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WO2020011354A1 - Mélange miscible à l'eau contenant des corps moulés en silice - Google Patents

Mélange miscible à l'eau contenant des corps moulés en silice Download PDF

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Publication number
WO2020011354A1
WO2020011354A1 PCT/EP2018/068841 EP2018068841W WO2020011354A1 WO 2020011354 A1 WO2020011354 A1 WO 2020011354A1 EP 2018068841 W EP2018068841 W EP 2018068841W WO 2020011354 A1 WO2020011354 A1 WO 2020011354A1
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WO
WIPO (PCT)
Prior art keywords
mixture
water
shaped bodies
methanol
moldings
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2018/068841
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German (de)
English (en)
Inventor
Christoph MÜLLER-REES
Klaus-Jürgen EDER
Lothar GEIGER
Richard Weidner
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Wacker Chemie AG
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Wacker Chemie AG
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Publication date
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Priority to PCT/EP2018/068841 priority Critical patent/WO2020011354A1/fr
Publication of WO2020011354A1 publication Critical patent/WO2020011354A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/02—Agglomerated materials, e.g. artificial aggregates
    • C04B18/021—Agglomerated materials, e.g. artificial aggregates agglomerated by a mineral binder, e.g. cement
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/02—Agglomerated materials, e.g. artificial aggregates
    • C04B18/022—Agglomerated materials, e.g. artificial aggregates agglomerated by an organic binder
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/06—Aluminous cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/10—Lime cements or magnesium oxide cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/18—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mixtures of the silica-lime type
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
    • C04B28/26—Silicates of the alkali metals
    • 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
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3009—Physical treatment, e.g. grinding; treatment with ultrasonic vibrations
    • C09C1/3036—Agglomeration, granulation, pelleting
    • 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
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3081—Treatment with organo-silicon compounds
    • 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
    • C01P2006/10—Solid density
    • 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
    • C01P2006/11—Powder tap density
    • 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
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00482—Coating or impregnation materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures

Definitions

  • the invention relates to a water-miscible mixture (M) containing shaped bodies (F) made of hydrophobicized pyrogenic silica and a process for producing a coating composition.
  • Literature perlite, expanded glass, silica granules and aerogels:
  • Thermal conductivities of the perlite used according to the prior art for thermal insulation plasters are low.
  • Thermal plasters provided with pearlites have WLF values
  • Aerogels are particularly delicate due to their small pore sizes and very thin pore surfaces.
  • EP0489319B1 describes them
  • a filler in thermal plaster should be as high as possible: According to the teaching of DE102012020841A1, the proportion of binder in the overall system should be as low as possible, so that the insulation effect of the plaster is not deteriorated too much.
  • the fillers used for insulating plasters must be hydrophobic, as described in EP2799409A1 for perlite. This statement is confirmed for aerogels in CH708679A2.
  • Insulation plastering applications like other solutions in the construction sector, are high-volume applications and therefore require one for them
  • the invention relates to a water-miscible
  • Thermal conductivity is measured at room temperature with the aid of a THB transient hot bridge analyzer from Linseis, D-95100 Selb, and for this measurement the molded bodies (F) are filled into a cylindrical measuring device which
  • Measuring sensor is inserted through a slot in the middle of the cylinder and the moldings (F) are then compressed, and a methanol wettability of the moldings (F) of at most 55 vol .-%, whereby the methanol wettability of the moldings (F) is measured that 2 mL of the shredded shaped bodies (F) are filled into transparent centrifuge tubes, then the centrifuge tubes with a
  • Methanol / water mixture containing 0, 10, 20, 30, 40, 50, 60, 70 or 80 vol.% Methanol are made up to 8 mL, the sealed centrifuge tubes are then shaken for 30 s and then centrifuged at 2,500 min-1 for 5 min., the sediment volumes are then read, converted into percent and plotted against the methanol content (in% by volume) and the turning point is determined, which in the curve obtained shows the methanol Wettability corresponds.
  • the mixture (M) can be used to produce insulation materials that are non-flammable, inexpensive and easy to use
  • Hydrophobicized fumed silica is one
  • the shaped bodies (F) show better cost performance, since the shaped bodies (F) are made up of pyrogenic silica and the underlying pyrogenic silica has already formed the pore structure necessary for good thermal insulation performance after compression.
  • the shaped bodies (F) can also be incorporated into a binder, such as e.g. a plaster matrix can be incorporated without destroying the porous structure, while the
  • Particle sizes above about 1 mm can be incorporated into a typical hydrophilic plaster matrix without destroying it.
  • An insulating material with moldings (F) is after
  • Mixture (M) preferably contains a binder
  • inorganic binders are cement, such as Portland cement, white cement,
  • inorganic binders are lime-based binders, such as hydrated lime Ca (OH) 2, which is characterized by dry adsorption
  • Lime (CaO) is obtained and hydraulic lime, namely calcium hydroxide Ca (OH) 2, which is mixed with small amounts of a hydraulic binder, in particular cement.
  • a hydraulic binder in particular cement.
  • Other examples of inorganic binders are
  • gypsum-based binders such as calcium sulfate hemihydrate or hemihydrate (CaS04 * 0.5 H2O), in the alpha and in the beta
  • Model plaster or insulating plaster English stucco or plaster of paris
  • anhydrites CaS04, anhydrite I, II and III
  • the phases calcium sulfate dihydrate, calcium sulfate hemihydrate and anhydrite I, II and III in their various forms can be different
  • Ratios and mixtures arise multi-phase plaster.
  • Other types of gypsum such as screed gypsum, marble gypsum, anhydrite,
  • Hydrofluoric acid or organic carboxylic acids are suitable.
  • inorganic binders are examples of inorganic binders.
  • Silicone resins and alkali silicate preferably of the general formula (SZO2) m (M2O) nr where M is selected from Li, Na, K and NH4 and mixtures thereof and the molar ratio m: n
  • organic binders are water-based thermosetting binders, such as epoxy resin or polyurethane, and dispersion binders based on thermoplastic acrylate, styrene-acrylate or styrene-butyl acrylate polymers.
  • Shaped bodies (F) preferably have a bulk density of 60-250 g / L, particularly preferably 65 to 200 g / L, in particular 70 to 160 g / L, in each case determined in accordance with DIN ISO 697.
  • the moldings (F) can be produced by any method from all hydrophilic known to those skilled in the art
  • the moldings (F) are preferably produced in a process in which
  • step ii) the mixture from step i is deaerated and
  • step iii) the mixture from step ii is compressed to a target bulk density.
  • Granulation preferably takes place during the compaction in step iii.
  • Fumed silicas or precipitated silicas or mixtures thereof are preferably used in the production of the shaped bodies (F). Furthermore, silicas with a BET surface area according to DIN 66131 (determined with nitrogen) of between 50 and 800 m 2 / g are particularly preferred.
  • Silicas with a surface area between 150 and 400 m 2 / g are used.
  • hydrophilic means that the Si-OH groups accessible on the surface and the
  • Silicas are wettable by water.
  • Shaped body (F) additives are added, which can absorb, scatter or reflect heat rays in the infrared range. They are commonly referred to as IR opacifiers.
  • clouders preferably have a maximum in the IR spectral range of preferably between 1.5 and 10 m.
  • Particle size of the particles is preferably between 0.5-15 ml. Examples of such substances are preferred
  • Silicon dioxide such as. B. aerogels, precipitated silicas, arcing silicas, Si0 2 -containing dusts, which by oxidation of volatile silicon monoxide in the
  • Silicates such as calcium silicate, magnesium silicate and
  • Mixed silicates such as olivine can be produced with acids. Furthermore, naturally occurring compounds containing SiO 2 are used, such as diatomaceous earth and diatomaceous earth.
  • the mixture preferably contains hydrophilic
  • Silicic acid which is coated with hydrophobicizing agent in step i, at least 85% by weight, particularly preferably
  • organosilicon compounds e.g. organosilanes, organosiloxanes or silicone resins
  • hydrocarbons e.g. paraffins, waxes, carboxylic acids, especially fatty acids
  • the preferred hydrophobicizing agents are liquid, reactive organosilanes, organosiloxanes or at 25 ° C.
  • Silicone resins are used, which have hydrophobic properties and to react with the Si-OH groups of the
  • the water repellents can be used neat or in any mixtures.
  • Hydrophobing agent chosen so that the hydrophobizing effect is not fully developed before the compression step iii.
  • Organosilanes of the general formula are preferably used as water repellents
  • n and m can be 0, 1, 2, or 3 and the sum n + m is less than or equal to 3 and
  • R 1 is a saturated or mono- or polyunsaturated, monovalent, optionally with -CN, -NCO, -NR 3 , -COOH, -COOR 3 , -halogen, -acrylic, -epoxy, -SH, -OH or -CONR 3 2 substituted Si-C bonded Ci-C2o _ hydrocarbon residue, preferably a Ci-Cis hydrocarbon residue, or an aryl residue, or C 1 -C 15 hydrocarbonoxy residue, preferably a Ci-Cs hydrocarbonoxy residue, particularly preferably a C 1 - C 4 - hydrocarbonoxy radical, in each of which one or more methylene units which are not adjacent to one another by groups -0-, -CO-, -COO-, -OCO-, or -OCOO-, -S-, or -NR 3 - can be replaced and in which one or more, not each other
  • R 2 is hydrogen or a saturated or mono- or polyunsaturated, monovalent, optionally with -CN, -NCO, -NR 3 2, -COOH, -COOR 3 , -halogen, -acrylic, -epoxy, -SH, -OH or - CONR 3 2 substituted Si-C bonded Ci-C2o _ hydrocarbon residue, preferably a Ci-Cis hydrocarbon residue, or an aryl residue, or Ci-Ci5-hydrocarbonoxy residue, preferably a Ci-Cs-hydrocarbonoxy residue, particularly preferably a C 1 -C 4 - hydrocarbonoxy radical, in each of which one or more methylene units which are not adjacent to one another are formed by groups -0-, -CO-, -COO-, -OCO-, or -OCOO-, -S-, or -NR 3 - Can be replaced and in which one or more, not each other
  • R 3 has the same meaning as R 2 , and R 2 and R 3 may be the same or different,
  • X is a C-0 bonded Ci-Ci5 hydrocarbon residue, preferably a Ci-Cs hydrocarbon residue, particularly preferably a C 1 -C 3 - Is a hydrocarbon radical, or an acetyl radical, or a halogen radical, preferably chlorine, or hydrogen, or an OH radical,
  • R 11 has the meaning of R 1 and R 22 have the meaning of R 2 , i and j can be 0, 1, 2 or 3 and the sum of i + j is 3 and
  • Y can be the group NH or -0-.
  • building blocks can be contained in any mixtures
  • R 4 has the meaning of R 1 and R 5 have the meaning of R 2
  • Z have the meaning of X and can each be the same or different
  • a and b can be 0, 1, 2 or 3, with the proviso that the sum a + b is 3.
  • Cyclic organosiloxanes are preferably used.
  • Organopolysiloxanes used consisting of preferably 2 units of the general formula III-a and preferably 1 to 100,000 units of the general formula III-b and preferably 1 to 500 units of the general formula III-d, preferably 1 to 50,000 units of the general formula III-b and
  • general formula III-d and very particularly preferably 1 to 5000 units of the general formula III-b and 1 to 100 units of the general formula III-d, where R 4 is preferably methyl and R 5 is preferably -CH2-CH2-CH2-NH2 or -CH2-CH2-CH2-NH-CH2-CH2-NH2.
  • Chain-shaped organopolysiloxanes are preferably used, consisting preferably of 2 units of the general formula III-a and preferably 1 to 100,000 units of the general formula III-b, preferably 1 to 50,000 units of the general formula III-b, particularly preferably 1 to 10,000 units of the general Formula III-b, and particularly preferably 1 to 5000 units of the general formula III-b, R 4 preferably methyl. Chain-shaped organosiloxanes are particularly preferred
  • the R 4 is preferably methyl and the Z is preferably -OH.
  • the kinematic viscosity of the organosiloxanes measured at 25 ° C. is preferably 1 mm 2 / s to 100000 mm 2 / s, preferably 2 mm 2 / s to 10000 mm 2 / s and particularly preferably 5 mm 2 / s to 1000 mm 2 / s , OH-terminated are particularly preferred
  • Crosslinked or partially crosslinked are also preferred.
  • Organopolysiloxanes so-called silicone resins, are used, which are preferably the building blocks of
  • general formula III-a and building blocks of the general formula III-e contain, particularly preferably with R 4 equal to methyl, a equal to 3 and b equal to 0, or those which preferably
  • the amount of hydrophobizing agent added in step i depends on the specific surface area (BET surface area) of the
  • the amount added is preferably between 0.5 and 20% by weight, preferably between 1 and 15% by weight, particularly preferably between 5 and 12% by weight, in each case based on the mixture as a whole.
  • the components are mixed.
  • the hydrophobicizing agent is preferably added in liquid form during the preparation of the mixture, it being necessary for the individual components to be thoroughly mixed. The adsorption of the
  • Hydrophobing agent is preferably carried out by spraying the silica with the liquid hydrophobizing agent in the
  • the temperature is preferably selected so that the hydrophobicizing agent used does not yet react completely with the silanol groups on the silica surface during the mixing process in step i and before the compaction. This temperature setting ensures that the coated silica largely behaves like a hydrophilic silica in terms of processability in terms of compression, in particular granulation.
  • Hydrophobing agents are generally chosen so that intimate mixing is ensured.
  • the mixture is preferably stored only briefly.
  • the storage period of the mixture is generally chosen so that the hydrophobicizing agent used does not yet react completely with the silanol groups on the silica surface during the mixing process or before compaction.
  • the storage period until compaction is preferably at most 15 days, particularly preferably at most 1 week, in particular at most 3 days, very particularly preferably
  • the material is compacted and granulated immediately.
  • Adequate ventilation can be achieved, for example, by very slow compression. Such slow compression steps cannot be used economically for large-scale, in particular continuous, production. It is therefore advantageous to actively deaerate the silica. This can be achieved, for example, by using reduced pressure. A can already occur during the venting
  • volume decrease of the mixture take place.
  • the deaeration and subsequent compression and granulation can be carried out either in different devices or in a device that fulfills both functions.
  • step ii After the mixture has been produced in step i, it is preferably brought to the desired density by compacting or pressing in step ii. This is preferred in order to adjust the pore size with regard to an optimal insulation effect and to be able to obtain mechanically stable granules. In general, higher compaction results in harder,
  • a preferably takes place simultaneously during the compression
  • Free-flowing moldings are often used for applications in building insulation.
  • Shaped bodies are generally understood to mean all shapes which can be produced by means of devices for compacting powders known to the person skilled in the art.
  • Shaped bodies (F) are preferably understood to mean shapes which can be produced by compaction by means of rollers (smooth or perforated) (for example sleeves, sleeves, platelets, rods, briquettes, tablets, pellets, spheres, lenses, fragments, fragments).
  • the average size of the shaped bodies (F) is at least in one dimension, preferably in two dimensions, particularly preferably in all three dimensions, at most 100 mm, particularly preferably at most 50 mm,
  • the compacting is preferably carried out as a dry compacting in such a way that the mixture is pressed in a compacting unit between two rotating rollers, wherein
  • rollers particularly preferably at least one, particularly preferably both rollers has depressions, such as flutes, troughs or pillows.
  • the rollers can be straight or concave.
  • the compacted material formed in this way is then sieved and fractionated to the desired particle size fraction.
  • an apparatus from Hosokawa Alpine Compaction can be used.
  • At least one roller is designed in such a way that on the roller surface
  • Suppression can be generated (filter roller) through which the mixture to be compacted is sucked onto the roller and thereby vented. Preferably takes place after suction and
  • Compression takes place in succession in one device.
  • the supply of the silica to the compacting unit can be done by means of all means known to the person skilled in the art, such as
  • funnels and screw conveyors are used for metering and conveying, which at least partially have surfaces (e.g. the screw itself, the wall or special fittings) on which a negative pressure can be generated and thus the ventilation
  • Granules that exceed the size required for the application are separated and / or crushed. This can be carried out by all methods known to the person skilled in the art, such as, for example, breaking, classifying or grinding. The fragments obtained are then separated into different grain fractions. For example, a sieve mill from Hosokawa Alpine can be used for this
  • Particles can also be separated, which the
  • Hydrophobing agents react with the silanol groups of the silica. In a preferred embodiment, this takes place without tempering, e.g. by storage at room temperature.
  • the storage time of the shaped bodies (F) at room temperature is preferably at least 3 days, preferably at least one
  • This final waterproofing can also be achieved by increasing the temperature
  • the shaped bodies (F) are tempered at a temperature of preferably from 60 to 300 ° C. and preferably from 70 to 130 ° C.
  • the final binding of the hydrophobicizing agent to the SiOH groups after the granulation can also be accelerated by adding catalytically active substances.
  • catalytically active substances for this purpose, all compounds known to the person skilled in the art for activating functional organosilicon compounds, such as Brödsted or Lewis acids, can be used.
  • Br ⁇ ndsted acids are hydrochloric acid, sulfuric acid or nitric acid, preferred as Br ⁇ ndsted acid
  • tin or titanium compounds for example tin or titanium compounds such as tin alkoxides or titanium alkoxides.
  • the shaped bodies (F) can, however, also be produced by pressing hydrophilic fumed silica and subsequent treatment with hydrophobicizing agents, for example by
  • Hydrophilic fumed silica is first compacted and, after compacting has been carried out, it is subsequently hydrophobized in a second step, e.g. in DE 10 2012 211 121 Al
  • the proportion by weight of moldings (F) which is outside a size range of 0.1 mm to 15 mm is particularly preferred preferably a range from 0.5 mm to 10 mm, very particularly preferably a range from 0.8 mm and 6.0 mm, particularly preferably a range from 1.0 mm and 4.0 mm
  • these moldings are preferably compacted to the desired bulk density.
  • the thermal conductivity of the shaped bodies (F) in the form of a loose bed is preferably at most
  • Measuring device are filled, the measuring sensor is inserted through a slot in the middle of the cylinder and the molded body (F) are then compressed.
  • the moldings (F) preferably have a C content of 1 to 7% by weight, particularly preferably 1 to 6% by weight, in particular 1 to 5% by weight.
  • the water-miscible mixture (M) preferably contains 20 to 95% by volume, particularly preferably 40 to 90% by volume,
  • the mixture (M) may contain further additives which are selected from fillers and additives, such as air entraining agents, binder auxiliaries, fluxes, retarders, Water repellents, pigments and agents for improving workability.
  • fillers and additives such as air entraining agents, binder auxiliaries, fluxes, retarders, Water repellents, pigments and agents for improving workability.
  • fillers are non-reinforcing fillers, i.e. fillers with a BET surface area of up to 50 m 2 / g, such as quartz, diatomaceous earth, calcium silicate, zirconium silicate, zeolites, metal oxide powder, such as aluminum, titanium, iron, or zinc oxides or their mixed oxides, barium sulfate,
  • Silicic acid, carbon black, such as furnace black and acetylene black and silicon-aluminum mixed oxides with a large BET surface area Silicic acid, carbon black, such as furnace black and acetylene black and silicon-aluminum mixed oxides with a large BET surface area.
  • Fillers can be hydrophobic, for example
  • organosilanes or organosiloxanes by treatment with organosilanes or organosiloxanes or by etherification of hydroxyl groups to alkoxy groups.
  • It can be a type of filler, a mixture of at least two fillers can also be used.
  • pigments examples include earth pigments such as chalk, ocher, umber, green earth, mineral pigments such as titanium dioxide, chrome yellow, red lead, zinc yellow, zinc green, cadmium red, cobalt blue, organic pigments such as sepia, Kasseler Braun, indigo, azo pigments, antrachinoid, Indigoide, dioxazine, quinacridone,
  • Phthalocyanine, isoindolinone and alkali blue pigments whereby many of the inorganic pigments also act as fillers and vice versa.
  • the content of fillers in the mixture (M) is the same.
  • the invention also relates to a method in which the mixture (M) which is miscible with water is combined with water to form a
  • Coating compound is mixed.
  • mixture (M) with 50 to 180 parts by weight, particularly preferably 80 to 160 parts by weight,
  • the coating composition is preferably processed to insulating materials, in particular thermal insulation plasters.
  • HDK® T30 hydrophilic, pyrogenic silica from Wacker Chemie AG with a BET surface area of 300 m2 / g.
  • HDK® N20 hydrophilic, pyrogenic silica from Wacker Chemie AG with a BET surface area of 200 m2 / g.
  • HDK® V15 hydrophilic, pyrogenic silica from Wacker Chemie AG with a BET surface area of approx. 150 m2 / g.
  • OH-term. PDMS OH-terminated polydimethylsiloxane from Wacker Chemie AG with a kinematic viscosity in the range of 12-15 mm 2 / s.
  • Other aids All other laboratory chemicals were obtained from common suppliers.
  • Perlite for comparative tests:
  • AeroBall® supplier Aero Dämmtechnik, Müllheim; Grain size: 0.5-0.7 mm; Bulk density: approx. 78 kg / m 3
  • Polydimethylsiloxane as a hydrophobizing agent for this purpose, part (approx. 10%) of the hydrophilic pyrogenic silica to be coated is stirred in a container with the total amount of OH-terminated polydimethylsiloxane until an optically homogeneous mixture of the powdery hydrophilic pyrogenic silica in the liquid OH-terminated
  • Polydimethylsiloxane has arisen.
  • the stirring takes place e.g. by a magnetic stirrer or by a dissolver.
  • a stamp is then applied to the press mold, to which the
  • the stamp is pressed onto the mold filled with powder mixture.
  • the target density is controlled by the amount of the powder mixture.
  • the feed of the stamp must be selected so that the air can slowly escape over the edge of the stamp (ventilation) without large amounts of the fine pyrogenic silica
  • the feed of the punch is interrupted at about 80-90% for about 10 minutes (venting through the gap between the punch and the mold).
  • the target density is then compacted and another 10 minutes waiting before demolding.
  • the stamp is then relaxed, the mixture compacted in this way to form a plate (the plate thickness is approximately 20 mm) is removed from the press mold and then mechanically comminuted. Any formed bodies larger than 4 mm are separated using a sieve and comminuted so that they pass through the 4 mm sieve.
  • the fine fraction of the shaped bodies created in this way is then sieved using a hand sieve (mesh size 1 mm).
  • the bulk density of the shaped bodies is determined based on DIN ISO 697.
  • the material to be examined is poured into a vessel with a known volume (1 L). Surplus material is wiped off with a bar. The weight of the bed is determined by weighing and the bulk density is calculated therefrom. b) Thermal conductivity of the moldings
  • the thermal conductivity is determined at
  • THB Transient Hot Bridge Analyzer (THB-100) from Linseis, D-95100 Selb, using an HTP sensor.
  • THB-100 Transient Hot Bridge Analyzer
  • the measuring time is 45 seconds with a measuring current of 27 mA and a current for temperature measurement of 10 mA.
  • the sensor is calibrated on a plate reference sample with the
  • 100 mL of the filler to be analyzed is poured into a cylindrical measuring device (material: PP, height 100 mm, cylinder diameter 80 mm), in the middle of which there is a slot (dimensions: 25 x 2 mm) through which the
  • Measuring sensor is inserted. Hydraulic plungers press the molded bed slightly from both ends during the entire measurement. c) hydrophobicity of the shaped bodies (qualitative)
  • the hydrophobicity is assessed in two steps:
  • Molded bodies are hardly wettable by water and float completely on the water surface.
  • Partially hydrophobic moldings are wettable, but mostly float on the water surface.
  • moldings can be wetted immediately and sink down in the water within a few minutes. b) Test after 6 weeks of storage of the moldings in water:
  • Molded bodies are hardly wettable by water and at least 80% (number) float on the water surface.
  • Methanol wettability is a measure of the hydrophilicity / hydrophobicity of silica materials.
  • 2 mL (+ - 0.05 mL) of the molded body to be examined are filled into a transparent centrifuge tube and then with a previously prepared methanol / water mixture (0, 10, 20,
  • the components for a cementitious binder matrix are mixed in a ratio according to Table 1 using a stirrer until an optically homogeneous dry mixture is formed. By not adding one
  • Porosity agents in this plaster mixture can better compare the values for the thermal conductivity of the test bodies formed therefrom, since porosity agents usually have a strong influence on the thermal conductivity of applied thermal insulation plasters.
  • Dry mixture containing plaster mixture and molded body (F) with water (pasting) is carried out as follows: - Preliminary test to determine the amount of water required for a test specimen: 200 mL of the components in Table 1
  • Shaped body (F) (or the filler not according to the invention for comparison) are mixed until an optically homogeneous mixture has formed. This homogeneous dry mixture is then placed in a Toni mixer (mortar mixer, from Testing, Berlin, content 5 L) and to this
  • the relative amount of water determined beforehand is placed in a Toni mixer, after which the homogenized plaster / molded body / reference filler mixture is added under
  • the paste produced under 4c) is transferred to a formwork (PE ring from our own production, diameter 200 mm) and first air-dried at 23 ° C for 3 days.
  • the training period from the time between the addition of the dry mixture to the water provided until the formation of a homogeneous, pasted plaster is an empirically important measurement variable in practice for assessing which
  • thermal insulation plaster can be made before its (manual or mechanical) application. Typical values for commercially available thermal insulation plasters are in the range of a few 10 seconds. Test specimens with dry mixtures, for which the duration determined in this way until they are homogenized in the water is 300 s and more, are denoted by “> 300” and are not in practice reasonable
  • the thermal conductivity is based on DIN EN
  • the shaped bodies (F) are as in point 2 above.
  • test specimens are as described in point 4.
  • Enriched thermal plaster is the decisive criterion for the homogenization of the dry mix with the
  • Shaped bodies can be used in insulating plasters with regard to their duration of homogenization, but as expected they show hydrophilic properties (negative hydrophobicity tests).
  • Cf. 6 and cf. 7 perlite-based hydrophobic (reference) fillers available on the market and used for this purpose are processed: Homogenization and hydrophobicity properties are sufficiently good for their use in thermal insulation plasters, but their thermal conductivity is significantly higher than that of the moldings used according to the invention.
  • Hydrophilic fumed silica can affect the mixing time
  • Shaped body with the aqueous plaster system required which is due to a minimum number of reactive SiOH groups,
  • Shaped articles (F) with methanol wettability of more than 55% are too hydrophobic to be able to be incorporated into water within a maximum incorporation period that is acceptable in practice for the target application of thermal insulation plaster.
  • Shaped body used according to the invention (made of
  • Hydrophobing agent PDMS Hydrophobing agent
  • Hydrophobing agents in the moldings lead to a stronger hydrophobization, which is particularly positive in the hydrophobicity long-term behavior.
  • hydrophobic moldings result in a longer incorporation period until they are homogenized with water.
  • Fumed silicas (WACKER HDK® T30, BET ⁇ 300 m 2 / g) coated with less than 15% by weight OH-terminated
  • Water repellents PDMS can be homogenized sufficiently well with water, whereby - depending on the customer's requirements - their water repellency properties can be specifically adjusted.
  • the thermal conductivity of the moldings (F) listed in these examples is in the range between 19 and 22 mW / (m K) (measured in bulk with the aid of a THB
  • Test specimens for molded articles based on pyrogenic silica are between 65 and 70 mW / (m K) and are therefore also approx. 30 mW / (m K) below the thermal conductivity values of test specimens with pearlite-based fillers.
  • Shaped bodies (F) used according to the invention have bulk densities in the range from 80 to 150 g / L in the tests carried out, and they are also particularly mechanically stable.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Civil Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Compounds (AREA)

Abstract

L'invention concerne un mélange (M) miscible à l'eau contenant des corps moulés (F) en silice pyrogénée hydrophobisée ayant une conductivité thermique mesurée, dans le lit, de 35 mW/(m K) maximum. La conductivité thermique est mesurée à la température ambiante à l'aide d'un analyseur à pont chaud transitoire THB de la société Linseis, D-95100 Selb, et pour cette mesure les corps moulés (F) sont introduits dans un dispositif de mesure cylindrique. Le capteur de mesure est inséré dans une fente ménagée au centre du cylindre et les corps moulés (F) sont ensuite compactés et la mouillabilité au méthanol des corps moulés (F) est de 55 % en volume maximum. La mouillabilité au méthanol des corps moulés (F) est mesurée. L'invention est caractérisée en ce que des tubes transparents à centrifuger sont remplis chacun avec 2 ml de corps moulés broyés (F) puis les tubes transparents à centrifuger sont remplis avec un mélange méthanol/eau contenant 0, 10, 20, 30, 40, 50, 60, 70 ou 80 % en volume de méthanol jusqu'à atteindre 8 ml, puis les tubes à centrifuger fermés sont agités pendant 30 s, puis centrifugés à 2500 min-1 pendant 5 min, les volumes de sédiment sont ensuite lus et convertis en pourcentage 2 et représentés graphiquement en fonction de la teneur en méthanol (en % en volume). On détermine le point d'inflexion qui correspond à la mouillabilité au méthanol dans la courbe obtenue. L'invention concerne également un procédé de production d'une composition de revêtement dans lequel le mélange (M) miscible à l'eau est mélangé à de l'eau.
PCT/EP2018/068841 2018-07-11 2018-07-11 Mélange miscible à l'eau contenant des corps moulés en silice Ceased WO2020011354A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4527814A1 (fr) * 2023-08-09 2025-03-26 Xella Baustoffe GmbH Matériau isolant en vrac lié et son utilisation ainsi que procédé de fabrication d'un matériau isolant en vrac renforcé

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Publication number Priority date Publication date Assignee Title
EP0489319B1 (fr) 1990-12-05 1996-02-28 BASF Aktiengesellschaft Mousse composite à faible conductivité thermique
DE102012020841A1 (de) 2011-12-05 2013-06-06 Franken Maxit Mauermörtel GmbH & Co. Mineralschaum und Verfahren zur Herstellung desselben
DE102012211121A1 (de) 2012-06-28 2014-01-02 Evonik Industries Ag Granuläre, funktionalisierte Kieselsäure, Verfahren zu deren Herstellung und deren Verwendung
EP2799409A1 (fr) 2013-05-03 2014-11-05 EMPA Eidgenössische Materialprüfungs- und Forschungsanstalt Enduits à base d'aérogel thermiquement isolant
CH708679A2 (de) 2013-10-14 2015-04-15 Adt Aero Dämm Technik Gmbh Dämmputz für die Innen- und Aussenisolation von Bauwerken, das Verfahren zu seiner Herstellung, seine Verwendung und ein damit isoliertes Bauwerk.
WO2015090615A1 (fr) 2013-12-20 2015-06-25 Interbran Systems Ag Mélange sec de matériau de construction et enduit d'isolation thermique résultant
DE102015216505A1 (de) * 2015-08-28 2017-03-02 Wacker Chemie Ag Silica Formkörper mit geringer thermischer Leitfähigkeit
EP2543652B1 (fr) 2010-03-05 2017-07-19 Kyungdong One Corporation Isolant thermique utilisant une perlite expansée à alvéoles fermés
WO2018134275A1 (fr) * 2017-01-18 2018-07-26 Evonik Degussa Gmbh Matériau granulaire thermo-isolant et son procédé de fabrication
WO2018153493A1 (fr) * 2017-02-27 2018-08-30 Wacker Chemie Ag Procédé de fabrication de granulés en silice hydrophobe

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0489319B1 (fr) 1990-12-05 1996-02-28 BASF Aktiengesellschaft Mousse composite à faible conductivité thermique
EP2543652B1 (fr) 2010-03-05 2017-07-19 Kyungdong One Corporation Isolant thermique utilisant une perlite expansée à alvéoles fermés
DE102012020841A1 (de) 2011-12-05 2013-06-06 Franken Maxit Mauermörtel GmbH & Co. Mineralschaum und Verfahren zur Herstellung desselben
DE102012211121A1 (de) 2012-06-28 2014-01-02 Evonik Industries Ag Granuläre, funktionalisierte Kieselsäure, Verfahren zu deren Herstellung und deren Verwendung
EP2799409A1 (fr) 2013-05-03 2014-11-05 EMPA Eidgenössische Materialprüfungs- und Forschungsanstalt Enduits à base d'aérogel thermiquement isolant
CH708679A2 (de) 2013-10-14 2015-04-15 Adt Aero Dämm Technik Gmbh Dämmputz für die Innen- und Aussenisolation von Bauwerken, das Verfahren zu seiner Herstellung, seine Verwendung und ein damit isoliertes Bauwerk.
WO2015090615A1 (fr) 2013-12-20 2015-06-25 Interbran Systems Ag Mélange sec de matériau de construction et enduit d'isolation thermique résultant
DE102015216505A1 (de) * 2015-08-28 2017-03-02 Wacker Chemie Ag Silica Formkörper mit geringer thermischer Leitfähigkeit
WO2018134275A1 (fr) * 2017-01-18 2018-07-26 Evonik Degussa Gmbh Matériau granulaire thermo-isolant et son procédé de fabrication
WO2018153493A1 (fr) * 2017-02-27 2018-08-30 Wacker Chemie Ag Procédé de fabrication de granulés en silice hydrophobe

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4527814A1 (fr) * 2023-08-09 2025-03-26 Xella Baustoffe GmbH Matériau isolant en vrac lié et son utilisation ainsi que procédé de fabrication d'un matériau isolant en vrac renforcé

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