EP2310320A1 - Composés de cuivre nanoparticulaires modifiés en surface - Google Patents

Composés de cuivre nanoparticulaires modifiés en surface

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Publication number
EP2310320A1
EP2310320A1 EP09780084A EP09780084A EP2310320A1 EP 2310320 A1 EP2310320 A1 EP 2310320A1 EP 09780084 A EP09780084 A EP 09780084A EP 09780084 A EP09780084 A EP 09780084A EP 2310320 A1 EP2310320 A1 EP 2310320A1
Authority
EP
European Patent Office
Prior art keywords
copper compounds
acid
modified nanoparticulate
copper
solution
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Withdrawn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
EP09780084A
Other languages
German (de)
English (en)
Inventor
Andrey Karpov
Hartmut Hibst
Michael Triller
Eike Hupe
Michael Maier
Jörg HABICHT
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP09780084A priority Critical patent/EP2310320A1/fr
Publication of EP2310320A1 publication Critical patent/EP2310320A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • 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
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A01N59/20—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/006—Compounds containing, besides copper, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Definitions

  • the present invention relates to processes for the preparation of surface-modified nanoparticulate copper compounds and of aqueous suspensions which contain surface-modified nanoparticulate copper compounds. Furthermore, the invention relates to the surface-modified nanoparticulate copper compounds obtainable by these processes and aqueous suspensions of these copper compounds and their use as antimicrobial active ingredient or catalyst.
  • Wood preservatives often contain antimicrobial agents based on finely divided copper compounds.
  • WO 2004/091875 describes the use of aqueous suspension comprising microparticulate copper compounds (for example copper hydroxide, copper (I) oxide, copper (II) oxide, copper carbonate) for wood preservation applications.
  • the suspensions were prepared by wet-milling coarsely crystalline powders in the presence of suitable dispersing aids and contain particles having a particle size in the range from 40 nm to 1500 nm and an average particle size of about 200 nm.
  • WO 2005/1 10692 describes aqueous suspensions containing microparticulate copper compounds (for example copper hydroxide, copper carbonate) for wood preservation.
  • the suspensions with mean particle sizes in the range of about 200 nm to about 400 nm were also prepared by wet milling in the presence of dispersants.
  • the wood preservative formulations disclosed in WO 2006/042128 include u. a. poorly soluble copper compounds, which were also brought by grinding in a finely divided form.
  • a disadvantage of grinding processes is that particles with an average particle size of ⁇ 100 nm are accessible only at great expense and by means of a very large energy input.
  • US 2002/01 12407 describes the preparation of inorganic nanoparticulate particles having an average size of 2 to 500 nm, preferably ⁇ 100 nm (determined by dynamic light scattering, DLS), by partial or complete alkaline hydrolysis of at least one metal compound, which is either in one aqueous medium dissolved or suspended in nanoparticulate form, in the presence of water-soluble comb polymers.
  • DLS dynamic light scattering
  • Nanoparticles are particles of the order of nanometers. Their size is in the transition region between atomic or monomolecular systems and continuous macroscopic structures. In addition to their usually very large surface, nanoparticles are characterized by particular physical and chemical properties, which differ significantly from those of larger particles. For example, nanoparticles often have a lower melting point, absorb light only at shorter wavelengths, and have different mechanical, electrical, and magnetic properties than macroscopic particles of the same material. By using nanoparticles as building blocks, many of these special properties can also be used for macroscopic materials (Winnacker / Kuchler, Chemischetechnik: Processes and Products, (Ed .: R. Dittmayer, W. Keim, G. Kreysa, A. Oberholz), Vol. 2: New Technologies, Chapter 9, Wiley-VCH Verlag 2004).
  • nanoparticles refers to particles having an average diameter of from 1 to 500 nm, determined by means of light scattering.
  • An object of the invention was to provide processes for the preparation of surface-modified nanoparticulate copper compounds and of aqueous suspensions which contain surface-modified nanoparticulate copper compounds. Another object of the invention was the provision of new surface-modified nanoparticulate copper compounds and aqueous suspensions of these copper compounds and their use as antimicrobial agent or catalyst.
  • the invention therefore provides a process for the preparation of surface-modified nanoparticulate copper compounds, comprising the steps:
  • step b) mixing the solutions 1 and 2 prepared in step a) at a temperature in the range from 0 to 100 ° C., whereby the surface-modified nanoparticulate copper compounds form and precipitate out of the solution to form an aqueous dispersion, c) separating the surface-modified nanoparticulate copper compounds from the aqueous dispersion obtained in step b), and
  • step c) optionally drying of the surface-modified nanoparticulate copper compounds obtained in step c).
  • the copper compounds obtainable by the process according to the invention can be present both in anhydrous form and in the form of corresponding hydrates.
  • the preparation of the solution 1 described in step a) can be carried out, for example, by dissolving a water-soluble copper salt in water or an aqueous solvent mixture.
  • An aqueous solvent mixture may contain, in addition to water, for example, water-miscible alcohols, ketones or esters such as methanol, ethanol, acetone or ethyl acetate.
  • the water content in such a solvent mixture is usually at least 50% by weight, preferably at least 80% by weight.
  • the water-soluble copper salts may be, for example, copper halides, acetates, sulfates or nitrates.
  • Preferred copper salts are copper chloride, copper acetate, copper sulfate and copper nitrate. These salts dissolve in water to form copper ions, which are two-fold positively charged and attached to the six water molecules [Cu (H2 ⁇ ) 6 2+ ].
  • the concentration of copper ions in the solution 1 is generally in the range of 0.05 to 2 mol / l, preferably in the range of 0.1 to 1 mol / l.
  • solution 1 may also contain other metal ions (M k + ), which optionally precipitate in step b) together with the copper ions.
  • M k + metal ions
  • These may be, for example, ions of alkaline earth or transition metals, preferably magnesium, calcium, chromium, cobalt, nickel, zinc or silver ions, more preferably zinc or silver ions.
  • the other metal ions are present in lesser number than the copper ions.
  • solution 2 contains at least one anion, which forms a precipitate with copper ions and is not a hydroxide ion.
  • anion are, for example, anions of mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, boric acid, sulphurous acid, etc. or anions of organic acids such as oxalic acid, benzoic acid, maleic acid, etc. and polyborates such as B4O7 2 " Solution 2 may, of course, additionally contain hydroxyl ions.
  • the anion which forms a precipitate with copper ions and is not a hydroxide ion, can be formed from a precursor compound only in the course of the reaction proceeding in step b).
  • the anion is present in masked form in the precursor compound and is liberated therefrom during mixing of solutions 1 and 2 and / or by temperature change.
  • the precursor compound can be present both in solution 1 and in solution 2 or in both solutions.
  • Dimethyl carbonate may be mentioned as an example of such a precursor compound from which carbonate ions can be released in an alkaline medium (compare M. Faatz et al., Adv. Mater. 2004, Vol. 16, pages 996 to 1000).
  • At least one of the two solutions 1 and 2 contains at least one water-soluble polymer.
  • a "water-soluble polymer” is understood to mean a polymer from which at room temperature, in general, at least 0.01% by weight dissolves in water and which is up to a concentration of 50% by weight in water, preferably 75% by weight
  • the at least one water-soluble polymer serves for surface modification of the copper compounds and helps to stabilize them in nanoparticulate form.
  • the water-soluble polymers to be used according to the invention may be anionic, cationic, nonionic or zwitterionic polymers. Their molecular weight is generally in the range of about 800 to about 500,000 g / mol, preferably in the range of about 1000 to about 30,000 mol. They may be homopolymers or copolymers and their molecular structure may be both linear and branched. Preference is given to water-soluble polymers having a comb structure.
  • Suitable monomers from which the water-soluble polymers to be used according to the invention are obtainable include, for example, o-unsaturated carboxylic acids and their esters, amides and nitriles, N-vinylcarboxamides, alkylene oxides, unsaturated sulfonic acids and phosphonic acids, and amino acids.
  • polycarboxylates are used as water-soluble polymers.
  • Polycarboxylates in the context of this invention are polymers based on at least one ⁇ , ⁇ -unsaturated carboxylic acid, for example acrylic acid, methacrylic acid, dimethacrylic acid, ethacrylic acid, maleic acid, citraconic acid, methylenemalonic acid, crotonic acid, isocrotonic acid, fumaric acid, mesaconic acid and itaconic acid.
  • polycarboxylates based on acrylic acid, methacrylic acid, maleic acid or mixtures thereof are used.
  • the proportion of the at least one o ⁇ -unsaturated carboxylic acid in the polycarboxylates is generally in the range of 20 and 100 mol%, preferably in the range of 50 and 100 mol%, particularly preferably in the range of 75 and 100 mol%.
  • the polycarboxylates to be used according to the invention can be used both in the form of the free acid and partially or completely neutralized in the form of their alkali metal, alkaline earth metal or ammonium salts. However, they can also be used as salts of the respective polycarboxylic acid and triethylamine, ethanolamine, diethanolamine, triethanolamine, morpholine, diethylenetriamine or tetraethylenepentamine.
  • the polycarboxylates may also contain other comonomers which are polymerized into the polymer chain, for example the esters, amides and nitriles of the abovementioned carboxylic acids such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate , Hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyisobutyl acrylate, hydroxyisobutyl methacrylate, monomethyl maleate, dimethyl maleate, maleic monoethyl maleate, diethyl maleate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, acrylamide, methacrylamide, N-dimethylacrylamide, N-tert-but
  • Suitable copolymerizable comonomers include allylacetic acid, vinylacetic acid, acrylamidoglycolic acid, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate or acrylamidomethylpropanesulfonic acid and also monomers containing phosphonic acid groups such as vinylphosphonic acid , Allylphosphonic acid or acrylamidomethanepropanephosphonic acid.
  • the monomers containing acid groups can be used in the polymerization in the form of the free acid groups and in partially or completely neutralized with bases form.
  • copolymerizable compounds are N-vinylcaprolactam, N-vinylimidazole, N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole, vinyl acetate, vinylpropionate, isobutene, styrene, ethylene oxide, propylene oxide or ethyleneimine, and also compounds with more methacrylate as a polymerizable double bond such as diallyl ammonium chloride, ethylene glycol dimethacrylate, diethylene glycol diacrylate, allyl, trimethylolpropane triacrylate, triallylamine, tetraallyloxyethane, rat Triallylcyanu-, diallyl maleate, tetraallylethylenediamine, Divinylidenharnstoff, pentaerythritol rythritdi-, pentaerythritol and pentaerythritol tetraallyl ether, N, N
  • mixtures of said comonomers are suitable for the preparation of the polycarboxylates according to the invention.
  • polycarboxylate ethers are used as water-soluble polymers
  • polycarboxylates are under the brand name Sokalan ® (Fa. BASF SE) are commercially available.
  • the water-soluble polymer is polyaspartic acid, polyvinylpyrrolidone or copolymers of an N-vinylamide, for example N-vinylpyrrolidone, and at least one further, a polymerizable group-containing monomers, for example with monoethylenically unsaturated Cs-Cs -Carbonklaren such as acrylic acid, methacrylic acid, Cs-Cso-alkyl esters of monoethylenically unsaturated Cs-Cs carboxylic acids, vinyl esters of aliphatic Cs-Cso-carboxylic acids and / or with N-alkyl or N, N-dialkyl-substituted amides of acrylic acid or Methacrylic acid with Cs-ds-alkyl radicals act.
  • a polymerizable group-containing monomers for example with monoethylenically unsaturated Cs-Cs -Carbonkla
  • polyaspartic acid is used as the water-soluble polymer.
  • polyaspartic acid in the context of the present invention comprises both the free acid and the salts of polyaspartic acid, for.
  • salts of polyaspartic acid for example, sodium, potassium, lithium, magnesium, calcium, ammonium, alkylammonium, zinc and iron salts or mixtures thereof.
  • nonionic water-soluble polymers are used.
  • a nonionic water-soluble polymer is surface-active substances whose chemical structure has between 2 and 1000 -CH 2 CH 2 O- groups, preferably between 2 and 200 -CH 2 CH 2 O- groups, particularly preferably between 2 and 80 -CH 2 CH 2 O- Includes groups. These groups are formed, for example, by addition of a corresponding number of ethylene oxide molecules to hydroxyl- or carboxyl-containing substrates and generally form one or more contiguous ethylene glycol chains whose chemical structure is of the formula - (- CH 2 CH 2 O-) n - with n of about 2 to about 80 corresponds.
  • At least one substance from one of the following groups is used as nonionic water-soluble polymer: Addition products of 2 to 80 moles of ethylene oxide and optionally 1 to 15 moles of propylene oxide
  • Alkylphenols having 1 to 5 carbon atoms in the alkyl group having 1 to 5 carbon atoms in the alkyl group
  • Sucrose - sugar alcohols (eg sorbitol)
  • sugar alcohols eg sorbitol
  • Alkyl glucosides eg methyl glucoside, butyl glucoside, lauryl glucoside
  • Polyglucosides eg cellulose
  • Polyalkylene glycols whose structure comprises between 2 and 80 ethylene glycol units.
  • At least one substance from one of the following groups is used as nonionic water-soluble polymer:
  • Alkylphenols having 1 to 5 carbon atoms in the alkyl group having 1 to 5 carbon atoms in the alkyl group
  • Polymers are available under the trade name Cremophor ® (Fa. BASF SE) in trade.
  • the ethylene oxide addition products can always also contain a small proportion of the above-listed free hydroxyl or carboxyl groups-containing substrates in technical quality. In general, this proportion is less than 20 wt .-%, preferably less than 5 wt .-%, based on the total amount of the nonionic water-soluble polymer.
  • the water-soluble polymers used are homopolymers and copolymers of N-vinylcarboxamides. These polymers are prepared by homo- or copolymerization of z. N-vinylformamide, N-vinylacetone amide, N-alkyl-N-vinylformamide or N-alkyl-N-vinylacetamide. Of the N-vinylcarboxamides, N-vinylformamide is preferably used, particularly preferably homopolymers of N-vinylformamide.
  • the water-soluble polymers of N-vinylcarboxamides to be used according to the invention may, in addition to from 100 to 20% by weight of the N-vinylcarboxamides, optionally contain from 0 to 80, preferably from 5 to 30,% by weight of copolymerized comonomers, in each case based on Total composition of the polymers.
  • the comonomers are, for example, monoethylenically unsaturated carboxylic acids having 3 to 8 C atoms, such as acrylic acid, methacrylic acid, dimethacrylic acid, ethacrylic acid, maleic acid, citraconic acid, methylenemalonic acid, allylacetic acid, vinylacetic acid, crotonic acid, fumaric acid, mesaconic acid and itaconic acid.
  • Acrylic acid, methacrylic acid, maleic acid or mixtures of said carboxylic acids are preferably used from this group of monomers.
  • the monoethylenically unsaturated carboxylic acids are used either in the form of the free acids or in the form of their alkali metal, alkaline earth metal or ammonium salts in the copolymerization. But they can also be used as salts of the respective acid and triethylamine, ethanolamine, diethanolamine, triethanolamine, morpholine, diethylenetriamine or tetraethylenepentamine.
  • suitable comonomers are, for example, the esters, amides and nitriles of the abovementioned carboxylic acids, eg. Methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyisobutyl acrylate, hydroxyisobutyl methacrylate, maleic acid monomethyl ester, dimethyl maleate, maleic acid monoethylester, maleic acid diethyl ester, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, acrylamide, methacrylamide, N-dimethyl acrylamide, N-tert-butylacrylamide, acrylonitrile, methacrylonitrile, dimethylamino
  • Suitable as further copolymerizable comonomers are acrylamidoglycolic acid, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate or acrylamidomethylpropanesulfonic acid and monomers containing phosphonic acid groups, such as vinylphosphonic acid, allylphosphonic acid or acrylamidomethanepropanephosphonic acid - right.
  • the monomers containing acid groups can be used in the polymerization in the form of the free acid groups as well as in form partially or completely neutralized with bases.
  • copolymerizable compounds are N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole, vinyl acetate, vinyl propionate, isobutene, styrene, ethylene oxide, propylene oxide or ethyleneimine, and also compounds diacrylate having more than one polymerizable double bond such as diallyl ammonium chloride, ethylene glycol dimethacrylate, diethylene acrylate, allyl methacrylate, trimethylolpropane triacrylate, triallylamine, Tetraallyloxye- than, triallyl cyanurate, diallyl maleate, tetraallylethylenediamine, Divinyliden- urea, pentaerythritol triacrylate, pentaerythritol and pentaerythritol tetraallyl ether
  • mixtures of said comonomers are suitable for preparing the water-soluble polymers of N-vinylcarboxamides according to the invention.
  • the polymers containing N-vinylcarboxamide units copolymerize these comonomers only in amounts such that the copolymers are still water-soluble.
  • nonionic water-soluble polymers having a comb-like molecular structure are used which are obtained, for example, by copolymerization of monomer mixtures containing macromonomers.
  • the structure of non-ionic water-soluble polymers of comb-like molecular structure can be described, for example, as a complexing polymer backbone having anionic and / or cationic groups and hydrophilic side chains or as a neutral hydrophilic polymer backbone with complexing anionic and / or cationic groups.
  • macromonomers are understood as meaning substances which have a molecular weight of preferably less than 500 000 D, in particular in the range from 300 to 100 000 D, particularly preferably in the range from 500 to 20 000 D, very particularly preferably in the range from 800 to 15000 D, have a substantially linear molecular structure and carry one end polymerizable group on one side.
  • macromonomers based on polyalkylene glycols are used for the preparation of water-soluble polymers having a comb-like molecular structure, which are end-capped with a polymerizable group on one side.
  • This may be, for example, a vinyl, allyl, (Meth) acrylic acid or amide group, wherein the corresponding macromonomers are described by the following formulas:
  • R 2 H or methyl
  • R 3 is as defined below and
  • P is a polyalkylene glycol radical of the general formula
  • R 10 is Ci-C ⁇ -alkyl
  • B is - (CH 2) t -, arylene, optionally substituted;
  • s is O to 500, preferably 0 to 20;
  • u is 1 to 5000, preferably 1 to 1000, particularly preferably 1 to 100;
  • w is 0 to 5000, preferably 0 to 1000;
  • y is 0 to 5000, preferably 0 to 1000;
  • z is 0 to 5000, preferably 0 to 1000.
  • Preferred compounds are those in which the polyalkylene glycol radical P is derived from a polyalkylene glycol which has been prepared using ethylene oxide, propylene oxide and butylene oxide and polytetrahydrofuran. Depending on the type of monomer used here, polyalkylene glycol residue P having the following structural units results.
  • R 9 to R 11 are branched or unbranched C 1 -Cs-Al ky I chains, preferably methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1, 1 -Dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2 Methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3- Dimethylbutyl, 1-ethylbutyl, 2-
  • alkyl radicals As preferred representatives of the abovementioned alkyl radicals, mention may be made of branched or unbranched C 1 -C 6 -, more preferably C 1 -C 4 -alkyl chains.
  • These water-soluble polymers having a comb-like molecular structure generally contain, in addition to about 90 to 10% by weight of the macromonomers described, also about 10 to 90, preferably 25 to 70% by weight of copolymerized comonomers which carry deprotonatable groups.
  • Comonomers can be, for example, monoethylenically unsaturated carboxylic acids having 3 to 8 carbon atoms, such as acrylic acid, methacrylic acid, dimethacrylic acid, ethacrylic acid, maleic acid, citraconic acid, methylenemalonic acid, allylacetic acid, vinylacetic acid, crotonic acid, fumaric acid, mesaconic acid and itaconic acid.
  • Acrylic acid, methacrylic acid, maleic acid or mixtures of said carboxylic acids are preferably used from this group of comonomers.
  • the monoethylenically unsaturated carboxylic acids are used either in the form of the free acids or in the form of their alkali metal, alkaline earth metal or ammonium salts in the copolymerization. However, they can also be used as salts of the respective acid and triethylamine, ethanolamine, diethanolamine, triethanolamine, morpholine, diethylenetriamine or tetraethylenepentamine.
  • Suitable comonomers are, for example, the esters, amides and nitriles of the abovementioned carboxylic acids, e.g. Methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyisobutyl acrylate, hydroxyisobutyl methacrylate, monomethyl maleate, dimethyl maleate, maleic acid monoethyl ester, maleic acid diethyl ester, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, acrylamide, methacrylamide, N-dimethylacrylamide, N-tert-butylacrylamide, acrylonitrile or methacrylonitrile, which according to their
  • Polymerization can be hydrolyzed into the water-soluble polymers with comb-like molecular structure to the corresponding free carboxylic acids.
  • the monomers in the copolymers may be randomly distributed or present as so-called block polymers.
  • the macromonomer-containing water-soluble polymers having a comb-like molecular structure contain these comonomers in copolymerized form only in amounts such that they are still water-soluble.
  • the concentration of the water-soluble polymers in the solutions 1 and / or 2 prepared in process step a) is generally in the range from 0.1 to 30 g / l, preferably from 1 to 25 g / l, particularly preferably from 5 to 20 g / l.
  • the mixing of the two solutions 1 and 2 in the process step b) is carried out at a temperature in the range from 0 0 C to 100 0 C, preferably in the range of 10 0 C to 95 ° C, more preferably in the range from 15 ° C to 80 0 C.
  • the time for mixing the two solutions in process step b) is, for example, in the range from 1 second to 6 hours, preferably in the range from 1 minute to 2 hours. In general, the mixing time is longer with discontinuous driving than with continuous driving.
  • the mixing in process step b) can be carried out, for example, by combining an aqueous solution of a copper salt, for example copper acetate or copper nitrate, with an aqueous solution of a mixture of a polyacrylate and oxalic acid.
  • a copper salt for example copper acetate or copper nitrate
  • an aqueous solution of a mixture of a polyacrylate and a copper salt for example, copper acetate or copper nitrate
  • an aqueous solution of a mixture of a polyacrylate and a copper salt such as copper acetate or copper nitrate, combined with an aqueous solution of a mixture of a polyacrylate and oxalic acid.
  • the mixing in process step b) is carried out by adding an aqueous solution of a mixture of a polyacrylate and oxalic acid to an aqueous solution of a mixture of a polyacrylate and a copper salt, for example of copper acetate or copper nitrate, or by metering aqueous oxalic acid solution to an aqueous solution of a mixture of a polyacrylate and a copper salt, for example of copper acetate or copper nitrate.
  • the surface-modified nanoparticulate copper compounds form, which precipitate out of the solution to form an aqueous suspension.
  • the mixing is preferably carried out with simultaneous stirring of the mixture. After complete combination of the two solutions 1 and 2, the stirring is preferably continued for a time in the range of 30 minutes and 5 hours at a temperature in the range of 0 ° C to 100 0 C.
  • a further preferred embodiment of the method according to the invention is characterized in that at least one of the method steps a) to d) are carried out continuously.
  • the process step b) is preferably carried out in a tubular reactor.
  • the separation of the precipitated copper compounds from the aqueous suspension in process step c) can be carried out in a manner known per se, for example by filtration or centrifugation. If necessary, the aqueous dispersion can be concentrated prior to isolation of the precipitated copper compounds, for example by means of a membrane process such as nano-, ultra-, micro- or crossflow filtration and optionally at least partially freed of unwanted water-soluble constituents, for example alkali metal salts such as sodium acetate or sodium nitrate.
  • step b) It has proved to be advantageous to carry out the separation of the surface-modified nanoparticulate copper compounds from the aqueous suspension obtained in step b) at a temperature in the range from 10 to 50 ° C., preferably at room temperature. It is therefore advantageous to optionally cool the aqueous suspension obtained in step b) to such a temperature.
  • the resulting filter cake can be dried in a conventional manner, for example in a drying oven at temperatures of 40 to 100 0 C, preferably from 50 to 80 ° C under atmospheric pressure to constant weight.
  • the surface-modified nanoparticulate copper compounds obtainable by the process according to the invention generally have particle sizes in the range from 1 to 200 nm, preferably in the range from 1 to 100 nm.
  • Another object of the present invention are surface-modified nanoparticulate copper compounds having a chemical composition according to the general formula
  • M k + is a metal ion with the valence k
  • X n - is an anion of valency n, which precipitates with copper ions and is not a hydroxide ion,
  • the valences of the ions are naturally integers.
  • the metal ions M k + may be, for example, ions of alkaline earth or transition metals, preferably magnesium, calcium, chromium, cobalt, nickel, zinc or silver ions, more preferably zinc or silver ions.
  • the metal ions M k + are present in lesser numbers than the copper ions (0 ⁇ x ⁇ 0.5).
  • the anions X n - and Y m " may be, for example, anions of mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, boric acid, sulphurous acid, etc. or anions of organic acids such as oxalic acid, benzoic acid, maleic acid, etc., and Polyborates such as B4O7 2 " act.
  • Y m - may also be a hydroxide ion.
  • x 0.
  • X n is selected from the group consisting of carbonate, phosphate, hydrogen phosphate, oxalate, borate and tetraborate ions.
  • Another object of the present invention is the use of surface-modified nanoparticulate copper compounds, which are prepared by the process according to the invention, as an antimicrobial agent or catalyst.
  • the surface-modified nanoparticulate copper compounds are redispersible in a liquid medium and form stable dispersions. This is particularly advantageous because the dispersions prepared from the copper compounds according to the invention need not be redispersed before further processing, but can be processed over a relatively long period of time.
  • the surface-modified nanoparticulate copper compounds are redispersible in water and form stable dispersions there. Since numerous applications of the surface-modified nanoparticulate copper compounds of the invention their If required for use in the form of an aqueous dispersion, it may be possible to dispense with their isolation as a solid.
  • a further subject of the present invention is therefore a process for the preparation of an aqueous dispersion of surface-modified nanoparticulate copper compounds, comprising the steps
  • step b) mixing the solutions 1 and 2 prepared in step a) at a temperature in the range of 0 to 100 0 C, wherein the surface-modified nanoparticulate
  • the aqueous dispersion formed in step b) can be concentrated in process step c), for example if a higher solids content is desired.
  • the concentration can be carried out in a manner known per se, for example by distilling off the water (at atmospheric pressure or at reduced pressure), filtering or centrifuging.
  • Suitable by-products are primarily salts dissolved in water which, in the reaction according to the invention, are formed between solutions 1 and 2 in addition to the desired surface-modified nanoparticulate copper compound, for example sodium chloride, sodium nitrate or ammonium chloride.
  • Such by-products can be largely removed from the aqueous dispersion, for example by means of a membrane process such as nano, ultra, micro or crossflow filtration.
  • a further preferred embodiment of the method according to the invention is characterized in that at least one of the method steps a) to c) are carried out continuously.
  • Another object of the present invention are aqueous dispersions of surface-modified nanoparticulate copper compounds having a chemical composition according to the general formula
  • M k + is a metal ion with the valence k
  • X n - is an anion of valency n, which precipitates with copper ions and is not a hydroxide ion,
  • the surface-modified nanoparticulate copper compounds in the aqueous dispersions according to the invention are coated with a polycarboxylate, for example with a polycarboxylate ether.
  • Another object of the present invention is the use of aqueous dispersions surface-modified nanoparticulate copper compounds prepared by the process according to the invention, as an antimicrobial agent or as a catalyst.
  • the invention will be explained in more detail with reference to the following examples.
  • Particle size distributions were determined by light scattering on the device Nanotrac U2059I (Microtrac Inc. Examples 1 and 2) or on the device Zetasizer Nano S (Fa.
  • the average particle size is determined by the volume fraction.
  • Solution 1 contained 79.8 g of copper acetate (Sigma-Aldrich, Cu content 32 g / 100 g) per liter and had a copper ion concentration of 0.4 mol / l.
  • Solution 1 was prepared at 75 ° C. and contained 139.65 g of copper acetate (Sigma-Aldrich, Cu content 32 g / 100 g) per liter and had a copper ion concentration of 0.7 mol / l.
  • Solution 2 contained 28 g of sodium hydroxide per liter and thus had a hydroxyl ion concentration of 0.7 mol / l.

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Abstract

La présente invention concerne un procédé de fabrication de composés de cuivre nanoparticulaires modifiés en surface ainsi que des suspensions aqueuses qui contiennent des composés de cuivre nanoparticulaires modifiés en surface. L’invention concerne également les composés de cuivre nanoparticulaires modifiés en surface obtensibles selon ce procédé et des suspensions aqueuses de ces composés de cuivre ainsi que leur utilisation comme principe actif ou catalyseur antimicrobien.
EP09780084A 2008-07-08 2009-07-02 Composés de cuivre nanoparticulaires modifiés en surface Withdrawn EP2310320A1 (fr)

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EP08159913 2008-07-08
EP09780084A EP2310320A1 (fr) 2008-07-08 2009-07-02 Composés de cuivre nanoparticulaires modifiés en surface
PCT/EP2009/058303 WO2010003870A1 (fr) 2008-07-08 2009-07-02 Composés de cuivre nanoparticulaires modifiés en surface

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KR20120113296A (ko) 2009-12-02 2012-10-12 바스프 에스이 표면-개질 나노미립자 구리 염을 사용한 식물병원성 미생물의 처리 방법
JP2013514161A (ja) 2009-12-17 2013-04-25 ビーエーエスエフ ソシエタス・ヨーロピア ナノスケールの鉄〜白金族金属粒子を含む金属酸化物支持材料
US20110230668A1 (en) * 2010-03-19 2011-09-22 Basf Se Catalyst for gas phase oxidations based on low-sulfur and low-calcium titanium dioxide
US8901320B2 (en) 2010-04-13 2014-12-02 Basf Se Process for controlling a gas phase oxidation reactor for preparation of phthalic anhydride
US8859459B2 (en) 2010-06-30 2014-10-14 Basf Se Multilayer catalyst for preparing phthalic anhydride and process for preparing phthalic anhydride
US9212157B2 (en) 2010-07-30 2015-12-15 Basf Se Catalyst for the oxidation of o-xylene and/or naphthalene to phthalic anhydride
NZ587127A (en) 2010-07-30 2013-09-27 Mattersmiths Technologies Ltd Sub-micron compositions
WO2012163679A1 (fr) 2011-05-27 2012-12-06 Basf Se Procédé pour lutter contre des micro-organismes phytopathogènes avec des sels de cuivre particulaires, modifiés par des copolymères amps
US9849512B2 (en) 2011-07-01 2017-12-26 Attostat, Inc. Method and apparatus for production of uniformly sized nanoparticles
WO2013014163A1 (fr) 2011-07-28 2013-01-31 Basf Se Procédé en continu pour la production de particules de sel de cuivre par mélange turbulent
CA2975394A1 (fr) 2015-01-29 2016-08-04 Basf Corporation Catalyseurs contenant du rhodium pour le traitement d'emissions d'automobiles
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WO2016168346A1 (fr) * 2015-04-13 2016-10-20 Attostat, Inc. Compositions de nanoparticules anti-corrosion
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US9963614B2 (en) 2015-05-18 2018-05-08 Eastman Kodak Company Copper-containing articles and methods for providing same
US10745570B2 (en) 2015-05-18 2020-08-18 Eastman Rodack Company Copper-containing articles
CN106517299B (zh) * 2016-11-17 2017-10-27 合肥学院 一种片状自组装碱式碳酸铜花球及其简易制备方法
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BRPI0915727A2 (pt) 2015-10-27
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NZ590176A (en) 2012-06-29
WO2010003870A1 (fr) 2010-01-14
PE20110204A1 (es) 2011-04-28
CN102076610A (zh) 2011-05-25
KR20110028389A (ko) 2011-03-17
JP2011527305A (ja) 2011-10-27
US20110206753A1 (en) 2011-08-25
AU2009268108A1 (en) 2010-01-14
CL2010001651A1 (es) 2011-05-13
CA2730600A1 (fr) 2010-01-14
ECSP11010803A (es) 2011-03-31
IL210007A0 (en) 2011-02-28

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