EP3077140A1 - Procédé de préparation de nanoparticules métalliques anisotropes et agent pour commander leur croissance - Google Patents

Procédé de préparation de nanoparticules métalliques anisotropes et agent pour commander leur croissance

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Publication number
EP3077140A1
EP3077140A1 EP14806275.5A EP14806275A EP3077140A1 EP 3077140 A1 EP3077140 A1 EP 3077140A1 EP 14806275 A EP14806275 A EP 14806275A EP 3077140 A1 EP3077140 A1 EP 3077140A1
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EP
European Patent Office
Prior art keywords
polyalkyleneimine
silver
process according
group
copolymer
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EP14806275.5A
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German (de)
English (en)
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EP3077140B1 (fr
Inventor
Manuel Arturo Lopez Quintela
Carlos VÁZQUEZ VÁZQUEZ
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Nanogap Sub NM Powder SA
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Nanogap Sub NM Powder SA
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Classifications

    • 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
    • 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
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/0547—Nanofibres or nanotubes

Definitions

  • the present invention relates to a process for preparing anisotropic metal nanoparticles and to anisotropic metal nanoparticles thus obtained.
  • nanofibers being one of the most important due to their application potentials in the preparation of nanocomposites based on non- metal materials (ceramics, polymers, glasses, etc.) in order to render metal properties to these materials.
  • Applications such as new antistatic nanocomposites, nanocomposites for shielding against electromagnetic radiation, nanocomposites and nanocomposite liquids for heat transfer, etc. make this a topic of great importance in recent technology.
  • Silver Nanofibers (Ag NF) for the manufacturing of TCFs, new methods must be developed for their preparation that meet the following requirements: high aspect ratios (> 200-300), small NF diameters ( ⁇ 50nm), low synthesis temperatures ( ⁇ 140°C), ambient pressure and air conditions (i.e. no controlled atmosphere, e.g. oxygen or nitrogen).
  • the polyol method is the most popular (see for example the review paper from X. Li et al, Cryst. Res. Technol. 201 1 , 5, 427). It was firstly reported by Ducamp-Sanguesa et al (J. Solid State Chem. 1992, 100, 272) and later by Sun et al. (Chem. Mater. 2002, 14, 4736; Nano Lett. 2002, 2, 165) and it is based in the reduction of AgN0 3 in the presence of Pt seeds and polyvinylpyrrolidone (PVP) as protecting agent to avoid aggregation. During the last decade, the method was deeply studied and improved.
  • PVP polyvinylpyrrolidone
  • protecting/capping agents different from PVP have also been reported for the synthesis of Ag NW even at low temperatures, but they do not meet some of the previous requirements.
  • some of protecting/capping agents like cetyltrimethylammonium bromide (CTAB, N.R. Jana et al, Chem. Commun. 2001 , 617), Vitamin C (Y. Liu et al, Mater. Res. Bull. 2005, 40, 1796), Vitamin B2 (M.N. Nadagouda et al, J. Nanomater. 2008, 782358), dodecyl benzene sulfonic acid (DBS, G.J. Zhou et al, J. Cryst.
  • CAB cetyltrimethylammonium bromide
  • Vitamin C Y. Liu et al, Mater. Res. Bull. 2005, 40, 1796
  • Vitamin B2 M.N. Nadagouda et al, J. Nanomater. 2008, 78
  • US 2013/0255444 A1 describes a process for producing silver nanowires which comprises a polymer obtained by polymerizing polymerizable monomers containing monomers of a N-substituted (meth)acrylamide that reacts with a silver compound in a polyol at a temperature from 25 °C to 180 °C under nitrogen atmosphere.
  • JP 2013194290 discloses a process to obtain copper nanowires which comprises the use of a copolymer of polyethyleneimine and polyethylene glycol.
  • the inventors of the present invention have found that by using polyethylenimine (PEI) as capping/reducing agent and controlling the reaction conditions, it is possible to obtain and control the formation of nanofibers, which fulfils all the previous requirements for the production of silver nanofibers for the manufacturing of TCF; the nanofibers have aspect ratios above 300 and diameters below 50 nm; the process can be performed at low temperatures, i.e. below 140 °C, at atmospheric pressure and in air conditions, i.e. without the need of inert atmospheres, therefore improving the scale-up processes.
  • PEI polyethylenimine
  • one aspect of the present invention relates to a process for preparing anisotropic metal nanoparticles comprising the step of reducing the transition metal cation of a salt to oxidation state zero in the presence of a solvent and a polyalkyleneimine or a copolymer where one of the copolymer units is selected from a polyalkyleneimine and the other unit is selected from the group consisting of alkides, polyesters, polyvinyl alcohol, polyvinyl acetate, polyacrylamides, polyacrylic acid and polyisocyanates, wherein the alkyleneimine to metal cation molar ratio is above 10.
  • Another aspect of this invention refers to anisotropic metal nanoparticles obtained by the process of the invention.
  • Another further aspect refers to the use of a polyalkyleneimine or a copolymer where one of the copolymer units is selected from a polyalkyleneimine and the other unit is selected from the group consisting of alkides, polyesters, polyvinyl alcohol, polyvinyl acetate, polyacrylamides, polyacrylic acid and polyisocyanates for preparing anisotropic metal nanoparticles.
  • Anisotropic metal nanoparticle of the present invention refers to metal nanoparticles having the shape selected from the group consisting of nanofibers, nanotriangles, nanostars, nanodiscs, nanocubes, nanotetrahedrons or nanoprisms, preferable anisotropic metal nanoparticle in the present invention are nanofibers.
  • Nanofibers are nanoparticles having elongated shape in one direction; they can be found as well in the literature as nanocylinders, nanorods, nanowires or nanotubes, all these names are encompassed in the present invention for the term nanofiber.
  • the term nanofiber in the present invention relates to nanoparticles (nanocylinders, nanorods, nanowires or nanotubes) that have a diameter less than 200 nm and a length along their major axis from 0.2 to 1000 ⁇ .
  • the diameter of the nanofibers is preferably less than 150 nm, particularly desirably less than 100 nm and even more preferably less than 75 nm.
  • Preferred embodiments have diameters between 10 and 70 nm, between 15 and 60 nm, and more preferably between 18 and 53 nm.
  • the diameter is an arithmetic mean of the respective diameters of 100 silver nanofibers which may be obtained by observation with a scanning electron microscope.
  • the length along the major axis of the nanofibers of the invention is preferably between 1 and 800 ⁇ , preferably between 3 and 400 ⁇ , preferably between 5 and 200 ⁇ , preferably between 7 and 100 ⁇ .
  • the nanofibers of the present invention may be defined by their aspect ratio.
  • “Aspect ratio” or “ratio” in the present invention refers to the following relation:
  • the nanofibers of the present invention present an aspect ratio ranging from 300 to 10000. In other embodiments the nanofibers of the present invention present an aspect ratio ranging from 300 to 8000, from 300 to 6000, from 300 to 4000, from 300 to 3000, from 310 to 2000, from 320 to 1500, or from 330 to 1000.
  • the other anisotropic nanoparticles of the present invention are nanodiscs, nanotriangles, nanosquares, nanostars, nanocubes, nanotetrahedrons and nanoprisms. Therefore, isotropic nanoparticles such as nanospheres are not encompassed in the present invention.
  • the anisotropic nanoparticles of the invention are characterized in that one of the dimensions is less than 1000 nm. In some preferred embodiments, the smallest dimension is less than 500 nm, preferably is less than 250 nm, less than 100nm or even less than 50 nm.
  • the metal of the anisotropic metal nanoparticles is selected from a transition metal, preferably a transition metal selected from the groups 10 and 1 1 , preferably a transition metal selected from the group consisting of silver, gold, copper, palladium, platinum and nickel, more preferably a transition metal selected from the group consisting of silver, gold and copper, more preferably a transition metal selected from silver and gold, and most preferably the anisotropic metal nanoparticles are anisotropic silver nanoparticles.
  • anisotropic metal nanoparticles are silver, gold, copper, palladium, platinum or nickel nanofibers. In a more preferred embodiment the anisotropic metal nanoparticles are silver nanofibers.
  • the process of the present invention comprises the step of reducing a transition metal cation of a salt to oxidation state zero in the presence of a solvent and a polyalkyleneimine and/or a copolymer where one of the copolymer units is selected from a polyalkyleneimine.
  • the solvent and/or the polyalkyleneimine and/or a copolymer where one of the copolymer units is selected from a polyalkyleneimine act as a reducing agent of the transition metal cation.
  • all the metal atoms of the anisotropic nanoparticle are in oxidation state zero.
  • the step of reducing is the same as “reduction step” and in the present invention means that in that step a cation is reduced to oxidation state zero.
  • the "transition metal cation” is preferably a cation of a transition metal selected from the group consisting of silver, gold, copper, palladium, platinum and nickel, more preferably a cation of a transition metal selected from the group consisting of silver, gold and copper, preferably a cation of a transition metal selected from silver and gold, and more preferably the transition metal cation is a silver cation.
  • the expression "transition metal cation of a salt” refers to salts that comprise the metal cation. The anion of the salt is not relevant for the present invention. Suitable anions include inorganic and organic anions. They are normally polyatomic oxyanions of non- metals.
  • Non-limiting examples of anions of the metallic salt are nitrates, nitrites, oxides, oxalates, borates (including fluoroborates, pyrazolylborates, etc.), carbonates, phosphates, sulfates, chlorates, acetates, citrates and halides (e.g., fluorides, chlorides, bromides and iodides), azides, sulfonates, carboxylates (such as, e.g., formates, acetates, propionates, oxalates and citrates), substituted carboxylates (including halogenocarboxylates such as, e.g., trifluoroacetates, hydroxycarboxylates, aminocarboxylates, etc.) and salts and acids wherein the transition metal is part of the anion (such as, e.g., hexachloroplatinates, tetrachloroaurate, tung
  • transition metal salts useful in the present invention are silver nitrate, silver chloride, silver sulfate, silver sulfamate, silver chlorate, and silver perchlorate; gold nitrate, gold chloride, gold sulfate, gold sulfamate, gold chlorate, and gold perchlorate; copper nitrate, copper chloride, copper sulfate, copper sulfamate, copper chlorate, and copper perchlorate; and salts of organic acids such as silver acetate and silver lactate; gold acetate and gold lactate; copper acetate and copper lactate; and the correspondent nickel, palladium and platinum salts.
  • the silver cation is obtained from using one of the following silver salts: silver nitrate, silver nitrite, silver oxide, silver fluoride, silver hydrogen fluoride, silver carbonate, silver oxalate, silver azide, silver tetrafluoroborate, silver acetate, silver propionate, silver butanoate, silver ethylbutanoate, silver pivalate, silver cyclohexanebutanoate, silver ethylhexanoate, silver neodecanoate, silver decanoate, silver trifluoroacetate, silver pentafluoropropionate, silver heptafluorobutyrate, silver trichloroacetate, silver 6,6,7,7,8,8,8 heptafluoro-2,2-dimethyl-3,5-octanedioate, silver lactate, silver citrate, silver glycolate, silver glyconate, silver benzoate, silver salicylate, silver phenyla
  • the silver salt is selected from the group consisting of silver nitrate, silver nitrite, silver oxide, silver fluoride, silver hydrogen fluoride, silver carbonate, silver oxalate, silver azide, silver tetrafluoroborate. silver acetate, silver propionate, silver butanoate, silver ethylbutanoate or silver pivalate as well as combinations of any two or more of the foregoing.
  • the silver salt is a silver salt of inorganic acid, more preferably silver nitrate.
  • a “solvent” must be present during the reducing step.
  • the solvent is preferably a polar solvent.
  • the solvent is selected from the group consisting of aliphatic glycols, aliphatic, cycloaliphatic and aromatic alcohols, ether alcohols, aminoalcohols, esters, ethers, sulfoxides, ionic liquids, water and mixtures thereof.
  • the aliphatic, cycloaliphatic and aromatic alcohols are selected from methanol, ethanol, propanol, isopropanol, isobutanol, isopentanol, butanol, pentanol, cyclopentanol, hexanol, cyclohexanol, octanol, decanol, isodecanol, undecanol, dodecanol, tetradecanol, hexadecanol, benzyl alcohol, butyl carbitol and the terpineols.
  • the ether alcohols are selected from the monoalkyi ethers of diols such as, e.g., the Ci -6 monoalkyi ethers of Ci -6 alkanediols and polyetherdiols derived therefrom, preferably selected from the monomethyl, monoethyl, monopropyl and mono butyl ethers of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1 ,3-propanediol, and 1 ,4-butanediol such as, e.g., 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol and 2-butoxyethanol.
  • the monoalkyi ethers of diols such as, e.g., the Ci -6 monoalkyi ethers of Ci -6 alkanediols and polyetherdiols derived therefrom, preferably selected from the monomethyl, monoethyl, monoprop
  • the aminoalcohols are selected from ethanolamine, amides such as, e.g., dimethylformamide, dimethylacetamide 2-pyrrolidone and N- methylpyrrolidone.
  • the ethers are selected from tetrahydrofuran and tetrahydropyran.
  • the esters are selected from ethyl acetate and ethyl formate.
  • the sulfoxide is dimethylsulfoxide.
  • the ionic liquids are selected from [BMIm][MeS04] (also called 1 -butyl-3-methylimidazolium methylsulfate or methanesulfonate)), 1 ,3-dimethylimidazolium 1 ,1 ,1 -trifluoro-N- [(trifluoromethyl)sulfonyl]methanesulfonamide, 1 -butyl-1 -methylpyrrolidinium 1 ,1 ,1 - trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 1 -butyl-3-methylimidazolium 1 ,1 ,1 -trifluoro-N-[(trifluoromethyl)sulfonyl]methanesulfonamide; 1 -butyl-3-methylimidazolium bis(perfluoroethylsulfonyl)imide
  • the solvent is selected from the group consisting of ethylene glycol, propylene glycol, glycerol, water and mixtures thereof. In a particular embodiment the solvent is a mixture of ethylene glycol and water.
  • the solvent acts at the same time as solvent and as reducing agent.
  • the solvents that act at the same time as solvent and as reducing agent are selected from aliphatic glycols, aromatic alcohols, polyols, ketones, amides, amines, esters, ionic liquids and mixtures thereof.
  • the aliphatic alcohols, polyols and/or glycols that act at the same time as solvent and as reducing agent are selected from methanol, ethanol, 1 - propanol, 2-propanol, 1 -butanol, 1 -pentanol, 2-pentanol, tert-butyl alcohol, tert-amyl alcohol, and cyclohexanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, tetra-ethylene glycol, polyethylene glycol that is liquid at the reaction temperature, such as for example, polyethylene glycol 300, 1 ,2-propanediol, di- propylene glycol, 1 ,2-butanediol, 1 ,3-butanediol, 2,3-butanediol, 1 ,4-butanediol and glycerol, preferably is selected from ethylene glycol, propylene glycol,
  • the aromatic alcohol that acts at the same time as solvent and as reducing agent is benzyl alcohol.
  • the ketone is selected from 3-hydroxybutanone, 2,3-butanedione and methyl isobutylketone.
  • the amide is selected from ⁇ , ⁇ -dimethylformamide (DMF) and formamide.
  • the amine is oleylamine.
  • the ester is (-)- ethyl-L-lactate.
  • the ionic liquid is [BMIm][MeS04].
  • a reducing agent In a reducing step it is essential the presence of a reducing agent.
  • said reducing agent is the polyalkyleneimine and/or a copolymer where one of the copolymer units is selected from a polyalkyleneimine.
  • the further reducing agent is selected from the group consisting of polyalkyleneimine, a copolymer where one of the copolymer units is selected from a polyalkylenimine; an organic reducing agent, in particular an organic reducing agent selected from the group consisting of ascorbic acid, oxalic acid, formic acid, diethyl 1 ,4-dihydro-2,6-dimethyl-3,5-pyridinedicarboxylate, tributylstannane, tributyltin hydride, trichlorosilane, triethylphosphine, trimethylphoshpine, triphenylphosphine, triphenylphosphite, triethylsilane, tris(trimethylsilyl)silane; an inorganic reducing agent; in particular an inorganic reducing agent selected from the group consisting of: sodium borohydride, hydrazine, lithium and aluminium hydride, hydroxy
  • the reducing agent is a polyalkyeneimine and/or a copolymer where one of the copolymer units is selected from a polyalkyleneimine which, as commented, is present in the reaction media of the present invention.
  • further reducing agents may be present as listed above.
  • Polyalkyleneimine refers to a polymer having a repeating unit composed of an amine group and an alkyl spacer.
  • the polyalkyleneimine is a substituted or unsubstituted, linear, branched or dendrimeric polyalkyleneimine selected from the group consisting of: polyethyleneimine, polypropyleneimine, polybutyleneimine polypentyleneimine, polyhexyleneimine, polyheptyleneimine and polyoctyleneimine.
  • the polyalkyleneimine is a substituted or unsubstituted, linear, branched or dendrimeric polyethyleneimine (PEI) or polypropyleneimine.
  • polyalkyleneimine is a substituted or unsubstituted, linear, branched or dendrimeric polyethyleneimine (PEI). In a more preferred embodiment is unsubstituted branched polyethyleneimine. Unsubstituted polyalkyleneimines do not present substituents nor in the alkyl neither in the amino group.
  • Substituted polyalkyleneimines present at least one substituent in the alkyl and/or in the amino group.
  • the substituents are selected from: alkyl selected from methyl, ethyl, propyl and butyl;-OH; and hydroxyalkyl selected from hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl.
  • Linear polyalkyleneimines contain all secondary amines, in contrast to branched polyalkyleneimines which contain primary, secondary and tertiary amino groups. Totally branched polyalkyleneimines are named dendrimeric polyalkyleneimines.
  • the polyalkyleneimine has an average molecular weight in a range of 800 to 1000000, of 1200 to 800000, of 1800 to 500000, of 2000 to 250000, of 3000 to 100000, of 4000 to 75000, of 5000 to 50000, of 6000 to 30000, preferably of 8000 to 28000.
  • a "copolymer where one of the copolymer units is selected from a polyalkyleneimine” is selected from random copolymers, block copolymers and graft copolymers wherein one unit the polyalkyleneimine is as defined above, preferably polyethyleneimine, and the other unit may be selected from alkides, polyesters, polyvinyl alcohol, polyvinyl acetate, polyacrylamides, polyacrylic acid and polyisocyanates.
  • alkyleneimine to metal cation molar ratio refers to the molar ratio between alkyleneimine monomers of the polyalkyleneimine or copolymer of polyalkyleneimine and the metal cation.
  • the molar amount of the alkyleneimine is calculated by dividing the mass (in grams) of the polyalkyleneimine used by the molecular weight of the alkyleneimine monomer unit.
  • the molar amount of the alkyleneimine is calculated by dividing the mass (in grams) relative to the polyalkyleneimine portion of the copolymer by the molecular weight of the alkyleneimine monomer unit.
  • the "ethyleneimine to metal cation molar ratio" is calculated dividing the mass (in grams) of PEI used by the molecular weight of the monomer unit, in this case -(CH2-CH2-NH)-, i.e. 43.04 Da.
  • silver is the metal cation (Ag + ) and the moles of the silver cation are equivalent to the moles of silver in the salt.
  • the alkyleneimine to metal cation molar ratio is in the range between above 10 and 1000, preferably between 12 and 500, preferably between 15 and 100, preferably between 20 and 50, and more preferably around 25.
  • the ethyleneimine to Ag + molar ratio is in the range between above 10 and 1000, preferably between 12 and 500, preferably between 15 and 100, preferably between 20 and 50, and more preferably around 25.
  • the reduction step reaction temperature should preferably be below 140 °C, preferably below 130 °C, preferably below 120 °C, and more preferably below 1 10 °C. In a particular embodiment, the reaction temperature should preferably range from room temperature, or 25 °C, to 140 °C, from 50-1 10 °C, from 60 °C-105 °C.
  • a reducing catalyst is present in the reaction media of the reduction step.
  • said catalyst is a halide ion selected from fluoride, chloride and bromide, more preferably chloride.
  • the chloride ions employed by the present invention may be formed by dissolving inorganic salts or organic salts in the polar solvent of the reaction media.
  • salts from which chloride ions are formed may include: alkaline metal chlorides such as lithium chloride, sodium chloride, and potassium chloride; alkaline earth metal chlorides such as magnesium chloride and calcium chloride; earth metal chlorides such as aluminum chloride; chlorides of zinc group metals such as zinc chloride; chlorides of carbon group metals such as tin chloride; chlorides of transition metals such as manganese chloride, iron chloride, cobalt chloride, and zirconium oxychloride; amine hydrochlorides such as ammonia hydrochloride, which may also be called ammonium chloride, hydrazine hydrochloride, methylamine hydrochloride, dimethylamine hydrochloride, triethylamine hydrochloride, ethylamine hydrochloride, diethylamine hydrochloride, triethylamine hydrochloride, propylamine hydrochloride, dipropylamine hydrochloride, tripropylamine hydrochloride, buty
  • the inorganic salt containing the reducing catalyst in the reaction media of the reduction step is sodium chloride.
  • reaction media refers to the physical environment that encompasses all the appropriate conditions for starting the reduction step.
  • Viscosity enhancers useful for the present invention are selected from the group consisting of natural gums such as AGAR, acacia, tragacanth, sodium alginate, alkali-soluble latex, karaya, guar gum, etc; cellulose derivatives such as carboxymethyl cellulose, sodium carboxymethylcellulose, carboxymethyl guar, carboxymethyl hydroxypropyl guar, carboxymethylhydroxyethyl cellulose, sodium carboxymethyl hydroxyethylcellulose, methylcarboxymethyl cellulose, carboxymethyl starch, sodium alginate, alkali-soluble latex, and combinations thereof; microcrystalline cellulose; chitosan; synthetic polymers such as anionic acrylamide copolymer, amphoteric acrylamide copolymer, polyacrylic acid, acrylic acid copolymer, polyvynil pyrrolideone, polyvinyl alcohol and combinations thereof; clays such as
  • an atomic quantum cluster is also present in the reaction media of the reduction step, the AQC are known in the art as particles consisting in a material formed exclusively by zero-oxidation-state transition metal atoms with less than 200 metal atoms and with a size of less than 2 nm.
  • the zero-oxidation-state transition metal atoms of the AQCs present in the invention are selected from Au, Ag, Co, Cu, Pt, Fe, Cr, Pd, Ni, Rh, Pb and combinations thereof.
  • the transition metal atoms are selected from Cu, Ag, Au, Pt, Pd, Ni and combinations thereof and more preferably are selected from Cu, Au and Ag zero- oxidation-state atoms.
  • the AQCs are formed by between 2 and 55 zero-oxidation-state transition metal atoms. In another embodiment, the AQCs consist of between 2 to 27 zero-valent transition metal atoms. In a further embodiment the AQCs consist of between 2 to 15 zero-valent transition metal atoms. In another further embodiment the AQCs consist of between 2 to 5 zero-valent transition metal atoms.
  • the mean size of the AQCs is between 0.3 nm and 1 .2 nm, in a particular embodiment the size is less than 1 nm. In a preferable embodiment they have an approximate size between 0.3 nm and 0.9 nm, and in another embodiment between 0.3 nm and 0.5 nm.
  • tetrabutylammonium bromide is also present in the reaction media.
  • Tetrabutylammonium bromide improves the process for preparing anisotropic metal nanoparticles. Without being bound to any particular theory, tetrabutylammonium bromide improves the process of the present invention by helping to stabilize the initial seeds that are formed in the reaction media, resulting in a more homogeneus size distribution.
  • Anisotropic metal nanoparticles are also formed when tetrabutylammonium bromide is not present in the reaction media, however said nanoparticles show a higher heterogeneity on their diameter and length.
  • the invention relates to a process for producing anisotropic metal nanoparticles comprising allowing a polyalkyleneimine and/or a copolymer where one of the copolymer units is selected from a polyalkyleneimine to react with a transition metal cation of a salt in the presence of a polar solvent, a reducing catalyst, and a reducing agent.
  • another capping agent may be present in the reaction media.
  • the further capping agent is select from the group consisting of:
  • N-vinyllactams such as, e.g., N-vinylpyrrolidone, N-vinyl-2-piperidone and N- vinylcaprolactam;
  • vinyl acetal, vinyl butyral, vinyl alcohol and ethers and esters thereof such as, e.g., vinyl acetate, vinyl propionate and methylvinylether), allyl alcohol and ethers and esters thereof, N-vinylimidazole, N-vinyl-2-methylimidazoline, and the hydroxystyrenes; and
  • the nanoparticles obtained by the process of the invention are attached to at least one polyalkyleneimine molecule or to a copolymer where one of the copolymer units is selected from a polyalkyleneimine.
  • the polyalkyleneimine is polyethyleneimine (PEI).
  • Example 1 Synthesis of Ag nanofibers with an aspect ratio (r) equal to approximately 350 (T129) To a 0.5L round bottom flask with mechanical stirring was added ethylene glycol (221 g) at 90 °C, branched PEI (MW:25000) (2.4 g), Cu AQCs (1 x10 "3 mg), 12mM NaCI solution (2.8ml_), tetrabutylammonium bromide (50 ⁇ _) (concentration ⁇ 97, 5g/L) and AgN0 3 (0.75g) dissolved in ethylene glycol (27.6 g). The reaction is constantly stirred for 67 hours. Ag nanofibers with average diameter of 43 ⁇ 14 nm and average length of 16 ⁇ 6 ⁇ are obtained as shown in Figure 1. The ethyleneimine (55.76 mmol of monomeric unit) to silver cation (4.41 mmol) molar ratio ([PEI]/[Ag + ]) is equal to 12.63.

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  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

L'invention concerne un procédé de préparation de nanoparticules métalliques anisotropes, comprenant une étape de réduction de cation de métal de transition d'un sel à un état d'oxydation nul en présence d'un solvant et d'un polyalkylèneimine ou d'un copolymère dans lequel l'une des unités copolymères est sélectionnée à partir du polyalkylèneimine, le rapport molaire alkylèneimine-cation métallique étant supérieur à 10. L'invention concerne également les nanoparticules métalliques anisotropes obtenues au moyen du procédé et l'utilisation du polyalkylèneimine ou de son copolymère pour les préparer.
EP14806275.5A 2013-12-03 2014-12-03 Procédé de préparation de nanoparticules métalliques anisotropes et utilisation d'un agent destiné à réguler la croissance de celles-ci Active EP3077140B1 (fr)

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EP14806275.5A EP3077140B1 (fr) 2013-12-03 2014-12-03 Procédé de préparation de nanoparticules métalliques anisotropes et utilisation d'un agent destiné à réguler la croissance de celles-ci

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EP13382492.0A EP2881197A1 (fr) 2013-12-03 2013-12-03 Procédé de préparation de nanoparticules métalliques anisotropes et agent destiné à réguler la croissance de celles-ci
PCT/EP2014/076382 WO2015082530A1 (fr) 2013-12-03 2014-12-03 Procédé de préparation de nanoparticules métalliques anisotropes et agent pour commander leur croissance
EP14806275.5A EP3077140B1 (fr) 2013-12-03 2014-12-03 Procédé de préparation de nanoparticules métalliques anisotropes et utilisation d'un agent destiné à réguler la croissance de celles-ci

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EP3077140A1 true EP3077140A1 (fr) 2016-10-12
EP3077140B1 EP3077140B1 (fr) 2021-09-01

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UA111105C2 (uk) * 2014-07-08 2016-03-25 ТОВАРИСТВО З ОБМЕЖЕНОЮ ВІДПОВІДАЛЬНІСТЮ "НаноМедТраст" Біосумісний колоїдний розчин наночасток срібла в неводному полярному розчиннику та спосіб його одержання
KR20160053352A (ko) * 2014-11-03 2016-05-13 경희대학교 산학협력단 다기능성 고분자와 환원제를 이용한 금속나노입자의 제조방법
US10076785B2 (en) * 2016-07-18 2018-09-18 Zerovalent Nanometals, Inc. Method of producing metallic nano particle colloidal dispersions

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JP2009024124A (ja) * 2007-07-23 2009-02-05 Kawamura Inst Of Chem Res ポリマー／シリカ複合ナノ構造体、ポリマー／金属類／シリカ複合ナノ構造体及びシリカ系無機構造体の製造方法
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EP2881197A1 (fr) 2015-06-10
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