DE10206468A1 - Pesticides - Google Patents

Abstract

The invention relates to crop protection agents containing at least one copolymer obtainable by radical copolymerization of DOLLAR AA) acryloyldimethyltauric acid and / or acryloyldimethyltaurates, DOLLAR AB) optionally one or more olefinically unsaturated, non-cationic, comonomers, DOLLAR AC) optionally one or more olefinically unsaturated, cationic comonomers, DOLLAR AD) optionally one or more silicon-containing component (s), DOLLAR AE) optionally one or more fluorine-containing component (s), DOLLAR AF) optionally one or more macromonomers, DOLLAR AG) the copolymerization optionally in the presence of at least one polymer Additive is carried out, DOLLAR AH) with the proviso that component A) is copolymerized with at least one component selected from one of groups D) to G).

Description

The present invention relates to the use of comb-shaped, Copolymers containing acryloyldimethyltaurate in crop protection products.

Pesticides (herbicides, insecticides, fungicides, bactericides, molluscids, nematicides and Rodenticides) are chemical or natural substances found in plant cells, - tissue or parasitic organisms penetrate into or on the plant and Damage and / or destroy weeds and plant pests.

The largest share of pesticides are herbicides, followed by insecticides and Fungicides.

Pesticides and mixtures can be used undiluted or preferably use 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 Formulation of the active ingredient requires certain additives to achieve the desired application properties with regard to solubility, viscosity, dispersing and emulsifying power, crystallization inhibition, adhesion and wetting power, Anti-baking behavior, compatibility etc. to accomplish.

It has now been found that a new family of polymers based on Acryloyldimethyltauric acid as a thickener, consistency agent, emulsifier, Dispersant, and / or stabilizer, crystallization inhibitor, and adhesive and wetting agent can serve and formulate a variety of pesticidal Formulations are excellent.

• A) Acryloyldimethyltaurinsäure und/oder Acryloyldimethyltauraten,
• 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,
• D) gegebenenfalls einer oder mehreren mindestens monofunktionellen, zur radikalischen Polymerisation befähigten, siliziumhaltigen Komponente(n),
• E) gegebenenfalls einer oder mehreren mindestens monofunktionellen, zur radikalischen Polymerisation befähigten, fluorhaltigen Komponente(n),
• 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 einer Komponente ausgewählt aus einer der Gruppen D) bis G) copolymerisiert wird.

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) 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) optionally one or more at least monofunctional, silicon-free component (s) capable of radical polymerization,
• E) optionally one or more at least monofunctional fluorine-containing component (s) capable of radical polymerization,
• 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, the Macromonomers are not silicon-containing component D) or fluorine-containing component E),
• 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) with the proviso that 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.

The Acryloyldimethyltauraten can be the inorganic or organic salts of Acryloyldimethyltaurinsäure (Acrylamidopropyl-2-methyl-2-sulfonic acid). The Li ⁺ , Na ⁺ , K ⁺ , Mg ⁺⁺ , Ca ⁺⁺ , Al ⁺⁺⁺ 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 (C ₁ -C ₂₂ ) alkyl radicals or (C ₂ -C ₁₀ ) 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-mentioned 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 is based on the total mass of the copolymers Acryloyldimethyltauric acid or acryloyldimethyltaurates at least 0.1% by weight, preferably 20 to 99.5% by weight, particularly preferably 50 to 98% by weight.

All olefinically unsaturated, non-cationic ones can be used as comonomers B) Monomers are used whose reaction parameters involve copolymerization Acryloyldimethyltauric acid and / or acryloyldimethyltaurates in the respective Allow reaction media.

Preferred comonomers B) are unsaturated carboxylic acids and their Anhydrides and salts, and their esters with aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic alcohols with a Carbon number from 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 are Amines can independently of one another be (C ₁ -C ₂₂ ) alkyl radicals or (C ₂ -C ₁₀ ) hydroxyalkyl radicals. 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%.

Open-chain N-vinylamides are further preferred as comonomers B) N-vinylformamide (VIFA), N-vinylmethylformamide, N-vinylmethylacetamide (VIMA) and N-vinylacetamide; Cyclic N-vinyl amides (N-vinyl lactams) with a ring size of 3 to 9, preferably N-vinylpyrrolidone (NVP) and N-vinylcaprolactam; Amides the acrylic and methacrylic acid, preferably acrylamide, methacrylamide, N, N-dimethyl-acrylamide, N, N-diethylacrylamide and N, N-diisopropylacrylamide; alkoxylated acrylic and Methacrylamides, preferably hydroxyethyl methacrylate, hydroxymethyl methacrylamide, Hydroxyethyl methacrylamide, hydroxypropyl methacrylamide and succinic acid mono- [2- (methacryloyloxy) ethyl ester]; N, N-dimethylaminomethacrylate; diethylaminomethyl; Acrylic and methacrylamidoglycolic acid; 2- and 4-vinyl pyridine; vinyl acetate; methacrylate; styrene; acrylonitrile; Vinyl chloride; stearyl; lauryl; vinylidene chloride; and / or tetrafluoroethylene. Also suitable as comonomers B) are inorganic acids and their salts and esters. Preferred acids are vinylphosphonic acid, vinylsulfonic acid, Allylphosphonic acid and methallylsulfonic acid and their salts and esters.

The proportion by weight of the 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.

All olefinically unsaturated monomers come as comonomers C) cationic charge in question, which are able to in the chosen Reaction media with acryloyldimethyltauric acid or its copolymers form. The resulting distribution of the cationic charges over the Chains across can be statistical, alternating, block, or gradient-like. It is pointed out that the cationic comonomers C) include those too understand the cationic charge in the form of a betaine, wear zwitterionic or amphoteric structure.

Comonomers C) in the context of the invention are also amino-functionalized precursors, which are converted into their corresponding quaternaries (e.g. Reaction with dimethyl sulfate, methyl chloride), zwitterionic (e.g. reaction with Hydrogen peroxide), betaine (e.g. reaction with chloroacetic acid), or amphomeric derivatives can be transferred.

Are particularly preferred as comonomers C)
Diallyldimethylammonium chloride (DADMAC),
[2- (methacryloyloxy) ethyl] trimethylammonium chloride (MAPTAC),
[2- (acryloyloxy) ethyl] trimethylammonium chloride,
[2-methacrylamidoethyl] trimethyl ammonium chloride,
[2- (acrylamido) ethyl] trimethylammonium chloride,
N-methyl-2-vinyl pyridinium chloride
N-methyl-4-vinyl pyridinium chloride
dimethylaminoethyl
dimethylaminopropylmethacrylamide,
Methacryloylethyl-N-oxide and / or
Methacryloylethyl betaine.

The proportion by weight of the comonomers C) can, based on the total mass of the Copolymers, 0.1 to 99.8% by weight, preferably 0.5 to 30% by weight and particularly are preferably 1 to 20% by weight.

The polymerizable, silicon-containing components D) are all at least simply olefinically unsaturated compounds suitable among the respective selected reaction conditions are capable of radical copolymerization. The distribution of the individual silicone-containing monomers over the resulting polymer chains do not necessarily take place statistically. The formation of, for example, block (also multiblock) or gradient-like structures is in the sense of the invention. Combinations of two or several different silicone-containing representatives are also possible. The Use of silicone-containing components with two or more polymerization-active groups lead to the formation of branched or cross-linked Structures.

Preferred silicone-containing components are those of the formula (I)

R ¹ -Z - [(Si (R ³ R ⁴ ) -O-) _w - (Si (R ⁵ R ⁶ ) -O) _x -] - R ² (I)

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 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 connect the silicone-containing polymer chain to the reactive end group R ¹ . Preferred bridges Z are -O-, - ((C ₁ -C ₅₀ ) alkylene) -, - ((C ₆ -C ₃₀ ) arylene) -, - ((C ₅ -C ₈ ) cycloalkylene) -, - (( C ₁ -C ₅₀ ) alkenylene) -, - (polypropylene oxide) _n -, - (polyethylene oxide) _o -, - (polypropylene oxide) _n (polyethylene oxide) _o -, where n and o independently of one another represent numbers from 0 to 200 and the distribution the EO / PO units can be statistical or block-shaped. Also suitable as bridge groupings Z are - ((C ₁ -C ₁₀ ) alkyl) - (Si (OCH ₃ ) ₂ ) - and - (Si (OCH ₃ ) ₂ ) -.

The polymer middle section is made up of silicone-containing repeat units represents.

The radicals R ³ , R ⁴ , R ⁵ and R ⁶ independently of one another are -CH ₃ , -O-CH ₃ , -C ₆ H ₅ or -OC ₆ H ₅ .

The indices w and x represent stoichiometric coefficients that are independent from each other 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 on the one hand an aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (C ₁ -C ₅₀ ) hydrocarbon radical (linear or branched) or -OH, -NH ₂ , -N (CH ₃ ) ₂ , -R ⁷ or for the structural unit [-ZR ¹ ]. 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 -O-Si (CH ₃ ) ₃ , -O-Si (Ph) ₃ , -O-Si (O-Si (CH ₃ ) ₃ ) ₂ CH ₃ ) and -O-Si (O -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 to crosslink the resulting polymer structures.

Formula (I) describes not only vinylically functionalized, silicone-containing Polymer species with a typical polymer distribution, but also defined Discrete molecular weight compounds.

Particularly preferred silicone-containing components are the following acrylic- or methacrylic-modified silicone-containing components: methacryloxypropyldimethylsilyl end-blocked polydimethylsiloxanes (f = 2 to 500)

Methacryloxypropyl endblocked polydimethylsiloxanes (f = 2 to 500)

Vinyldimethoxysilyl endblocked polydimethylsiloxanes (f = 2 to 500)

Based on the total mass of the copolymers, the content of silicon-containing Components up to 99.9% by weight, preferably 0.5 to 30% by weight, in particular preferably 1 to 20% by weight.

As polymerizable, fluorine-containing components E) are all at least simple suitable olefinically unsaturated compounds, among those chosen in each case Reaction conditions are capable of radical copolymerization. there the distribution of the individual fluorine-containing monomers over the resulting Polymer chains do not necessarily take place statistically. Also the Formation of, for example, block (also multiblock) or gradient-like Structures is in the sense of the invention. Combinations of two or more different, fluorine-containing components E) is also possible, wherein monofunctional representatives lead to the formation of comb-shaped structures, whereas di-, tri-, or polyfunctional components E) at least lead partially networked structures.

Preferred fluorine-containing components E) are those of the formula (II).

R ¹ -YC _r H _2r C _s F _2s CF ₃ (II)

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 is} preferably vinyl, allyl, methallyl, methylvinyl, acrylic (CH ₂ = CH-CO-), methacrylic (CH ₂ = C [CH ₃ ] -CO-), crotonyl, senecionyl , Itaconyl, maleinyl, fumaryl or styryl radical, particularly preferably an acrylic and methacrylic radical.

A suitable chemical bridge Y is required to connect the fluorine-containing group to the reactive end group R ¹ . Preferred bridges Y are -O-, -C (O) -, -C (O) -O-, -S-, -O-CH ₂ -CH (O -) - CH ₂ OH, -O-CH ₂ - CH (OH) -CH ₂ -O-, -O-SO ₂ -O-, -OS (O) -O-, -PH-, -P (CH ₃ ) -, -PO ₃ -, -NH-, -N (CH ₃ ) -, -O- (C ₁ -C ₅₀ ) alkyl-O-, -O-phenyl-O-, -O-benzyl-O-, -O- (C ₅ -C ₈ ) cycloalkyl -O-, -O- (C ₁ -C ₅₀ ) alkenyl-O-, -O- (CH (CH ₃ ) -CH ₂ -O) _n -, -O- (CH ₂ -CH ₂ -O) _n - and -O - ([CH-CH ₂ -O] _n - [CH ₂ -CH ₂ -O] _m ) _o -, 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.

Preferred fluorine-containing components E) according to formula (II) are
Perfluorohexylethanol methacrylate,
Perfluorhexoylpropanol methacrylate,
Perfluoroctyethanol methacrylate,
Perfluoroctylpropanol methacrylate,
Perfluorhexylethanolylpolygycolether methacrylate,
Perfluorhexoyl-propanolyl-poly [ethylene glycol-co-propylene glycol] acrylate,
Perfluoroctylethanolyl-poly [ethylene glycol-block co-propylene glycol] methacrylate,
Perfluoroctylpropanolyl-polypropylene-glycol ether methacrylate.

Based on the total mass of the copolymer, the content of fluorine-containing Components up to 99.9% by weight, preferably 0.5 to 30% by weight, in particular preferably 1 to 20% by weight.

The macromonomers F) are at least simple olefinic functionalized polymers with one or more discrete Repeat units and a number average molecular weight greater than or equal to 200 g / mol. In the case of copolymerization, mixtures can also be chemically different Macromonomers F) are used. The macromonomers are around polymer structures consisting of one or more repeating unit (s) are built up and a characteristic molecular weight distribution for polymers exhibit.

Preferred macromonomers F) are compounds of the formula (III).

R ¹ -Y - [(A) _v - (B) _w - (C) _x - (D) _z ] -R ² (III)

R ¹ represents a polymerizable function from the group of the vinylically unsaturated compounds which are suitable for building polymer structures by radical means. R ¹ preferably represents 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 bridging group Y is required to connect the polymer chain to the reactive end group. Preferred bridges Y are -O-, -C (O) -, -C (O) -O-, -S-, -O-CH ₂ -CH (O -) - CH ₂ OH, -O-CH ₂ - CH (OH) -CH ₂ O-, -O-SO ₂ -O-, -O-SO ₂ -O-, -O-SO-O-, -PH-, -P (CH ₃ ) -, -PO ₃ -, -NH- and -N (CH ₃ ) -, particularly preferably -O-.

The polymeric middle part of the macromonomer is characterized by the discrete Repeat units A, B, C and D represent. preferred Repeating units A, B, C and D are derived from acrylamide, methacrylamide, Ethylene oxide, propylene oxide, AMPS, acrylic acid, methacrylic acid, methyl methacrylate, Acrylonitrile, maleic acid, vinyl acetate, styrene, 1,3-butadiene, isoprene, isobutene, Diethylacrylamide and diisopropylacrylamide.

The 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 sum of the four coefficients must be ≥ 1 on average.

The distribution of the repeating units over the macromonomer chain can be statistical, block-like, alternating or gradient-like.

R ^{2 represents} a linear or branched aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (C ₁ -C ₅₀ ) hydrocarbon radical, OH, -NH ₂ , -N (CH ₃ ) ₂ or is identical to the structural unit [-YR ¹ ].

In the case of R ² equal to [-YR ¹ ], these are difunctional macromonomers which are suitable for crosslinking the copolymers.

Particularly preferred macromonomers F) are acrylic or methacrylic monofunctionalized alkyl ethoxylates of the formula (IV).

R ₃ , R ₄ , R ₅ and R _{6 are} independently hydrogen or n-aliphatic, iso-aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (C ₁ -C ₃₀ ) hydrocarbon radicals.

R ₃ and R ₄ are preferably H or -CH ₃ , particularly preferably H; R ₅ is H or -CH ₃ ; and R ₆ is an n-aliphatic, iso-aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (C ₁ -C ₃₀ ) hydrocarbon radical.

v and w are again the stoichiometric coefficients regarding the Ethylene oxide units (EO) and propylene oxide units (PO). are v and w independently of one another 0 to 500, preferably 1 to 30, the sum of v and w must be ≥ 1 on average. The distribution of the EO and PO units over the Macromonomer chains can be statistical, block-like, alternating or gradient-like his. Y stands for the bridges mentioned above.

Further particularly preferred macromonomers F) have the following structure according to formula (IV):

Also particularly suitable as macromonomers F) are esters of (meth) acrylic acid with
(C ₁₀ -C ₁₈ ) fatty alcohol polyglycol ethers with 8 EO units (Genapol® C-080)
C ₁₁ oxo alcohol polyglycol ethers with 8 EO units (Genapol® UD-080)
(C ₁₂ -C ₁₄ ) fatty alcohol polyglycol ethers with 7 EO units (Genapol® LA-070)
(C ₁₂ -C ₁₄ ) fatty alcohol polyglycol ethers with 11 EO units (Genapol® LA-110)
(C ₁₆ -C ₁₈ ) fatty alcohol polyglycol ethers with 8 EO units (Genapol® T-080)
(C ₁₆ -C ₁₈ ) fatty alcohol polyglycol ethers with 15 EO units (Genapol® T-150)
(C ₁₆ -C ₁₈ ) fatty alcohol polyglycol ethers with 11 EO units (Genapol® T-110)
(C ₁₆ -C ₁₈ ) fatty alcohol polyglycol ethers with 20 EO units (Genapol® T-200)
(C ₁₆ -C ₁₈ ) fatty alcohol polyglycol ethers with 25 EO units (Genapol® T-250)
(C ₁₈ -C ₂₂ ) fatty alcohol polyglycol ethers with 25 EO units and / or
iso (C ₁₆ -C ₁₈ ) fatty alcohol polyglycol ethers with 25 EO units.

The Genapol® 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 based on the total mass of the copolymers up to 99.9% by weight can be used. The ranges are preferably 0.5 to 30% by weight and 70 to 99.5% by weight application. Portions are particularly preferred from 1 to 20% by weight and 75 to 95% by weight.

Preferred copolymers are those which are obtained by copolymerization of at least the Components A), B) and F) are available.

Also preferred as copolymers are those obtained by copolymerization at least components A), C) and F) are available.

Also preferred as copolymers are those obtained by copolymerization at least components A), F) and G) are available.

Also preferred as copolymers are those obtained by copolymerization at least components A), B) and G) are available.

In a preferred embodiment, the copolymerization is in the presence carried out at least one polymeric additive G), the additive G) before the actual copolymerization of the polymerization medium in whole or in part is added dissolved. The use of several additives G) is also according to the invention. Crosslinked additives G) can also be used. The additives G) or their mixtures only have to be wholly or partly in the selected polymerization medium be soluble. During the actual The polymerization step, the additive G) has several functions. On the one hand it prevents the formation of cross-linked in the actual polymerization step Polymer components in the copolymer being formed and, on the other hand, the additive G) according to the generally known mechanism of graft copolymerization statistically attacked by active radicals. This causes that depending on the additive G) more or less large proportions thereof are incorporated into the copolymers. In addition, suitable additives G) have the property of being the solution parameters of the copolymers formed during the radical polymerization reaction to change such that the average molecular weights to higher values be moved. Compared to analog copolymers without the addition of Additives G) have been produced, show those which are added with additives G) were produced, advantageously a significantly higher viscosity in aqueous Solution.

Preferred additives G) are in water and / or alcohols, preferably in t-butanol, soluble homo- and copolymers. Copolymers also include those with to understand more than two different types of monomers.

Homo- and copolymers are particularly preferred as additives G) N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, ethylene oxide, propylene oxide, Acryloyldimethyltauric acid, N-vinylcaprolactam, N-vinylmethylacetamide, acrylamide, Acrylic acid, methacrylic acid, N-vinylmorpholide, hydroxyethyl methacrylate, Diallyldimethylammonium chloride (DADMAC) and / or [2- (methacryloyloxy) - ethyl] trimethylammonium chloride (MAPTAC); Polyalkylene glycols and / or Alkylpolyglycols.

Particularly preferred additives G) are polyvinylpyrrolidones (e.g. Luviskol K15®, K20® and K30® from BASF), poly (N-vinylformamide), poly (N- Vinyl caprolactams) and copolymers of N-vinyl pyrrolidone, N-vinyl formamide 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 during 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 a further preferred embodiment, the inventive Copolymers cross-linked, i. H. they contain comonomers with at least two polymerizable vinyl groups.

Preferred crosslinkers are methylene bisacrylamide; methylenebismethacrylamide; ester 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, preferred Allyl (meth) acrylate, triallyl cyanurate, maleic acid diallyl ester, polyallyl ester, Tetraallyloxyethane, triallylamine, tetraallylethylene diamine; Allylester the Phosphoric acid; and / or vinylphosphonic acid derivatives.

Trimethylolpropane triacrylate (TMPTA) is particularly preferred as the crosslinking agent. The proportion by weight 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 can be used as the polymerization medium Solvents are used that relate to radical polymerization reactions behave largely inert and advantageously the formation of medium or high Allow molecular weights. Water is preferred; lower alcohols; preferably methanol, ethanol, propanols, iso-, sec.- and t-butanol, particularly preferably t-butanol; Hydrocarbons from 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 at normal pressure and even under increased or reduced pressure. If necessary, the Polymerization also under a protective gas atmosphere, preferably under Nitrogen.

To initiate the polymerization, high-energy electromagnetic radiation, mechanical energy or the usual chemical polymerization initiators, such as organic peroxides, e.g. B. benzoyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide, cumene hydroperoxide, dilauroyl peroxide or azo initiators, such as. B. azodiisobutyronitrile (AlBN) can be used. Inorganic peroxy compounds, such as, for. B. (NH ₄ ) ₂ S ₂ O ₈ , K ₂ S ₂ O ₈ or H ₂ O ₂ , 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 (e.g. benzenesulfonic acid, toluenesulfonic acid etc.) as reducing component.

All solvents which relate to one another can serve as the polymerization medium radical polymerization reactions behave largely inert and the Allow formation of high molecular weights. Water is preferred and lower, tertiary alcohols or hydrocarbons with 3 to 30 carbon atoms. In a particularly preferred embodiment is t-butanol as Reaction medium used. 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 ones Solvents (e.g. water / hydrocarbons). Basically, all types of Suitable reaction control to the polymer structures of the invention lead (solution polymerization, emulsion process, precipitation process, High pressure process, suspension process, bulk polymerization, Gel polymerization etc.).

Precipitation polymerization is particularly suitable, particularly preferably that Precipitation polymerization in tert-butanol.

The following examples and applications are intended to illustrate the invention explain, but without restricting it to them.

example 1

In a 1 l four-necked flask with a stirrer, internal thermometer, gas inlet tubes for Nitrogen and ammonia and reflux condenser was provided, 470 g tert. Submitted butanol.

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.

The contents of the flask were rendered inert with nitrogen while stirring and opened using a heating bath Heated to 60 ° C.

After the temperature had been reached, 1.5 g of dilauroyl peroxide were used as the initiator added and heated to 80 ° C. with further nitrogen flushing.

The mixture was refluxed for 4 hours at the specified temperature touched.

Example 2

As described under 1, but using 95 g of an ester formed from methacrylic acid and (C _12/14 ) fatty alcohol polyglycol ether with 7 EO units (Genapol® LA-070) instead of the (C ₂₂ ) fatty alcohol polyglycol ether with 25 EO units ,

Example 3

In a 1 l Quickfit flask with a stirrer, internal thermometer, gas inlet pipes for Nitrogen and ammonia and reflux condenser was provided, 470 g tert. Submitted butanol.

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 the initiator and the mixture was heated to 80 ° C. while purging with nitrogen.

The mixture was refluxed for 4 hours at the specified temperature touched.

After the reaction had ended, the polymer was removed by suction extraction with solvent and isolated by subsequent vacuum drying.

The following list shows 93 copolymers that are used for the formulation of the agents according to the invention are particularly suitable. The different copolymers Nos. 1 to 93 are available according to the following manufacturing methods 1, 2, 3 and 4.

Procedure 1

These polymers are in tert after the precipitation process. Butanol can be produced. there the monomers were placed in t-butanol, the reaction mixture was rendered inert and then the reaction after heating to 60 ° C by adding the corresponding t-butanol-soluble initiator (preferably dilauroyl peroxide) started. After the reaction has ended (2 hours), the polymers are filtered off with suction Solvent and isolated by subsequent vacuum drying.

Procedure 2

These polymers can be prepared in water using the gel polymerization process. 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 O ₈ ). The polymer gels are then crushed and the polymers isolated after drying.

Procedure 3

These polymers can be prepared in water using the emulsion process. The monomers are mixed in a water organ. 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 Na ₂ S ₂ O ₈ ). The polymer emulsions are then evaporated (cyclohexane acts as a tug for water), thereby isolating the polymers.

Procedure 4

These polymers are after the solution process in organic solvents (preferably toluene, for example also tertiary alcohols) can be prepared. The monomers submitted in the solvent, the reaction mixture rendered inert and then the Reaction after heating to 70 ° C by adding suitable initiators or Initiator systems (preferably dilauroyl peroxide) started.

The reaction mixture is worked up by customary methods and in accordance with the respective requirement profile. Polymers with hydrophobic side chains, uncrosslinked



Polymers with hydrophobic side chains, cross-linked

Polymers with hydrophobic side chains, cross-linked, grafted

Polymers with silicon-containing groups, uncrosslinked

Polymers with silicon-containing groups, cross-linked

Polymers with hydrophobic side chains and cationic groups, uncrosslinked



Polymers with hydrophobic side chains and cationic groups, cross-linked

Polymers with fluorine-containing groups

Polymers with fluorine-containing groups, grafted

Multifunctional polymers



Chemical name of the reactants AMPS: cryloyldimethyl taurate, optionally Na or NH4 salt
Genapol® T-080: C ₁₆ -C ₁₈ fatty alcohol polyglycol ether with 8 EO units
Genapol® T-110: C ₁₂ -C ₁₄ fatty alcohol polyglycol ether with 11 EO units
Genapol® T-250: C ₁₆ -C ₁₈ fatty alcohol polyglycol ether with 25 EO units
Genapol® LA-040: C ₁₂ -C ₁₄ fatty alcohol polyglycol ether with 4 EO units
Genapol® LA-070: C ₁₂ -C ₁₄ fatty alcohol polyglycol ether with 7 EO units
Genapol® OX-100: C ₁₂ -C ₁₅ oxo alcohol polyglycol ether with 10 EO units
Genapol® O-150 methacrylate: C ₁₆ -C ₁₈ fatty alcohol polyglycol ether methacrylate with 15 EO units,
Genapol® LA-250 crotonate: C ₁₂ -C ₁₄ fatty alcohol polyglycol ether crotonate with 25 EO units
Genapol® T-250 methacrylate: C ₁₆ -C ₁₈ fatty alcohol polyglycol ether methacrylate with 25 EO units
Genapol® T-250 acrylate: C ₁₆ -C ₁₈ fatty alcohol polyglycol ether methacrylate with 25 EO units
BB10®: polyoxyethylene (10) behenyl ether
BB25®: polyoxyethylene (25) behenyl ether
TMPTA: trimethylolpropane triacrylate
Poly-NVP: poly-N-vinyl pyrrolidone
Silvet® 867: siloxane polyalkylene oxide copolymer
MBA: methylene-bis-acrylamide
AMA: allyl methacrylate
®Y-12867: siloxane polyalkylene oxide copolymer
Silvet® 7608: polyalkylene oxide-modified heptamethyltrisiloxane
Silvet® 7280: polyalkylene oxide-modified heptamethyltrisiloxane
DADMAC: diallyldimethylammonium chloride
HEMA: 2-hydroxyethyl methacrylate
Quat: 2- (methacryloyloxy) ethyltrimethylammonium chloride
Fluowet® AC 600: perfluoroalkyl ethyl acrylate
Span® 80: sorbitan ester

The described comb-shaped, Copolymers containing acryloyldimethyltaurate both in crosslinked and in uncrosslinked form. While networked systems e.g. B. excellent Property profiles with regard to emulsion stabilization showed thickened especially with the help of the uncrosslinked variants electrolyte-containing systems are known to be very difficult or not at all with polyelectrolytes are thickened.

The polymers according to the invention are also suitable as thickeners and Dispersants, as emulsifiers, suspending agents with thickening action and Consistency generator for emulsions and suspensions, as well as, adhesives, thickeners, Dispersant and emulsifier of solid-containing preparations. You can do that too Mixtures of the polymers are used. The emulsifying, stabilizing and / or consistency-giving effect of the polymers according to the invention in Emulsions are created by an association of the polymer side chains with each other, and by an interaction of the polymer side chains with the hydrophobic Oil components caused or intensified. Polymers with a high proportion of Hydrophobic side chains have a high dispersing or emulsifying capacity good a high susceptibility of funds.

The polymers according to the invention are suitable for use 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).

The crop protection agents according to the invention can be pesticides from the group of 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, Clopyralid, 2,4-D, 2,4-DB, Dalapon, Dicamba, Dichlorprop, Diclofop, Endothall, Fenac, Fenoxaprop, Flamprop, Fluazifop, Flumiclorac, Fluoroglycofen, Fomesafen, Fosamine, Glufosinate, Haloxyfop, Imazapic, Imazamethabenz, Imazamox, Imazapyr, Imazaquin, Imazethapyr, Ioxynil, MCPA, MCPB, Mecoprop, Methylarsonic acid / MSMA, Naptalam, Picloram, 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 (Spiroxamine) and Fenpropidine, as well as morpholine derivatives such as aldimorph, dodemorph and Fenpropimorph.

Azinphos-methyl may preferably be mentioned as insecticidal active compounds, Azinphosethyl, 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.

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 found here are between 1:10 to 500: 1, in particular 1: 4 to 4: 1.

Concentrate formulations that are diluted before use can do this Pesticide in the weight amounts 5 to 60%, preferably 20 to 40% and the AMPS Contain copolymer in amounts of 3 wt .-% to 50 wt .-%. The Weight ratio of AMPS copolymer to pesticide can be between 1:20 to 1: 1, preferably 1:10 to 1: 2.

Alternatively, the formulations according to the invention can be in solid form as a powder, Pellets, tablets or granules are made that are used before Water can be dissolved. 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 weight amounts of 5% to 50%, preferably 10% to 30%.

The formulations according to the invention can also be the usual Thickeners, anti-gel agents, freezing agents, solvents, dispersants, Emulsifiers, preservatives, other 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. contain.

Xanthan gum and / or cellulose, for example, can be used as thickeners Carboxy-, methyl-, ethyl- or propyl cellulose, silicas and attapulgite in Quantities of 0.01 to 5% based on the finished agent are used. All conventional organic solvents are suitable as organic solvents on the one hand are not very miscible with water, but on the other hand the ones used Dissolve active ingredients well or form a suitable continuous phase. Aliphatic and aromatic hydrocarbons are preferred, optionally halogenated hydrocarbons, such as toluene, xylene, Tetrachloromethane, chloroform, methylene chloride, dichloroethane, ester and ethyl acetate. Organic acids and their esters, for example, can be used as preservatives Ascorbic acid, ascorbic palmitate, sorbate, benzoic acid, methyl- and propyl-4- Hydroxybenzoate, propionates, phenol, for example 2-phenylphenate, 1,2-benzisothiazolin-3-one, formaldehyde, sulfurous acid 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, if necessary silanated silica; paraffins; Waxes and microcrystalline waxes and their Mixtures with silanized silica. Mixtures of different ones are also advantageous Foam inhibitors, e.g. B. those made of silicone oil, paraffin oil and / or waxes. Cold stabilizers that can be used are all the usual substances used for this purpose act. Examples include urea, glycerin and propylene glycol.

All common acids and their salts can be used as buffers. Preferably phosphate buffers, carbonate buffers, citrate buffers may be mentioned.

Suitable dispersants and emulsifiers are nonionic, amphoteric, cationic and anionic surfactants.

Suitable surface-active substances are preferably addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles 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 ₁₈ ) alkylamines; secondary ether amines and alkoxylated secondary ether amine derivatives; (C ₁₂ -C ₁₈ ) fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol; Glycerol monoesters and diesters and sorbitan / sorbitol monoesters and diesters of saturated and unsaturated fatty acids having 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 especially polyglycerol esters, e.g. B. polyglycerol polyricinoleate and polyglycerol poly-12-hydroxystearate; Carboxamides, e.g. B. decanecarboxylic acid dimethyl amide; high molecular weight silicone compounds, e.g. B. Dimethylpolysiloxanes with an average molecular weight of 10,000 to 50,000 g / mol.

Anionic surfactants, e.g. B. alkali and ammonium salts of linear or branched alkyl (en) sulfates having 8 to 22 carbon atoms, (C ₁₂ -C ₁₈ ) alkyl sulfonic acids and (C ₁₂ -C ₁₈ ) alkyl aryl sulfonic acids; Bis (phenolsulfonic acid) ether and its alkali or ammonium salts, isethionates, preferably cocoyl isethionate; Naphthalenesulfonic acid and / or sulphosuccinates.

For solid formulations, polyvinylpyrrolidone is used as the binder, Polyvinyl alcohol, carboxymethyl cellulose, sugar, for example sucrose, sorbitol, or strength.

Suitable as thinners, absorbers or carriers are carbon black, tallow, kaolin, Aluminum, calcium or magnesium stearate, sodium tripolyphosphate, Sodium tetraborate, sodium sulphate, silicates and sodium benzoate.

Cellulose, for example carboxymethyl cellulose, acts as disintegrant, Polyvinyl pyrrolidone, sodium or potassium acetate, carbonates, bicarbonates, Sesquicarbonates, ammonium sulfate or potassium hydrogen phosphate. Alcohol ethoxylates / propoxylates can be used as wetting agents.

The formulations according to the invention can be carried out according to the customary methods be used.

Aqueous concentrates and solid formulations are used before application the appropriate amount of water diluted. Per hectare Pesticide amounts in the range of 0.1 to 5 kg, preferably 0.3 to 2.5 kg applied. The proportion of the adjuvant AMPS copolymer according to the invention is in the range of 0.1 to 3.0 kg / ha. The volume of the spray created Pesticide formulation is in the range of 50 to 1000 l / ha.

The use of the polymers gives the user extensive freedom in Choice of its components. The formulations show a high compatibility of the Components with each other (pesticides, salts, adjuvants etc.), high solubility of pesticides and agrochemical salts as well as 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. Formulation examples (all figures in% by weight) oil-in-water emulsion (EW)

Formulations 1 and 2 are prepared

• - add water and emulsifier;
• - Mix / dissolve crop protection agent with solvent;
• - Active ingredient solution by slowly dropping in the water phase using Emulsify high-speed stirrers (e.g. Ultra Turrax)
• - Stir in the thickener in the emulsion
  
  
  

Example 3 Example 4 Example 5 Example 6 Method of preparation of the emulsion concentrates (EC)

• - Mix / dissolve crop protection agent with solvent
• - Add anionic and nonionic emulsifiers and then homogenize

Suspension concentrate with atrazine Brookfield; 20 ° C; 30 rpm; Spindle No. 3

• - Introduce water, dispersant and glycol
• - crop protection agent using high-speed stirrer (e.g. Ultra-Turrax) disperse in the water / surfactant phase
• - Use a Perl mill to grind the dispersion to a particle size of approx. 10 µm
• - Slowly stir in the thickener and defoamer into the dispersion

Chemical name of the commercial products used

Solvesso 150 (Exxon Chemicals): aromatic hydrocarbon mixture
Dispersant LFS (Clariant GmbH): poly (arylalkyl) phenol polyethylene glycol phosphoric acid salt
Kelzan (Kelco): Xanthan gum
Phenylsulfonate CA (Clariant GmbH): calcium alkylbenzenesulfonate
Emulsogen EL (Clariant GmbH): Ethoxylated vegetable oil
Defoamer SE 57 (Wacker): polydimethylsiloxane + filler

Claims (9)

1. Plant protection products, characterized in that they contain at least one copolymer, obtainable by radical copolymerization of A) acryloyldimethyltauric acid and / or acryloyldimethyltaurates, 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) optionally one or more at least monofunctional, silicon-free component (s) capable of radical polymerization, E) optionally one or more at least monofunctional fluorine-containing component (s) capable of radical polymerization, 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, the Macromonomers are not silicon-containing component D) or fluorine-containing component E), 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) with the proviso that component A) is copolymerized with at least one component selected from one of groups D) to G). 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 carbon 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-vinyl pyridine, 4-vinyl pyridine, vinyl acetate; Styrene, acrylonitrile, Vinyl chloride, vinylidene chloride, tetrafluoroethylene, vinylphosphonic acid or their Esters or salts, vinyl sulfonic acid or their esters or salts, allylphosphonic acid or their esters or salts and / or methallylsulfonic acid or their esters or Salts. 3. Composition according to claim 1, characterized in that it is the comonomers C)
Diallyldimethylammonium chloride (DADMAC),
[2- (methacryloyloxy) ethyl] trimethylammonium chloride (MAPTAC),
[2- (acryloyloxy) ethyl] trimethylammonium chloride,
[2-methacrylamidoethyl] trimethyl ammonium chloride,
[2- (acrylamido) ethyl] trimethylammonium chloride,
N-methyl-2-vinyl pyridinium chloride
N-methyl-4-vinyl pyridinium chloride
dimethylaminoethyl
dimethylaminopropylmethacrylamide,
Methacryloylethyl-N-oxide and / or
Methacryloylethyl betaine. 4. Composition according to at least claim 1, characterized in that the macromonomers F) are compounds of the formula (III),

R ¹ -Y - [(A) _v - (B) _w - (C) _x - (D) _z ] -R ² (III)

where R ^{1 is} a polymerizable function from the group of vinylically unsaturated compounds, preferably a vinyl, allyl, methallyl, methylvinyl, acrylic, methacrylic, crotonyl, senecionyl, itaconyl, maleinyl, fumaryl or styryl radical , represents;
Y is a bridging group, preferably -O-, -S-, -C (O) -, -C (O) -O-, -O-CH ₂ -CH (O -) - CH ₂ OH, -O-CH ₂ -CH (OH) -CH ₂ O-, -O-SO ₂ -O-, -O-SO ₂ -O-, -O-SO-O-, -PH-, -P (CH ₃ ) -, -PO ₃ -, -NH- and -N (CH ₃ ) -;
A, B, C and D independently of one another discrete chemical repeat units, preferably originating from acrylamide, methacrylamide, ethylene oxide, propylene oxide, AMPS, acrylic acid, methacrylic acid, methyl 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 on average ≥ 1; and
R ^{2 represents} a linear or branched aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (C ₁ -C ₅₀ ) hydrocarbon radical, OH, -NH ₂ or -N (CH ₃ ) ₂ or is equal to [-YR ¹ ]. 5. Means according to claim 1, characterized in that it is in the polymeric additives G) to homo- or copolymers of N-vinylformamide, N-vinyl acetamide, N-vinyl pyrrolidone, ethylene oxide, propylene oxide, 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. Composition according to at least one of claims 1 to 5, characterized characterized in that the copolymers are cross-linked. 7. Composition according to claim 1, characterized in that it by copolymers Precipitation polymerization and solution polymerization in tert-butanol become. 8. Composition according to claim 1, characterized in that they, based on the finished agents containing 0.01 to 10 wt .-% of the copolymers. 9. Composition according to claim 1, characterized in that the copolymers are water-soluble, water-swellable or oil-soluble.