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
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
  • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2

Definitions

• the invention relates to the use of mixtures of
• R is hydrogen or C ⁇ -C 4 alkyl and X is halogen, N0 2 , CN and SCN, and their metal complexes and acid addition salts, as biocides.
• X is halogen, N0 2 , CN and SCN, and their metal complexes and acid addition salts, as biocides.
• EP-A-0 331 528 discloses copolymers of ethylene and dialkylaminoalkylacrylamides with biocidal activity.
• Antimicrobial polymers containing vinylphosphonium and vinylsulfonium groups have been described in J. Poly. Be. Part A: Polym. Chem., Vol. 31, 335, 1441, 1467 and 2873 (1993) and Arch. Pharm. (Weinheim) 321, 89 (1988).
• Biocidally active copolymers of N-vinylpyrrolidone and vinylamines are made of macromol. Chem., Suppl. Volume 9, 25 (1985) known.
• 5-Aminoisothiazoles have already been described as coupling components in azo dyes (EP-A 362 708, EP-A 315 898).
• herbicidal EP-A 640 597, DE-A 24 34 922, DE-A 22 49 162, FR 2132691, US 4,032,321, US 4,032,322, ZA 7202352
• bactericidal and virucidal activity L. Kuczynski et. Al., Pol. J. Pharmacol. Pharm. (1984), 36 (5), 485-491
• the present invention has for its object to provide new biocidal agents.
• the polymers contained as component A) in the mixtures to be used according to the invention are known from the prior art, cf. EP-B-0 071 050 and EP-B-0 216 387.
• Polymers containing units can be obtained, for example, by polymerizing mixtures which
• Open-chain N-vinylcarboxamides of the formula I are, for example, N-vinylformamide, N-vinyl -N-methylfor amide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl -N-ethylacetamide, N-vinyl-N-Me- thylpropionamide and N-vinylpropionamide.
• the open-chain vinyl carboxamides can be used alone or as a mixture in the polymerization. From this group of monomers, preference is given to using N-vinylformamide.
• the polymers containing ethyleneimine units are polyethyleneimines which are obtained by polymerizing ethyleneimine in the presence of acids, Lewis acids or acid-releasing catalysts such as alkyl halides, for example methyl chloride, ethyl chloride, propyl chloride, methylene chloride, trichloromethane, carbon tetrachloride or tetrabromomethane are available.
• the polyethyleneimines have, for example, molecular weights Mw of 300 to 1,000,000.
• polymers containing ethyleneimine units which are obtained by grafting polyamidoamines with ethyleneimine or by grafting polymers of open-chain N-vinylcarboxamides of the formula I with ethylene imin are available. Grafted polyamidoamines are known, for example, from US-A-4 144 123.
• the polymers to be used according to the invention contain 0.1 to 100, preferably 10 to 90 mol% of vinyl amine or ethyleneimine units as component (a). Of the polymers containing ethyleneimine units, preference is given to using polyethylene having molecular weights of from 500 to 500,000.
• Polymers containing vinylamine units can be modified by copolymerizing the monomers of the formula I with other monomers during the preparation.
• the monomers in question include vinyl formate, vinyl acetate, vinyl propionate, C_ to C ⁇ alkyl vinyl ethers, monoethylenically unsaturated C 3 to Cs carboxylic acids, their esters, nitriles, amides and, if available, also the anhydrides, N-vinyl urea, N -Vinyl - imidazole and N-vinylimidazolines.
• Examples of the monomers of group (b) mentioned are vinyl esters of saturated carboxylic acids having 1 to 6 carbon atoms, such as vinyl formate, vinyl acetate, vinyl propionate and vinyl butyrate, monoethylenically unsaturated
• C 3 - to C 8 -carboxylic acids such as acrylic acid, methacrylic acid, dimethyl-acrylic acid, ethacrylic acid, crotonic acid, vinyl acetic acid, allyl acetic acid, maleic acid, fumaric acid, citraconic acid and itaconic acid and their esters, anhydrides, amides and nitriles.
• Anhydrides which are preferably used are, for example, maleic anhydride, citraconic anhydride and itaconic anhydride.
• Suitable esters which are derived, for example, from alcohols having 1 to 6 carbon atoms, are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isobutyl acrylate, hexyl acrylate or glycols or polyalkylene glycols, where in each case only one OH group of the glycols or polyglycols with a monoethylenically unsaturated carboxylic acid is esterified, for example hydroxyethyl acrylate, hydroxymethacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate and hydroxybutyl methacrylate.
• the basic acrylates can be used in the form of the free bases, the salts with mineral acids or carboxylic acids or in quaternized form.
• suitable as comonomers are acrylonitrile, methacrylonitrile, N-vinylimidazole and substituted N-vinylimidazoles such as N-vinyl-2-methylimidazole and N-vinyl-2-ethylimidazole, N-vinylimidazoline and substituted N-vinylimidazolines, for example N-vinyl-2-methylimidazoline.
• monomers containing sulfo groups such as, for example, vinylsulfonic acid, allylsulfonic acid, styrene sulfonic acid and 3-sulfopropyl acrylate, can also be used as other monoethylenically unsaturated monomers.
• the polymers containing vinylamine units preferably contain
• (b) 1 to 99 mol% units of monomers from the group of open-chain N-vinylcarboxamides, vinyl formate, vinyl acetate, vinyl propionate, C] _- to C ⁇ alkyl vinyl ether, N-vinyl urea, acrylic acid, methacrylic acid, maleic acid and the anhydrides , Esters, nitriles and amides of the carboxylic acids mentioned, N-vinylimidazoles, N-vinylimidazolines and / or vinyl alcohol units, the sum of (a), (b) and (c) in mol% always being 100 .
• the polymers containing vinylamine units can also be modified to the extent that monomer mixtures are used in the copolymerization which, as comonomer (c), contain up to 5 mol of a compound having at least two ethylenically unsaturated double bonds in the molecule.
• Crosslinked copolymers are then formed which contain up to 5 mol% units of monomers with at least two ethylenically unsaturated double bonds polymerized in the molecule. If crosslinkers are used in the copolymerization, the amount preferably used is 0.05 to 2 mol%.
• the use of the monomers (c) also increases the molecular weight of the copolymers.
• Suitable compounds of this type are, for example, methylene-bis -acryl amide, esters of acrylic acid or methacrylic acid with polyhydric alcohols, for example glycol dimethacrylate or glycerol trimethacrylate, and polyols esterified at least twice with acrylic acid or methacrylic acid, such as pentaerythritol and glucose.
• Suitable crosslinkers are also divinylethyleneurea, divinylbenzene, N, N'-divinylurea, divinyldioxane, pentaerythritol triallyl ether and pentaallylsucrose.
• water-soluble monomers for example glycol diacrylate or glycol diacrylates or glycol dimethacrylates of polyethylene glycols having a molecular weight of up to 3000.
• the copolymers have K values of 5 to 300, preferably 10 to 200. The K values are determined according to H. Fikentscher in 5% aqueous saline solution at pH 7, a temperature of 25 ° C. and a polymer concentration of 0.5% .-%. 5
• the polymers containing vinylamine units are prepared by known processes by polymerizing open-chain N-vinylcarboxamides of the formula I.
• solvents or diluents preferred.
• inert diluents in which the open-chain N-vinylcarboxamides are soluble are suitable.
• inert solvents such as methanol, ethanol, isopropanol, n-propanol, n-butanol, sec-
• the polymerization can be carried out continuously or batchwise. It takes place in the presence of radical-forming polymerization initiators, for example in amounts from 0.01 to 20, preferably 0.05 to
• the polymerization can optionally be carried out solely by exposure to high-energy radiation, e.g. Electron beams or UV rays are initiated.
• Suitable regulators are, for example, organic compounds containing sulfur in bound form. These include, for example
• mercapto compounds such as mercaptoethanol, mercaptopropanol,
• the monomers are usually polymerized in an inert gas atmosphere with the exclusion of atmospheric oxygen. Good mixing of the reactants is generally ensured during the polymerization. In the case of smaller batches in which a reliable removal of the heat of polymerization is ensured, the monomers can be copolymerized discontinuously by heating the reaction mixture to the polymerization temperature and then allowing the reaction to proceed. These temperatures are in the range from 40 to 180 ° C., it being possible to work under normal pressure, reduced or else elevated pressure. Polymers with a high molecular weight are obtained if the polymerization is carried out in water. This can, for example, for the production of water-soluble polymers in aqueous solution, as a water-in-oil emulsion or after Ver ⁇ go done the reverse suspension.
• the polymerization is preferably carried out in a pH range from 4 to 9, in particular from 5 to 8. In many cases it is advisable to work in the presence of buffers, e.g. add primary or secondary sodium phosphate to the aqueous phase.
• the hydrolysis is preferably carried out in the presence of water under the action of acids, bases or enzymes, but can also be carried out in the absence of acids, bases or enzymes.
• the hydrolysis is carried out to such an extent that 0.1 to 100 mol%, preferably 1 to 99 mol%, of the copolymerized monomer units III are eliminated from the polymer.
• Those polymers which contain 1 to 99 mol% of vinylamine units and 1 to 99 mol% of units of the formula III, preferably N-vinylformamide units, are particularly preferably used according to the invention, the sum in mol% always being 100 .
• Acids suitable for the hydrolysis are, for example, mineral acids, such as hydrogen halide (gaseous or in aqueous solution), sulfuric acid, nitric acid, phosphoric acid (ortho-, meta- or polyphosphoric acid) and organic acids, for example C 1 -C 5 -carboxylic acids, such as formic acid , Acetic acid and propionic acid or the aliphatic or aromatic sulfonic acids, such as methanesulfonic acid, benzenesulfonic acid or toluenesulfonic acid.
• Hydrochloric acid or sulfuric acid is preferably used for the hydrolysis.
• the pH is 0 to 5.
• For each formyl group equivalent in the polymer 0.05 to 1.5 equivalents of acid, preferably 0.4 to 1.2 equivalents, are required.
• metal hydroxides of metals of the first and second main group of the periodic system can be used, for example lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, strontium hydroxide and barium hydroxide are suitable.
• ammonia and alkyl derivatives of ammonia can also be used, for example alkyl- or arylamines, for example triethylamine, monoethanolamine, diethanolamine, tri- ethanolamine, morpholine or aniline.
• the pH is 8 to 14.
• the bases can be used in solid, liquid or, if appropriate, also in the gaseous state, diluted or undiluted.
• Ammonia, sodium hydroxide solution or potassium hydroxide solution are preferably used as bases for the hydrolysis.
• the hydrolysis in the acidic or in the alkaline pH range takes place, for example, at temperatures from 30 to 170, preferably 50 to 120 ° C. It is complete after about 2 to 8, preferably 3 to 5 hours.
• a method in which the bases or acids are added in aqueous solution for hydrolysis has proven particularly useful.
• a neutralization is generally carried out, so that the pH of the hydrolyzed polymer solution is 2 to 8, preferably 3 to 7. Neutralization is necessary if the progress of the hydrolysis of partially hydrolyzed polymers is to be avoided or delayed.
• the hydrolysis can also be carried out with the aid of enzymes.
• copolymers of open-chain N-vinyl-carboxamides of the formula I and at least one of the comonomers mentioned above a further modification of the polymers optionally occurs in that the copolymerized comonomers are also hydrolyzed.
• vinyl alcohol units are formed from polymerized units of vinyl esters.
• the polymerized vinyl esters can be completely or partially hydrolyzed.
• the hydrolyzed copolymer in addition to unchanged vinyl acetate units, does not include vinyl alcohol units and units of the formulas III and IV.
• Units of monoethylenically unsaturated carboxylic acid anhydrides form carboxylic acid units in the hydrolysis.
• Polymerized monoethylenically unsaturated carboxylic acids are not chemically changed during the hydrolysis.
• ester and amide units saponify
• Carboxylic acid units Units of amides or carboxylic acids, for example, are formed from polymerized monoethylenically unsaturated nitriles. Polymerized N-vinylurea can also be used to form vinylamine units. The degree of hydrolysis of the copolymerized comonomers can easily be determined analytically.
• Polymeric seeds to be used preferably
• These polymers are either partially or completely hydrolyzed homopolymers of vinylformamide or polyethyleneimines.
• the partially hydrolyzed homopolymers of N-vinylformamide preferably contain
• the mixtures to be used according to the invention have a strong microbicidal action and can therefore be used to control unwanted microorganisms.
• the mixtures and the formulations prepared therefrom are intended to destroy harmful organisms by chemical means, to deter them, to render them harmless, to prevent them from being damaged or to combat them in some other way.
• the mixtures or their formulations to be used according to the invention prevent the microbial attack on technical materials, i.e. they can be used for in-can preservation. They are also used for the biocidal finishing of products, i.e. they can be used for film preservation.
• Technical materials are to be understood as non-living materials as they occur in technical / industrial processes.
• Technical materials that are to be protected from microbial change or destruction by the use of the mixtures or formulations according to the invention are, for example:
• Water treatment is understood to mean the addition of the polymers or formulations to process water, for example to combat slime in the paper industry or to control harmful organisms in the sugar industry. They prevent or control the growth of microorganisms in cooling circuits, humidifiers, or in drilling and production fluids in the petroleum industry.
• the mixtures and their formulations can also be used in disinfection.
• Bacteria, viruses, spores, yeasts, fungi, algae and slime organisms may be mentioned as examples of microorganisms which can cause a degradation or a change in technical materials.
• the polymers or their preparations to be used according to the invention preferably act against bacteria, yeasts and fungi.
• microorganisms The following genera may be mentioned as microorganisms:
• the mixtures to be used according to the invention can be converted into customary formulations and preparations, such as, for example, emulsions, suspensions, dispersions, solutions, powders, pastes or in combination with carrier materials.
• surface-active substances for example, anionic surfactants such as alkyl sulfonates, ether sulfates; nonionic surfactants such as fatty alcohol ethoxylates, fatty alcohol ester ethoxylates, sorbitan esters, polyalkylene glycols; amphoteric surfactants
• complexing agents e.g.
• ethylene diamine tetraacetic acid nitrilotriacetic acid acetic acid, methyl nitrate triacetic acid, methylglycosylate acetic acid, methyl nitrate triacetic acid, methyl methacrylate
• alcohols such as ethanol, n-propanol, i-propanol, or glycols, for example propylene glycol, polypropylene glycol
• acids or bases for example phosphoric acid, sodium hydroxide solution
• inorganic salts and / or other additives for example corrosion additives, foam suppressants, straightening agents, dyes are added to the formulations and preparations.
• microbicidally active compounds such as fungicides, bactericides and / or herbicides, insecticides and / or other active substances are used to broaden the spectrum of activity or to achieve them special effects are added.
• synergistic effects are obtained, i.e. the spectrum of action of the mixture exceeds the action of the individual components.
• Such substances are known per se to the person skilled in the art and are described in the literature.
• the mixing ratio of components A and B in the mixtures or formulations to be used according to the invention is not critical per se and can be chosen over a wide range.
• the mixing ratio (weight ratio) is in the range from 1: 1000 to 1000: 1, preferably from 1: 100 to 100: 1 and particularly preferably in the range from 20:80 to 80:20.
• the K values of the polymers A were determined in 5% by H. Fikentscher, Cellulose-Chemie, Vol. 13, 58 to 64 and 71 to 74 (1932). -% aqueous saline solution at 25 ° C and pH 7 and a polymer concentration of 0.5 wt. - Determined.
• Microbicides and microbistatic properties are determined experimentally. Very suitable test methods have been described in detail by the German Society for Hygiene and Microbiology (DGHM) for the testing of disinfectants.
• DGHM German Society for Hygiene and Microbiology
• Tube dilution tests were carried out in accordance with the "Guidelines for the Testing and Evaluation of Chemical Disinfection Procedures (Status 01.01.81, procedure slightly modified)" with casein peptone soybean meal peptone medium.
• the dilution was carried out with water of standardized hardness without further aids such as Surfactants.
• the pH was adjusted to 7.2 + 0.2 using 0.1 mol / 1 NaOH or 0.1 mol / 1 HC1.
• the test concentrations were graded according to the concentration levels proposed by the DGHM.
• the evaluation was carried out after 72 hours of incubation at 36 ° C.

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• 1998
  • 1998-09-05 BR BR9812042-5A patent/BR9812042A/pt not_active Application Discontinuation
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