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WO2012107377A1 - Particules tensioactives inorganiques et procédé pour la production desdites particules - Google Patents

Particules tensioactives inorganiques et procédé pour la production desdites particules Download PDF

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WO2012107377A1
WO2012107377A1 PCT/EP2012/051917 EP2012051917W WO2012107377A1 WO 2012107377 A1 WO2012107377 A1 WO 2012107377A1 EP 2012051917 W EP2012051917 W EP 2012051917W WO 2012107377 A1 WO2012107377 A1 WO 2012107377A1
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particles
kaolinite
particles according
oil
emulsions
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Thomas BÜSGEN
Arno Nennemann
Julia Hitzbleck
Josef Breu
Dunja Hirsemann
Ramona Deinlein
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Covestro Deutschland AG
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Bayer MaterialScience AG
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/04—Compounds of zinc
    • C09C1/043—Zinc oxide
    • 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
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    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/10—Compounds of cadmium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/402—Satin white, modifications thereof, e.g. carbonated or silicated; Calcium sulfoaluminates; Mixtures thereof, e.g. with calcium carbonate or kaolin
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2002/30—Three-dimensional structures
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/86—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by NMR- or ESR-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/42—Clays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic compounds

Definitions

  • the invention relates to platelet-shaped, anisotropic, polar, inorganic particles whose basal surfaces are selectively functionalized in such a way that they have a surfactant effect.
  • the different in their chemical composition basal surfaces of polar, inorganic particles are hydrophilized or hydrophobic with organic or inorganic molecules.
  • the interaction with polar, aqueous or non-polar, organic substances can be controlled, e.g.
  • No. 7,781,509 (B2) describes the functionalization of sheet silicates with unsaturated cationic compounds and an alkoxyamine.
  • preactivated particles are then mixed with a monomer solution and the polymerization started from the sheet silicate surface.
  • Selective functionalization of different particle surfaces with different compounds is not described. The functionalization is only intended to improve the interaction between filler and surrounding, homogeneous polymer matrix, not to compatibilize different polymer phases.
  • US6986943 (B1) describes the functionalization of particles, u. a. Phyllosilicates included kaolinite, in several steps. However, not different particle surfaces are selectively functionalized, but the functionalizations bind to each other.
  • WO2009063257 (A2) describes the process for the production of microcapsules from clay particles and a crosslinker for encapsulating active ingredients for agriculture.
  • the clay material preferably kaolin, is surface modified with aminopropyltriethoxysilane and dispersed in water. At the phase boundary of an oil-in-water emulsion, the clay particles react with the crosslinking agent dissolved in the organic phase to form a crosslinked microcapsule shell.
  • tubular kaolin, halloysite which consists of rolled aluminosilicate layers and therefore does not have two different outer surfaces, is preferred.
  • JP09221316 includes an alumina composite of a 1: 1 phyllosilicate (preferably kaolin), which is first cleaved and then surface-modified with a silane or titanate coupling agent.
  • the main application for such composites is the control of the rheological properties of dispersions (thickening effect).
  • both basal surfaces are selectively functionalized and to adjust the polarity of the clay particles to increase the dispersibility and / or emulsifiability of the particles.
  • W09843598 (A2) describes the use of an organically modified clay material for the stabilization of cosmetic / pharmaceutical emulsions which additionally contain ascorbic acid.
  • the functionalization of the clay materials preferably bentonite (the main mineral component is the 2: 1 layered montmorillonite), is carried out by ion exchange with ammonium cations.
  • US5362314 includes a varnish comprising a clay-stabilized emulsion of bitumen in which the clay material is present in an amount sufficient to emulsify the bitumen, in combination with a cohesive-requiring additive selected from the group consisting of amines, Amidoamines and mixtures thereof is selected.
  • Kaolin is mentioned among other clay materials, but the advantage of 1: 1-layer silicates over 2: 1 layer silicates, namely to make a selective and different surface modification of both basal surfaces is not mentioned. Instead, attapulgite (a magnesium aluminum phyllosilicate) is preferred.
  • the cohesion promoting agent is not used to functionalize the particle surface.
  • HU72477 describes the conversion of by-products of petroleum refineries with alkylsulfonic acid in a colloidal solution by treatment with an emulsifying catalyst, namely natural silicate minerals such as bentonite or kaolin with potassium stearate or triethanolamine as peptizer.
  • an emulsifying catalyst namely natural silicate minerals such as bentonite or kaolin with potassium stearate or triethanolamine as peptizer.
  • FR845426 involves the dispersion of hydrocarbons, especially tar, with kaolinite types as an additive.
  • an emulsion auxiliary such as the sodium salt of the sulfonated cetyl alcohol or higher alcohols is added to the emulsion.
  • Janus particles can e.g. be used to stabilize emulsions.
  • Such solids-stabilized emulsions so-called “Pickering emulsions”, were discovered by Pickering as early as 1907.
  • the stabilization of emulsions was further developed by the introduction of solid particles into the interfaces of two immiscible liquids and theoretically investigated [Phys.Chem Chem. Phy., 2007, 9, 6298] Although the wettability of particles was considered in these studies, their structural condition and modification were not investigated.
  • the object of the present invention is to provide platelet-shaped particles which, in addition to the so-called Pickering effect, stabilize emulsions / mixtures of immiscible phases against segregation.
  • a method is needed that selectively exploits the different composition and thus chemical reactivity of basal surfaces of anisotropic, polar, inorganic particles in order to selectively functionalize them with organic molecules in order to adjust the hydrophilicity / hydrophobicity of the different surfaces.
  • the utilization of the anisotropy of the starting materials used and functionalization in dispersion is advantageous over the prior art, consuming to modify isotropic particles unilaterally, for which purpose the particles are e.g. be brought to a phase interface and functionalized there.
  • the object of the described invention selectively functionalized particles to stabilize emulsions of immiscible liquids or dispersions of solid particles in liquids or to achieve a phase transfer between immiscible polymers.
  • An advantage over the prior art is that the particles of the invention no additional additives such as organic surfactants must be used as phase mediators, which may adversely affect the properties of the resulting product, since they are often not long-term stability or degraded by environmental influences.
  • the functionalized particles of the invention it is not necessary to functionalize hydrophobic polymer particles of a polymer dispersion itself with ionic groups in order to disperse them in polar media.
  • Disadvantage of this currently used known method is the presence of many counterions in the dispersion, which lead, for example, in dispersion paints, inter alia, to a reduced corrosion protection of these paints.
  • the object is achieved in that platelet-shaped particles of anisotropic, polar, inorganic materials are used as the starting material for such particles having a surfactant or phase-promoting action, the basal surfaces of which have a lower chemical composition.
  • these particles should possess different surfaces with compatibility to the different phases to be mixed.
  • the starting materials in dispersion are selectively surface-modified in order, for example, to adjust the hydrophilicity / hydrophobicity of the different surfaces in a targeted manner.
  • the platelet-shaped morphology of the particles means that a large proportion of the total surface area of these particles is attributable to the opposing, chemically different basal areas.
  • the invention accordingly provides platelet-shaped, inorganic particles having anisotropic crystal structure and with different surface composition of their basal surfaces, characterized in that at least one of their basal surfaces is selectively covalently and / or covalently bonded to the basal surface by means of organic or inorganic compounds which are in particular polar or ionic or ionically bonded, is functionalized so that the particles have a surfactant effect.
  • Suitable starting materials for such particles are all known anisotropic, polar, inorganic materials, in particular having wurtzite structure, preferably but not limited to those from the series: zinc oxide, cadmium sulfide, cadmium selenide, cadmium telluride, gallium nitride, silver iodide or certain 1: 1 phyllosilicates, in particular kaolinite whose basal surfaces have a different chemical composition.
  • Preferred starting material for such particles are 1: 1 sheet silicates, particularly preferably kaolinite.
  • the particles which are characterized in that the two basic surface layers have a different elemental composition and both are functionalized.
  • the particles have a diameter with a number average in the range of 1 to 15 ⁇ and a layer thickness with an average value of 50 to 80 nm.
  • catechols, alcohols, diols, polyols, phosphine oxides, phosphines, alkenes, amines, ammonium and phosphonium compounds preferably catechols and / or alkylammonium compounds, more preferably choline and / or primary alkylammonium compounds, are used for functionalizing the basal surfaces.
  • platelet-shaped particles of phyllosilicates are used as the starting material for the described, phase-mediating particles whose basal surfaces differ in their chemical composition.
  • Kaolinite is particularly preferably used. Kaolinite is a polar anisotropic 1: 1 layer silicate. This means that the basal surfaces are terminated differently, one carries negatively charged Si 2 0 5 -Tetraedersch Anlagenen, the other Aluminol groups. This diverse chemical composition alone already leads to a different hydrophilicity and chemical reactivity of the surfaces. Because of this, the basal surfaces can be differently functionalized in order to increase the hydrophilicity, hydrophobicity and thus the polarity and / or to influence the interaction with the surrounding matrix on the one side and the dispersed particles or emulsion droplets.
  • the invention also provides a process for the preparation of the novel particles, characterized in that a dispersion of platelet-shaped, inorganic particles, with anisotropic crystal structure and with different surface composition of their basal surfaces is produced in an aqueous dispersion medium, the dispersion a radio ti from the series: Alcohols, diols, polyols, phosphine oxides, phosphines, alkenes, amines, catechols and organic cations, preferably choline, or cationic compounds with hydrophobic carbon chains, in particular ammonium or phosphonium compounds is added, the mixture is stirred vigorously and the functionalized particles, in particular by centrifugation, isolated and optionally subsequently heat treated at elevated temperature.
  • a radio ti from the series: Alcohols, diols, polyols, phosphine oxides, phosphines, alkenes, amines, catechols and organic cations, preferably choline,
  • the heat treatment is preferably carried out at a temperature of 20 to 200 ° C, preferably from 30 to 150 ° C and particularly preferably from 40 to 80 ° C.
  • a preferred embodiment of the method is characterized in that the dispersion of the particles is carried out using a rotary mixer according to the rotor / stator principle.
  • Another object of the invention is the stabilization of emulsions of immiscible liquids and the phase transfer between immiscible Polymers.
  • Emulsions of polymers in solvents in particular emulsions of hydrophobic polymers in aqueous solvents, are preferably stabilized here.
  • the invention also relates to the use of the novel particles described herein as dispersing aids, in particular for the preparation and stabilization of emulsions, in particular of oil in water or water in oil emulsions.
  • the invention also relates to the use of the novel particles described here as phase mediators for polymer blends.
  • the invention also relates to the use of the new particles described herein as dispersing aids for polymer dispersions, preferably for polyurethane dispersions.
  • the main aspect of the invention is the utilization of the Janus character of 1: 1 layer silicates and other platelet-shaped, polar, anisotropic, inorganic particles which are described in US Pat above publications was not provided.
  • a specific modification of the various basal surfaces of a 1: 1 layer silicate in a dispersion feasible while this is not true for a 2: layered silicate or other non-polar, anisotropic particles.
  • Phyllosilicates are composed of layers of a Si 2 0 5 -Tetraeder GmbH and octahedral layers in which a cation, especially aluminum, iron and magnesium octahedrally surrounded by hydroxide or oxygen. It can be both a Si ? 0. ⁇ - Tetrahedroncrisicht with an octahedral layer (two-layer or 1: 1-layered silicate) and two tetrahedral layers with egg ner octahedral layers (three-layer or 2: 1-layer silicate) connected. Two-layer minerals are uncharged; the individual shells are held together by D i po 1-dipole interactions, hydrogen bonds, and van der Waals forces.
  • Example 1 Modification of the phyllosilicates with catechol
  • 300 mg of the layered silicate to be modified (kaolinite, hectorite and montmorillonite) are mixed in ethanolic solution with 0.23 mmol of a catechol.
  • the reaction mixture is allowed to react at 60 ° C for 18 hours.
  • the modified kaolinite is washed 10 times with 50 ml of ethanol to eliminate catechol adsorbed on the surface, and then dried at 60 ° C.
  • Example 3 Modification of the kaolinites with catechol and alkylammonium chains
  • a catechol is synthesized carrying an MR-active linker that has high NMR sensitivity and high natural abundance. For this purpose, 300 mg of kaolinite in ethanolic solution with 0.23 mmol of a catechol, which carries a phosphorus linker, added. The reaction mixture is allowed to react at 60 ° C for 18 hours.
  • the modified kaolinite is washed 10 times with 50 ml of ethanol to eliminate catechol adsorbed on the surface, and then dried at 60 ° C.
  • the analysis of the modification is carried out by solid-state NMR.
  • the NMR spectra are recorded at room temperature with an Avance II 300 Magnetic Angle-Spinning (MAS) spectrometer at a corresponding Larmor frequency of 121.5 MHz with a rotation frequency of 12.5 kHz.
  • the samples are in standard 4 mm Zr0 2 rotors and standard double resonance MAS probe (Bruker).
  • the signals are referenced to an 85% H 3 P0 4 ---- solution for reference.
  • Example 5 Modification of the tetrahedral side of kaolinite using complex cations
  • 300 mg of kaolinite are dispersed in an aqueous solution of the complex cation Ru (bypy) 3 2+ of different concentration.
  • the solutions are stirred for one hour at room temperature and then measured the filtered supernatant of the solution by means of US-Vis spectroscopy at a wavelength of 453 nm. From the difference to the corresponding stock solution a maximum adsorption of 2.0 meq / l OOg kaolinite can be determined. In this way, the adsorption of the complex cation on the kaolinite surface can be detected quantitatively.
  • Ru (bypy) 3 2+ dyes the kaolinite particles because of its high adsorption coefficient.
  • Flow potential measurements prove that the negative potential of the kaolinite particles prior to the modification is reduced in magnitude by the addition of the complex cations and can also be reloaded with the corresponding electrolyte background.
  • Zeta potential measurements of the samples before and after the modifications show a significantly reduced zeta potential.
  • Further flow potential measurements with different inorganic or organic cations, all showing a reduction of the potential, show that cations in general are able to modify kaolinite.
  • kaolinite particles can be modified on both sides, ie on the octahedral side and the tetrahedral side. These doubly modified kaolinite particles are analyzed by TOF-SIMS time-of-fiight secondary ion mass spectroscopy (TOF-SIMS). For this purpose, the kaolinite particles are sedimented on a gold or Si surface from a very dilute solution. This results in an orderly orientation, which specifically introduces a deposition of modi fied Kaolinitkpumblen. In this case, the modified kaolinite particles deposit on the gold surface with the tetreaser side facing away from it.
  • TOF-SIMS time-of-fiight secondary ion mass spectroscopy
  • the mass fragments detected by SIMS can only be assigned to the catechol modifier located on the upside-down side of the particles.
  • the phosphorus is to identify the particle, while a Ru mass signal of the modifier of the tetrahedral side is not measurable.
  • the silicon surface on the other hand, all the particles separate so that the tedra leather side faces away from the surface, while the octahedral side faces the substrate. This can clearly show the ruthenium of the complex cation are identified on the surface of the kaolinite particles, while no phosphorus signal is to be identified on the particle surface.
  • Example 2 a 2% strength by weight aqueous suspension of the particles functionalized according to Example 1, Example 2 or Example 3 is prepared. 25 mL of this suspension are mixed with 3 mL, 7 mL, 10 mL, 13 mL, 17 mL and 20 mL, respectively, of oil. These were paraffin or silicone oil. The suspensions with the corresponding oil fractions are stirred on a hotplate for 1 hour at 60 ° C. in a screw-on glass vessel.
  • the samples After cooling to room temperature, the samples are treated for further homogenization with a disperser (Ultra-Turrax®) at 15500 rpm for 1 minute. The samples are assessed after 2 days.
  • a disperser Ultra-Turrax®
  • All emulsions are oil-in-water emulsions.
  • the oil droplets are encased by the layer of silicate particles.
  • the oil phase has a lower density and therefore floats on top.
  • the oil droplets stabilized by silicate particles frame. It is therefore an oil-in-water emulsion that floats on the water phase.
  • An oil phase can hardly be perceived in most cases because the solid particles completely emulsify the oil phase.
  • the solid initially introduced in the aqueous phase is required almost completely at the interface.
  • the emulsion droplets produced are stable in water. If you put the emulsion droplets in water frame them. The framed droplets are very stable. However, when the emulsion droplets are placed in oil, no droplets are discernible after some time and the organophilized solid is dispersed in the oil. This creates a turbidity of the oil phase.
  • the water phase is very clear because the solid content that has coated the oil droplets of the emulsion does not change into the liquid phase. In the case of the emulsions prepared, these are clearly oil-in-water emulsions which cream depending on the droplet diameter.
  • Example 8 Emulsion stabilization by alkylammonium-modified sheet silicates
  • kaolinite In kaolinite, on the other hand, only a basal plane is modified by the alkylammonium chains, and thus hydrophobization is performed only on a basal plane. This results in a sustained interfacial activity of the thus modified particles.
  • the water phase in the mixtures with kaolinite In contrast to the samples with hectorite and montmorillonite, the water phase in the mixtures with kaolinite is not cloudy, but clear and there is little or no sediment. This means that the interfacial activity of the A 1 ky lammonium chain modified kaolinite particles is much larger than that of hectorite or montmorillonite particles.
  • reflected-light microscope images of the emulsions made with alkylammonium re-modified phyllosilicate, water and silicone oil show very different behavior. While the emulsions stabilized by kaolinite show a very homogeneous size distribution of the emulsion droplets, the emulsions stabilized by montmorillonite and hectorite are very polydisperse. In addition, in the samples with the 2: 1 sheet silicates, areas are to be recognized which have no emulsion droplets and consist only of agglomerated solid.
  • Example 9 Emulsion stabilization by choline-modified layered silicates
  • the choline-modified phyllosilicates are used to prepare emulsions with paraffin oil.
  • the sample prepared with modified kaolinite shows a clear creaming of the water-in-oil emulsion. Due to the kaolinite particles or the modified kaolinite surface, however, there is no refraction of the emulsion and it remains stable for months. The water phase shows a slight haze. Sediment is barely visible.
  • the emulsions made with modified montmorillonites and hectorites break the frothed emulsion. This creates a much smaller Percentage of the creamed emulsion compared to the kaolinite-made emulsion.
  • the two sides hydrophilically modified particles thus cause no stabilization of the emulsion, which forms a clear oil phase. Only in the case of hectorite samples with very low oil contents of 3 mL and 7 mL is there no complete refraction of the emulsion.
  • the very small montmorillonite and hectorite particles remain sediment-stable in the water phase, while the remaining particles settle as sediment. This can be recognized by a pronounced proportion of sediment.
  • hydrophilic modification of a 2: 1 layered silicate degrades the emulsion-forming ability because the layered silicate shows no tendency to form an interface with the nonpolar oil layer. It is therefore energetically more favorable if the montmorillonite modified with chol and hectorite remains in the water phase, while the choline-modified kaolinite, which is distinguished by its one-sided modification, still has the ability to stabilize a creamed oil-in-water emulsion.
  • Example 10 Viscosity measurement of emulsions stabilized with phyllosilicates
  • Silicone oil-water emulsions with hectorites and kaolinites which have been modified by dodecylammonium are measured by way of example on the rheometer.
  • a very low shear rate of 100 s -1 is applied in a plate-plate geometry and the viscosity of the emulsions is measured.
  • the viscosity of the hectorite-stabilized emulsion is twice as high as that of the kaolinite-stabilized emulsion, which has a viscosity of about 64 mPas. This can be attributed to the fact that the modified emulsions with modified hectorites as stabilizer have no defined emulsion droplets, but z. T. consist of aggregates or the emulsion droplets are cross-linked with each other three-dimensional, as the Auflichtmikroskopische examination of the particles of Example 8 shows.
  • the emulsions stabilized with dodecylammonium-modified kaolinites are an emulsion with a defined droplet size which has no cross-linking of the oil droplets with one another, since they have a very good flow behavior.
  • the modified hectorite particles tend to agglomerate between the individual oil droplets.
  • Silicon oil-water emulsions with hectorites and kaolinites modified by dodecylammonium are subjected to centrifugal force in a rotor.
  • the samples are moved in a transparent vessel perpendicular to the axis of rotation r and meanwhile in Time intervals measured the transmission of the sample at certain points of the sample vessel.
  • the emulsions contain a lot of solid and thus significantly reduce the transmission compared to pure oil or water.
  • all vessels are filled with pure emulsion, which corresponds to a transmission in the entire measured range of 0%.
  • the transmission measurement was realized after 30 seconds and 30 minutes at a speed of 3000 rpm.
  • the kaolinite-stabilized emulsion has larger areas in the measuring cell after only 30 seconds, which have a high degree of transparency. In these areas there is no emulsion, but a pure oil or water phase is formed. A significant compression of the emulsion layer can be observed. Moderate shaking, however, can restore a homogeneous emulsion.
  • Example 7 silicone oil-water emulsions are prepared with unmodified phyllosilicates (kaolinite, hectorite and Montmorrelonit).
  • Example 13 Phase mediator of a polymer mixture (PS / PMMA) by kallyolin particles which have been iodinated on both sides
  • the interfacial tension of the two Kaolinitbasal lake is matched to that of the polymer mixture polystyrene (PS) / polymethyl methacrylate (PMMA).
  • PMMA chains are grafted onto the octahedron side of the kaolinite, by adding 200 mg of the copolymer poly (2 (2,3-dihydroxy-benzoyloxypropyl) methyl methacrylate) 46 -iiaimethylmethacrylat ⁇ in 50 ml of THF with 1 g of kaolinite analogous to Example 1 to Reaction is brought.
  • THF polymethyl methacrylate
  • the particles flocculate because this modification reduces the zeta potential of the tetrahedral basal surface to zero.
  • the double-sided modification can be detected by 13 C solid-state NMR, infrared spectroscopy (IR) and thermogravimetric analysis (TGA). Both in the IR spectrum and in the 13 C-NMR clear bands or signals can be seen, which are uniquely caused by the modification by the graft-grafted copolymers. With TGA it can be determined that the modification of both basal surfaces makes up about 5% by weight of the total sample. It can be deduced that the entire basal surfaces are covered with polymer chains. The selectivity of the modification on octahedral or tetrahedral basal surface can be demonstrated by the different results from the stability measurements of the various modified kaolinite suspensions in water and THF.
  • the kaolinite particles modified on both sides are introduced into a 17% strength by weight PS-PMMA 3-7 polymer solution in THF and, for better dispersion, are agitated with ultrasound at 40 ° C. for 15 minutes. Subsequently, a thin film is shaken out of this solution and, after drying, examined by means of SEM. A clear arrangement of the modified particles in the PS-PMMA interface can be seen. This arrangement in the interface can not be observed with unmodified kaolinite. From these results it can be concluded that the selective modification of the kaolinite basal surfaces with the respective phases of the polymer mixture brings about a greatly improved interfacial mediation.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

L'invention concerne de nouvelles particules tensioactives inorganiques et un procédé pour leur production. Les particules sont basées sur des particules inorganiques nanométriques en forme de plaquettes, ayant une structure polaire anisotrope, ayant une composition de surface différente de leurs surfaces basales, qui sont fonctionnalisées de manière sélective.
PCT/EP2012/051917 2011-02-09 2012-02-06 Particules tensioactives inorganiques et procédé pour la production desdites particules Ceased WO2012107377A1 (fr)

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DE102011003829.9 2011-02-09

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WO2025035956A1 (fr) * 2023-08-17 2025-02-20 清华大学 Particules janus à base de matériau naturel et leur procédé de préparation

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Publication number Priority date Publication date Assignee Title
WO2025035956A1 (fr) * 2023-08-17 2025-02-20 清华大学 Particules janus à base de matériau naturel et leur procédé de préparation

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