EP1569971A1 - Copolymeres a base de n-vinylamide utilises en tant qu'adjuvants et produits dans le domaine de la technologie agricole - Google Patents

Copolymeres a base de n-vinylamide utilises en tant qu'adjuvants et produits dans le domaine de la technologie agricole

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Publication number
EP1569971A1
EP1569971A1 EP03782264A EP03782264A EP1569971A1 EP 1569971 A1 EP1569971 A1 EP 1569971A1 EP 03782264 A EP03782264 A EP 03782264A EP 03782264 A EP03782264 A EP 03782264A EP 1569971 A1 EP1569971 A1 EP 1569971A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
monomer units
acid
methyl
carboxylic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03782264A
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German (de)
English (en)
Inventor
Lysander Chrisstoffels
Izaskun Manteca Zuazo
Reinhard Stierl
Rainer Berghaus
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BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1569971A1 publication Critical patent/EP1569971A1/fr
Withdrawn legal-status Critical Current

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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
    • A01N25/08—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate

Definitions

  • Copolymers based on N-vinylamide as adjuvants and agents for the agrotechnical sector are also possible.
  • the present invention relates to certain copolymers based on N-vinylamide and their use as an activity-improving adjuvant in the agrotechnical field and in particular in the field of crop protection. Appropriate agrotechnical means are also described.
  • the effective absorption of the active ingredient by the plant is of particular importance for the effectiveness of an agrotechnical agent. If this uptake takes place via the leaf, it presents itself as a complex transport process in which the active substance mass, for example a herbicide, first has to penetrate into the waxy cuticle of the leaf and then diffuse through the cuticle into the underlying tissues to the actual site of action ,
  • auxiliaries it is generally known and agricultural practice to add certain auxiliaries to formulations for improved effectiveness.
  • the amounts of active substance in the formulation can be reduced while the activity remains the same, as a result of which costs are minimized and existing legal regulations can be complied with if necessary.
  • the performance under unfavorable environmental conditions can be increased in individual cases by a suitable formulation. This means that incompatibilities of different active ingredients can also be used in one formulation.
  • Such auxiliary substances are sometimes referred to as adjuvants. They are often surface-active or salt-like compounds.
  • modes can ⁇ fikatoren, actuators, fertilizers and pH buffers can be distinguished.
  • 5 modifiers influence wetting, liability and spreading of a formulation.
  • Actuators break up the waxy plant cuticle and improve the penetration of the active ingredient into the cuticle both in the short term (in the minute range) and in the long term (in the hour range).
  • Fertilizers such as ammonium sulfate, ammonium nitrate or urea improve the absorption and solubility of the active substance, and they can reduce the antagonistic behavior of active substances.
  • pH buffers are conventionally used to optimally adjust the pH of the formulation.
  • surface-active substances can act as modifiers and actuators. It is generally assumed that suitable surface-active substances increase the effective contact area of liquids on leaves by reducing the surface tension
  • surfactants can dissolve or break up the epicuticular waxes, which facilitates absorption of the active ingredient.
  • some surface-active substances can also improve the solubility of active substances in formulations and thus avoid crystal formation or at least delay it. Finally, in certain cases, they can also influence the absorption of active substances by retaining moisture.
  • Adjuvants of the surface-active type are becoming more diverse
  • Synthetic surface-active substances that are usually used as actuators include polyoxyethylene condensates with alcohols, alkylphenols or alkylamines, which have HLB values in the range from 8 to 13.
  • the object of the present invention is to provide further copolymers based on N-vinylamide.
  • the present invention solves this problem by novel copolymers based on N-vinylamide and their use as adjuvants, and by the provision of agrotechnical agents which contain these copolymers.
  • the present invention therefore relates to copolymers containing monomer units
  • R 1 represents hydrogen or an aliphatic hydrocarbon radical having 3 to 40 carbon atoms, preferably branched or linear, saturated or unsaturated C 3 _ 40 alkyl;
  • R 2 , R 3 'R 4 independently of one another represent hydrogen or -CC-alkyl
  • w, x, z independently correspond to a value from 0 to 100, the sum of w, x and z being greater than 0;
  • y corresponds to a value from 1 to 20;
  • a copolymerized monomer wherein the copolymerized monomer, i.e. the monomer unit, in comparison to the actual monomer introduced into the polymerisation reaction, is not only structurally changed by the polymerisation reaction, but also has further modifications
  • the monomer units of the carboxylic acid esters can be derived from the monomers introduced into the reaction by esterification.
  • N-vinylamides include, in particular, non-cyclic representatives, such as N-vinylformamide and N-vinylacetamide, and N-vinyl acetate.
  • N-vinyl lactams according to the invention are cyclic atoms, of which those with 4 to 6 carbon atoms are of particular importance. These N-vinyl lactams can also be 1, 2 or
  • N-vinyl lactams include N-vinyl pyrrolidone, N-vinyl caprolactam and the corresponding N-vinyl lactams substituted with a methyl or ethyl group.
  • copolymers according to the invention contain a type of monomer unit (i), ie monomer units of an N-vinylamide.
  • copolymers according to the invention contain two or more types of monomer units (i), for example monomer units of two or more N-vinylamides, such as N-vinylpyrrolidone and another one containing N-vinylcaprolactam, N- Vinylformamide and N-Vinylacetamid selected N-Vinylamids.
  • the monomer units (i) present in the copolymer are composed essentially of monomer units of an N-vinylamide, preferably of N-vinylpyrrolidone.
  • copolymers comprise, in particular, monomer units (i) of the formula (VIIa)
  • a stands for the average number of monomer units of the formula (VIIa) in the copolymer and preferably corresponds to a number in the range from 40 to 4500, advantageously in the range from 65 to 5000 and in particular in the range from 80 to 3200.
  • Suitable monomer units (ii) are esters of ethylenically unsaturated carboxylic acid.
  • ethylenically unsaturated carboxylic esters with 4 to 8 and in particular 4 to 6 carbon atoms in the carboxylic acid part are preferred.
  • Acrylic acid esters and methacrylic acid esters should be mentioned in particular. Of these carboxylic acid esters, methacrylic acid esters are particularly preferred.
  • the carboxylic acid esters have alkoxylates of linear or branched, saturated or unsaturated, primary, secondary or tertiary alcohols or amines.
  • Alcohol radicals of the formula (I) in which R 1 is an alkyl radical having preferably 3 to 30 carbon atoms have proven to be particularly suitable according to the invention, the longer-chain and in particular those having 5 to 15, preferably 8 to 12 and in particular 10 to 12 carbon atoms of Are advantage.
  • Alkoxylate residues and especially ethoxy lat residues of the formula (Ia) are very particularly suitable
  • R 1 has the above meaning and is preferably branched or linear, saturated or unsaturated C 5 _ 15 alkyl
  • z corresponds to a value from 1 to 100 and is preferably between 1 and 30.
  • R 1 stands in particular for the following alkyl radicals: hexan-1-yl (capronyl), heptan-1-yl (enanthyl), octan-1-yl (capryl), nanan-l-yl (pelargonyl), decan-1 -yl (caprinyl), undecan-1-yl, dodecan-1-yl (lauryl), tridecan-1-yl, tetradecan-1-yl (myristyl) or pentadecan-1-yl.
  • branched alkyl radicals such as isodecanyl, isolauryl and isotridecanyol can also be mentioned, these branched alkyl radicals generally being a mixture of different radicals with a corresponding carbon number.
  • alkoxylation results from the reaction with suitable alkylene oxides, which generally have 2 to 15 and preferably 2 to 6 carbon atoms.
  • suitable alkylene oxides which generally have 2 to 15 and preferably 2 to 6 carbon atoms.
  • EO ethylene oxide
  • PO propylene oxide
  • BO butylene oxide
  • PeO pentylene oxide
  • HO hexylene oxide
  • One type of suitable alkoxylate radicals of the formula (I) or (ia) is based on one type of alkylene oxide.
  • alkoxylate radicals of the formula (I) is based on at least two different types of alkylene oxide. It is preferred to arrange several alkylene oxide units of one type as a block, so that there are at least two different alkylene oxide blocks, which are each formed from several units of the same alkylene oxides. If block alkoxylates of this type are used, it is preferred that the alkylene oxide part is composed of 3 and in particular 2 blocks.
  • the alkoxylate residues to be used according to the invention are ethoxylated or have at least one ethylene oxide block.
  • ethylene oxide blocks are combined in particular with propylene oxide or pentylene oxide blocks.
  • the respective degree of alkoxylation is obtained. This is usually a statistical mean, since the number of alkylene oxide units of the alcohol alkoxate residues resulting from the reaction varies.
  • the degree of alkoxylation i.e. the average chain length of the polyether chains suitable according to the invention can be determined by the molar ratio of alcohol or A in to alkylene oxide.
  • Alkoxylates with about 1 to 50, preferably about 1 to 20, in particular 1 to 10, alkylene oxide units (sum of w, x, z), in particular ethylene oxide units, are preferred.
  • the alkoxylation of the alcohols or alcohol mixtures can be catalyzed by strong bases, such as alkali metal hydroxides and alkaline earth metal hydroxides, Bronsted acids or Lewis acids, such as AlCl 3 , BF 3 etc. Catalysts such as hydrotalcite or dimethyl carbonate (DMC) can be used for narrowly distributed alcoholoxylates.
  • the alkoxylation is preferably carried out at temperatures in the range from approximately 80 to 250 ° C., preferably approximately 100 to 220 ° C.
  • the pressure is preferably between ambient pressure and 600 bar.
  • the alkylene oxide can be admixed with an inert gas, e.g. B. from about 5 to 60%.
  • the alcohols themselves are generally commercially available and can also be prepared in a manner known per se.
  • the so-called Guerbet alcohols which can be obtained, for example, by dimerizing corresponding primary alcohols at elevated temperature in the presence of alkaline condensing agents, should be mentioned in this connection;
  • the alcohol mixtures often referred to as "Cs-O alcohols” the main component of which is formed from at least one branched C 3 alcohol (isotridecanol) and which are generally obtainable by hydrogenation of hydroformylated trimerbutene;
  • the alcohol mixtures often referred to as "Cio-Oxoalcohols” the main component of which is formed from at least one branched C ⁇ o-alcohol (isodecanol) and which are generally obtainable by hydrogenation of hydroformylated trimer propene.
  • Copolymers according to the invention can contain several types of monomer units (ii), e.g. Have carboxylic acid esters with different carboxylic acids and / or different alkoxylate parts.
  • the monomer units (ii) present in the copolymer are derived from one and in particular one of the carboxylic acids described as preferred above.
  • Copolymers whose monomer units (ii) essentially consist of monomer units of the acrylic acid and in particular methacrylic acid esters have proven to be particularly suitable.
  • the copolymers comprise, in particular, monomer units (ii) of the formulas (VIIIb) and / or of the formula (VIIb2)
  • R represents one of the alkoxylate radicals described above.
  • b can be the same or different and represents the average number of monomer units of the formula (VIIIb) or (VIIb2) in the polymer and preferably a number in the range from 1 to 100, advantageously in the range from 5 to 50 and in particular in the range from 11 to 25 corresponds.
  • R is preferably an alkoxylate radical of the formula (I) and in particular of the formula (Ia).
  • any copolymerizable ethylenically unsaturated comonomers with at least one double bond are suitable as monomer units (iii).
  • Salts, esters and amides of acrylic acid or methacrylic acid are particularly worth mentioning.
  • the salts can be of any non-toxic metal, ammonium or substituted ammonium counterions, e.g. cations mentioned above under M be derived.
  • the esters can be derived from linear C 1 -C. branched C 3 -C o or carbocyclic C 3 -C o alcohols, of multifunctional alcohols with 2 to about 8 hydroxyl groups such as ethylene glycol, hexylene glycol, glycerol and 1,2,6-hexanetriol, of amino alcohols or of alcohol ethers such as methoxyethanol and ethoxyethanol.
  • the amides can be unsubstituted, N-alkyl-substituted or N-alkylamino-substituted or N, N-dialkyl-substituted or N, N-dialkylamino-disubstituted, in which the alkyl or alkylamino groups of linear C 1 -C 6, branched C 3 -C 3 or carbocyclic C 3 - C 0 units are derived.
  • the alkylamino groups can also be quaternized.
  • Comonomers which can also be used as monomer units (iii) are salts, esters and amides of substituted acrylic acids, the substituents on the carbon atoms being in the 2 or 3 position of the
  • Acrylic acid and are independently selected from -CC 4 alkyl, -CN and COOH. Are particularly preferred here Salts, esters and amides of methacrylic acid, ethacrylic acid and 3-cyanoacrylic acid.
  • component (iii) are comonomers of the general formula (II):
  • Y is selected from -OM, -OR 7 , -NH 2 , -NHR 7 , -N (R 7 ) 2 , where the radicals R 7 can be identical or different and are selected from hydrogen, linear or branched C ⁇ - C 40 alkyl, N, N-dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, hydroxypropyl, methoxypropyl and ethoxypropyl, wherein OR 7 should not be OH;
  • M is a cation selected from alkali, alkaline earth and transition metal cations, in particular Na + , K + , Mg ++ , Ca ++ and Zn ++ , NH 4 + , and quaternary ammonium cations, in particular alkylammonium, dialkylammonium, trialkylammonium and tetraalkylammonium; and
  • R 5 , R 6 are independently selected from hydrogen, linear or branched Ci-Cs-alkyl, methoxy, ethoxy, 2-hydroxyethoxy, 2-methoxyethoxy and 2-ethoxyethyl.
  • N, N-dialkylaminoalkyl acrylates and methacrylates are also suitable.
  • N, N-dialkylaminoalkyl acrylates and methacrylamides are also suitable.
  • R 8 represents hydrogen or -CC 8 alkyl
  • R 9 represents hydrogen or methyl
  • R 10 represents -C 2 -C 4 -alkylene, which can be substituted by alkyl
  • Preferred comonomers of the formula (III) are N, N-dimethylaminomethyl (meth) acrylate, N, -diethylaminomethyl (meth) acrylate,, -dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N - [3- (dimethylamino) propyl] methacrylamide and N- [3- (dimethylamino) propyl] acrylamide.
  • the expression "(meth) acrylate” stands for both "acrylate” and for "methacrylate”.
  • Allyl esters of linear C-- are also suitable .
  • N-vinylimidazoles of the general formula (IV) are also suitable.
  • pi3 - Ri5 independently of one another represent hydrogen, C 1 -C alkyl or phenyl.
  • Comonomers which can also be used as monomer units (iii) are olefins, ie in principle any unsaturated hydrocarbons with at least one ethylenically unsaturated, polymerizable double bond. Olefins with a terminal double bond are advantageous. Monoethylenically unsaturated olefins are preferred. Monoethylenically unsaturated olefins with a terminal double bond are particularly preferred.
  • Preferred olefins have 4 to 40, in particular 4 and preferably 8 to 24 carbon atoms. According to a particular embodiment, the olefins have 8 or 18 or 20 to 24 carbon atoms.
  • Suitable olefins include, for example, butene-1, butene-2, butadiene, 2-methylpropene-1 (isobutene), pentene-1, isoprene, 2-methylbutene-1, 3-methylbutene-1, hexene-1 and cyclohexadiene , 2-methylpentene-1, 3-methylpentene-1, 4-methylpentene-1, 2-ethylbutene-1, 4,4-dimethylbutene-l, 2,4-dimethylbutene-l, 2, 3-dimethylpentene-l , 3, 3-dimethylpentene-1, 2, 4-dimethylpentene-1, 3, 4-dimethylpentene-1, 4,4-dimethylpentene-1, octene-1, 2,4, 4-trimethylpentene-1, 2,4 , 4-trimethylpentene-2, diisobutene, in particular those which are technically as an isomer mixture of essentially 2,4,4-trimethylpentene-1 and 2,
  • ethylene, propylene and vinylidene chloride are also suitable as comonomers for the monomer units (iii).
  • Suitable monomer units (iii) are vinyl ethers, the alcohol part of which has 1 to 30 and preferably 1 to 20 carbon atoms.
  • C 1 -C 30 -Alkyl vinyl ether should be mentioned here in particular, it being possible for the alkyl radicals to be linear, branched or cyclic, unsubstituted or substituted.
  • Suitable alkyl vinyl ethers are, for example, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, dodecyl vinyl ether.
  • Comonomers to be mentioned in particular for the monomer units (iii) are methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, nyl acrylate -Butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, methyl ethacrylate, ethyl ethyl acrylate, n-butyl ethacrylate, iso-butyl ethacrylate, t-butyl ethacrylate, 2-ethyl hexyl ethacrylate, decyl ethacrylate, ste
  • Diallyldimethylammonium chloride vinylformamide, vinylmethylacetamide, vinylamine; Methyl vinyl ketone, vinyl pyridine, vinyl imidazole, vinyl furan, styrene, styrene sulfonate, allyl alcohol, and mixtures thereof.
  • methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, isobutyl acrylate, isobutyl imethacrylate, 2-ethylhexyl acrylate, stearyl acrylate, stearyl acrylate are particularly preferred ryl methacrylate, Nt-butylacrylamide, N-oct lacrylamide, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, hydroxyprop imethacrylate, styrene, unsaturated sulfonic acids such as acrylamidopropanesulfonic acid, vinyl formamide, vinyl methylacetamide, vinyl amine, 1-vinyl imidazole Vinyl-2-methylimidazole Vinyl-2
  • Comonomers or corresponding monomer units with a basic nitrogen atom can also be quaternized in the following way:
  • alkyl halides with 1 to 24 carbon atoms in the alkyl group e.g. Methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, propyl chloride, hexyl chloride, dodecyl chloride, lauryl chloride and benzyl halides, especially benzyl chloride and benzyl bromide.
  • Other suitable quaternizing agents are dialkyl sulfates, especially dimethyl sulfate or diethyl sulfate.
  • the quaternization of the basic amines can also be carried out with alkylene oxides such as ethylene oxide or propylene oxide in the presence of acids.
  • alkylene oxides such as ethylene oxide or propylene oxide
  • Preferred quaternizing agents are: methyl chloride, dimethyl sulfate or diethyl sulfate.
  • the quaternization can be carried out before or after the polymerization.
  • R 17 represents C 1 -C 40 alkyl
  • reaction products are (meth) acryloyloxyhydroxypropyltrimethylammonium chloride and (meth) acryloyloxyhydroxypropyltriethylammonium chloride.
  • the basic comonomers can also be cationized by mixing them with mineral acids such as e.g. Sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid or nitric acid, or with organic acids such as e.g. Formic acid, acetic acid, lactic acid or citric acid can be neutralized.
  • mineral acids such as e.g. Sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid or nitric acid
  • organic acids such as e.g. Formic acid, acetic acid, lactic acid or citric acid can be neutralized.
  • macromonomers such as, for example, silicone-containing macromonomers with one or more radical-polymerizable groups or alkyloxazoline macromonomers, as described for example in EP 408 311, can be used for the monomer units (iii).
  • macromonomers such as, for example, silicone-containing macromonomers with one or more radical-polymerizable groups or alkyloxazoline macromonomers, as described for example in EP 408 311, can be used for the monomer units (iii).
  • fluorine-containing monomers as described, for example, in EP 558 423, and crosslinking compounds or compounds which regulate the molecular weight can be used in combination or alone.
  • copolymers according to the invention contain essentially no monomer units (iii). Accordingly, these copolymers essentially consist of monomer units (i) and (ii).
  • the proportion of monomer units (i) is preferably 10 mol% to 99 mol%, advantageously 40 mol% to 95 mol% and in particular 60 mol% to 90 mol% and the proportion of monomer units (ii) 90 mol % to 1 mol%, advantageously 60 mol% to 5 mol% and in particular 40 mol% to 10 mol%.
  • copolymers according to the invention contain monomer units (iii). Accordingly, these copolymers essentially consist of monomer units (i),
  • the proportion of monomer units (i) is 60 mol% to 99 mol%, preferably in some cases 70 mol% to 95 mol% and in particular 85 mol% to 95 mol%, the proportion of monomer units (ii) 30 mol% to 1 mol%, advantageously 20 mol% to 3 mol% and in particular 15 mol% to 5 mol% and the proportion of monomer units (iii) up to 10 mol%, advantageously up to 5 mol% and in particular up to 1 mol%.
  • copolymers to be used according to the invention generally have a relatively small contact angle.
  • Particularly preferred are copolymers whose contact angle is less than 90 ° and preferably less than 75 ° if this is determined in a manner known per se using an aqueous solution containing 2% by weight of copolymer on a paraffin surface.
  • the surface-active properties of the copolymers depend in particular on the type and distribution of the monomer units.
  • the surface tension of copolymers to be used according to the invention which can be determined by the pendant drop method, is preferably in a range from 20 to 72 mN / m, in particular 30 to 65 mN / m, for a solution containing 0.1 to 2.0% by weight of copolymer.
  • Copolymers which are preferably to be used according to the invention therefore qualify as a -phiphilic substances.
  • the weight average molecular weight of the copolymers according to the invention is between 5,000 and 800,000, preferably between 7,500 and 600,000, particularly preferably between 10,000 and 400,000.
  • copolymers according to the invention are preferably not crosslinked.
  • the polymers according to the invention can be obtained by copolymerizing suitable monomers corresponding to the monomer units (i) and (ii) (monomers of groups (i) or (ii)) and optionally further comonomers (comonomers of group (iii) corresponding to the monomer units (iii) ) getting produced.
  • the monomers or comonomers can be formed using initiators which form free radicals and also by the action of high-energy radiation, which also includes the action of high-energy electrons. that should be polymerized (see, for example, EP 9 169 AI, EP 9 170 AI and EP 276 464, to which express reference is made).
  • the peroxo and / or azo compounds customary for this purpose can be used as initiators for the radical polymerization, for example alkali metal or ammonium peroxydisulfates, di-acetyl peroxide, dibenzoyl peroxide, succinyl peroxide, di-tert. -butyl peroxide, tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl permaleinate, cumene hydroperoxide, diisopropyl peroxidicarbamate, bis (o-toluoyl) peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide.
  • alkali metal or ammonium peroxydisulfates for example alkali metal or ammonium peroxydisulfates, di-acetyl peroxide, dibenzoyl peroxide, succinyl peroxide, di-
  • the amounts of initiator or initiator mixtures used, based on the amounts of monomer used, are between 0.01 and 10% by weight, preferably between 0.05 and 5% by weight.
  • the polymerization generally takes place in a temperature range from 40 to 200 ° C., preferably in the range from 50 to 140 ° C., particularly preferably in the range from 60 to 130 ° C. It is usually carried out under atmospheric pressure, but can also take place under reduced or elevated pressure, in the latter case preferably between 1 and 5 bar.
  • the polymerization can be carried out, for example, as solution polymerization, bulk polymerization, emulsion polymerization, reverse emulsion polymerization, suspension polymerization, reverse suspension polymerization or precipitation polymerization, without the methods which can be used being restricted thereto.
  • the procedure can be such that the monomers of group (i), the monomers of group (ii) and, if appropriate, further comonomers of group (iii) are mixed with one another and the mixtures are polymerized out after addition of a polymerization initiator.
  • the polymerization can also be be carried out continuously by first introducing a portion, for example 10%, of the mixture to be polymerized from monomers or comonomers of groups (i) and (ii) and, if appropriate, (iii) and initiator, the mixture being heated to the polymerization temperature and after starting the remainder of the mixture to be polymerized is added to the polymerization as the polymerization progresses.
  • the polymers can also be obtained by placing the monomers of group (i) in a reactor, heating to the polymerization temperature and at least one monomer from group (ii) and optionally another or more further comonomers from group (iii) and polymerization initiator either at once, batchwise or preferably continuously and polymerized.
  • the polymerization can be carried out with the aid of protective colloids, as described for example in DT 2840201.
  • the polymerization described above can also be carried out in a solvent.
  • suitable solvents are, for example, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-hexanol and cyclohexanol, and glycols, such as ethylene glycol, propylene glycol and butylene glycol, and the methyl or Ethyl ether of the dihydric alcohols, diethylene glycol, triethylene glycol, glycerin and dioxane.
  • solvents which are inert towards the carboxylic acid esters used.
  • the polymerization can also be carried out in water as a solvent.
  • the polymerization mixture is initially in the form of a solution which, depending on the amount of added monomers of groups (i) and (ii) and further comonomers of group (iii), is more or less readily soluble in water.
  • organic solvents such as monohydric alcohols having 1 to 3 carbon atoms, acetone or dimethylformamide.
  • the polymerization in water can also be carried out in such a way that the water-insoluble polymers are added in a conventional manner
  • Emulsifiers or protective colloids for example polyvinyl alcohol, are converted into a finely divided dispersion. 5
  • the emulsifiers used are, for example, ionic or nonionic surfactants whose HLB value is in the range from 3 to 13.
  • HLB value For the definition of the HLB value, reference is made to the publication by WC Griffin, J. Soc. Cos etic Che., Vol. 5, 249 (1954).
  • the amount of surfactants, based on the polymer is generally 0.1 to 10% by weight.
  • solutions or dispersions of the polymers are obtained. If solutions of the polymer are prepared in an organic solvent or in mixtures of an organic solvent and water, 5 to 2000, preferably 10 to 500 parts by weight of the organic solvent or are generally used per 100 parts by weight of the polymer of the solvent mixture.
  • copolymers which can be used according to the invention are in particular obtainable by copolymerization
  • copolymer CP ' obtained from the copolymerization can, if necessary, be subjected to one or more of the following further process measures:
  • the relative amounts of monomers and comonomers to be selected for copolymerization are the above statements on the ratios of monomer units (i) and (ii) and optionally (iii).
  • the polymerization of monomers and comonomers which lead directly to the desired copolymer CP is preferred.
  • the type of monomers or comonomers to be used does not depend only on the monomer units to be formed. Rather, it is expedient in many cases to polymerize monomers or comonomers which are converted into the desired monomer units after the polymerization reaction. This procedure can be due to the reaction and process technology. 5
  • the monomers that can be used for the monomer units (ii) can differ from the monomer units involved in the construction of the copolymer CP.
  • carboxylic acids or certain carboxylic acid derivatives can first be polymerized.
  • the monomer units (ii ') of the copolymer CP' formed therefrom are then generally subjected to one or more of the process measures (4), (5) and / or (6) described above, so that finally the copolymer CP or a Salt results from it.
  • carboxylic acid esters with short-chain, easily hydrolyzable ester groups such as alkyl esters with preferably 1 to 3 carbon atoms in the alkyl part, can also be polymerized, the alcohol part of which is subsequently split off and replaced by a further alcohol.
  • the copolymer CP 'obtainable by copolymerization can contain carboxyl groups and / or derivatized carboxyl groups, e.g. Contain ester groups which, if desired, are then reacted in a polymer-analogous reaction, generally with formation of the carboxylic acid esters.
  • Preferred polymer-analogous reactions are (4) solvolyses such as hydrolysis and alcoholysis of carboxylic acid derivatives and (5) esterifications of carboxyl groups.
  • copolymers CP to be used according to the invention can be obtained by (ii) selecting at least one ethylenically unsaturated carboxylic acid and copolymerizing it with the other monomers or comonomers, and at least part of the carboxyl groups of the resulting copolymerization product CP 'with ester formation using suitable Alcohols. 5
  • the polymer-analogous reaction following the polymerization can be carried out in the presence of a solvent, for example acetone or Tetrahydrofuran.
  • a solvent for example acetone or Tetrahydrofuran.
  • the copolymer CP ' is reacted directly with the derivatizing agent, for example an alcohol corresponding to the abovementioned formula (I).
  • the amount of reactants to be used depends on the degree of derivatization to be achieved.
  • the derivatization is an esterification reaction
  • this is carried out in the usual way, namely usually at an elevated temperature, e.g. 50 to 200 ° C and preferably at 80 to 150 ° C, optionally in the presence of a conventional catalyst, e.g. p-toluene sulfonic acid.
  • Typical reaction times are in the range from 0.5 to 20 and in particular 1 to 10 hours.
  • the conversion of anhydride groups present in the polymer is preferred. This can optionally be carried out without a solvent or in a solvent. If a solvent is used, those organic fluids are particularly suitable which are inert towards anhydride groups and which not only dissolve or swell the starting material but also the reaction product, namely the at least partially esterified copolymer.
  • the polymers can be neutralized, in part or in full, with bases before or after the polymerization in order, for example, to adjust the water solubility or water dispersibility to a desired level.
  • neutralizing agents for acid groups are mineral bases such as sodium carbonate, alkali metal hydroxides such as sodium hydroxide or potassium hydroxide, alkaline earth metal hydroxides, and ammonia, organic bases such as alkylamines, dialkylamines, trialkylamines, amino alcohols, especially isopropylamine, ethylamine, diisopropylamine, diethylamine, triethylamine, triisethylamine, triisopropylamine, Amino-2-methyl-1-propanol, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, tri (2-hydroxy-1-propyl) amine, 2-amino-2-methyl II, 3-propanediol, 2-amino -2-hydroxymethyl-l, 3-propanediol, and diamines, such as lysine, can be used.
  • mineral bases such as sodium carbonate
  • alkali metal hydroxides such as sodium hydroxide or potassium
  • copolymers according to the invention based on N-vinylamide have adjuvant, in particular active, changing properties.
  • the addition of such copolymers enables accelerated absorption of active substances by a plant to be treated with the active substance.
  • the following aspects in particular derive from the adjuvant effect when treating plants with one or more active substances:
  • the present invention therefore also relates to the use of the copolymers as an adjuvant in the treatment of plants.
  • the use according to the invention is particularly aimed at plant cultivation, agriculture and horticulture. In particular, it is used to control undesirable plant growth.
  • the present invention also relates to methods of treating plants corresponding to the above uses, a suitable amount of copolymer according to the invention being applied.
  • copolymers according to the invention can also be used in crops which are tolerant to the action of herbicides. Such cultures can be obtained for example by breeding and genetic engineering methods.
  • copolymers can be used as stand-alone products and co-applied together with at least one agent-containing agent, shortly before use mixed with at least one agent-containing agent and applied as a corresponding mixture, or as a Coformulant can be incorporated into the formulation as a ready mix.
  • compositions comprising
  • components of component (b) in the total weight of the composition of more than 0.5% by weight, preferably more than 1% by weight and in particular more than 5% by weight are advantageous.
  • components (b) in the total weight of the composition of less than 50% by weight, preferably less than 25% by weight and in particular less than 10% by weight are generally expedient.
  • the active ingredient (component (a)) can be selected from herbicides, fungicides, insecticides, acaricides, nematicides, and active ingredients which regulate plant growth.
  • Herbicidal crop protection agents can contain one or more of the following herbicidal crop protection agents, for example:
  • 1,3,4-thiadiazoles such as buthidazole and cyprazole, amides such as allidochlor, benzoylpropethyl, bromobutide, chlorothiamide, dimepiperate, dimethenamid, diphenamide, etobenzanide, flampropmethyl, fosamine, isoxaben, monalide, naptalame, pronamid, propanoic acid, bilafinic acid, aminafanic acid, aminafanoic acid, aminafanic acid, aminafanic acid, aminafanic acid, aminafanic acid, aminafanic acid, aminafanic acid, aminafanic acid, aminafanic acid, aminafanic acid, aminafanic acid, aminafanic acid, aminafanic acid, aminafanic acid, aminafanic acid, aminafanic acid, aminafanic acid, aminophosphoric acid Gluf
  • Sulphonamides such as flu etsulam, metosulam, triazolecarboxamides such as triazofenamide, uracils such as bromacil, lenacil, terbacil, furthermore benazolin, benfuresate, bensulide, benzofluor, butamifos, cafenstrole, chlorothal-dimethyl, cinmethylin, dichlobenil, endothilidefluid, fluoride, perfluoride, fluoro.
  • Preferred herbicidal crop protection agents are those of the sulfonylurea type, such as amidosulfuron, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron-methyl, flazasulfuron, halosulfuron-methyl, mimosulfuron, imazosulfuron prosulfuron, Pyrazosulfuron-ethyl, Rimsulfuron, Sulfometuron-ethyl, Thifensulfuron-methyl, Triasulfuron, Tribenuron-methyl, Triflu-sulfuron-methyl, Tritosulfuron.
  • sulfonylurea type such as amidosulfuron, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinos
  • herbicidal crop protection active ingredients are those of the cyclohexenone type, such as alloxydim, clethodim, cloproxydim, cycloxydim, sethoxydim and tralkoxydim.
  • Very particularly preferred herbicidal active compounds of the cyclohexenone type are: Tepraloxydi (cf. AGROW, No. 243,
  • the fungicidal compositions comprise one or more, for example, the following fungicidal active ingredients: sulfur, dithiocarbamates and their derivatives, such as Ferridimethyl-dithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate, manganese zinc ethylene di-amine-bis-dithiocarbamate, tetramethyl-thiuram disulfides, ammonia complex of zinc (N, N-ethylene-bis-dithiocarbamate), ammonia complex of zinc (N, N'-propylene-bis-dithiocarbamate), zinc (N, N '-propylene-bis-dithiocarbamate), N, N 'Polypropylene bis (thiocarba-moy1) disulfide;
  • sulfur, dithiocarbamates and their derivatives such as Ferridimethyl-dithiocarbamate, zinc dimethyl
  • Nitroderivatives such as dinitro- (1-methylhepty1) -phenylcrotona, 2-sec-butyl-4, 6-dinitrophenyl-3, 3-dimethylacrylate, 2-sec-butyl-4, 6-dinitrophenyl-isopropyl carbonate, 5-nitro-isophthalic acid -di-isopropyl ester;
  • heterocyclic substances such as 2-heptadecyl-2-imidazoline acetate
  • N-trichloromethylthio-phthalimide N-dichlorofluoromethylthio-N ',' -dimethy1-N-pheny1-sulfuric acid diamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-rhodan-methylthiobenzothiazole, 1,4-dichloro-2,5 -dimethoxybenzene, 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridine-2-thiol-l-oxide, 8-hydroxyquinoline or its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl -1,4-oxathiin, 2,3-dihydro-5-carboxani-lido-6-methyl-1,4-oxathiin-4,4-dioxide, 2-methyl-5,6-dihydro-4H-pyran-3 -carboxylic acid anilide, 2-methyl-
  • Anilinopyrimidines such as N- (4,6-dimethylpyrimidin-2-yl) aniline, N- [4-methyl-6- (1-propynyl) pyrimidin-2-yl] aniline, N- [4-methyl-6 cyclopropyl-pyrimidin-2-yl] aniline,
  • Phenylpyrroles such as 4- (2,2-difluoro-1,3-benzodioxol-4-yl) pyrrole-3-carbonitrile,
  • Usable growth regulators are, for example, the group of gibberellins. These include, for example, the Gibberellins GAi, GA 3 , GA 4 , GA 5 and GA 7 etc. and the corresponding exo-16, 17-dihydrogibberellins and the derivatives thereof, for example the esters with C 1 -C 4 -carboxylic acids. According to the invention, exo-16, 17-dihydro-GA 5 -13-acetate is preferred.
  • the active ingredient component (a) consists essentially of one or more of the following preferred active ingredients: bentazone, difenzoquat, pendimethalin, quinclorac, cycloxydi, quinmerac, sethoxydim, cinidon-ethyl, mecoprop, mecoprop-P , Dichlorprop, chloridazon, dicamba, metobromuro, profoxydi, tritosul uron, diflufenzopyr, s-dimethenamid, cyanazine, picolinafen, cyclosulfamuron, imazamethabenz-methyl, imazaquin, acifluorfen, nicosulfuron, sulfur, di-themianir Nitrothal-Isopropyl, Thiophhanate- Methyl, Metholachlor, Triforine, Carbendazim, Vinclozolin, Do- dine, fenpropimorph, e
  • the adjuvant effect of the copolymers according to the invention is particularly advantageous for active substances from the class of strobilurins, e.g. in pyraclostrobin, and active substances from the class of the triazoles, e.g. noticeable with metconazole, tebuconazole, triadimenol, triadimefon, cyproconazole, uniconazole, paclobutrazole, ipconazole and in particular epoxiconazole.
  • the present invention particularly relates to agents with high
  • the proportion of component (a) in the total weight of the composition generally makes up more than 10% by weight, preferably more than 15% by weight and in particular more than 20% by weight.
  • the proportion of component (a) in the total weight of the composition is expediently generally less than 80% by weight, preferably less than 70% by weight and in particular less than 60% by weight.
  • the formulations according to the invention can also contain customary auxiliaries and / or additives for the production of formulations in the agrotechnical field and in particular in the field of crop protection.
  • auxiliaries for example, surfactants, dispersing aids, wetting agents, thickeners, organic solvents, cosolvents, defoamers, carboxylic acids, preservatives, stabilizers, etc.
  • the agents comprise at least one (further) surfactant as surface-active component (c).
  • surfactant here denotes surface-active or surface-active agents.
  • Component (c) is added, in particular, as a dispersant or emulsifier, especially for dispersing a solid fraction in suspension concentrates. Furthermore, parts of component (c) can serve as wetting agents.
  • anionic, cationic, amphoteric and nonionic surfactants can be used, polymer surfactants and surfactants with heteroatoms being included in the hydrophobic group.
  • the anionic surfactants include, for example, carboxylates, especially alkali, alkaline earth and ammonium salts of fatty acids, e.g. Potassium stearate, commonly referred to as soaps; glutamates; Sarcosinates, e.g.
  • the cationic surfactants include, for example, quaternized ammonium compounds, in particular alkyltrimethylammonium and dialkyldimethylammonium halides and alkylsulfates, and pyridine and imidazoline derivatives, in particular alkylpyridinium halides.
  • the nonionic surfactants include, for example, other alkoxylates and especially ethoxylates, in particular
  • Fatty alcohol polyoxyethylene esters for example lauryl alcohol polyoxyethylene ether acetate,
  • Alkyl polyoxyethylene and polyoxypropylene ethers e.g. of linear fatty alcohols, alkylaryl alcohol polyoxyethylene ethers, e.g. Octylphenol polyoxyethylene ether, alkoxylated animal and / or vegetable fats and / or
  • Oils for example corn oil ethoxylates, castor oil ethoxylates,
  • Tallow fat ethox late glycerol esters, such as glycerol monostearate, - ' Fettalkoholalkox late and Oxoalkoholalkoxylate, especially of the linear type
  • Alkylphenol alkoxylates such as, for example, ethoxylated iso-octyl, octyl or nonylphenol, tributylphenol polyoxyethylene ether,
  • Alkyldimethylphosphine oxides such as tetradecyldimethylphosphine oxide.
  • amphoteric surfactants include, for example, sulfobetaines, carboxybetaines, and alk dimethylamine oxides, e.g. Tetradecyldimethylamine oxide.
  • the polymeric surfactants include, for example, di-, tri- and multiblock polymers of type (AB) X , ABA and BAB, for example end group-capped ethylene oxide / propylene oxide block copolymers, for example ethylenediamine-EO / PO block copolymers, polystyrene block copolymers.
  • Polyethylene oxide, and AB comb polymers eg polymethacrylate comb polyethylene oxide.
  • surfactants to be mentioned here by way of example are perfluorosurfactants, silicone surfactants, e.g. Polyether modified siloxanes, phospholipids such as lecithin or chemically modified lecithins, amino acid surfactants e.g. N-lauroyl glutamate and surface active homo- and copolymers, e.g. Polyacrylic acids in the form of their salts, polyvinyl alcohol, polypropylene oxide, polyethylene oxide, maleic anhydride-isobutene copolymers and vinylpyrrolidone-vinyl acetate copolymers.
  • silicone surfactants e.g. Polyether modified siloxanes
  • phospholipids such as lecithin or chemically modified lecithins
  • amino acid surfactants e.g. N-lauroyl glutamate
  • surface active homo- and copolymers e.g. Polyacrylic acids in the form of their salts, polyvinyl alcohol, polypropylene oxide
  • alkyl chains of the surfactants listed above are linear or branched radicals with usually 8 to 20 carbon atoms.
  • the further surfactant in component (c) is preferably selected from nonionic surfactants. Of these, those who prefer HLB values in the range from 2 to 16, preferably in the range from 5 to 16, and in particular in the range from 8 to 16, are preferred.
  • the proportion of component (c) in the total weight of the agent, if present, is generally less than 50% by weight, preferably less than 15% by weight and in particular less than 5% by weight.
  • compositions comprise as component (d) at least one further auxiliary.
  • Component (d) can serve a variety of purposes. Suitable auxiliaries are selected in accordance with the requirements in a customary manner by a person skilled in the art.
  • auxiliaries are selected from
  • compositions can comprise further solvents of soluble components or diluents of insoluble components of the composition.
  • mineral oils for example, mineral oils, synthetic oils as well as vegetable and animal oils, as well as low-molecular hydrophilic solvents such as alcohols, ethers, ketones and the like can be used.
  • aprotic or apolar solvents or diluents are to be mentioned, such as mineral oil fractions from medium to high boiling points, for example kerosene and diesel oil, and also coal tar oils, hydrocarbons, paraffin oils, for example C 8 to C o-hydrocarbons of the type n - or iso-alkane series or mixtures thereof, optionally hydrogenated or partially hydrogenated aromatics or alkyl aromatics from the benzene or naphthalene series, for example aromatic or cycloaliphatic C 7 to C 8 hydrocarbon compounds, aliphatic or aromatic carboxylic acid or dicarboxylic acid esters, fats or oils of plant or animal origin, such as mono-, di- and triglycerides, in pure form or as a mixture, for example in the form of oily natural product extracts, for example olive oil, jaöl, sunflower oil, castor oil, sesame oil, corn oil, peanut oil, rapeseed ⁇ oil, l
  • Cg to C 3 o -hydrocarbons of the n- or iso-alkane series are n- and iso-octane, -decane, -hexadecane, -octadecane, -eicosane, and preferably hydrocarbon mixtures, such as paraffin oil (the in technical quality can contain up to about 5% aromatics) and a C 8 -C 24 mixture which is commercially available from Texaco under the name Spraytex oil.
  • the aromatic or cycloaliphatic C 7 to Cig hydrocarbon compounds include in particular aromatic or cyclo-5-cloaliphatic solvents from the alkyl aromatic series. These compounds can be unhydrogenated, partially hydrogenated or fully hydrogenated.
  • solvents include, in particular, mono-, di- or trialkylbenzenes, mono-, di-, trialkyl-substituted tetralines and / or mono-, di-, tri- or tetraalkyl-substituted naphthalenes (alkyl is preferably Ci-C ⁇ - alkyl).
  • solvents examples include toluene, o-, -, p-xylene, ethylbenzene, isopropylbenzene, tert-butylbenzene and mixtures, such as the Exxon products sold under the name Shellsol and Solvesso, for example Solvesso 100, 150 and 200.5
  • Suitable monocarboxylic acid esters are oleic acid esters, in particular methyl oleate and ethyl oleate, lauric acid esters, in particular 2-ethylhexyl laurate, octyl laurate and isopropyl laurate, iso-0 propyl myristate, palmitic acid esters, in particular 2-ethylhexyl palmitate and isopropyl palmitate, stearic acid and 2-butyl ester, in particular stearate esters 2-ethylhexyl ethylhexanoate.
  • oleic acid esters in particular methyl oleate and ethyl oleate
  • lauric acid esters in particular 2-ethylhexyl laurate, octyl laurate and isopropyl laurate
  • iso-0 propyl myristate palmitic acid esters, in particular 2-eth
  • Suitable dicarboxylic acid esters are adipic acid esters, in particular dimethyl adipate, di-n-butyl adipate, di-n-octyl adipate, di-iso-octyl adipate, also called bis- (2-ethylhexyl) adipate, di-n-nonyl adipate, di-iso -nonyl adipate and ditridecyl adipate; Succinic esters, especially di-n-octyl succinate and di-iso-oc-0 tylsuccinate, and di- (iso-nonyl) cyclohexane-l, 2-dicarboxylate.
  • adipic acid esters in particular dimethyl adipate, di-n-butyl adipate, di-n-octyl adipate, di-iso-octyl adipate, also called
  • the proportion of the aprotic solvents or diluents described above in the total weight of the agent is generally less than 80% by weight, preferably less than 50% by weight and 5 in particular less than 30% by weight.
  • Some of these aprotic solvents or diluents can also have adjuvant, ie in particular effect-promoting, properties. This applies in particular to said mono- and dicarboxylic acid esters. From this point of view, such adjuvants can also be mixed as part of a further formulation (stand-alone product) with the copolymers according to the invention or agents containing them at a suitable point in time, generally shortly before application.
  • protic or polar solvents or diluents should be mentioned, for example C 2 -C 8 monoalcohols such as ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, cyclohexanol and 2-ethylhexanol, C 3 -C 8 ketones such as diethyl ketone, t-butyl methyl ketone and cyclohexanone, and aprotic amines such as N-methyl and 5 N-octyl pyrrolidone.
  • C 2 -C 8 monoalcohols such as ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, cyclohexanol and 2-ethylhexanol
  • C 3 -C 8 ketones such as diethyl ketone, t-butyl methyl
  • the proportion of the protic or polar solvents or diluents described above in the total weight of the agent is generally less than 80% by weight, preferably less than 0% by weight and in particular less than 30% by weight.
  • Anti-settling agents can also be used in particular for suspension concentrates. These serve primarily for rheological stabilization.
  • mineral products e.g. Bentonites, talcites and hectorites.
  • additives that may be useful are e.g. among mineral salt solutions, which are used to remedy nutritional and trace element deficiencies, non-phytotoxic oils and oil concentrates, anti-drift reagents, anti-foaming agents, in particular those of the silicone type, for example the Silicon SL marketed by the company Wacker, and the like. 5
  • the formulations can be used as an emulsifiable concentrate (EC), suspoemulsion (SE), oil-in-water emulsion (0 / W), water-in-oil emulsion (W / O), aqueous suspension concentrate, oil Suspension concentrate (SC), microemulsion (ME), etc. are available.
  • EC emulsifiable concentrate
  • SE suspoemulsion
  • SE oil-in-water emulsion
  • W / O water-in-oil emulsion
  • SC oil Suspension concentrate
  • ME microemulsion
  • the agents can be prepared in a manner known per se. For this, at least parts of the components are put together. It should be noted here that products, in particular commercial products, can be used, the components of which can contribute to different components. For example, a certain surfactant can be dissolved in an aprotic solvent so that this product contributes to various components. can. In addition, small proportions of less desirable substances can also be introduced with commercially available products. As a mixture, the combined products are then usually mixed intensively with one another to form a homogeneous mixture and, if necessary, for example in the case of suspensions, milled.
  • Mixing can be carried out in a manner known per se, e.g. by homogenizing with suitable devices such as KPG or magnetic stirrers.
  • Glass grinding media or other mineral or metallic grinding media generally in a size of 0.1-30 mm and in particular of 0.6-2 mm, can be used as grinding media.
  • the mixture is usually comminuted until the desired particle size is reached.
  • grinding in a circular mode i.e. continuous pumping, for example of an SC in a circle
  • a passage mode i.e. complete and repeated pumping or running through a batch.
  • the grinding can be done with conventional ball, bead or agitator mills, e.g. in a dyno mill (Bachofen), with batch sizes of, for example, 0.5 to 1 liter in the so-called passage mode. After several - in particular 4 to 6 - passages (pumping the slurry through the mill with the aid of a peristaltic pump), mean particle sizes of 0.5 to 10 ⁇ m are reached after microscopic evaluation.
  • the agents are usually converted into a form usable for use by dilution in the customary manner. Dilution with water or also aprotic solvents is preferred, for example using the tank mix method. Use in the form of a spray mixture is preferred. Can be applied pre- or post-emergence. Special advantages arise in the post-emergence experience.
  • the use according to the invention also includes the use of the copolymers according to the invention based on N-vinylamide as a "stand-alone" product.
  • the copolymers based on N-vinylamide are prepared in a suitable manner in order to be added to the agent to be applied shortly before use. There are particular advantages, particularly in spray treatment.
  • the agents according to the invention which already contain at least one N-vinylamide-based copolymer - or further plant treatment agents with the addition of at least one N-vinylamide-based copolymer as a "stand-alone" product - are thus included Diluted water that about 0.01 to 10, preferably about 0.05 to 5 and in particular 0.1 to 1 kg of at least one copolymer according to the invention are applied per ha.
  • alkyl include straight-chain or branched hydrocarbon groups, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-pentyl, n -Hexyl, n-octyl, 2-ethylhexyl, n-nonyl, iso-nonyl, n-decyl, iso-decyl, n-undecyl, iso-undecyl, n-dodecyl, iso-dodecyl, n-tridecyl, iso-tridecyl , Stearyl, n-eicosyl, preferably with - unless stated otherwise - 1 to 8, in particular 1 to 6 and particularly preferably 1 to 4, carbon atoms for short-chain radicals and 5 to 30, in
  • the branched long-chain radicals include above all 2-ethylhexyl, iso-nonyl, iso-decyl such as 2-propylheptyl, iso-undecyl, iso-dodecyl, and iso-tridecyl such as 2,4,6,8-tetramethyl-1 -nonyl, 3, 4, 6, 8-tetramethyl-1-nonyl and 5-ethyl-4,7-dimethyl-1-nonyl.
  • quantities are generally based on the total weight of an agent, unless stated otherwise.
  • the expression “essentially” generally denotes a percentage ratio of at least 80%, preferably of at least 90% and in particular of at least 95%.
  • Vinylpyrrolidone / Lutensol AT25MA copolymer 95/5 A solution of 342 g of N-vinylpyrrolidone, 18 g of Lutensol-AT-25 methacrylate (C 6 / C 8 fatty alcohol ethoxylate with 25 EO units) in 750 g of isopropanol is heated to 75 ° C. under an inert atmosphere. A solution of 0.9 g of 2,2'-azobis (2-methylbutyronitrile) (WAKO V59) in 50 g of isopropanol is added to the reaction mixture in 4 hours.
  • a solution of 306 g of vinyl pyrrolidone, 54 g of Lutensol AT 25 methacrylate (Ci 6 / C 8 fatty alcohol ethoxylate with 25 EO units) in 750 g of isopropanol is heated to 75 ° C. under an inert atmosphere.
  • a solution of 0.9 g of 2,2'-azobis (2-methylbutyronitrile) (WAKO V59) in 50 g of isopropanol is added to the reaction mixture in 4 hours. The mixture is then heated to 85 ° C. and 0.9 g of 2,2'-azobis (2-methylbutyronitrile) (WAKO V59) in 40 g of isopropanol are added all at once.
  • copolymers according to the invention in the sense of an adjuvant, significantly increase the fungicidal activity of pyraclostrobin or epoxiconazole.

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Abstract

La présente invention concerne des copolymères à base de N-vinylamide et leur utilisation en tant qu'adjuvants d'amélioration de rendement dans le domaine de la technologie agricole et notamment dans le domaine de la protection des végétaux. L'invention a également pour objet des produits de technologie agricole correspondants. Les copolymères utilisés sont des copolymères obtenus à partir de vinylamides et d'esters d'acide carboxylique éthyléniquement insaturés qui sont alcoxylés.
EP03782264A 2002-12-02 2003-12-01 Copolymeres a base de n-vinylamide utilises en tant qu'adjuvants et produits dans le domaine de la technologie agricole Withdrawn EP1569971A1 (fr)

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DE10256162 2002-12-02
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DE102004020544A1 (de) 2004-04-27 2005-11-24 Basf Ag Copolymere mit N-heterocyclischen Gruppen und deren Verwendung als Additiv in Waschmitteln
EP1756188B1 (fr) * 2004-06-08 2007-12-05 Basf Aktiengesellschaft Compositions polymeres amphiphiles et utilisation
AU2006237133B2 (en) * 2005-04-18 2012-01-19 Basf Se Preparation containing at least one conazole fungicide a further fungicide and a stabilising copolymer
WO2008040786A1 (fr) * 2006-10-05 2008-04-10 Basf Se Polymères en peigne et leur utilisation pour la préparation de formulations de substance active ou à effet
PL2088855T3 (pl) * 2006-11-30 2010-08-31 Basf Se Preparaty agrochemiczne zawierające kopolimery na bazie mono i diestrów etylenowo nienasyconych kwasów dikarboksylowych
CA2668564A1 (fr) * 2006-11-30 2008-06-05 Basf Se Preparations agrochimiques contenant des copolymeres n-vinylamide
WO2009040248A1 (fr) * 2007-09-27 2009-04-02 Basf Se Agents améliorant la systémicité
JP5604154B2 (ja) * 2010-04-02 2014-10-08 株式会社メニコン ポリマー材料、眼用レンズ及びコンタクトレンズ
JP2014519502A (ja) * 2011-05-27 2014-08-14 ビーエーエスエフ ソシエタス・ヨーロピア 農薬製剤用の分散剤としてのｎ−ビニルカルボキサミドとジアリルジアルキルアンモニウム塩のコポリマー
HUE035342T2 (en) * 2012-04-04 2018-05-02 Basf Se Agroforulation with an amide, polyalkylene glycol (meth) acrylate and alkyl (meth) acrylate copolymer

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1069142A1 (fr) * 1999-07-15 2001-01-17 Clariant GmbH Polymères solubles dans l'eau et leur utilisation dans des produits cosmétiques et pharmaceutiques

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3966902A (en) * 1972-05-12 1976-06-29 Airwick Industries, Inc. Polymer complex carriers for an active ingredient
CS271433B1 (en) * 1988-07-08 1990-09-12 Vacik Jiri Hydrophylic copolymer and method of its production
US5019998A (en) * 1989-01-30 1991-05-28 Battelle Memorial Institute Knowledge system and method for simulating chemical controlled release device performance
US5407717A (en) * 1993-04-14 1995-04-18 Minnesota Mining And Manufacturing Company Crosslinked absorbent pressure sensitive adhesive and wound dressing
US5776856A (en) * 1997-02-04 1998-07-07 Isp Investments Inc. Soluble polymer based matrix for chemically active water insoluble components
US5904927A (en) * 1997-03-14 1999-05-18 Northeastern University Drug delivery using pH-sensitive semi-interpenetrating network hydrogels
DE19815127A1 (de) * 1998-04-03 1999-10-07 Basf Ag Mittel mit Copolymerisaten aus N-Vinylcarbonsäureamiden und Monomeren mit hydrophobem Rest, und Verwendung dieser Copolymerisate
DE19843904A1 (de) * 1998-09-24 2000-03-30 Basf Ag Feste Dosierungsform mit polymerem Bindemittel
JP2002327102A (ja) * 2000-12-01 2002-11-15 Clariant Gmbh アクリロイルジメチルタウリン酸をベースとするコポリマーおよび相乗作用添加物を含有する組成物
DE10059816C1 (de) * 2000-12-01 2002-04-18 Clariant Gmbh Verwendung von Additiven zur Inhibierung der Gashydratbildung
DE10059829A1 (de) * 2000-12-01 2002-06-13 Clariant Gmbh Gepfropfte Kammpolymere auf Basis von Acryloyldimethyltaurinsäure
DE10163888A1 (de) * 2001-12-22 2003-07-10 Clariant Gmbh Pflanzenschutzformulierungen in Form von Suspensionen
DE10163887A1 (de) * 2001-12-22 2003-07-10 Clariant Gmbh Wässrige Pflanzenschutzformulierungen
JP3879844B2 (ja) * 2001-12-26 2007-02-14 ライオン株式会社 洗浄性防汚剤組成物及び洗浄性防汚物品

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1069142A1 (fr) * 1999-07-15 2001-01-17 Clariant GmbH Polymères solubles dans l'eau et leur utilisation dans des produits cosmétiques et pharmaceutiques

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AU2003289925A1 (en) 2004-06-23
US20060229209A1 (en) 2006-10-12

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