg, bevorzugt 0,3 bis 2,5 kg ausgebracht. Der Anteil des erfindungsgemäßen Adjuvant AMPS-Copolymer liegt im Bereich von 0,1 bis 3,0 kg/ha. Das Volumen der für die Aussprühung erstellten Pestizidformulierung liegt im Bereich von 50 bis 1000 l/ha. Durch den Einsatz der Polymere erhält der Anwender weitgehende Freiheit bei der Wahl seiner Komponenten. Die Formulierungen zeigen eine hohe Kompatibilität der Komponenten untereinander (Pestizide, Salze, Adjuvants etc.), eine hohe Löslichkeit der Pestizide und agrochemischen Salze sowie eine ausgezeichnete Lagerstabilität. Die Polymere wirken als Lösungsvermittler. Aussalzeffekte werden unterdrückt bzw. minimiert.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.
Die Formulierungen sind üblicherweise auf einen pH Wert im Bereich 2 bis 12, bevorzugt pH 3 bis 8 eingestellt.The formulations are usually adjusted to a pH in the range 2 to 12, preferably pH 3 to 8.
Formulierungsbeispiele (alle Angaben in Gew.-%)Formulation examples (all figures in% by weight)
Öl-in-Wasser Emulsion (EW)Oil-in-water emulsion (EW)
1 21 2
Malathion 40 EW (Vergleichsbeispiel) (erfindungsgemäß)Malathion 40 EW (comparative example) (according to the invention)
[%] [%][%] [%]
Malathion (95 %) 42,0 42,0Malathion (95%) 42.0 42.0
Deioni. Wasser 21 ,0 21 ,2Deioni. Water 21, 0 21, 2
Solvesso 150 20,0 25,1Solvesso 150 20.0 25.1
Dispergiermittel LFS 7,0 —Dispersant LFS 7.0 -
Kelzan (2 % wässrige Lösung) 10,0 10,0Kelzan (2% aqueous solution) 10.0 10.0
Polymer nach Beispiel 1 (100 %) — 1,7Polymer according to Example 1 (100%) - 1.7
Viskosität 720 mPas 790 mPasViscosity 720 mPas 790 mPas
Serum 0% 0%Serum 0% 0%
Serum (nach 4 Wochen bei 25°C) 3% 2% (Serum = Abtrennung einer organischen Phase)Serum (after 4 weeks at 25 ° C) 3% 2% (serum = separation of an organic phase)
Herstellweise der Formulierungen 1 und 2:Formulation 1 and 2:
- Wasser und Emulgator vorlegen;- add water and emulsifier;
- Pflanzenschutzwirkstoff mit Lösemittel mischen/lösen; Wirkstofflösung durch langsames zutropfen in Wasserphase mittels Hochgeschwindigkeitsrührer (z.B. Ultra Turrax) emulgieren Verdicker in Emulsion einrühren- Mix / dissolve crop protection agent with solvent; Emulsify the active ingredient solution by slowly dropping it in the water phase using a high-speed stirrer (eg Ultra Turrax). Stir the thickener into the emulsion
3 43 4
Emulsion-Konzentrate (EC) (Vergleichsbeispiel) (erfindungsgemäß)Emulsion concentrates (EC) (comparative example) (according to the invention)
[%] [%][%] [%]
Trifluralin 48,0 48,0Trifluralin 48.0 48.0
Solvesso 150 45,0 50,6Solvesso 150 45.0 50.6
Emulsogen EL/Phenylsulfonat CA 7,0 —Emulsogen EL / phenyl sulfonate CA 7.0 -
Polymer nach Beispiel 1 (100 %) 1,4Polymer according to Example 1 (100%) 1.4
Beispiel 3: WasserhärteExample 3: Water hardness
20 ppm 342 ppm 500 ppm20 ppm 342 ppm 500 ppm
Emulgierverhalten grob grob grobEmulsifying behavior coarse coarse coarse
1 Stunde Geringe Rahm-/ Geringe Rahm-/ Geringe Rahm-/1 hour low cream / low cream / low cream /
Ölabscheidung Ölabscheidung ÖlabscheidungOil separation oil separation oil separation
2 Stunden Geringe Rahm-/ Geringe Rahm-/ Geringe Rahm-/2 hours low cream / low cream / low cream /
Ölabscheidung Ölabscheidung ÖlabscheidungOil separation oil separation oil separation
6 Stunden 0,5 % Rahm-/ 0,5 % Rahm-/ 0,5 % Rahm-/6 hours 0.5% cream / 0.5% cream / 0.5% cream /
Ölabscheidung Ölabscheidung ÖlabscheidungOil separation oil separation oil separation
24 Stunden 1 ,0 % Rahm-/ 1 ,0 % Rahm-/ 0,5 % Rahm-/24 hours 1, 0% cream / 1, 0% cream / 0.5% cream /
Ölabscheidung Ölabscheidung ÖlabscheidungOil separation oil separation oil separation
Beispiel 4: WasserhärteExample 4: Water hardness
20 ppm 342 ppm 500 ppm20 ppm 342 ppm 500 ppm
Emulsionsstabilität gut gut grobEmulsion stability good good rough
1 Stunde Keine Rahm-/ Keine Rahm-/ Geringe Rahm-/1 hour no cream / no cream / low cream /
Ölabscheidung Ölabscheidung Ölabscheidung Stunden Keine Rahm-/ Geringe Rahm- 0,5 % Rahm- Ölabscheidung abscheidung bildungOil separation Oil separation Oil separation hours No cream / low cream 0.5% cream Oil separation separation formation
6 Stunden Geringe Rahm- Geringe Rahm- 0,5 % Rahm-/ abscheidung abscheidung Ölabscheidung 24 Stunden 0,5 % Rahm-/ 0,5 % Rahm-/ 1 ,0 % Rahm-/ Ölabscheidung Ölabscheidung Ölabscheidung6 hours low cream - low cream - 0.5% cream / oil separation oil separation 24 hours 0.5% cream / 0.5% cream / 1, 0% cream / oil separation oil separation oil separation
5 65 6
Emulsion-Konzentrate (EC) (Vergleichsbeispiel) (erfindungsgemäß)Emulsion concentrates (EC) (comparative example) (according to the invention)
[%] [%][%] [%]
Rapsöl 80,0 96,0Rapeseed oil 80.0 96.0
Emulsogen EL/Phenylsulfonat CA 20,0Emulsogen EL / phenyl sulfonate CA 20.0
Polymer nach Beispiel 2 (100 %) 4,0Polymer according to Example 2 (100%) 4.0
Beispiel 5: WasserhärteExample 5: Water hardness
20 ppm 342 ppm 500 ppm20 ppm 342 ppm 500 ppm
Emulsionsstabilität gut gut gutEmulsion stability good good good
1 Stunde Keine Rahm-/ Keine Rahm-/ Keine Rahm-/1 hour No cream / No cream / No cream /
Ölabscheidung Ölabscheidung ÖlabscheidungOil separation oil separation oil separation
2 Stunden Keine Rahm-/ Geringe Rahm- Geringe Rahm-2 hours No cream / low cream- low cream-
Ölabscheidung abscheidung abscheidungOil separation separation separation
6 Stunden Geringe Rahm- 0,5 % Rahm-/ 0,5 % Rahm-/ abscheidung Ölabscheidung Ölabscheidung6 hours low cream - 0.5% cream / 0.5% cream / oil separation oil separation
24 Stunden 0,5 % Rahm-/ 1 ,0 % Rahm-/ 2,0 % Rahm-/24 hours 0.5% cream / 1.0% cream / 2.0% cream /
Ölabscheidung Ölabscheidung ÖlabscheidungOil separation oil separation oil separation
Beispiel 6: WasserhärteExample 6: Water hardness
20 ppm 342 ppm 500 ppm20 ppm 342 ppm 500 ppm
Emulsionsstabilität gut gut gutEmulsion stability good good good
1 Stunde Keine Rahm-/ Keine Rahm-/ Keine Rahm-/ Ölabscheidung Ölabscheidung Ölabscheidung1 hour No cream / No cream / No cream / Oil separation oil separation oil separation
2 Stunden Geringe Rahm-/ Geringe Rahm- Geringe Rahm- Ölabscheidung abscheidung abscheidung 6 Stunden 0,5 % Rahm-/ 0,5 % Rahm-/ 1,0 % Rahm-/ Ölabscheidung Ölabscheidung Ölabscheidung 24 Stunden 1,0 % Rahm-/ 1,0 % Rahm-/ 2,0 % Rahm-/ Ölabscheidung Ölabscheidung Ölabscheidung2 hours low cream / low cream low cream oil separation separation 6 hours 0.5% cream / 0.5% cream / 1.0% cream / oil separation oil separation oil separation 24 hours 1.0% cream / 1.0% cream / 2.0% cream / oil separation oil separation oil separation
Herstellweise der Emulsionskonzentrate (EC)Method of preparation of the emulsion concentrates (EC)
- Pflanzenschutzwirkstoff mit Lösemittel mischen/lösen- Mix / dissolve crop protection agent with solvent
- Anionische und nichtionische Emulgatoren hinzufügen und anschließend homogenisieren- Add anionic and nonionic emulsifiers and then homogenize
Suspensionskonzentrat mit Atrazine:Suspension concentrate with Atrazine:
7 8 97 8 9
(Vergleich) (erfindungsgemäß) (Vergleich)(Comparison) (according to the invention) (comparison)
[%] [%] [%][%] [%] [%]
Atrazine 99 % 43,6 43,6 43,6Atrazine 99% 43.6 43.6 43.6
Deionisiertes Wasser 41 ,3 48,5 41 ,3Deionized water 41, 3 48.5 41, 3
Ethylenglykol 4,3 4,3 4,3Ethylene glycol 4.3 4.3 4.3
Dispergiermittel LFS 2,1 — 2,1Dispersant LFS 2.1 - 2.1
Kelzan (2 % wässrige Lösung) 7,2 — —Kelzan (2% aqueous solution) 7.2 - -
Entschäumer SE 57 1 ,5 1 ,5 1,5Defoamer SE 57 1, 5 1, 5 1.5
Polymer nach Beispiel 3 (100 %) — 2,1 —Polymer according to Example 3 (100%) - 2.1 -
Viskosität [mPas] 610 920 120Viscosity [mPas] 610 920 120
Suspensibility [%] 84 88 —Suspensibility [%] 84 88 -
Brookfield; 20°C; 30 rpm; Spindle No. 3Brookfield; 20 ° C; 30 rpm; Spindle No. 3
Wasser, Dispergiermittel und Glykol vorlegenSubmit water, dispersant and glycol
Pflanzenschutzwirkstoff mittels Hochgeschwindigkeitsrührer (z.B. Ultra-Turrax) in Wasser-/Tensidphase dispergierenPlant protection agent using a high-speed stirrer (e.g. Ultra-Turrax) disperse in the water / surfactant phase
- Dispersion mittels Perl-Mühle auf eine Teilchengröße von ca. 10 μm vermählen- Use a Perl mill to grind the dispersion to a particle size of approx. 10 μm
- Verdicker und Entschäumer langsam in Dispersion einrühren- Slowly stir in the thickener and defoamer into the dispersion
Chemische Bezeichnung der eingesetzten Handelsprodukte:Chemical name of the commercial products used:
Solvesso 150 (Exxon Chemicals) aromatisches Kohlenwasserstoff-Gemisch Dispergiermittel LFS (Clariant GmbH) Poly-(arylalkyl)-phenol-polyethylenglykol- phosphorsäuresalzSolvesso 150 (Exxon Chemicals) aromatic hydrocarbon mixture dispersant LFS (Clariant GmbH) poly (arylalkyl) phenol polyethylene glycol phosphoric acid salt
Kelzan (Kelco) Xanthan gumKelzan (Kelco) xanthan gum
Phenylsulfonat CA (Clariant GmbH) Calcium-alkylbenzolsulfonat Emulsogen EL (Clariant GmbH) Ethoxyliert.es Pflanzenöl Defoamer SE 57 (Wacker) Polydimethylsiloxan + Füllstoff Phenylsulfonate CA (Clariant GmbH) calcium alkylbenzenesulfonate Emulsogen EL (Clariant GmbH) ethoxylated vegetable oil Defoamer SE 57 (Wacker) polydimethylsiloxane + filler

Claims

Patentansprüche: claims:
1. Pflanzenschutzmittel, dadurch gekennzeichnet, dass sie mindestens ein Copolymer, erhältlich durch radikalische Copolymerisation von A) Acryloyldimethyltaurinsäure und/oder Acryloyldimethyltauraten,1. Plant protection products, characterized in that they have at least one copolymer, obtainable by radical copolymerization of A) acryloyldimethyltauric acid and / or acryloyldimethyltaurates,
B) gegebenenfalls einem oder mehreren weiteren olefinisch ungesättigten, nicht kationischen, gegebenenfalls vernetzenden, Comonomeren, die wenigstens ein Sauerstoff-, Stickstoff-, Schwefel- oder Phosphoratom aufweisen und ein Molekulargewicht kleiner 500 g/mol besitzen, C) gegebenenfalls einem oder mehreren olefinisch ungesättigten, kationischen Comonomeren, die wenigstens ein Sauerstoff-, Stickstoff-, Schwefel- oder Phosphoratom aufweisen und ein Molekulargewicht kleiner 500 g/mol besitzen,B) optionally one or more further olefinically unsaturated, non-cationic, optionally crosslinking, comonomers which have at least one oxygen, nitrogen, sulfur or phosphorus atom and have a molecular weight of less than 500 g / mol, C) optionally one or more olefinically unsaturated cationic comonomers which have at least one oxygen, nitrogen, sulfur or phosphorus atom and have a molecular weight of less than 500 g / mol,
D) gegebenenfalls einer oder mehreren mindestens monofunktionellen, zur radikalischen Polymerisation befähigten, siliziumhaltigen Komponente(n),D) optionally one or more at least monofunctional, silicon-free component (s) capable of radical polymerization,
E) gegebenenfalls einer oder mehreren mindestens monofunktionellen, zur radikalischen Polymerisation befähigten, fluorhaltigen Komponente(n),E) optionally one or more at least monofunctional fluorine-containing component (s) capable of radical polymerization,
F) gegebenenfalls einem oder mehreren einfach oder mehrfach olefinisch ungesättigten, gegebenenfalls vernetzenden, Makromonomeren, die jeweils mindestens ein Sauerstoff-, Stickstoff-, Schwefel- oder Phosphoratom besitzen und ein zahlenmittleres Molekulargewicht größer oder gleich 200 g/mol aufweisen, wobei es sich bei den Makromonomeren nicht um eine siliziumhaltige Komponente D) oder fluorhaltige Komponente E) handelt, G) wobei die Copolymerisation gegebenenfalls in Gegenwart mindestens eines Polymeren Additivs mit zahlenmittleren Molekulargewichten von 200 g/mol bis 109 g/mol erfolgt, H) mit der Maßgabe, dass die Komponente A) mit mindestens einerF) optionally one or more mono- or poly-olefinically unsaturated, optionally crosslinking, macromonomers, each having at least one oxygen, nitrogen, sulfur or phosphorus atom and having a number-average molecular weight greater than or equal to 200 g / mol, where it is in the Macromonomers are not silicon-containing component D) or fluorine-containing component E), G) where the copolymerization is optionally carried out in the presence of at least one polymeric additive with number-average molecular weights of 200 g / mol to 10 9 g / mol, H) with the proviso that component A) with at least one
Komponente ausgewählt aus einer der Gruppen D) bis G) copolymerisiert wird, enthalten.Component selected from one of groups D) to G) is copolymerized.
2. Mittel nach Anspruch 1 , dadurch gekennzeichnet, dass es sich bei den Comonomeren B) um ungesättigte Carbonsäuren, Salze ungesättigter Carbonsäuren, Anhydride ungesättigter Carbonsäuren, Ester ungesättigter Carbonsäuren mit aliphatischen, olefinischen, cycloaliphatischen, arylaliphatischen oder aromatischen Alkoholen mit 1 bis 22 C-Atomen, offenkettige N-Vinylamide, cyclische N-Vinylamide mit einer Ringgröße von 3 bis 9, Amide der Acrylsäure, Amide der Methacrylsäure, Amide substituierter Acrylsäuren, Amide substituierter Methacrylsäuren, 2-Vinylpyridin, 4-Vinylpyridin, Vinylacetat; Styrol, Acrylnitril, Vinylchlorid, Vinylidenchlorid, Tetrafluorethylen, Vinylphosphonsäure oder deren Ester oder Salze, Vinylsulfonsäure oder deren Ester oder Salze, Allylphosphonsäure oder deren Ester oder Salze und/oder Methallylsulfonsäure oder deren Ester oder Salze handelt.2. Composition according to claim 1, characterized in that it is in the Comonomers B) around unsaturated carboxylic acids, salts of unsaturated carboxylic acids, anhydrides of unsaturated carboxylic acids, esters of unsaturated carboxylic acids with aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic alcohols with 1 to 22 C atoms, open-chain N-vinylamides, cyclic N-vinylamides with a ring size of 3 to 9, amides of acrylic acid, amides of methacrylic acid, amides of substituted acrylic acids, amides of substituted methacrylic acids, 2-vinylpyridine, 4-vinylpyridine, vinyl acetate; Styrene, acrylonitrile, vinyl chloride, vinylidene chloride, tetrafluoroethylene, vinylphosphonic acid or its esters or salts, vinylsulfonic acid or its esters or salts, allylphosphonic acid or its esters or salts and / or methallylsulfonic acid or its esters or salts.
3. Mittel nach Anspruch 1 , dadurch gekennzeichnet, dass es sich bei den Comonomeren C) um Diallyldimethylammoniumchlorid (DADMAC),3. Composition according to claim 1, characterized in that the comonomers C) are diallyldimethylammonium chloride (DADMAC),
[2-(Methacryloyloxy)ethyl]trimethylammoniumchlorid (MAPTAC),[2- (methacryloyloxy) ethyl] trimethylammonium chloride (MAPTAC),
[2-(Acryloyloxy)ethyl]trimethylammoniumchlorid,[2- (acryloyloxy) ethyl] trimethylammonium chloride,
[2-Methacrylamidoethyl]trimethylammoniumchlorid,[2-methacrylamidoethyl] trimethyl ammonium chloride,
[2-(Acrylamido)ethyl]trimethylammoniumchlorid, N-Methyl-2-vinylpyridiniumchlorid[2- (acrylamido) ethyl] trimethylammonium chloride, N-methyl-2-vinylpyridinium chloride
N-Methyl-4-vinylpyridiniumchloridN-methyl-4-vinyl pyridinium chloride
Dimethylaminoethylmethacrylat,dimethylaminoethyl
Dimethylaminopropylmethacrylamid,dimethylaminopropylmethacrylamide,
Methacryloylethyl-N-oxid und/oder Methacryloylethyl-betain handelt.Methacryloylethyl-N-oxide and / or methacryloylethyl-betaine.
4. Mittel nach mindestens Anspruch 1 , dadurch gekennzeichnet, dass es sich bei den Makromonomeren F.) um Verbindungen der Formel (III) handelt,4. Composition according to at least claim 1, characterized in that the macromonomers F.) are compounds of the formula (III),
R1 - Y - [(A)v - (B)w - (C)x - (D)J - R2 (III)R 1 - Y - [(A) v - (B) w - (C) x - (D) J - R 2 (III)
wobei R1 eine polymerisationsfähige Funktion aus der Gruppe der vinylisch ungesättigten Verbindungen, bevorzugt einen Vinyl-, Allyl-, Methallyl-, Methylvinyl-, Acryl-, Methacryl-, Crotonyl-, Senecionyl-, Itaconyl-, Maleinyl-,where R 1 is a polymerizable function from the group of the vinylically unsaturated compounds, preferably a vinyl, allyl, methallyl, Methyl vinyl, acrylic, methacrylic, crotonyl, senecionyl, itaconyl, maleinyl,
Fumaryl- oder Styrylrest, darstellt;Represents fumaryl or styryl;
Y eine verbrückende Gruppe, bevorzugt -O-, -S-, -C(O)-, -C(0)-0-,Y is a bridging group, preferably -O-, -S-, -C (O) -, -C (0) -0-,
-0-CH2-CH(0-)-CH2OH, -O-CH2-CH(OH)-CH20-, -0-S02-0-, -0-S02-0-, -O-SO-O-, -PH-, -P(CH3)-, -P03-, -NH- und -N(CH3)- darstellt;-0-CH 2 -CH (0 -) - CH 2 OH, -O-CH 2 -CH (OH) -CH 2 0-, -0-S0 2 -0-, -0-S0 2 -0-, -O-SO-O-, -PH-, -P (CH 3 ) -, -P0 3 -, -NH- and -N (CH 3 ) -;
A, B, C und D unabhängig voneinander diskrete chemischeA, B, C and D are independently discrete chemical
Wiederholungseinheiten, bevorzugt hervorgegangen aus Acrylamid,Repeat units, preferably originating from acrylamide,
Methacrylamid, Ethylenoxid, Propylenoxid, AMPS, Acrylsäure, Methacrylsäure,Methacrylamide, ethylene oxide, propylene oxide, AMPS, acrylic acid, methacrylic acid,
Methylmethacrylat, Acrylnitril, Maleinsäure, Vinylacetat, Styrol, 1,3-Butadien, Isopren, Isobuten, Diethylacrylamid und Diisopropylacrylamid, insbesondere bevorzugt Ethylenoxid, Propylenoxid darstellen; v, w, x und z unabhängig voneinander 0 bis 500, bevorzugt 1 bis 30, betragen, wobei die Summe aus v, w, x und z im Mittel >1 ist; undMethyl methacrylate, acrylonitrile, maleic acid, vinyl acetate, styrene, 1,3-butadiene, isoprene, isobutene, diethylacrylamide and diisopropylacrylamide, particularly preferably ethylene oxide, propylene oxide; v, w, x and z independently of one another are 0 to 500, preferably 1 to 30, the sum of v, w, x and z being> 1 on average; and
R2 einen linearen oder verzweigten aliphatischen, olefinischen, cycloaliphatischen, arylaliphatischen oder aromatischen (Cι-C5o)-Kohlenwasserstoffrest, OH, -NH oder -N(CH3) darstellt oder gleich [-Y-R1] ist.R 2 represents a linear or branched aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (-C-C 5 o) hydrocarbon radical, OH, -NH or -N (CH 3 ) or is equal to [-YR 1 ].
5. Mjttel nach Anspruch 1 , dadurch gekennzeichnet, dass es sich bei den polymeren Additiven G) um Homo- oder Copolymere aus N-Vinylformamid, N-Vinylacetamid, N-Vinylpyrrolidon, Ethylenoxid, Propylenoxid,5. Mjttel according to claim 1, characterized in that the polymeric additives G) are homo- or copolymers of N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, ethylene oxide, propylene oxide,
Acryloyldimethyltaurinsäure, N-Vinylcaprolactam, N-Vinylmethylacetamid, Acrylamid, Acrylsäure, Methacrylsäure, N-Vinylmorpholid, Hydroxymethylmethacrylat, Diallyldimethylammoniumchlorid (DADMAC) und/oder [2-(Methacryloyloxy)-ethyl]trimethylammoniumchlorid (MAPTAC); Polyalkylenglykole und/oder Alkylpolyglykole handelt.Acryloyldimethyltauric acid, N-vinylcaprolactam, N-vinylmethylacetamide, acrylamide, acrylic acid, methacrylic acid, N-vinylmorpholide, hydroxymethyl methacrylate, diallyldimethylammonium chloride (DADMAC) and / or [2- (methacryloyloxy) ethyl] trimethylammonium chloride (MAPTAC); Polyalkylene glycols and / or alkyl polyglycols.
6; Mittel nach mindestens einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die Copolymere vernetzt sind.6 ; Agent according to at least one of claims 1 to 5, characterized in that the copolymers are crosslinked.
7. . Mittel nach Anspruch 1 , dadurch gekennzeichnet, dass sie Copolymere durch Fällungspolymerisation und Lösungspolymerisation in tert.-Butanol hergestellt werden. 7.. Agent according to claim 1, characterized in that it copolymers are prepared by precipitation polymerization and solution polymerization in tert-butanol.
8. Mittel nach Anspruch 1 , dadurch gekennzeichnet, dass sie, bezogen auf die fertigen Mittel, 0,01 bis 10 Gew.-% der Copolymere enthalten.8. Composition according to claim 1, characterized in that they contain, based on the finished compositions, 0.01 to 10 wt .-% of the copolymers.
9. Mittel nach Anspruch 1 , dadurch gekennzeichnet, dass die Copolymere wasserlöslich, wasserquellbar oder öllöslich sind. 9. Composition according to claim 1, characterized in that the copolymers are water-soluble, water-swellable or oil-soluble.
PCT/EP2003/001272 2002-02-16 2003-02-10 Plant protecting agents WO2003067981A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008046075A1 (en) * 2008-09-08 2010-03-11 Evonik Röhm Gmbh (Meth) acrylate monomer, polymer and coating agent

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996000251A1 (en) * 1994-06-24 1996-01-04 The Dow Chemical Company Novel amphipathic graft copolymers, their preparation, compositions thereof, and methods of their use
WO1999066004A1 (en) * 1998-06-15 1999-12-23 The Lubrizol Corporation Aqueous composition containing a water-soluble or water-dispersable synthetic polymer
EP1069142A1 (en) * 1999-07-15 2001-01-17 Clariant GmbH Water soluble polymers and their use in cosmetic and pharmaceutic products
WO2001060877A1 (en) * 2000-02-16 2001-08-23 Clariant Gmbh Copolymers and their use as drift control agents

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996000251A1 (en) * 1994-06-24 1996-01-04 The Dow Chemical Company Novel amphipathic graft copolymers, their preparation, compositions thereof, and methods of their use
WO1999066004A1 (en) * 1998-06-15 1999-12-23 The Lubrizol Corporation Aqueous composition containing a water-soluble or water-dispersable synthetic polymer
EP1069142A1 (en) * 1999-07-15 2001-01-17 Clariant GmbH Water soluble polymers and their use in cosmetic and pharmaceutic products
WO2001060877A1 (en) * 2000-02-16 2001-08-23 Clariant Gmbh Copolymers and their use as drift control agents

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008046075A1 (en) * 2008-09-08 2010-03-11 Evonik Röhm Gmbh (Meth) acrylate monomer, polymer and coating agent

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