WO2016198421A1 - Production de particules composites - Google Patents

Production de particules composites Download PDF

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Publication number
WO2016198421A1
WO2016198421A1 PCT/EP2016/062961 EP2016062961W WO2016198421A1 WO 2016198421 A1 WO2016198421 A1 WO 2016198421A1 EP 2016062961 W EP2016062961 W EP 2016062961W WO 2016198421 A1 WO2016198421 A1 WO 2016198421A1
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WO
WIPO (PCT)
Prior art keywords
nanoparticles
particles
composite particles
types
disperse phase
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PCT/EP2016/062961
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German (de)
English (en)
Inventor
Thomas Kister
Tobias Kraus
Original Assignee
Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh
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Priority to EP16728294.6A priority Critical patent/EP3302854A1/fr
Publication of WO2016198421A1 publication Critical patent/WO2016198421A1/fr

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    • 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
    • B22F1/056—Submicron particles having a size above 100 nm up to 300 nm
    • 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
    • B22F1/14—Treatment of metallic powder
    • B22F1/145—Chemical treatment, e.g. passivation or decarburisation
    • 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
    • B22F1/14—Treatment of metallic powder
    • B22F1/148—Agglomerating
    • 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
    • B22F1/0545—Dispersions or suspensions of nanosized particles

Definitions

  • the invention relates to the production of composite particles.
  • nanoparticles with low dispersity are arranged at interfaces to regular structures. This has been found, for example, by the evaporation of films. In the case of spherical particles, very regular structures can form, as they are also known from atomic structures.
  • Lacava et al. (Lacava et al. Nano Lett. 2012, 12, 3279- 3282) are known to be able to re-assemble ⁇ lar structures in emulsions nanoparticles. Their structure can be described by Lennard Jones potentials.
  • the object of the invention is to provide a method for producing composite particles.
  • the object is achieved by a method comprising the steps of: a) providing an emulsion comprising at least two liquid phases, and at least two types of nanoparticle angles, wherein the nanoparticles in the dispersed phase ver ⁇ are divided;
  • Emulsions are generally understood to mean heterogeneous systems which consist of two liquids which are immiscible or only slightly miscible with one another, which are usually referred to as phases.
  • phases In an emulsion, one of the two liquids is dispersed in the form of very fine droplets in the other liquid (disperse phase). The other phase is called a continuous phase.
  • Oil-in-water emulsion (O / W emulsion).
  • the basic character of an O / W emulsion is characterized by the water.
  • a water-in-oil emulsion (W / O emulsion) is the reverse principle, with the basic character being determined by the oil.
  • it is an oil-in-water emulsion. If the two liquids are water and oil and oil droplets are finely dispersed in water, this is an oil-in-water emulsion (O / W emulsion, eg milk).
  • O / W emulsion oil-in-water emulsion
  • the basic character of an O / W emulsion is characterized by the water.
  • a water-in-oil emulsion (W / O emulsion, eg butter) is the reverse principle, with the basic character being determined by the oil.
  • the oil phase may comprise different water immiscible liquids. Preference is given to organic solvents having a boiling point of below 100 ° C., preferably below 80 ° C.
  • the oil phase can therefore be liquid under the process conditions
  • Alkanes include, preferred are linear, branched or cynch ⁇ specific C5-Ci4-alkanes, linear, branched or cyclic C5-C14-alkenes, aromatics, heteroaromatics, Carbonklareester, ethers sawn preferably linear, branched or cyclic Cs-Ci2 alkanes.
  • n-pentane, n-hexane, n-heptane, n-octane preferably branched alkanes are isopentane, 2-methylpentane, 3- methylpentane
  • examples of cyclic alkanes are cyclopentane or cyclohexane.
  • aromatics are benzene or toluene.
  • the alkanes can also non-polar substituents such as halogens tra ⁇ gen.
  • the composition comprises at least one emulsifier (surfactant).
  • emulsifier surfactant
  • These can be ionic, z.
  • the one or more anionic or nonionic emulsifiers can advantageously be selected from the group consisting of a) partial fatty acid esters and fatty acid esters of polyhydric alcohols and their ethoxylated derivatives (eg glyceryl monostearate, sorbitan stearate, glyceryl stearyl citrate, sucrose stearate).
  • alkylaryl polyglycol ethers e.g. B. Alkylphenol polyglycol ethers (e.g., Triton X)
  • Emulsifiers can be characterized by the interfacial tension at the phase boundary of an emulsion. This is also true ⁇ be the pressure acting within the dispersed phase.
  • the interfacial tension can be determined with a tensiometer using the pendant-drop method and the Young-Laplace equation, and the internal pressure can then be calculated using the Laplace equation.
  • the emulsifiers present in the emulsion are preferably present in a concentration above the critical micelle concentration concentration (CMC, cricital micelle concentration).
  • CMC critical micelle concentration concentration
  • the emulsifiers are present in a range up to 100 times this critical micelle concentration (CMC).
  • the emulsion provided is an emulsion having an average dispersed phase size of less than 10 ⁇ m, in particular less than 5 ⁇ m.
  • the size of the disperse phase was determined by optical microscopy and dynamic light scattering.
  • the disperse phase preferably comprises free-floating droplets. It is especially not arranged ⁇ as a film on a surface.
  • the composition comprises at least two types of nanoparticles.
  • nanoparticles are understood as meaning particles which have a diameter of less than 1 ⁇ m, preferably less than 200 nm (measured with TEM as the average of at least 50 particles).
  • the nanoparticles used have a size of less than 100 nm, preferably less than 50 nm, more preferably less than 20 nm, most preferably less than 15 nm, in particular 4 or 8 nm.
  • the size of the particles is independently thereof preferably at least 0.5 nm, in particular at least 1 nm.
  • It is preferably spherical particles.
  • the composition comprises at least two types of nanoparticles.
  • the term "type of nanoparticles” is understood to mean an amount of nanoparticles which in its characteristic parameters, such as size (average diameter, size distribution), chemical composition, internal structure (porosity, crystallinity), possibly surface modification, match . Usually, such parameters can be uniquely adjusted via the production process of the nanoparticles.
  • At least two types of nanoparticles differ at least in size and / or chemical composition.
  • At least two types of nanoparticles differ in size at least.
  • the size difference is at least 20%, based on the type of nanoparticles with the respective smaller diameter.
  • the at least two types of nanoparticles under the failed ⁇ therefore in terms of their size at least by a factor of 1.2, more preferably at least a factor of 1.5.
  • the Size difference should not be a factor of 100, preferably Fak ⁇ tor 50, are.
  • the quantitative ratio of the different types of particles can be varied within wide ranges. In addition to the external conditions, it can influence the formed composite structure. Preferred is a ratio of two species according to their size of 1: 2 to 50: 1 as the ratio of the smaller particles to the larger particles.
  • the smaller particles are preferably present in the same amount or in excess, in particular in a ratio of 1: 1 to 30: 1, very particularly 1: 1 to 20: 1.
  • Nanoparticles are used in each case preferred, which addresses per ⁇ wells a low dispersity with respect aufwei- on their size.
  • a maximum standard deviation is preferably ⁇ 10% and in particular ⁇ 5%. This can be calculated by statistical analysis of TEM images of at least 50 particles. The particles are selected randomly.
  • No more than four types of nanoparticles are preferably used with different size, especially not more than three, most preferably two types of nano Parti ⁇ angles. It can be used the same size also nanoparticles with different Supremeset ⁇ wetting but, preferably using two types of different size are available min ⁇ least.
  • the nanoparticles are arranged within the disperse phase.
  • the particles are preferably present in a concentration of more than 0.5 mg / mL, in particular above 1 mg / mL, especially over 2 mg / mL.
  • the nanoparticles used are solid particles or solid particles of any suitable material. It can be organic, inorganic or compo ⁇ sitpgreging organic and inorganic materials. Can preferably han spindles ⁇ inorganic particles. Preference is given to nanoparticles of metal, including metal alloys, metal or Halbmetallverburchgengen, in particular metal chalcogenides. For this purpose, all metals or semimetals (hereinafter abbreviated as M) can be used.
  • Preferred metals or semimetals M for the metal or semimetal compounds are, for example, Mg, B, Al, Ga, In, Si, Ge, Sn, Pb, Y, Ti, Zr, V, Nb, Ta, Mo, W, Fe, Cu , Ag, Zn, Cd, Ce and La or mixtures thereof.
  • particles of one element are particles of carbon, such as carbon black or activated carbon, of a semiconductor, such as silicon (including technical Si, ferrosilicon and pure silicon) or of germanium, or of a metal, such as, for example, Mg, B, Al, Ga, In, iron (including steel), chrome, tin, copper, aluminum, titanium, silver, gold and zinc.
  • particles of an alloy may be particles of bronze or brass.
  • Examples of the preferred metal compounds and compounds of semiconductor elements or boron are oxides which are optionally hydrated, such as ZnO, CdO, SiO 2 , GeO 2 , TiO 2 , Al coated rutile, ZrO 2 , CeO 2 , SnO 2 , Al 2 O 3 (in all Modifi ⁇ cations, in particular as corundum, boehmite, AIO (OH), also as aluminum hydroxide), manganese oxides, in 2 03, Y 2 Ü3, La 2 Ü3, iron oxides such as Fe 2 0 3 , Cu 2 0, Ta 2 0 5 , Nb 2 0 5 , V 2 0 5 , Mo0 3 or W0 3 , BaO and CaO, corresponding mixed oxides, eg indium tin oxide (ITO), antimony tin oxide (ATO), fluorine-doped tin oxide ( FTO), Calciumwolfra- mat, and those having a perovskite structure, such as BaT
  • suitable particles are magnetite, maghemite, spinels (eg MgO.Al 2 O 3 ), mullite, eskolait, tialite, SiO 2 -TiO 2 , or bioceramics, for example calcium phosphate and hydroxyapatite.
  • particles of glass or ceramic examples of play to particles, usually for the production of glass (eg. As borosilicate glass, soda lime glass or silica glass), glass ceramic or ceramic (for example, based on the oxides S1O 2, BeO, Al 2 0 3 , ZrÜ 2 or MgO or the corresponding mixed oxides, Ele ⁇ ro and magnetoceramics, such as titanates and ferrites, or non-oxide ceramics, such as silicon nitride, silicon carbide, boron nitride or boron carbide) are used. It can also be particles that serve as fillers or pigments.
  • glass eg. As borosilicate glass, soda lime glass or silica glass
  • glass ceramic or ceramic for example, based on the oxides S1O 2, BeO, Al 2 0 3 , ZrÜ 2 or MgO or the corresponding mixed oxides, Ele ⁇ ro and magnetoceramics, such as titanates and ferrites, or non-oxide ceramics
  • fillers based on SiO 2 such as quartz, cristobalite, tripolite, novaculite, kieselguhr, silica, fumed silicas, precipitated silicas and silica gels, silicates, such as talc, pyrophyllite, kaolin, mica, muscovite, phlogopite, vermiculite, wollastonite and perlites, carbonates, such as calcites, dolomites, chalks and synthetic calcium carbonates, carbon black, sulfates, such as barite and light latex, iron mica, glasses, aluminum hydroxides, aluminum oxides and titanium dioxide.
  • SiO 2 such as quartz, cristobalite, tripolite, novaculite, kieselguhr, silica, fumed silicas, precipitated silicas and silica gels
  • silicates such as talc, pyrophyllite, kaolin, mica, muscovite, phlogopite
  • oxide particles - lo ⁇ chen or hydrated oxide particles in particular metal or semi-metal oxides, hydrated metal or semi-metal oxides, metals, alloys or mixtures thereof.
  • oxides or hydrated oxides at least one element selected from Mg, Ca, Sr, Ba, Al, Si, Sn, Pb, Bi, Ti, Zr, V, Mn, Nb, Ta, Cr, Mo, W, Fe, Co, Ru, Zn, Ce, Y, Sc, Eu, In and La or mixtures thereof.
  • Particularly preferred examples are Zr0 2, Ti0 2, Sn0 2, ITO (indium tin oxide), ATO (antimony ⁇ doped tin oxide), In 2 0 3, Y 2 0 3, Ce0 2, BaTi0 3, SnTi0 3, ZnO , BaO and CaO, which are optionally hydrated.
  • the preparation of the starting particles may be carried out in conventional manner, condensation methods, for example, by flame pyrolysis, plasma processes, gas phase, colloid techniques, Rezipitationsverfah- reindeer, emulsion processes Sol-gel processes, controlled nucleation and wax ⁇ tumsreae, MOCVD processes and (micro). These methods are described in detail in the literature. Suitable particles may also be commercially available. For example, commercially available brine can be used.
  • the nanoparticles can also be doped, preferably with at least ⁇ least another metal.
  • any suitable metal compound can be added during the preparation of the particles, eg an oxide, a salt or a complex compound, for example, halides, nitrates, sulfates, carboxylates (eg acetates) or acetylacetonates, the as molecular precursors in the Her ⁇ position of the particles be used.
  • the other metal may be present in the compound in any suitable oxidation precursor.
  • suitable metals for the metal compound are W, Mo, Zn, Cu, Ag, Au, Sn, In, Fe, Co, Ni, Mn, Ru, V, Nb, Ir, Rh, Os, Pd and Pt.
  • Particularly preferred metals for Do ⁇ orientation are Mg, Ca, Y, Sc, and Ce, in particular for Zr0 second are con ⁇ concrete examples of metal compounds for doping Y (NO 3 ) 3 ' 4 H 2 O, Sc (NO 3 ) 3 ' 6 H 2 O, W0 3 , Mo0 3 , FeCl 3 , silver acetate, zinc chloride, cupric chloride, indium (III) oxide and stannous acetate.
  • the atomic ratio of dopant metal / element of the basic ⁇ compound can be selected as desired and is, for example of 0, 0005: 1 to 0.2: 1st
  • the nanoparticles can be used in the form of a powder or a suspension in a dispersant.
  • the powder is suspended in a dispersant.
  • the suspension can be used as it is or Dis ⁇ pergierstoff can be ⁇ exchanged by known methods with another, more suitable for the particular purpose dispersant.
  • the nanoparticles can also be obtained in the dispersant by precipitation or reduction of a dissolved precursor in situ.
  • the nanoparticles obtained are amorphous or partially crystalline nanoparticles.
  • molecular precursors of the particles which are dissolved in a solvent for example a reduction, condensation and / or precipitation reaction, can be subjected.
  • the molecular precursors may be, for example, hydrolyzable compounds, salts, or soluble Hyd ⁇ roxide.
  • the conversion into solid particles can eg
  • a general method for producing nanoscale particles from hydrolyzable compounds is the sol-gel method.
  • sol-gel process are typically hydrolysable compounds with water, if necessary, is hydrolyzed under acid or base catalysis and optionally at ⁇ least partially condensed.
  • the hydrolysis and / or condensation Onsre lead to the formation of compounds or condensates with hydroxy, oxo groups and / or oxo bridges, which serve as precursors.
  • the sol which forms may by suitable parameters, for example Kondensati ⁇ onsgrad, solvents or pH, to be set for the coating composition of desired viscosity. Further details of the sol-gel process can be found, for example, in CJ Brinker, GW Scherer: "Sol-Gel Science - The Physics and Chemistry of Sol-Gel Processing", Academic Press, Boston, San
  • the modification can be covalent or non-covalent.
  • the particles can also be modified during their synthesis. Surface modification of particles can be accomplished simply by mixing the particles with the surface modifier. The reaction is carried out in a Lö ⁇ solvents and, if necessary, by mechanical or ther ⁇ mix energy supply and / or by addition of catalyst.
  • Suitable surface modifiers are compounds which have on the one hand via one or more groups which can react or present on the surface of the particles reactive groups (such as OH groups) or atoms (such as gold or silver atoms) interactions ⁇ ken suitable can.
  • the surface modifying agent can, for example covalent, coordinative (complex formation) and ionic (Salzar ⁇ term) bonds to the surface of the nanoparticles, currencies Among the pure interactions, dipole-dipole interactions, hydrogen bonds, and van der Waals interactions are examples. Preference is given to the formation of covalent bonds, ionic bonds or complexation.
  • the surface modifiers have a re ⁇ tively low molecular weight normally.
  • the molecular weight may be less than 1,500, more preferably less than 1,000, and preferably less than 700, and most preferably less than 500, but also a higher molecular weight, eg up to 2,000 and more, is possible.
  • African inorganic and organic acids bases, chelating agents, complex formers ⁇ , such as .beta.-diketones, proteins, which may have complex-forming struc ⁇ reindeer, amino acids, thiols or silanes are suitable.
  • the surface modifier may, in a preferred embodiment, be a complexing agent which modifies by complexing on the surface of the particles.
  • Specific examples of surface modifiers are saturated bought or unsaturated mono- and polycarboxylic ent ⁇ speaking anhydrides, acid chlorides, esters and acid amides, amino acids, proteins, imines, nitrites, isonitriles, xyharmen epoxy, mono- and polyamines, .beta.
  • Dicarbonyl compounds such as ⁇ -diketones, oximes, alcohols, alkyl halides, alkylthiols, metal compounds which have a functional group which can react with the surface groups of the particles, for example silanes with hydrolyzable groups having at least one non-hydrolyzable group.
  • Examples of compounds used for surface modification are listed below: Examples of carboxylic acids which atoms preferably 1 to 24 carbon containing saturated monocarboxylic acids (eg formic acid, acetic acid, propionic acid, butyric acid, Pentankla ⁇ acid, hexanoic acid, capric acid, stearic acid, phenylacetic acid, benzoic acid,), saturated polycarboxylic acids having 2 or more carboxyl groups (for example oxalic acid, malonic acid, adipic acid, Bern ⁇ acid, glutaric acid and phthalic acid), unsaturated carboxylic ⁇ acids (eg Acryiklare, methacrylic acid, crotonic acid, maleic ⁇ acid, fumaric acid and Oleic acid) and hydroxycarboxylic acids (eg, glycolic acid, lactic acid, malic acid and citric acid) and derivatives of carboxylic acids, such as anhydrides, esters (preferably C 1 -C 4 -alkyl esters,
  • Examples of ⁇ -dicarbonyl compounds which preferably contain 4 to 12, more preferably 5 to 8, carbon atoms are acetylacetone, 2,4-hexanedione, 3,5-heptanedione, acetoacetic acid and C 1 -C 4 -alkyl acetoacetate; and functionalized dicarbonyl compounds, such as 2-acetoacetoxyethyl methacrylate, hexafluoroacetylacetone and acetoacetamide.
  • silanes are compounds of
  • hydrolytically removable groups X are hydrogen, halogen (F, Cl, Br or I, in particular Cl or Br), alkoxy (eg. Ci-6-alkoxy, such as methoxy, ethoxy, n-propoxy, i-propoxy and n-, i-, sec- or tert-butoxy), aryloxy (preferably ⁇ C6-io ⁇ aryloxy, such as phenoxy), alkaryloxy, for example Benzoy- loxy, acyloxy (eg, Ci-6-acyloxy, preferably Ci 4-acyloxy such as acetoxy or propionyloxy) and alkylcarbonyl (eg C 2 -7-alkylcarbonyl such as acetyl).
  • alkoxy eg. Ci-6-alkoxy, such as methoxy, ethoxy, n-propoxy, i-propoxy and n-, i-, sec- or tert-butoxy
  • aryloxy preferably
  • H 2 with alkyl, aryl and / or aralkyl, mono- or disubstituted amino examples of the alkyl, aryl and / or aralkyl radicals given below for R being amido, such as benzamido or aldoxime or ketoxime groups ,
  • Two or three groups X can also be linked to one another, for example in the case of Si-polyol complexes with glycol, glycerol or pyrocatechol.
  • the groups mentioned may optionally contain substituents such as halogen, hydroxy, alkoxy, amino or epoxy.
  • Preferred hydrolytically removable groups X are halogen, alkoxy groups and acyloxy groups.
  • Particularly preferred hydrolysed ⁇ table removable radicals are Ci-4-alkoxy, especially methoxy or ethoxy.
  • R is the same or different at each occurrence for a non-hydrolytically cleavable radical.
  • the hydrolytically non-cleavable radicals R are, for example, alkyl (eg Ci-2o ⁇ alkyl, especially Ci-4-alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl and tert-butyl), alkenyl (eg C2-2o-alkenyl, especially C2-4-alkenyl, such as vinyl, 1-propenyl, 2-propenyl and butenyl), alkynyl (eg C2-2o-alkynyl, especially C2 -4 ⁇ alkynyl such as ethynyl or product pargyl), aryl (in particular, C6-io ⁇ aryl such as phenyl and naphthyl) and corresponding aralkyl and alkaryl groups such as tolyl and benzyl, and cyclic C3-Ci2 _ alky
  • the radicals R may have customary substituents, which may be functional groups, via which, if required, also a crosslinking, for example with the organic macromolecule, via organic groups is possible.
  • Typical sub ⁇ substituents are, for example, halogen (eg chlorine or fluorine), epoxide (eg glycidyl or glycidyloxy), hydroxy, ethers, esters, amino, monoalkylamino, dialkylamino, optionally substituted anilino, amide, carboxy, alkenyl, alkynyl, acrylic, acryloxy, me- thacryl, methacryloxy, mercapto, cyano, alkoxy, isocyanato, Al ⁇ dehyd, keto, alkylcarbonyl, acid anhydride, and phosphoric acid.
  • halogen eg chlorine or fluorine
  • epoxide eg glycidyl or glycidyloxy
  • hydroxy ether
  • These substituents are bonded to the silicon atom via divalent bridging groups, in particular alkylene, alkenylene or arylene bridging groups, which may be interrupted by oxygen or -NH groups.
  • the bridging groups contain z. B. 1 to 18, preferably 1 to 8 and in particular 1 to 6 carbon atoms.
  • the divalent bridging groups mentioned are derived, for example, from the abovementioned monovalent alkyl, alkenyl or aryl radicals. Of course, the radical R may also have more than one functional group.
  • hydrolytically non-removable groups R having functional groups through which crosslinking is possible are a glycidyl or glycidyloxy- (C 1 - 20) alkylene radical, such as beta-glycidyloxyethyl, ⁇ -glycidyloxypropyl, ⁇ -
  • fluorine-substituted radicals R are 1H, 1H, 2H, 2H-perfluorooctyl or 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl.
  • Particularly preferred radicals are ⁇ -glycidyloxypropyl and (meth) acryloxypropyl. This is
  • Preferred radicals R are alkyl groups having preferably 1 to 4 carbon atoms, in particular methyl and ethyl, and also aryl radicals such as phenyl. a can assume the values 0, 1, 2, 3 or 4, preferably 0, 1, 2 or 3.
  • organosilanes of the general formula (1) with a equal to 1 are compounds of the following formulas:
  • CH 2 CH-CH 2 -Si (OC 2 H 5 ) 3
  • CH 2 CH-CH 2 -Si (OOCCH 3 ) 3
  • CH 2 C (CH 3 ) COO-C 3 H 7 -Si (OC 2 H 5 ) 3
  • hydrolyzable silanes of the general formula (1) with a being 0 are Si (OCH 3 ) 4 , Si (OC 2 H 5 ) 4 , Si (on or iC 3 H 7 ) 4 , Si (OC 4 H 9 ) 4 , SiCl 4 , HSiCl 3 , Si (OOCCH 3 ) 4 .
  • thiols are compounds alkylthiols.
  • the alkyl radicals of the thiols can be substituted by further functional groups.
  • Typical substituents include halogen (for example chlorine or fluorine), epoxy (eg, glycidyl or glycidyloxy), hydroxy, ether, ester, amino, monoalkylamino, dialkylamino, ge ⁇ optionally substituted anilino, amide, carboxy, alkenyl, alkynyl, acrylic, acryloxy, Methacryl, methacryloxy, mercapto, cyano, alkoxy, isocyanato, aldehyde, keto, alkylcarbonyl, acid ⁇ anhydride and phosphoric acid.
  • Preference is given to groups which increase the affinity of the nanoparticles for the disperse phase.
  • thiols are linear and branched thiols, such as ethanethiol, 1-propanethiol, 2-propanethiol, 1-butanethiol, sec. Butylmercaptan, tert. -Butylmercaptan,
  • Ri represent to R4 optionally different aliphatic, aromati ⁇ specific or cycloaliphatic groups preferably having from 1 to 12, especially 1 to 8 carbon atoms, such as Alkyl groups having 1 to 12, in particular 1 to 8 and particularly preferably 1 to 6 carbon atoms (eg, methyl, ethyl, n- and i-propyl, butyl or hexyl), and X is an inorganic or organic anion is, for example, acetate, OH ⁇ , Cl ⁇ , Br or I ⁇ .
  • the carbon chains of these compounds can be replaced by 0-; S, or NH groups are interrupted.
  • Such surface modifiers are, for example, oxaalkanoic acids, it being possible for 1, 2, 3 or more oxa groups to be present. Examples are cencicre Trioxade-, 3-Oxabutan Textre, 2, 6-Dioxahoptanklare and their Homo ⁇ loge.
  • the carbon chains may also carry other functional groups, for example fluoride groups.
  • the type of modification also depends on the type of nanoparticles used. This makes it easy to modify gold particles, especially with thiols.
  • the aim of the surface modification is to promote the interaction of the particles with the disperse phase and thus to achieve a better accumulation of the particles in the disperse phase.
  • the interaction of the particles with each other can be influenced.
  • the particles used can also be coated with another material.
  • the pressure on the disperse phase is exerted by different emulsifiers. From ⁇ dependent on the size of the disperse phase, the pressure exerted by the choice of the emulsifier can be adjusted.
  • the size of the disperse phase can be influenced, for example, by evaporation, in particular selective evaporation and / or external pressure.
  • the pressure on the disperse phase is exerted by selective evaporation of the disperse phase.
  • This can be achieved by selecting the boiling points of the phases forming the emulsion such that, under the conditions of the emulsion, the disperse phase vaporizes faster than the surrounding phase. This makes it possible, by increasing the temperature and / or reducing the pressure, to achieve a selective vaporization of the disperse phase. If emulsifiers are used, they should also not evaporate under these conditions. Since the disperse phase is finely divided, its boiling point need not be lower than the boiling point of the surrounding phase. Due to the large surface, the disperse phase evaporates faster than the continuous phase.
  • the boiling point of the disperse phase ⁇ only up to 30 ° C, preferably up to 20 ° C higher than the boiling point of the continuous phase. This makes it sufficient to bring the emulsion to a temperature below the boiling point of the disperse phase, so that even by the increased vapor pressure, an evaporation of the disperse phase is achieved. As a result, the droplets of the disperse phase shrink and it is applied according to pressure on the disperse phase.
  • This pressure can be influenced. A certain emulsifier leads under the same conditions to the same pressure and thus to the same structure. Another emulsifier applies correspondingly higher or lower pressure.
  • the pressure on the disperse phase is exerted by external pressure on the emulsion. This can be done by pressurizing the emulsion in a closed container. Preference is given to a pressure of at least 1.5 bar. Preferably, a pressure is not higher than 50 bar.
  • both methods can also be combined.
  • the pressure exerted by the evaporation can be intensified by external pressure. This can also be done sequentially. As a result, different structures can be obtained when using the same emulsifier.
  • the composite particles according to the invention form.
  • the structure in the nanometer range could also be influenced by external pressure.
  • the composite particles obtained under external pressure are stable even under atmospheric conditions.
  • the resulting composite particles can be isolated, for example by centrifugation or sedimentation.
  • the nanoparticles may also have reactive groups which, for example, allow crosslinking of the particles with one another or with a matrix.
  • the invention also relates to composite particles obtainable by the process according to the invention.
  • the invention also relates to composite particles, comprising at least two types of nanoparticles, wherein at least one type of nanoparticles is periodically regularly arranged and thereby forms at least one ordered structure.
  • ⁇ preferably three dimensional periodic structures. Periodically arranged periodically means that the relative arrangement of the particles is repeated at regular intervals.
  • At least two types of nanoparticles differ at least in size and / or chemical composition, more preferably at least in size.
  • Parts of the nanoparticles can also be arranged in irregular shapes ⁇ SSIG.
  • Such periodic structures can be detected by small angle scattering or by TEM.
  • the ordered structure, or make the geord ⁇ Neten structures at least 50 vol .-% of a composite particle.
  • the composite particles comprise at least 20, in particular at least 30, nanoparticles.
  • the composite particles obtained preferably have a mittle ⁇ ren diameter of less than 2 .mu.m, especially less than 1 ym on.
  • Examples of ordered structures of the composite particles are AB13 structures, Janus structures, in which two different periodic structures are formed, and core-shell structures, in which an ordered inner core is surrounded by a shell.
  • core-shell structures in which an ordered inner core is surrounded by a shell.
  • different types of nanoparticles form certain parts of the structure.
  • the composite particles according to the invention allow the simple production of structurally defined arrangements of different nanoparticles.
  • catalytically active nanoparticles can be arranged in defined structures.
  • nanoparticles By selecting the nanoparticles, composite structures with specific properties can be generated in a simple manner, in particular if each type of nanoparticles brings in their specific properties. As a result, multifunctional composite particles can be obtained.
  • nanoparticles For example, different absorption and / or emission properties of the nanoparticles can be used. Examples are the plasmonic absorption of metallic nanoparticles with the fluorescence emission of semiconductor quantum dots. Also, photocatalytically active nanoparticles such as T1O 2 can be excited accordingly. Also the combination of different conductive nanoparticles (ITO, ATO) is possible. Also, magnetic nanoparticles can be used.
  • the resulting composite particles are isolable, they can be incorporated into other matrices.
  • the composite particles may also contain polymers which are added in dissolved form to the disperse phase of the emulsion. This can be useful, for example, to keep particles in the composite particle at a distance or to produce temperature-switchable composite particles.
  • suitable surface modifiers make it possible to produce composite particles that later change their structure when heated.
  • the particles can be produced under pressure at elevated temperature and have a specific structure and property. Later (for example, if they are installed in a composite), they are heated and the composite particles change structure and property. This is facilitated by the fact that different structures were obtained by the pressure.
  • composite particles of magnetic and optical ⁇ rule or catalytic particles are also possible.
  • the composite particles can be manipulated in the magnetic field and could be used in a location-specific manner. This may be important, for example, when the composite particles are used in liquid films or gels.
  • Fig. 2 Interfacial tension between n-hexane and water with various emulsifiers at 25 ° C and 50 ° C;
  • Fig. 3 TEM images of composite particles prepared at different pressures and un ⁇ the same emulsifier.
  • FIG. 1 shows composite particles of 1-hexadecanethiol-coated gold nanoparticles with diameters of 4 nm and 8 nm in a ratio of 13: 1 or with the concentrations of 3.9 ⁇ 10 15 and 3 ⁇ 10 14 particles per milliliter as TEM image (transmission electron microscopy) (TEM) and SAXS. All Comp ⁇ sitp firmware were prepared in hexane-in-water emulsions with different emulsifiers; (a) composite particles made with Triton X-100; SAXS measurement of these Kompositparti ⁇ kel. The peaks correspond to an AB13 structure, (b) Janus composite particles obtained with Triton X-102, X-165 or SDS.
  • TEM image transmission electron microscopy
  • FIG. 3 shows under a) the composite particles obtained with Triton X-100 and 1 bar. There are obtained analogously to ⁇ Fi gur 1 a) composite.
  • FIG. 3 b) it is shown that when the pressure (2 bar) is increased, corresponding Janus particles are prepared analogously to 1 b) and further increase in pressure (4 bar) analogously to 1 c) core-shell particles FIG. 3 c) to be obtained.
  • Gold nanoparticles of various sizes were prepared according to Wu and Zheng (Wu et al., Chin. Chem. Lett., 2013, 24, 457).
  • the size of the nanoparticles was determined from TEM images (JEOL JEM 2010 at 200 kV and ImageJ 1.45s). Gold nanoparticles with a size of 4 nm (dispersity 8%) and 8 nm (dispersity 5%) were obtained.
  • the resulting emulsions were heated to 50 ° C until the disperse phase (hexane) had evaporated (about 4 to 12 hours).
  • the composite particles obtained were mixed with TEM and small-angle X-ray scattering (SAXS, Xeuss 2.0; rich Xenocs SA, Grenoble, Frank ⁇ ; with Cu K-alpha at 0.154 nm; Hybrid Photon photon
  • the interfacial tension was measured using the pendant drop method.
  • the outline of a drop was taken with a digital camera and the Young's Laplace equation calculated the interfacial tension. All measurements were carried out on a contact angle measuring device (OCA 35, Dataphysics, Neuhausen, Germany) at 25 ° C and 50 ° C.
  • OCA 35 contact angle measuring device
  • the water emulsifier mixture was filled into a quartz glass cuvette. Pure n-hexane was filled in a glass syringe. The volume of the hexane droplet was sized so that the droplet was about to detach from the cannula. After the drop was stabilized, the drop was taken for one minute at one frame per second and then evaluated using the Young-Laplace equation.

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Abstract

L'invention concerne un procédé de fabrication de particules composites, selon lequel des particules composites présentant un agencement structuré de nanoparticules sont obtenues à partir d'une émulsion comprenant au moins deux types de nanoparticules. Lesdites particules sont obtenues par application d'une pression sur la phase dispersée de l'émulsion.
PCT/EP2016/062961 2015-06-08 2016-06-08 Production de particules composites WO2016198421A1 (fr)

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CN102908961B (zh) * 2012-09-10 2014-08-27 上海交通大学医学院附属新华医院 功能性纳米颗粒复合非交联微球及其制备方法和应用

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CN100348622C (zh) * 2006-01-12 2007-11-14 上海交通大学 制备单分散有机/无机复合纳米微球的聚合方法
DE102008021006A1 (de) * 2008-04-25 2009-11-05 Byk-Chemie Gmbh Partikuläre Wachskomposite und Verfahren zu deren Herstellung sowie deren Verwendung

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CN102908961B (zh) * 2012-09-10 2014-08-27 上海交通大学医学院附属新华医院 功能性纳米颗粒复合非交联微球及其制备方法和应用

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