EP2274123A2 - Nanoparticules métalliques stabilisées avec des polyéthylène imines ou des polyvinyle amines dérivées - Google Patents

Nanoparticules métalliques stabilisées avec des polyéthylène imines ou des polyvinyle amines dérivées

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Publication number
EP2274123A2
EP2274123A2 EP09722099A EP09722099A EP2274123A2 EP 2274123 A2 EP2274123 A2 EP 2274123A2 EP 09722099 A EP09722099 A EP 09722099A EP 09722099 A EP09722099 A EP 09722099A EP 2274123 A2 EP2274123 A2 EP 2274123A2
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EP
European Patent Office
Prior art keywords
reaction
silver
acid
polyvinylamines
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.)
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Application number
EP09722099A
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German (de)
English (en)
Inventor
Gerrit Luinstra
Wolfgang Schrof
Udo Goedert
Robert Feuerhake
Tobias Joachim Koplin
Imme Domke
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BASF SE
Original Assignee
BASF SE
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Priority to EP09722099A priority Critical patent/EP2274123A2/fr
Publication of EP2274123A2 publication Critical patent/EP2274123A2/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/62—Metallic pigments or fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • 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
    • C01G29/00—Compounds of bismuth
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G5/00—Compounds of silver
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G55/00—Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G7/00—Compounds of gold
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties

Definitions

  • Metal nanoparticles stabilized with derivatized polyethylenimines or polyvinylamines are provided.
  • the invention relates to metal nanoparticles stabilized with derivatized polyethylenimines or polyvinylamines.
  • Metallic nanoparticles in a wide variety of applications, such as fibers, paints, films, binders, adhesives, and resins, has been widely documented.
  • Metallic nanoparticles can be used as catalysts or in printing inks, as precursors for printing electronic circuits or for soldering, or they are used because of their special optical, photonic, magnetic or chemical properties.
  • Silver nanoparticles are additionally known for their ability to to rid aqueous solutions of harmful microorganisms.
  • Biotin-bound silver nanoparticles are known as highly sensitive sensors.
  • a major problem associated with the use of metal nanoparticles is their inherent instability which results in coagulation and, ultimately, precipitation of dendritic metal particles which are significantly larger than 100 nm. This is also disadvantageous for the applications outlined above, in that the nanodisperse system has the highest efficiency, and agglomeration, for example, reduces the catalytic activity or the biocidal effect or leads to an increase in the sintering temperature when used in printing inks. It is also desirable that all nanoparticles are in contact with the surrounding medium to be fully effective.
  • A. Dawn et al., Langmuir 2007, 23, 5231 to 5237 describe the preparation of monodisperse silver nanoparticles in the presence of poly-o-methoxyaniline (POMA) as a reducing and stabilizing polymer.
  • POMA poly-o-methoxyaniline
  • An aqueous silver nitrate solution is added to a solution of POMA in chloroform, and the silver nanoparticles are formed at the phase interface.
  • nanoparticles with a mean diameter between 12.0 and 21, 9 nm are formed. Only very dilute solutions of POMA and silver nitrate are used.
  • the colloidal core consists of polystyrene, the shell of poly (N-isopropylacrylamide) which is crosslinked by N, N'-methylbisacrylamide.
  • the core / shell particles contain 10.4% by weight of silver nanoparticles in a size of 8.5 ⁇ 1.5 nm.
  • the silver nanoparticles are obtained by reduction of silver nitrate in an aqueous suspension containing the Contains core / shell particles, prepared with sodium borohydride.
  • Gautam et al., Synthetic Metals, 157 (2007), pp. 5-10 describe the preparation of silver nanoparticles having a particle size in the range of 10 to 30 nm.
  • An aqueous silver nitrate solution is reduced with polyvinyl alcohol (PVA) PVA simultaneously stabilizes the nanoparticles formed.
  • PVA polyvinyl alcohol
  • the silver-PVA nanocolloid solution is aged at 2 to 5 ° C for 30 to 50 hours, heated and poured into thin layers of 1 to 5 mm thick. After burning off the polymer at 300 to 400 0 C in air remains a finely divided powder of silver nanoparticles. At silver concentrations of> 5% by weight, agglomeration of the primary particles occurs.
  • Silver nanoparticles may also be formed by reduction of silver cations in the presence of polyvinylpyrrolidone (PVP) with sodium borohydride, citric acid or sodium citrate as described in Karpov et al., Colloid Journal 2007, Vol. 69, pp. 170-179, and U.S. Pat cited therein.
  • PVP polyvinylpyrrolidone
  • WO 2005/077329 describes a method in which silver nanoparticles are deposited on the surface of porous polymer particles.
  • the polymer particles are produced by emulsion polymerization in the presence of an emulsifier and stabilizer, preferably gelatin, starch, hydroethyl cellulose, carboxymethyl cellulose, polyvinyl pyrolidone, polyvinyl alkyl ether, polyvinyl alcohol or polydimethylsiloxane / polystyrene block copolymer.
  • the silver nanoparticles are then deposited by reduction of silver salts, for example with hydrazine, LiAIBH 4 , NaBH 4 or ethylene oxide.
  • the silver / polymer composite nanospheres are used in cosmetic compositions.
  • WO 2004/086044 describes biotin-bound silver nanoparticles as a highly sensitive sensor.
  • DE 10 2006 017 696 A1 describes a process for the preparation of metal particle sols having a metal particle content of ⁇ 1 g / l, in which a metal salt solution containing a solution containing hydroxyl ions, which by dissolving bases such as LiOH, NaOH, KOH, aliphatic or aromatic amines in Water is reacted, and the resulting solution is reduced with a reducing agent in the presence of a dispersant which stabilizes the particles formed, is reduced.
  • a metal salt solution containing a solution containing hydroxyl ions which by dissolving bases such as LiOH, NaOH, KOH, aliphatic or aromatic amines in Water is reacted, and the resulting solution is reduced with a reducing agent in the presence of a dispersant which stabilizes the particles formed, is reduced.
  • the processes of the prior art usually lead to systems in which the metal nanoparticles are embedded in the polymer particles and thus can not develop their special properties. Examples of such specific properties are the macroscopic conductivity, the biocidal efficacy, the optical resonance, the magnetic properties, the catalytic properties and the ability to sinter together to form conductive structures of the metal nanoparticles. Also, many of the prior art processes are cumbersome and involve multi-step syntheses and / or sophisticated purification procedures to obtain the final product. Also, with many prior art methods, only a low concentration of metal nanoparticles is obtained.
  • the object of the present invention is to provide a process for producing metal nanoparticles, which is suitable for producing highly concentrated aqueous solutions of metal nanoparticles, in particular silver, platinum and palladium nanoparticles, without it comes to agglomeration of the metal nanoparticles.
  • the object is achieved by metal nanoparticles stabilized with derivatized polyethylenimines or polyvinylamines and a process for the preparation thereof, in which a metal salt solution is reduced in the presence of the derivatized polyethylenimines or polyvinylamines with a reducing agent.
  • Suitable polyethyleneimines or polyvinylamines whose derivatives can be used according to the invention are described below under A to F.
  • polyethyleneimine homopolymers can be used, which may be present in uncrosslinked or crosslinked form.
  • the polyethyleneimine homopolymers can be prepared by known processes, as described, for example, in Rompps Chemie Lexikon, 8th ed. 1992, pp. 3532-3533, or in Ullmanns Enzyklopadie der Technischen Chemie, 4th edition 1974, Vol. 8, p. 212. 213 and the literature cited therein. They have a molecular weight in the range of approx. 200 to 1,000,000 g / mol.
  • Corresponding commercial products are available under the name Lu pasol ® from BASF SE or the name Epomin ® from Nippon Shokubai.
  • Polyethyleneimines for the purposes of the present invention are also polymers comprising ethyleneimine units which are obtainable by grafting polyamidoamines with ethyleneimine. These can be crosslinked with the crosslinkers mentioned under A.
  • Grafted polyamidoamines are known, for example, from US Pat. No. 4,144,123 or DE-B-2,434,816.
  • the polyamidoamines are obtainable, for example, by condensation of
  • dibasic carboxylic acids such as oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, itaconic acid, adipic acid, tartaric acid, citric acid, propane tricarboxylic acid, butanetetracarboxylic acid, glutaric acid, suberic acid, sebacic acid, terephthalic acid and their esters, acid chlorides or anhydrides mixed with up to 50 mol% of monobasic amino acids, monohydric hydroxycarboxylic acids and / or monobasic carboxylic acids,
  • dibasic carboxylic acids such as oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, itaconic acid, adipic acid, tartaric acid, citric acid, propane tricarboxylic acid, butanetetracarboxylic acid, glutaric acid, suberic acid, sebacic acid, terephthalic acid and their esters, acid chlorides or anhydr
  • Polyalkylenepolyamines are compounds which contain at least 3 basic nitrogen atoms in the molecule, for example diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N- (2-aminoethyl) -1,3-propanediamine and N, N 'Bis (3-aminopropyl) ethylene diamine.
  • diamines examples include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,8-diaminooctane, isophoronediamine, 4,4'-diaminodiphenylmethane, 1,4-bis - (3-aminopropyl) piperazine, 4,9-dioxadodecane-1, 12-diamine, 4,7,10-trioxatridecane-1, 13-diamine or a, z-diamino compounds of polyalkylene oxides.
  • the condensation of the compounds (i) and (ii) takes place as described, for example, in EP-B 0 703 972.
  • the graft polymers generally contain 10 to 90 wt .-% of polyamidoamines as graft and 90 to 10 wt .-% of ethyleneimine as a graft.
  • Polyethyleneimines for the purposes of the present invention are also polymers containing ethyleneimine units which are obtainable by grafting polyvinylamines with ethyleneimine or oligomers of ethyleneimine.
  • Polyvinylamines are obtained by complete or partial saponification of polymers of open-chain N-vinylcarboxamides of the general formula (I)
  • the saponification degree is generally 5 to 100%.
  • the graft polymers can be crosslinked.
  • the graft polymers generally contain 10 to 90 wt .-% of polyvinylamine as a graft and 90 to 10 wt .-% of ethyleneimine as a graft.
  • polyethyleneimines also include the polymers corresponding to the compounds listed under A to C of higher homologs of ethyleneimine, such as propyleneimine (2-methylaziridine), 1- or 2-butylenimine (2-ethylaziridine or 2,3-dimethylaziridine ), Understood.
  • ethyleneimine is preferred.
  • Polyvinylamines in the context of the invention are also the copolymers of (a) 0.1 to 100% by moles of N-vinylcarboxamides of the formula (I) and (b) 0 to 99.9% by moles of Vmyiformsal, Vinyiaeetal, VmylpropionaL Vinyiaikohoi, N-vinyl urea & loff. N-vinylpyrrolidone, N-vinylpiperidone, N-vinylmicrolactam, N, N-divinylideneurea Lind / or N ⁇ Vinyi ⁇ Imldazoi. where the sum of (a) and (b) gives 100 moL%, which are at least partially solved.
  • Preferred polyethyleneimines whose derivatives are used according to the invention are the homopolymers of ethyleneimine described under A and the graft polymers of polyamidoamines described under B with ethyleneimine.
  • Preferred polyethyleneimines and graft polymers of polyamidoamines with ethyleneimine are those having a molecular weight in the range from 500 to 2,000,000 g / mol, more preferably from 1,000 to 100,000 g / mol, in particular from 5,000 to 50,000 g / mol.
  • polyethyleneimines or polyvinylamines mentioned under A to F are derivatized by the reactive nitrogen atoms
  • alpha, beta-unsaturated carbonyl compounds are acrylic acid and acrylic esters, for example alkyl acrylates and hydroxyalkyl acrylates, methacrylic acid and methacrylic acid esters, for example alkyl methacrylates and hydroxyalkyl methacrylates , Acrolein, arylamide and acrylonitrile;
  • reaction with compounds nucleophilically substitutable by the imine nitrogen preferably with hydrocarbon compounds, in particular alkyl compounds or alkylene compounds, which have one or two suitable leaving groups, for example acetate, brosylate, mesylate, nosylate, tosylate, trifluoroacetate, trifluorosulfonate, Chlorine, bromine or iodine;
  • hydrocarbon compounds in particular alkyl compounds or alkylene compounds, which have one or two suitable leaving groups, for example acetate, brosylate, mesylate, nosylate, tosylate, trifluoroacetate, trifluorosulfonate, Chlorine, bromine or iodine
  • Examples are organic and inorganic halides, in particular alkyl halides, alkyl trifluoroacetates, Al kyl (bromine) toluenesulfonates and alkyl phenates such as methyl chloride, methyl trifluoroacetate, trimethylsilyl
  • dialdehydes and / or diketones are, for example, glyoxal and 1, 3-pentanedione;
  • diepoxides diepoxides, halohydrin ethers and / or bishalohydrin ethers
  • suitable diepoxides are, for example, 1,6-hexanediol bisglycidyl ether, and also bisglycidyl ethers of oligo- and polyethylene glycols
  • reaction products of halohydrins for example epichlorohydrin, with alkylene glycols and polyalkylene glycols having from 2 to 100 ethylene oxide or propylene oxide units;
  • reaction with alkylene carbonates for example ethylene carbonate or propylene carbonate
  • bischloroformates for example 2,2-dimethylpropylene-bischloroformate
  • reaction with isocyanates for example with diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate and diphenylmethane diisocyanate;
  • diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate and diphenylmethane diisocyanate
  • Preferred derivatization reactions are (1) 1,4-addition (Michael addition) to alpha, beta-unsaturated carbonyl compounds;
  • polyethyleneimines A are reacted with a diepoxide and / or bischlorohydrin ether and then reacted with one or more alpha, beta-unsaturated carbonyl compounds; for example, they are reacted with 1,6-hexanediol bisglycidyl ether or the bisglycidyl ether of a polyalkylene glycol and then reacted with (meth) acrylic acid, alkyl (meth) acrylate, for example methyl acrylate, and / or hydroxyalkyl (meth) acrylate, for example hydroxyethyl acrylate or 4-hydroxybutyl acrylate.
  • Preferred alkyl (meth) acrylates are the C 1 -C 6 -alkyl (meth) acrylates
  • preferred hydroxyalkyl (meth) acrylates are the hydroxy-C 1 -C 6 -alkyl (meth) acrylates.
  • polyethyleneimines A are reacted with a diepoxide and / or bischlorohydrin ether and subsequently reacted with a carboxylic acid ester, for example ethyl acetate.
  • polyethyleneimines A are reacted with acrylic acid, hydroxyalkyl acrylates, for example hydroxyethyl acrylate or 4-hydroxybutyl acrylate, and / or acrylamides, for example N-tert-butylacrylamide or N-isopropylacrylamide or other N-substituted acrylamides.
  • Preferred acrylamides are the N-Ci-C 6 -alkylacrylamides.
  • polyamidoamines B are reacted with acrylic acid.
  • polyamidoamines B are reacted with a diepoxide and / or bischlorohydrin ether, for example the bisglycidyl ether of a polyalkylene glycol, and then reacted with acrylic acid.
  • a diepoxide and / or bischlorohydrin ether for example the bisglycidyl ether of a polyalkylene glycol
  • the derivatization of the polyalkyleneimines is generally carried out at temperatures of - 30 0 C to 300 0 C in the gas phase, optionally under pressure, or in solution.
  • the derivatization is preferably carried out in the same medium in which the preparation of the nanoparticles has also taken place. It is preferred at temperatures from 50 to 150 0 C, in particular carried out at 75 to 95 ° C.
  • Preferred reaction medium is water.
  • the metal nanoparticles are generally prepared by reduction of the corresponding metal salts with a reducing agent in the presence of the derivatized polyalkyleneimines or polyvinylamines.
  • Suitable reducing agents may be organic or inorganic reducing agents. Examples are alcohols such as methanol or ethanol, amino alcohols such as 1, 2-aminoethanol, diethanolamine, aldehydes such as formaldehyde or acetaldehyde, ketones, carboxylic acids such as formic acid, acetic acid or oxalic acid, alkenoic acids such as 5-pentenoic acid, hydrazine or hydrazine derivatives, azo compounds such as AIBN (azobisisobutyronitrile), carboxylic anhydrides, amides, amines, ethers, esters, alkenes, dienes, thio compounds, mono- or polysaccharides, phosphorus or arsenic derivatives, hydrogen or carbon oxides.
  • AIBN azobis
  • Suitable inorganic reducing agents are hydrogen, metals such as zinc, calcium and magnesium, and metal hydrides such as sodium borohydride, furthermore Sn (II) salts, Fe (II) salts, thiosulfates, thiosulfites, phosphites, phosphines, sulfides and disulfides.
  • Particularly preferred organic reducing agents are formic acid or formaldehyde. This produces carbon dioxide, which can be easily removed from the reaction mixture. For example, carbon dioxide can be removed from the reaction mixture by stripping with air.
  • diethanolamine, 5-pentenoic acid, ascorbic acid and citric acid are also preferred.
  • ethanol, methanol, ethylene glycol, diethylene glycol, hydrazine and oxalic acid are particularly preferred.
  • Preferred inorganic reducing agents are sodium borohydride, Sn (II) salts, Fe (II) salts, thiosulfates, thiosulfites, phosphites, phosphines, sulfides and disulfides.
  • an alcohol is used both as a solvent and as a reducing agent.
  • no further reducing agent is used.
  • This method is basically described in Atf. Funct. Mater. 2003, 13 No.2: Synthesis of nanoscaled ZnO particles by thermolysis of metal salt precursor in diethylene glycol; J. Mater. Res. Vol. 10, no. 1: Synthesis of spherical ZnO nano particles by the hydrolysis of Zn acetate in diethylene glycol; J. SoI-GeI Be. Techn.
  • the metal nanoparticles are generally prepared by reduction at temperatures of - made 30 to 300 ° C and pressures between 10 mbar and 100 bar, preferably at temperatures of 0 to 100 0 C, particularly preferably at 20 to 95 ° C. Preferably, working at atmospheric pressure, so that special vacuum devices or pressure vessels are not required.
  • the temperature of the reduction of the metal salt solution can be selected so that the reaction is completed at the latest after 24 hours, preferably at the latest after 10 hours, and in particular after 5 hours at the latest.
  • this temperature may be in the case of silver as metal and formic acid as a reducing agent of 30 to 50 0 C.
  • the metal nanoparticles stabilized according to the invention can consist of copper, silver, gold, palladium, nickel, platinum, rhodium, iron, bismuth, iridium, ruthenium or rhenium or also of two or more of these metals.
  • These metals may be in the form of their oxides, nitrates, phosphates, sulfates, sulfites, phosphonites, nitrites, borates, aluminates, silicates, cyanides, isocyanates, thioisocyanates, halides, perchlorates, periodates, perbromates, chlorates, iodates, bromates, hypochlorites or even in Form of complex compounds are present.
  • Suitable complex compounds are silver-ammonia complexes, diaminodichloropalladate, tetrachloropalladate or tetrachloroplatinate. It is also possible to use salts of a plurality of different metals which can be reduced simultaneously or in succession.
  • Preferred metals are copper, silver, gold, nickel, palladium, platinum, cobalt, rhodium, iridium, iron, ruthenium and osmium. Particularly preferred are copper, silver, palladium and platinum.
  • Silver is used, for example, in the form of silver oxide, silver acetate, silver nitrate or a silver oxide / silver nitrate mixture, palladium as alkali metal tetrachloro palladate, palladium (II) nitrate, palladium (II) acetate, tetraaminopalladium (II) nitrate, ammonium hexachloropalladate (IV), Diaminopalladium (II) chloride, bis (triphenylphosphine) palladium (II) chloride, bis (2,4-pentanedionato) palladium (II), 1,2-bis (diphenylphosphino) -ethanadium palladium (
  • the reduction can be carried out in organic solvents such as alcohols, polyols, esters, chlorinated hydrocarbons, phenols, DMSO, DMF, NMP and ethers such as THF, dioxane or dioxolane.
  • organic solvents such as alcohols, polyols, esters, chlorinated hydrocarbons, phenols, DMSO, DMF, NMP and ethers such as THF, dioxane or dioxolane.
  • Other reaction media are conceivable, such as molten salts or ionic liquids.
  • Preferred solvent Water or aqueous-organic solvent mixtures, glycol and diethylene glycol, particularly preferred are water and aqueous-organic solvent mixtures.
  • the alcohol can act as a reducing agent.
  • Suitable monohydric alcohols are ethanol, methanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-butanol.
  • Pentanol 3-methoxybutanol, n-hexanol, 3-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2, 6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol and diacetone alcohol.
  • Preferred monohydric alcohols are selected from glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Ethylenglykolmonopropyl- ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, Ethylenglykolmo- nophenylether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylenglykolmonopropylether, Diethylenglykolmo- nobutylether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene lenglykolmonoethylether, Propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and dipropylene glycol mono
  • polyhydric alcohols for example diols, which are preferably selected from the group consisting of 1, 2-ethanediol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 2.3 Butanediol, 1, 4-butanediol, but-2-en-1, 4-diol, 1, 2-pentanediol, 1, 5-pentanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 1 , 2-hexanediol, 1, 6-hexanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, octanediol, 1, 10-decanediol, 1, 2-dodecaned
  • diols are polyether homopolymers having OH functionality such as polyethylene glycol, polypropylene glycol and polybutylene glycol, binary copolymers such as ethylene glycol / propylene glycol and ethylene glycol / butylene glycol copolymers, non-branched ternary copolymers such as ethylene glycol / propylene glycol / ethylene glycol, propylene glycol / ethylene glycol / Propylene glycol and ethylene glycol / Buylenglykol / ethylene glycol copolymers.
  • polyether homopolymers having OH functionality such as polyethylene glycol, polypropylene glycol and polybutylene glycol
  • binary copolymers such as ethylene glycol / propylene glycol and ethylene glycol / butylene glycol copolymers
  • non-branched ternary copolymers such as ethylene glycol / propylene glycol / ethylene glycol, propylene glycol / ethylene glyco
  • suitable diols are polyether block copolymers having OH functionality, such as binary block copolymers, such as polyethylene glycol / polypropylene glycol and polyethylene glycol / polybutylene glycol, non-branched ternary block copolymers with alkyl chains, such as polyethylene glycol / polypropylene glycol / polyethylene glycol, polypropylene glycol / polyethylene glycol / polypropylene glycol and polyethylene glycol / polybutylene glycol / polyethylene glycol terpolymers.
  • binary block copolymers such as polyethylene glycol / polypropylene glycol and polyethylene glycol / polybutylene glycol
  • non-branched ternary block copolymers with alkyl chains such as polyethylene glycol / polypropylene glycol / polyethylene glycol, polypropylene glycol / polyethylene glycol / polypropylene glycol and polyethylene glycol / polybutylene glycol / polyethylene glycol
  • polyhydric alcohols having less than 10 carbon atoms is particularly preferred, especially those which are liquid at 25 ° C. and 1013 mbar, for example ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 2,3-butanediol, pentanediol, hexanediol and octanediol, with ethylene glycol and 1, 2-propanediol are particularly preferred.
  • Suitable polyhydric alcohols are furthermore triols, for example 1,1,1-tris (hydroxymethyl) ethane, 1,1,1-tris (hydroxymethyl) propane, 2-ethyl-2-hydroxymethyl-1,3-propanediol, 1, 2,6-hexanetriol, 1, 2,3-hexanetriol and 1, 2,4-butanetriol.
  • triols for example 1,1,1-tris (hydroxymethyl) ethane, 1,1,1-tris (hydroxymethyl) propane, 2-ethyl-2-hydroxymethyl-1,3-propanediol, 1, 2,6-hexanetriol, 1, 2,3-hexanetriol and 1, 2,4-butanetriol.
  • sugar alcohols such as glycerol, threitol, erythritol, pentaerythritol and pentitol can be used.
  • the derivatization of the polyethyleneimines or polyvinylamines and the preparation of the nanoparticles can be carried out as a so-called one-pot reaction without isolation of intermediates in one and the same reaction medium.
  • the polyethylenimine or polyvinylamine is first derivatized by reaction with the derivatizing agent (s), and then the metal nanoparticles are generated in the presence of the derivatized polyethylenimines or polyvinylamines by adding metal salt and reducing agent. It is also possible to reduce metal salt solutions of two or more different metals simultaneously or in succession, metal nanoparticles of two or more different metals being obtained. be. In this case, successive reduction steps can be carried out with different reducing agents.
  • UV-vis spectra were recorded between 200 and 800 nm using a Hewlett-Packard 8453 spectrometer in absorption mode in 1 cm glass cuvettes, with a suitable dilution selected.
  • TE M images were generated using a FEI CM120 device operating at 100kV, and the result was captured using a Gatan bioscan digital camera.
  • DLS (Dynamic Light Scattering) spectra were recorded on a Malvern ZetasizerNano S device at 23 ° C and at an angle of 173 °.
  • the evaluation of the measurement data was carried out according to ISO standard 13321: 1996E.
  • the obtained autocorrelation function was logarithmized and approximated with a third order polynomial.
  • the mean z-value was calculated from the quadratic coefficients using temperature, viscosity, refractive index and laser light wavelength as constants in the Stokes-Einstein relation.
  • the distribution was calculated using the Malvern software (CONTIN procedure by S. Provencher).
  • a polyamidoamine is prepared by condensing adipic acid with diethylenetriamine and subsequently grafted in aqueous solution with sufficient ethyleneimine so that the polyamidoamine per grafted nitrogen atom group contains 6.7 grafted ethyleneimine units.
  • 321 g of a 62% aqueous solution of this polymer are placed in a four-necked flask with intensive stirrer and reflux condenser, diluted with 479 g of demineralized water and heated with stirring to an internal temperature of 95 ° C. This air is constantly introduced. When the internal temperature of 95 ° C is reached, 87 g of acrylic acid are added dropwise within 2 hrs.
  • a polyamidoamine is prepared by condensation of adipic acid with diethylenetriamine and subsequently grafted in aqueous solution with sufficient ethyleneimine so that the polyamidoamine per grafted nitrogen atom contains 6.7 grafted ethyleneimine units.
  • 362 g of a 62% aqueous solution of the polyamidoamine are placed in a four-necked flask with intensive stirrer and reflux condenser, with 540 g of deionized water diluted and heated with stirring to an internal temperature of 95 ° C. This air is constantly introduced. When the internal temperature of 95 ° C is reached, 98.1 g of acrylic acid are added dropwise within 2 hrs.
  • a polyamidoamine is prepared by condensing adipic acid with diethylenetriamine and subsequently grafted in aqueous solution with sufficient ethyleneimine so that the polyamidoamine per grafted nitrogen atom contains 6.7 grafted ethyleneimine units.
  • This product is crosslinked by reaction with a single bismuth glycidyl ether of a polyethylene glycol of average molecular weight 2000 as described in Example 3 of US-A 4,144,123.
  • An ethyleneimine unit-containing polymer having a broad molecular weight distribution (polydispersity of 400) is obtained.
  • the following examples show the broad applicability of the functionalization reaction.
  • the reactions were carried out in a 100 L stainless steel reactor. Polyethyleneimine is introduced into the reactor and heated to 95.degree. The reactants are added over a period of 2 hours with vigorous stirring. The reaction mixture is then cooled to 25 ° C and analyzed unreacted reactants with headspace GC. In all cases, high sales are achieved.
  • PEI polyethyleneimine
  • AIPA acrylic acid isopropylamide, 20% by weight in water
  • the product is a dark, red-brown, viscous solution with a solids content of 17.42%.
  • the turnover is 100%.
  • the product had a silver content of 55 wt .-%, the supernatant contained 38 wt .-% silver.
  • the TEM analysis showed separate particles with silver crystallites on the surface of the polymer particles which were in contact with the medium. Diluting the pasty mass by a factor of 100,000 with water did not precipitate silver, reflecting the high colloidal stability of these polymer-silver particle complexes.
  • the original UV-vis spectrum with a Maximum at 410 nm and a small shoulder at 470 nm was retained. A TEM image is shown in FIG.
  • Example 59 In a glass reactor, 26.1 parts of silver oxide were suspended in 5 parts of the solution of Example 3. 3.5 parts of a 98% by weight formic acid were added all at once. A vigorous gas evolution was observed, at the same time the reaction mixture turned dark. Finally, the mixture was heated to 40 0 C and left for 30 minutes at this temperature. The isolated dark brown pasty mass had a peak in the UV-vis spectrum at 410 nm, which is characteristic for small silver nanoparticles.
  • Example 14 In a glass reactor, 4 parts of silver oxide and 1 part of silver nitrate solution are suspended in a part of the solution of Example 14. Another 4 parts of the polymer solution of Example 14 are added in two equal portions, forming an off-white mixture. This is heated to 40 0 C, and there are added 1, 5 parts of formic acid in 5 portions. After 2 hours the reaction is complete and the mixture is cooled to room temperature. The isolated dark brown pasty mass has a peak in the UV-vis spectrum at 410 nm, which is characteristic of small silver nanoparticles on.
  • Example 14 In a glass reactor, 1 part of the solution from Example 14 is diluted with 5 parts of water. A mixture of 4 parts silver oxide and 1 part silver nitrate is added and the mixture is heated to 40 ° C. Then 1.5 parts of formic acid are added in 5 portions. Finally, another 4 parts of the solution of Example 14 are added in two equal portions, forming an off-white mixture. This is heated to 40 0 C. After 2 hours, the reaction is complete. The resulting dark solution has a peak in the UV-vis spectrum at 410 nm.
  • Example 63 In a glass reactor, 1 part of the solution of Example 14 and 2 parts of water are mixed. 4 parts of silver oxide and 1 part of silver nitrate are added to the mixture. Subsequently, 1.5 parts of formic acid are added in 5 portions. Subsequently, a further 4 parts of the solution from Example 14 are added in 2 equal portions. A whitish mixture is formed. This is heated to 40 ° C. After 2 hours, the reaction is complete. The resulting dark solution has a peak in the UV-vis spectrum at 410 nm.
  • Example 63 Example 63
  • a solution of the pasty mass from Example 58 with a silver content of 2 wt .-% is applied with a doctor blade to a glass substrate and dried at room temperature or at 250 0 C in a vacuum. A film of 200 ⁇ m thickness is obtained. The dried at room temperature film can be redissolved in water. The dried at 250 ° C film has an electrical resistance of 2 M ⁇ over a length of 4 cm. After treatment in air at 300 ° C. for 2 hours, a conductive film of sintered silver particles having a resistance of less than 1 ⁇ over a length of 4 cm is obtained.
  • Procedure A x parts of water and y parts of aqueous silver nitrate solution (500 g / L) are placed in a reactor. The mixture is shaken at 500 rpm and heated to the reaction temperature of 45 ° C. The polymer solutions of Examples 1 to 6, 9, 1 1 and 16 to 29 are added at once. In some cases, a white precipitate is formed. Subsequently, a stoichiometric amount, based on the metal content, of formic acid (51 g / L) is added all at once.
  • FIG. 3 shows a TE M pick-up of example 74.
  • FIG. 4 shows a TE M pick-up of example 84.
  • Example 3 The product of Example 3 (7.5 parts) having a solids content of 50 g / l was heated to 45 ° C. 5 parts of a solution of potassium tetrachloropalladate (100 g / l) were added all at once. A white precipitate forms, which slowly dissolves again during the reaction. Subsequently, a solution of sodium borohydride in water (4.1 parts containing 42 g / l sodium borohydride) was added. The reaction mixture was stirred for 4 hrs, taking a black color. TEM analysis showed the presence of metal nanoparticles. In another approach (Example 98), the sodium borohydride solution was added in 4 portions. The result was the same. A TE M Auf would take the polymer particles Figure 5 again. The polymer particles appear in lighter gray and the metal nanoparticles in darker gray on the surface of the polymer particles.
  • Examples 137 and 138 7.5 parts of the product of Example 3 having a solids content of 50 g / l were heated to 45 ° C. 5 parts of a solution of potassium tetrachloroplatinate (200 g / l) were added in one portion. Subsequently, 4.1 parts of a solution of formaldehyde in water (33.4 g / l) were added. The reaction mixture was stirred for 4 h, during which the solution turned black (Example 99). The TEM analysis shows the presence of metal nanoparticles. In a further batch (Example 100), a sodium borohydride solution in 4 portions was added. The results did not differ. A TEM image of the product obtained is shown in FIG.
  • Examples 139 to 145 x parts of a residual solution of potassium chloroplatinate and 7.5 ml of an aqueous solution of the reaction product of Example 14 were placed in a reactor. The mixture was stirred at 500 rpm and heated to the reaction temperature of 80 0 C. Subsequently, a stoichiometric amount, based on the metal content, of diethanolamine (166.6 g / l) was added all at once. The reaction mixture was left at 80 ° C. for 24 hours and stirred at 300 rpm for 5 minutes each hour. Finally, it was cooled to room temperature. Then, x parts of potassium chloropaladate were added. The mixture was stirred at 500 rpm and heated to the reaction temperature of 70 ° C.
  • a TEM image of the product obtained is shown in FIG. 7.

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Abstract

L'invention concerne des nanoparticules métalliques et leur procédé de fabrication dans lequel une solution de sels métalliques est réduite en présence de la polyéthylène imine ou de la polyvinyle amine dérivée avec un agent de réduction. Des solutions de sels métalliques de deux ou plusieurs métaux différents peuvent être réduites simultanément ou successivement, des nanoparticules métalliques étant obtenues à partir de deux ou plusieurs métaux différents. Les métaux préférés sont l'argent, le palladium et le platine. Des agents de réduction appropriés sont par exemple l'acide formique, le formaldéhyde, la diéthanolamine, l'acide pentène-5-oïque et le borohydrure de sodium. L'argent peut être utilisé sous la forme d'oxyde d'argent et/ou de nitrate d'argent, le palladium sous la forme de tétrachloropalladate de métal alcalin ou de nitrate de palladium (ll) et le platine sous la forme de tétrachloroplatinate de métal alcalin ou de nitrate de tétraamino-platine (ll).
EP09722099A 2008-03-19 2009-03-17 Nanoparticules métalliques stabilisées avec des polyéthylène imines ou des polyvinyle amines dérivées Withdrawn EP2274123A2 (fr)

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WO2009115506A3 (fr) 2010-05-06
US20110020170A1 (en) 2011-01-27

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