WO2009138256A1 - Procédé d'incorporation de nanoparticules de céramique dans une masse fondue de polymère - Google Patents

Procédé d'incorporation de nanoparticules de céramique dans une masse fondue de polymère Download PDF

Info

Publication number
WO2009138256A1
WO2009138256A1 PCT/EP2009/051391 EP2009051391W WO2009138256A1 WO 2009138256 A1 WO2009138256 A1 WO 2009138256A1 EP 2009051391 W EP2009051391 W EP 2009051391W WO 2009138256 A1 WO2009138256 A1 WO 2009138256A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
nanoparticles
dispersion
matrix polymer
melt
Prior art date
Application number
PCT/EP2009/051391
Other languages
German (de)
English (en)
Inventor
Dirk Opfermann
Norbert Güntherberg
Helmut Steininger
Original Assignee
Basf Se
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Basf Se filed Critical Basf Se
Publication of WO2009138256A1 publication Critical patent/WO2009138256A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
    • 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

Definitions

  • the invention relates to a method for incorporating ceramic nanoparticles into a polymer melt.
  • submicron additives of TiO 2 , Al 2 O 3 , SiO 2 , Kaolin and talc are suspended in ethylene glycol and the glycolic suspensions incorporated by means of a twin-screw extruder in the polyamide 6 matrix, wherein the glycol excess is removed by means of a degassing immediately.
  • the pulverulent additives are predispersed in ethylene glycol by means of a toothed disc dissolver and ground in a horizontal rubbing ball mill with glass beads, polyethyleneimine being added as dispersing aid.
  • a disadvantage of the process described therein is that a high-boiling solvent is used with ethylene glycol.
  • the high-boiling ethylene glycol is difficult to remove from the melt. Since the degassing of the apparatus is limited, only comparatively small amounts of ethylene glycol can be used.
  • US 2005/0256242 describes the incorporation of a ceramic nano-filler present in a supercritical fluid into a polymer melt by means of an extruder.
  • various clay minerals are mentioned, as supercritical fluids, among others, nitrogen, carbon dioxide, carbon tetrafluoride, trichlorofluoromethane, argon, pentane, cyclohexane, ammonia and water.
  • a disadvantage of this process is the complicated use of supercritical fluids.
  • WO 2006/11 1302 discloses a method for producing a molding compound from thermoplastic material containing nanoscale, inorganic particles, in which the thermoplastic material is mixed in the melt state with the nanoparticles and a solubilizer in an extruder with screw conveying, wherein pressures and temperatures are adjusted, that the solubilizer is in the supercritical state.
  • nanoscale particles particles of indium Tin oxide, silica, aluminum hydroxide, zinc oxide, titanium oxide, barium sulfate and carbon black having an average primary particle size of 4 to 999 nm described.
  • Preferred solubilizers are carbon dioxide, nitrous oxide, xenon, krypton, methanol, ethanol, isopropanol and isobutanol. The volatiles are removed in another extruder or in a vented extruder.
  • the aqueous suspension is conveyed substantially without pressure into the extruder. Thus, there is a sudden evaporation of the solvent upon contact with the polymer melt.
  • EP-A 0 816 421 describes the incorporation of a suspension of inorganic nanoparticles having a particle size between 30 and 1800 nm, optionally a dispersing aid and a polyester (B) in water or an organic solvent having a boiling point of at most 240 ° C. into the melt a polyester (A) by means of a single-screw or twin-screw degassing extruder.
  • the suspension is added to the solid granules.
  • the evaporation of the solvent takes place even before the melting of the granules. This procedure can lead to agglomeration of the nanoparticles.
  • WO 99/03914 describes the preparation of a nanoparticle-containing polyester composite material in which a platelet-shaped clay mineral having a particle diameter of 10 to 1000 nm and a particle thickness of less than 2 nm and a water-soluble polyester dispersed in water and the aqueous dispersion with a Polyester is compounded in an extruder.
  • the object of the invention is to provide a process for the preparation of mixtures (compounds) of polymers and finely divided ceramic nanoparticles by incorporation of dispersions of the nanoparticles into a polymer melt, which does not agglomerate the nanoparticles in the polymer melt.
  • the object is achieved by a method for incorporating nanoparticles of a ceramic material into a polymer melt of a matrix polymer with the steps
  • step (c) dispersing the surface-modified ceramic nanoparticles in the mixture from step (b), whereby a stable dispersion of the nanoparticles is obtained
  • step (D) incorporating the dispersion of step (c) in a melt of further matrix polymer in an extruder having a plurality of pressure zones, wherein the
  • Nanoparticles containing dispersion is brought into contact with the melt in a first pressure zone at a pressure which is above the vapor pressure of the
  • Suitable ceramic materials of which the ceramic nanoparticles consist essentially may be: zinc oxide, silica, alumina, titania, zirconia and ceria.
  • Ceramic nanoparticles which are preferably used in the process according to the invention are nanoparticles of zinc oxide, silicon dioxide and aluminum oxide.
  • a first step surface-modified ceramic nanoparticles are optionally provided in the form of a powder or in the form of a suspension.
  • the ceramic nanoparticles are prepared by precipitation from alcoholic or aqueous-alcoholic solutions of the corresponding salts by addition of alkalis.
  • a surface modification can be achieved by carrying out the precipitation in the presence of a surface modifier or subsequently treating the suspension with a surface modifier. From the suspension, a powder can be obtained by evaporation of the solvent.
  • the nanoparticle-containing suspensions or powders are commercially available.
  • Suitable alcohols are, for example, methanol, ethanol, n-propanol and isopropanol.
  • Suitable alkalis are, for example, LiOH, NaOH, KOH and NH 4 OH.
  • Ceramic nanoparticles can be produced, for example, as described in JP 04-357114.
  • ZnO nanoparticles (0 ⁇ 50 nm) are prepared by hydrolysis of a solution of a Zn salt (eg zinc chloride, zinc nitrate, zinc sulfate or zinc acetate).
  • Suitable solvents are, for example, alcohols such as methanol, ethanol, n-propanol or isopropanol or mixtures of an alcohol and water. It is carried out at a temperature ⁇ 60 0 C and a pH ⁇ 9. The pH is adjusted by adding an alkaline solution, for example an aqueous solution of NaOH or KOH. If the reaction temperature is ⁇ 60 ° C. or the pH is ⁇ 9, the ZnO-hydrosol is formed. A surface modification can then be carried out in organic solvent.
  • a Zn salt eg zinc chloride, zinc nitrate, zinc sulfate or zinc acetate.
  • Suitable solvents are
  • Ceramic nanoparticles can be further prepared as in JP 11-279524. Accordingly, nanoparticulate ZnO particles (1 nm ⁇ 0 ⁇ 20 nm) are obtained by mixing an ethanolic solution of a Zn salt (for example zinc chloride, zinc nitrate, zinc stearate or zinc oleate) with an ethanolic solution of alkali (potassium hydroxide, sodium hydroxide or ammonia) a pH ⁇ 8, more preferably at a pH ⁇ 7.2 prepared. The mixing can be carried out both continuously and batchwise. If desired, then, an ethanol-soluble hydrophobic compound having a polar group (for example, oleic acid, stearic acid) may be incorporated.
  • a Zn salt for example zinc chloride, zinc nitrate, zinc stearate or zinc oleate
  • alkali potassium hydroxide, sodium hydroxide or ammonia
  • ZnO particles are treated with N-lauroyl-L-glutamic acid.
  • a nonionic silicone-based surface-active agent and silicone oil is then removed.
  • Ceramic nanoparticles can also be prepared as described in EP 1 157 064.
  • a zinc oxide gel containing ZnO nanoparticles (0 ⁇ 15 nm) is prepared by basic hydrolysis of a Zn compound in alcohol or an alcohol / water mixture.
  • the hydrolysis can be carried out in the presence of suitable surface modifiers.
  • the process is characterized in that the precipitate precipitated during the hydrolysis is allowed to mature until the ZnO has completely flocculated, then this is compacted into a gel and separated from the supernatant phase (by-products).
  • Preferred zinc salt is zinc acetate
  • preferred base is KOH and more preferred alcohol is methanol.
  • the base is preferably used in a substoichiometric manner.
  • Ceramic nanoparticles can also be prepared as described in DE 103 20 435. There is described 1.) the discontinuous production of ZnO particles, in which a methanolic zinc acetate solution with a methanolic KOH solution in a ratio KOH / Zn of 1, 7 - 1, 8 is added with stirring, at a temperature matured from 40 to 65 ° C. over a period of 5 to 50 minutes and then cooled to a temperature of ⁇ 25 ° C.
  • Suitable alcohols are methanol, ethanol, n-propanol and isopropanol.
  • Suitable alkalis are LiOH, NaOH, KOH, NH 4 OH.
  • the process is characterized in that the metal salt solutions are added to the alkaline solutions and the pH is maintained at> 7 throughout the reaction.
  • Ceramic nanoparticles can also be prepared as described in US 2006/0222586. Described is a process for the preparation of ZnO sols containing crystalline ZnO nanoparticles (0 ⁇ 15 nm) by a) hydrolysis of a Zn salt in an ethylene glycol solution at pH 8 to 11, b) optionally concentration of the precipitate on ZnO Concentrations 0.3 - 3 mol / L by settling and removal of the supernatant solvent and c) Aging of the precipitate at 40 - 100 0 C for 1-6 hours, until a transparent SoI has formed.
  • the resulting ceramic nanoparticles generally have an average particle diameter in the range from 1 to 250 nm, preferably from 1 to 50 nm, particularly preferably from 1 to 20 nm.
  • Suitable surface modifiers generally have an anchor group reactive with the ceramic material and a moiety compatible with the solvent of the dispersion to be prepared and the matrix polymer.
  • the surface modification of the nanoparticles causes the steric and / or electronic stabilization of the particles. This prevents the reaggregation or reagglomeration of the nanoparticles.
  • Preferred anchor groups are carboxyl, sulfonate, phosphonate and siloxane groups.
  • Suitable carboxyl-containing surface modifiers are, for example, dicarboxylic acids, alpha-hydroxycarboxylic acids such as lactic acid or dioxoheptanoic acid and trioxadecanoic acid.
  • Dicarboxylic acids and alpha-hydroxycarboxylic acids have a particularly strong anchoring on the nanoparticles.
  • the polarity of the anchoring group-bound residues of the surface modifier is matched to the polarity of the matrix polymer.
  • Trioxadecanoic acid and dioxaheptanoic acid are particularly suitable as surface modifiers for zinc oxide nanoparticles if the nanoparticles are to be incorporated into SAN as a matrix polymer.
  • the surface modifiers may also be tailored to the reactivity of the matrix polymer.
  • a maleic anhydride group-containing surface modifier can be used when NH 2 group-containing polyamides are used as a matrix polymer. This results in an anchoring of the matrix polymer with the modifier.
  • the surface modifier is generally present in amounts of 0.1 to 40% by weight, preferably 0.1 to 10% by weight, based on the mass of the nanoparticles.
  • the surface of the nanoparticles can additionally be coated.
  • ZnO or TiO 2 particles may be provided with a SiO 2 envelope to counteract the photocatalytic activity of these particles. This coating can be done simultaneously with the surface modification.
  • a solvent exchange step follows, in which the solvent of the nanoparticle suspension is replaced by another solvent.
  • step (b) the surface-modified ceramic nanoparticles are mixed with a carrier polymer dissolved in an organic solvent which is compatible with the matrix polymer and / or with the matrix polymer itself.
  • the surface-modified ceramic nanoparticles are then dispersed in the mixture (step (c)).
  • This step is also referred to as "topcoating", the polymer added is accordingly referred to as a topcoating polymer
  • the topcoating polymer may be the matrix polymer or a carrier polymer other than but compatible with the matrix polymer.
  • the solvent selection is determined by its solution properties for the respective polymer (carrier polymer or matrix polymer) and the position of the boiling point, which may be neither too low nor too high relative to the processing temperature of the polymer. Too low a boiling point when dosing the dispersion in the extruder leads to a too rapid evaporation of the solvent at the injection nozzle and thus to a clogging of the nozzle by the solidifying dispersion therein. Too high a boiling point, especially above the processing temperature of the polymer in the extruder, prevents complete extraction from the melt within the vent zones of the extruder.
  • the boiling point of the solvent is at least 10 ° C., preferably at least 60 ° C., below the processing temperature of the polymer melt in the extruder. In general, the boiling point of the solvent is in the range of 80 to 210 ° C., preferably in the range of 100 to 160 ° C.
  • Preferred solvents are tetrahydrofuran, dimethylformamide, benzyl alcohol, cyclopentanone, cyclohexanone, toluene, xylene, N-methylpyrrolidone and methyl isobutyl ketone, and hexafluoroisopropanol.
  • a soluble carrier polymer may also be chosen for the purpose of varnishing. It is important to ensure that the carrier polymer does not adversely affect the properties of the final product or during the extrusion of the polymer melt from this, z. B. by decomposition into low molecular weight components, is largely expelled.
  • Ultramid 1 C (PA 6 / PA 66 copolymer) is added as a carrier polymer when the ceramic nanoparticles in polyamide 6 (PA 6, poly-epsilon-caprolactam) are to be incorporated as a matrix polymer. This is processing in the encryption in PA 6 largely degraded at temperatures of about 240 0 C.
  • SANMA styrene / acrylonitrile / maleic anhydride copolymer
  • the energy that can be introduced by shear through the screws of the extruder is not sufficient to distribute very small, aggregated nanoparticles with sufficient freedom from disruption. Therefore, a processing step upstream of compounding in the extruder is required in which the aggregates are broken up to primary particle level and stably dispersed in the carrier medium. Possible processes are kneading of the nanoparticles in a "polymer paste" and / or wet grinding in a polymer solution.
  • the kneading process in which high energy inputs are possible by the processing of a highly viscous product, can only be used for the production of a suitable masterbatch (highly concentrated compound) if it is possible by swelling or dissolution of the polymer to reduce the processing temperature to such an extent that it causes damage of the matrix polymer can be kept negligibly small.
  • a suitable masterbatch highly concentrated compound
  • Investigations on the ZnO / SAN system have shown that suitable wet grinding can avoid the formation of large aggregates.
  • the degree of division in the compound was independent of the use of a dispersing aid, but has a markedly positive effect on the sedimentation stability and thus probably also on the stability of the dispersion against reagglomeration.
  • negative influences of the dispersing aid on the mechanical properties of the material must be assumed, so that its concentration should always be kept as small as possible.
  • the dispersion can be stirred, z. B. with a dissolver disk, and optionally carried out in the heat.
  • the temperature is for example 60 0 C to 80 0 C when Ultramid 1 C (PA 6 / PA 66) is added as a carrier polymer and worked with benzyl alcohol as a solvent.
  • the embarklackpoly- mer (carrier polymer or matrix polymer) is preferably added in small portions. Further Auflackpolymer is preferably added only when the previous portion has completely dissolved.
  • the optimum amount of finish polymer added in step (d) can be determined empirically. It is generally in the range of 5 to 30 wt .-%, based on the total mixture. For example, it is about 20% by weight for a nanoparticle dispersion of trioxadecanoic acid-modified ZnO nanoparticles in DMF as a solvent when a SAN having an acrylonitrile content of 23% is added.
  • the polymer limit concentration in the dispersion can be determined by means of UV-Vis spectroscopy. Reaggregation processes, which are a consequence of an excessively high polymer concentration, lead to a significant transmission loss in the wavelength range around 500 nm +/- 50 nm. An upper limit for the polymer concentration is also set by the viscosity of the dispersion. This should still be good pumpable.
  • Auflackpolymer carrier polymer or matrix polymer
  • the dispersion in a mill or kneader is at low concentrations of the surface modifier, e.g. B. in a surface modification of the nanoparticles with a siloxane, preferably, since otherwise a homogeneous, aggregate-free distribution of nanoparticles in the mixture is often no longer possible.
  • the nanoparticle aggregates are broken up by impulse transfer and the components are separated from each other.
  • the addition of a dispersing aid may be expedient.
  • the dispersing unit is a grinding vessel, for example a steel container filled with SAZ balls into which the mixture of nanoparticle dispersion and lacquer polymer is filled. Mixture and SAZ balls are set in motion by rotating perforated discs. The released heat is dissipated by a cooling medium.
  • the grinding conditions time, grinding type, size and filling, speed) are usually chosen so that the primary particles are not destroyed and thus the particle size distribution is not adversely affected.
  • step (d) the dispersion from step (c) is incorporated in an extruder into a melt of the matrix polymer.
  • Preferred matrix polymers are thermoplastics such as polystyrene, SAN, ABS, ASA, PVC, polyamide-6, polyamide-66, polyoxymethylene, PSU (polysulfone), polymethyl methacrylate, polycarbonate, polyethylene terephthalate and polybutylene terephthalate.
  • thermoplastics such as polystyrene, SAN, ABS, ASA, PVC, polyamide-6, polyamide-66, polyoxymethylene, PSU (polysulfone), polymethyl methacrylate, polycarbonate, polyethylene terephthalate and polybutylene terephthalate.
  • a suitable extruder for incorporating the nanoparticle dispersion is constructed as shown in FIG. This is preferably a co-rotating, close-meshing twin-screw extruder.
  • the matrix polymer is metered in at the beginning of the extruder and completely plasticized by a melting zone suitable for the matrix polymer. Thereafter, the melt is thawed by backfeeding screw elements and built up a pressure. The height of this dynamic pressure depends on the solvent used in the nanodispersion.
  • the temperature of the polymer melt is generally from 160 to 340 ° C., preferably from 200 to 300 ° C.
  • the dynamic pressure must be above the vapor pressure of the solvent at the melt temperature of the polymer. In general, the dynamic pressure is 1 to 30 bar, preferably 5 to 15 bar.
  • the nanoparticle dispersion is injected.
  • various pump systems are used for pressure build-up (gear pump, HPLC pump, diaphragm piston pump, eccentric screw pump).
  • the pressure prevailing in the injection zone ensures that the dispersion continues to be present as a liquid. Additional mixing elements in the injection zone mix the nanoparticle dispersion and the melt.
  • the melt flows via the recirculating screw elements into the first vacuum zone (2nd pressure zone).
  • the solvent boils and changes to the vapor phase.
  • the resulting solvent vapor is removed via the vacuum system.
  • several vacuum zones (2nd and more pressure zones) can be arranged one behind the other. These zones are separated by recirculating elements.
  • the applied vacuum should be better in the following vacuum zone than in the previous one.
  • the pressure in the 1st vacuum zone is between 1013 (ambient pressure) and 900 mbar (absolute), preferably 1013 to 950 mbar.
  • the pressure in the second vacuum zone is between 100 and 500 mbar, preferably 100 to 200 mbar.
  • the pressure in the 3rd vacuum zone is between 5 and 50 mbar, preferably 5 to 10 mbar.
  • an entrainer can also be used.
  • the entrainer can be added between the degassing stages.
  • This entraining agent must be such that the solvent used in the nanodispersion in the entraining agent has a high solubility.
  • Suitable entraining agents are generally low-boiling solvents, for example low-boiling alcohols, water, CO 2 and N 2 .
  • the content of the resulting polymer melt of finely divided ceramic nanoparticles is generally 0.05 to 10, preferably 0.1 to 3,% by volume, based on the sum of all components of the melt.
  • the polymer melt containing the finely divided ceramic nanoparticles is preferably processed further by extrusion directly into films or other semifinished products. Another possibility is the production of granules.
  • the granules can be processed in downstream processing processes, such as the injection molding, to form parts.
  • the invention also provides a polymer material comprising a matrix polymer and finely divided nanoparticles of a ceramic material obtainable by the process according to the invention.
  • the content of nanoparticles is 0.05-0.8% by volume, preferably 0.1-0.5% by volume.
  • the matrix polymer is a styrene / acrylonitrile copolymer (SAN).
  • the nanoparticles are zinc oxide nanoparticles. These are surface-modified in a special embodiment with a silane or with trioxadecanoic acid.
  • the inclusion of the finely divided nanoparticles in the matrix polymer results in an improvement in the fracture-mechanical properties of the matrix Polymer material.
  • the fracture toughness of the polymeric material at least 1 of the invention, 2 MPa m 1/2 and the fracture energy may be at least 350 J / m 2, respectively.
  • Z-COTE MAX Surface-modified zinc oxide
  • SAN-VLN SAN-VLN (15% by weight) is now added to this dispersion and the mixture is heated to 60 to 80 ° C. while heating the dispersion.
  • the clear 'solution' are added with stirring, z. B. with a dissolver disc, and optionally in the heat (60 0 C to 80 0 C, Example Ultramid 1 C in benzyl alcohol) added small amounts of polymer. Additional polymer is not added until everything has dissolved.
  • the maximum amount of polymer is to be determined empirically. It is about 20% by weight for SAN with 23% acrylonitrile content in a submitted ZnO-DMF solution.
  • the ZnO is surface-modified with trioxadecanoic acid.
  • a suitable measurement method for determining the limit concentration is UV-Vis spectroscopy, which reacts sensitively in the wavelength range around 500 nm +/- 50 nm with a transmission loss on Reaggregations revitalize in the beginning.
  • An upper limit for the polymer concentration may also be set by the viscosity of the mixture. This must still be pumpable.
  • the Auflackpolymer is usually identical to the matrix polymer in which the nanoparticles are to be dispersed homogeneously in the extruder.
  • the extruder used is a ZSK 30 (co-rotating twin-screw extruder, diameter 30 mm) from Coperion Werner & Pfleiderer.
  • the length / diameter ratio of the screw is 41.
  • the extruder runs at a speed of 250 rpm and a temperature of 240 ° C.
  • SAN-VLN SAN-VLN
  • the abovementioned nanodispersion is metered in via a gear pump at 1.1 kg / h.
  • Ambient pressure is present in the 1st vacuum zone, 200 mbar absolute in the 2nd vacuum zone and 50 mbar absolute in the 3rd vacuum zone.
  • the nanocompound is discharged through a hole nozzle (diameter 4 mm) as a strand and granulated, or extruded as a film.
  • Figures 1 and 2 show the resulting distribution of ZnO nanoparticles in the polymer in TEM images at 2 different magnifications.
  • the distribution in the matrix polymer is very uniform.
  • the method of the carrier polymer can be used.
  • a compatible, soluble polymer is added to the dispersion.
  • An example of this is the use of soluble Ultramid 1 C in insoluble Ultramid B27 (PA6).
  • Zinc oxide modified with trioxadecanoic acid is stirred in cyclohexanone by means of a dissolver. .
  • This dispersion contains 9.3 wt .-% ZnO in cyclohexanone with an average diameter of 19 nm
  • PA will now be given 6 / 6.6 Copo- lymer (15 weight percent) and under heating (60-80 0 C) of the dispersion disbanded
  • the extruder used is a ZSK 30 (co-rotating twin-screw extruder, diameter 30 mm) from Coperion Werner & Pfleiderer.
  • the length / diameter ratio of the screw is 41.
  • the extruder runs at a speed of 250 rpm and a temperature of 240 ° C.
  • the abovementioned nanodispersion is metered in via a gear pump at 1.1 kg / h.
  • Ambient pressure is present in the 1st vacuum zone, 200 mbar absolute in the 2nd vacuum zone and 50 mbar absolute in the 3rd vacuum zone.
  • the nanocompound is discharged via a perforated nozzle (diameter 4 mm) as a strand and granulated or extruded as a film (thickness -6 mm).
  • the matrix material used was SAN.
  • ZnO-A has an average particle diameter of 30 nm with an aspect ratio (length / diameter) of 4.
  • ZnO-B has a mean particle diameter of 10 nm with an aspect ratio of 3. All materials were supplied by BASF SE, Germany.
  • the ZnO particles were surface modified to achieve good dispersion prior to mixing.
  • the ZnO-A particles were modified with dimethoxydiphenylsilane / triethoxycaprylsilane crosspolymer.
  • the ZnO-B particles were modified with trioxadecanoic acid.
  • thermoplastic / ZnO blends were made on a twin screw extruder ZSK-30 from Werner & Pfleiderer at a speed of 300 Rpm exactly as described in Example 2. Before molding, the green sheets were dried under vacuum at 80 ° C. for 36 hours. The resulting sheets were then compression molded at 200 ° C. and 50 bar into 6 mm and 4 mm sheets.
  • SENB single-edge-notch bending
  • C From the applications of the bending load against the expansion, the fracture toughness, Kic, and the fracture energy, G
  • the fracture toughness and fracture energy of ZnO-modified composites with different volume fractions are shown in Tables 1 and 2.
  • Tables 1 and 2 For the unmodified thermoplastic, an average fracture toughness of 1, 10 ⁇ 0.05 MPa m 1/2 and a fracture energy of 310 ⁇ 22 J / m 2 were determined.
  • the fracture toughness and fracture energy increased by 16% and 21%, respectively.
  • the fracture toughness decreased by 5% to 1, 06 ⁇ 0.03 MPa m 1/2 .
  • the fracture toughness and fracture energy further decreased to 0.98 ⁇ 0.02 MPa m 1/2 and 202 ⁇ 19 J / m 2, respectively.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un procédé d'incorporation de nanoparticules d'un matériau céramique dans une masse fondue d'un polymère matriciel, le procédé consistant (a) à préparer des nanoparticules de céramique à surface éventuellement modifiée sous la forme d'une poudre ou d'une suspension, (b) à mélanger les nanoparticules de céramique à surface modifiée à un polymère support dissous dans un solvant organique, lequel polymère support est compatible avec le polymère matriciel, et/ou au polymère matriciel lui-même, (c) à disperser les nanoparticules de céramique à surface modifiée dans le mélange obtenu à l'étape (b), une dispersion stable des nanoparticules étant obtenue, et (d) à incorporer la dispersion obtenue à l'étape (c) dans une masse fondue d'un autre polymère matriciel dans une extrudeuse à plusieurs zones de pression, la dispersion étant mise en contact avec la masse fondue dans une première zone de pression à une pression supérieure à la pression de vapeur du solvant de la dispersion à la température de la masse fondue.
PCT/EP2009/051391 2008-05-14 2009-02-06 Procédé d'incorporation de nanoparticules de céramique dans une masse fondue de polymère WO2009138256A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP08156134.2 2008-05-14
EP08156134 2008-05-14

Publications (1)

Publication Number Publication Date
WO2009138256A1 true WO2009138256A1 (fr) 2009-11-19

Family

ID=40583141

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2009/051391 WO2009138256A1 (fr) 2008-05-14 2009-02-06 Procédé d'incorporation de nanoparticules de céramique dans une masse fondue de polymère

Country Status (1)

Country Link
WO (1) WO2009138256A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103172877A (zh) * 2013-03-06 2013-06-26 珠海市赛纬电子材料有限公司 一种纳米材料填充塑料粒子的生产方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993021127A1 (fr) * 1992-04-15 1993-10-28 Institut für Neue Materialien Gemeinnützige GmbH Procede de fabrication de poudres ceramiques modifiees en surface a granulometrie nanometrique
WO2006111302A1 (fr) * 2005-04-18 2006-10-26 Evonik Röhm Gmbh Matiere de moulage et elements de moulage en thermoplastique contenant des particules inorganiques nanometriques, procede pour realiser cette matiere de moulage et ces elements de moulage, et leurs utilisations

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993021127A1 (fr) * 1992-04-15 1993-10-28 Institut für Neue Materialien Gemeinnützige GmbH Procede de fabrication de poudres ceramiques modifiees en surface a granulometrie nanometrique
WO2006111302A1 (fr) * 2005-04-18 2006-10-26 Evonik Röhm Gmbh Matiere de moulage et elements de moulage en thermoplastique contenant des particules inorganiques nanometriques, procede pour realiser cette matiere de moulage et ces elements de moulage, et leurs utilisations

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
A. KOINE ET AL.: "Beeinflussung der Fliesseigenschaften von Polyamid 6 durch submikrone Additive", DIE ANGEWANDTE MAKROMOLEKULARE CHEMIE, vol. 241, 1996, pages 175 - 190, XP002527593 *
GUO L ET AL: "Synthesis and Characterization of Poly(vinylpyrrolidone)-Modified Zinc oxide nanoparticles", CHEMISTRY OF MATERIALS, AMERICAN CHEMICAL SOCIETY, WASHINGTON, US, vol. 12, 1 January 2000 (2000-01-01), pages 2268 - 2274, XP002346933, ISSN: 0897-4756 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103172877A (zh) * 2013-03-06 2013-06-26 珠海市赛纬电子材料有限公司 一种纳米材料填充塑料粒子的生产方法
CN103172877B (zh) * 2013-03-06 2015-09-09 珠海市赛纬电子材料有限公司 一种纳米材料填充塑料粒子的生产方法

Similar Documents

Publication Publication Date Title
EP1943296B1 (fr) Procede de fabrication de poudres ultrafines a base de polyamides, poudres ultrafines de polyamide et leur utilisation
EP1871825B1 (fr) Matiere de moulage et elements de moulage en thermoplastique contenant des particules inorganiques nanometriques, procede pour realiser cette matiere de moulage et ces elements de moulage, et leurs utilisations
CN108602687B (zh) 被覆碱土金属化合物微粒、有机溶剂分散液、树脂组合物和图像显示装置
EP2141124B1 (fr) Procédé de fabrication de particules d'hydroxyde de magnésium à grosse échelle et/ou, nano-échelle, revêtues, désagglomérées
EP2543457A1 (fr) Poudre contenant des particules centrales revêtues de polymère contenant des métaux, des oxydes de métal, des nitrures métalliques ou des nitrures semi-métalliques
EP1815967A2 (fr) Utilisation de poudre de polymère fabriquée à partir d'une dispersion dans un procédé et un corps de formage façonnant, fabriqués à partir de cette poudre de polymère
DE3855810T2 (de) Dispersion von Kalzium-Karbonat in Glycol
EP1931737A1 (fr) Procede pour produire des nanoparticules a surface modifiee d'oxydes metalliques, hydroxydes metalliques, et/ou hydroxydes d'oxydes metalliques
EP2154177B1 (fr) Procédé de fabrication de polymères thermoplastiques contenant des particules d'hydroxyde de magnésium à grosse échelle et/ou nano-échelle, revêtues, désagglomérées et un dispositif correspondant
JP2008545845A (ja) 改質ナノ粒子
JP2009107857A (ja) 分散性シリカナノ中空粒子及びシリカナノ中空粒子の分散液の製造方法
EP3509994B1 (fr) Poudre composite contenant du carbonate de calcium à particules microstructurées
EP3524279A1 (fr) Particules composites microstructurées
DE102005025719A1 (de) Verfahren zum Erzeugen einer Dispersion von desagglomeriertem Bariumsulfat in Kunststoffen oder Kunststoffvorstufen
EP1818380A1 (fr) Dispersion d'adhésif
EP2543696B1 (fr) Poudre contenant des noyaux de particules revêtus de polymère
CN108276610B (zh) 改性纳米沉淀硫酸钡粉体在制备降解材料中的应用
EP2141189B1 (fr) Procédé de fabrication de masses durcissables contenant des particules d'hydroxyde de magnésium nano-échelle, revêtues, désagglomérées, et de préférence fonctionnalisées, ainsi que particules d'agents de remplissage d'hydroxyde de magnésium réparties de manière homogène et désagglomérées à partir de polymères ou de composites durcis thermoplastiques ou duroplastiques
DE10297612T5 (de) Anorganisches Oxid
WO2009138256A1 (fr) Procédé d'incorporation de nanoparticules de céramique dans une masse fondue de polymère
DE102015011223A1 (de) Compounds aus thermoplastischen Kunststoffen und nanoskaligen anorganischen Feststoffen und Verfahren zu ihrer Herstellung
EP1229075B1 (fr) Composite de polymère thermoplastique à base d'amidon contenant des particules integrées nanoscopiques et leur procédé de préparation
DE10008473A1 (de) Metalloxide enthaltende Kunststoffkomposite
DE60022985T2 (de) Verstärkte polyamide mit hohem modul
EP1163291A1 (fr) Composites plastique contenant des oxydes metalliques

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09745589

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09745589

Country of ref document: EP

Kind code of ref document: A1