EP3609855A1 - Procédé de préparation de mousse minérale et son utilisation - Google Patents

Procédé de préparation de mousse minérale et son utilisation

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Publication number
EP3609855A1
EP3609855A1 EP18716615.2A EP18716615A EP3609855A1 EP 3609855 A1 EP3609855 A1 EP 3609855A1 EP 18716615 A EP18716615 A EP 18716615A EP 3609855 A1 EP3609855 A1 EP 3609855A1
Authority
EP
European Patent Office
Prior art keywords
composition
composition according
amounts
weight
silicate
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.)
Withdrawn
Application number
EP18716615.2A
Other languages
German (de)
English (en)
Inventor
Kurt SCHÜMCHEN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Interbran Raw Materials GmbH
Original Assignee
Interbran Raw Materials GmbH
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 Interbran Raw Materials GmbH filed Critical Interbran Raw Materials GmbH
Publication of EP3609855A1 publication Critical patent/EP3609855A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C04B28/006—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 mineral polymers, e.g. geopolymers of the Davidovits 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
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/02—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by adding chemical blowing agents
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • the present invention relates to the technical field of inorganic foams, in particular for purposes of thermal insulation or fire protection.
  • the present invention relates to a composition for producing an inorganic foam and to the use thereof for the production of inorganic foams and moldings.
  • the present invention relates to a process for the production of moldings from an inorganic foam.
  • the present invention relates to a molded article comprising an inorganic foam.
  • insulation boards based on plastic foams are generally used both indoors and outdoors.
  • the insulation boards are preferably used as external thermal insulation systems (ETICS), which are constructed of a plate-shaped insulating material, a reinforcing layer applied to the outside and a top coat.
  • EICS external thermal insulation systems
  • the insulation boards are usually based on plastic foams, in particular polystyrene foams (PS), such as polystyrene particle foam (EPS) or polystyrene extruder foam (XPS), or based on rigid polyurethane foams (PUR).
  • PS polystyrene foams
  • EPS polystyrene particle foam
  • XPS polystyrene extruder foam
  • PUR rigid polyurethane foams
  • Thermal insulation systems based on the aforementioned plastic insulating panels have excellent insulating properties under ideal conditions, but have the disadvantage that they form a vapor barrier and moisture from the masonry can not be released into the environment, which often leads to the formation of mold and algae.
  • the moisture increases the thermal conductivity of the system, which is why the theoretical heat transfer coefficients (U-values) according to EN ISO 6946 are often not achieved in practice.
  • thermal insulation composite systems ETICS have thicknesses of 50 to 20 cm in order to achieve sufficient thermal insulation, which often leads to a visual deterioration of the entire façade and a reduced incidence of light into the interior of the building through the windows.
  • thermal insulation composite systems thermal insulation composite systems
  • VIP vacuum insulation panels
  • plastic materials used after the period of use in case of damage can not be easily disposed of, recycled or recycled, but declared as hazardous waste and a costly and expensive disposal must be supplied.
  • diffusion-open insulation materials for example based on mineral wool or natural organic fibers, such as wood, cork, hemp and Scerratagen can be recycled or disposed of more easily, but they often lack the necessary mechanical stability and structural integrity; these systems are rather flexible and not dimensionally stable.
  • the so-called vapor-permeable systems have a significantly reduced insulating effect compared to plastic foam boards or vacuum insulation boards.
  • mineral building materials generally have a much higher density compared to plastic-based building materials or building materials based on organic natural materials, ie in the installation of insulation boards based on mineral materials significantly more weight must be applied to the house facade or the interior walls, which both the transport and attachment to a substrate as well as the handling of these insulation materials makes it much more difficult and expensive and thus more expensive.
  • many mineral materials suitable principally as insulating materials such as, for example, perlite or vermiculite, in particular in expanded form, have the serious disadvantage that they are present as particulate fillers. Although these particles are often highly porous, have excellent thermal insulation properties and some acceptable bulk density, but must be added to a binder to be processed into moldings, such as insulation boards.
  • binders however, has a number of disadvantages:
  • the binder often has a very high density and high thermal conductivity when using mineral binders, so that the heat transfer coefficient of a shaped body, in particular an insulating plate, is significantly worse than the heat transfer coefficient of used mineral insulating material or filler.
  • both the density and the heat transfer coefficient of the molded body obtained can be significantly improved, but only at the cost of increased flammability and a massively deteriorated environmental performance.
  • inorganic foams in particular of mineral foams, such as, for example, geopolymer foams. These are purely mineral or almost exclusively mineral based and have a low density and extremely low thermal conductivity.
  • Geopolymers are inorganic binders based on silicate, which are liquid in the uncrosslinked state and can be processed into moldings, but form solid three-dimensionally crosslinked structures after solidification and curing.
  • silicate silicate
  • the synthesis of synthetic geopolymers has also been extended to a variety of suitable materials, particularly waste products from industrial raw material extraction, such as blast furnace slag.
  • aluminosilicates in particular metakaolin
  • Geopolymers are generally activated in an alkaline manner, for example by reaction with concentrated sodium hydroxide solution, to give a liquid mixture which solidifies and hardens after some time.
  • Geopolymers can also be prepared by alkaline activation of, for example, clays, various ashes, in particular fly ash, natural pozzolans or suitable slags.
  • the binder system of the geopolymers is an amorphous silica gel, which is easily moldable in its uncured state and usually has good mechanical properties after curing.
  • EP 2 545 239 B1 relates to a component structure, in particular a window or door frame, which is filled with a foamed geopolymer.
  • the copolymer is formed by a mixture of metakaolin and mica and / or another laminar material and an aqueous alkali metal silicate solution which contains an alkali metal hydroxide.
  • DE 10 2014 003 104 A1 relates to a process for the production of foam or blowing masses or bodies from a raw material mixture with a solid with aluminosilicates, which form alkaline structures and polymeric structures and / or spatial networks and thereby harden, wherein the alkaline activation of the solid in the preparation of the curable raw material mixture is first introduced by the alumosilicate-containing solid is mixed with at least one alkaline activator and well homogenized, with complete curing of the geopolymer matrix takes place a swelling and / or foaming process.
  • alumosilicates in particular metakaolin, Humpsandsmehl, Trassmehl, oil shale, aluminum-containing silicate dust, pozzolans, basalt, clays are given and as the alkaline activator, water glass or an alkali metal hydroxide can be used.
  • the foaming agent used is aluminum powder or hydrogen peroxide.
  • DE 40 37 576 A1 relates to the production of foamed mineral structures for the production of moldings, wherein the mineral foams by reacting ground oxide mixtures based on slags from Siliaktschmelzen, in particular blast furnace slag, Schmelzbasalt, Tonerdschmelzzement and brick flours used, which with an alkaline activator in the form of a reacted aqueous alkali metal silicate.
  • foaming agents for example, inorganic peroxides such as sodium percarbonate or perborate, hydrogen peroxide and zinc powder or aluminum powder can be used.
  • the abovementioned method makes it possible to obtain geopolymer foams which can in principle be used as thermal insulation materials or for fire protection purposes.
  • a further object of the present invention is to provide a material which not only has very good heat-insulating properties, but also is non-combustible and is easy to handle and easy to dispose of or recycle.
  • the present invention proposes a composition according to claim 1 according to a first aspect of the present invention. Further advantageous embodiments of this aspect of the invention are the subject of the relevant subclaims.
  • Another object of the present invention - according to a second aspect of the present invention is the use of a composition for producing an inorganic foam according to claim 43.
  • Another object of the present invention according to a third aspect of the present invention is the use of a composition for producing an inorganic foam molding according to claim 44.
  • Yet another subject of the present invention according to a fourth aspect of the present invention is a method for producing a molded body from a geopolymer foam according to claim 45; Further advantageous embodiments of these aspects of the invention are the subject of the relevant subclaims.
  • Another object of the present invention according to a fifth aspect of the present invention a shaped body according to claim 57; Further advantageous embodiments of these aspects of the invention are the subject of the relevant subclaims.
  • the subject of the present invention - is thus a composition for producing an inorganic foam, in particular a geopolymer foam, containing
  • silicate binders such as, for example, geopolymers, especially when using silicate-containing material based on perlites, preferably expanded perlite, and fibers, inorganic foams which are extremely resilient to mechanical stress, in particular geopolymer foams, obtained, which also have excellent thermal insulation properties and low density.
  • the use of the composition according to the invention makes it possible to produce highly heat-insulating geopolymer foams which manage without further heat-insulating fillers.
  • the inorganic foams produced by the composition according to the invention in particular geopolymer foams, are mechanically highly stable, form stable foam structures and cure rapidly; Consequently, they can be easily processed into moldings, such as insulation boards.
  • the geopolymer foams produced in the composition according to the invention are non-combustible or safely removable and have the fire classes A1 or A2 according to DIN 4102.
  • composition according to the invention and the inorganic foams obtainable with it, in particular geopolymer foams are furthermore preferably of purely mineral or almost exclusively mineral composition, so that no potentially harmful or environmentally hazardous substances, such as plasticizers or preservatives, are used for their preparation have to. Because of this safety, the inorganic foams or geopolymer foams according to the invention produced with the composition according to the invention can readily be used as building materials both indoors and outdoors.
  • the composition according to the invention enables a time-saving, cost-effective and reproducible production of inorganic foams or geopolymer foams and is therefore outstandingly suitable for the industrial production of components, in particular insulating panels.
  • the inorganic foams or geopolymer foams obtainable with the composition according to the invention have in the hardened foam structure gas-filled cavities, so-called cells, which are enclosed by solid walls.
  • the inorganic foams or geopolymer foams are preferably closed-cell foams, ie the cavities or cells lie in the interior of the solid-state structure, are enclosed on all sides by walls and have no connection to the environment.
  • the inorganic foams or geopolymer foams according to the invention can be achieved.
  • At least the inorganic foams or geopolymer foams are mostly closed-cell foams, ie foams with a high proportion of closed pores.
  • a geopolymer is understood as meaning a silicate-based binder based on at least one aluminosilicate which has been reacted with an alkaline activator.
  • the purely inorganic or almost exclusively inorganic based binder system of a geopolymer is initially liquid and can be easily processed into moldings, for example by casting, but hardens quickly and forms extremely stable structures.
  • alkaline activation for example by inorganic alkalis, such as sodium hydroxide, or the reaction with alkali metal silicates, such as lithium water glass, at pH values above 12 silicate and aluminate ions are dissolved out of the solid state framework and condense subsequently, so that new complex three-dimensional structures arise.
  • inorganic alkalis such as sodium hydroxide
  • alkali metal silicates such as lithium water glass
  • the silicate-containing material is in particle form.
  • the silicate-containing material particle sizes in the range of 1 ⁇ to 10,000 ⁇ , in particular 2 ⁇ to 8.000 ⁇ , preferably 10 ⁇ to 5.000 ⁇ having.
  • the silicate-containing material is selected from the group of metakaolin, mica, blast furnace slag, blastfurnace slag, fly ash, microsilica, trass flour, oil shale, basalt, zeolites, silica aerogels, silica hybrid orgains, Vermiculite, in particular puffed vermiculite, perlite, in particular puffed perlite and mixtures thereof.
  • the silicate-containing material is selected from vermiculite, preferably expanded vermiculite, and perlite, preferably expanded perlite, and mixtures thereof.
  • the silicate-containing material is an aluminosilicate or contains at least one aluminosilicate; in particular, when selecting the silicate-containing materials mentioned above, it is preferable to ensure that at least one of the selected materials is one Aluminosilicate or contains an aluminosilicate.
  • the silicate-containing material is perlite, in particular expanded perlite.
  • blown perlite it is possible to produce highly porous, highly heat-insulating molded bodies with low density and, at the same time, high mechanical strength.
  • perlite in particular expanded perlite
  • perlite can be used in an outstanding manner as a binder for a geopolymer, in particular unresolved residues of the expanded perlite are homogeneously and finely distributed as highly porous fillers in the foam matrix and both the mechanical strength and the heat-insulating Advantageously influence the properties of the inorganic foam.
  • the silicate-containing material is a mixture of vermiculite, in particular expanded vermiculite, and / or perlite, in particular expanded perlite, and an airgel, in particular a silica airgel and / or a silica hybridiserogel.
  • a silica hybridogel is to be understood as meaning a silica airgel which contains from 1 to 20% by weight, in particular from 5 to Contains 15 wt .-%, based on the silica Hybhdaerogel, at least one polysaccharide.
  • the polysaccharide is usually selected from starch, gum arabic, xanthan, pectin, agarose, cellulose ethers, especially pectin and / or xanthan.
  • the polysaccharides are usually added already in the production of silica Hybridaerogel and form an extremely flexible, but at the same time stable matrix, which flexibly connects the individual silica airgel particles together and protects against excessive mechanical loads.
  • Silica Hybridaerogele have in comparison to conventional silica aerogels significantly improved mechanical properties with only slightly deteriorated thermal insulation properties.
  • a suitable method for preparing silica hybrid orgies is described, for example, in S. Zhao, WJ Malfait, A. Demilecamps, Y. Zhang, S. Brunner, L. Huber, P. Tingaut, A. Rigacci, T. Budtova and MM Koebel , "Strong, Thermally Superinsulating Biopolymer-Silica Airgel Hybrids by Cogelation of Silicic Acid with Pectin", Angewandte Chemie, 127, 48, 2015, pages 14490 to 14494.
  • the inorganic foams prepared using silica hybrid ore still have excellent fire protection properties and are hardly flame retardant.
  • silica aerogels are preferred over the use of silica hybrid orgains, since with the use of silica aerogels almost exclusively inorganic foams, in particular geopolymer foams, can be provided.
  • the thermal insulation of the resulting geopolymer foams can be significantly improved again.
  • the silicate-containing material usually has a weight-related ratio of vermiculite, in particular expanded vermiculite, and / or perlite, in particular expanded perlite, to silica airgel and / or Silica hybridiogel in the range of 100: 1 to 1:20, in particular 70: 1 to 1:15, preferably 50: 1 to 1:10, preferably 10: 1 to 1:10 on.
  • the silicate-containing material is a mixture of perlite, in particular expanded perlite, and a silica airgel and / or a silica Hybridaerogel.
  • the airgel in particular silica airgel, is incorporated in the pores of the vermiculite, in particular the expanded vermiculite, and / or the perlite, in particular the expanded perlite.
  • the mechanically very generally very sensitive airgel in particular silica airgel
  • the thermal insulation properties of the expanded perlite are again markedly increased.
  • the silicate-containing material is present in the form of composite particles, which are usually not completely dissolved by the geopolymer formation when selecting the aforementioned particle sizes, but partially retained and significantly improve the thermal insulation properties of the geopolymer foam.
  • the composite particles comprise vermiculite and / or perlite, in particular expanded vermiculite and / or expanded perlite, as a porous carrier material, the pores of the porous carrier material having at least one airgel.
  • the pores of the porous carrier material are filled with an airgel.
  • the properties of the perlite described below, in particular the expanded perlite, and / or the vermiculite, in particular the sewn vermiculite, and the airgel of the composite particles preferably also apply to the individual components in mixtures of the substances.
  • the composite particles usually have a bulk density in the range of 50 to 150 kg / m 3 , in particular 60 to 100 kg / m 3 , preferably 70 to 80 kg / m 3 , on.
  • the open porosity i. H. increases the volume of voids within the substrate associated with the environment to access a larger volume for storage of the airgel in the pores.
  • expanded perlite often has a very high proportion of closed pores, so that it is not possible to form an airgel in the pores of the porous carrier material, in particular of the perlite, or to store it there.
  • Reagent solutions which contain the educts for forming the aerogels do not enter the closed pores in the interior of the porous support material.
  • the composite particles are modified, in particular hydrophobicized, at least on their outer surface.
  • a surface modification in particular a hydrophobic treatment
  • the hydrophilicity and thus the absorption of water by the mineral carrier material can be limited or even completely avoided when using purely mineral carrier materials.
  • the surface modification in particular hydrophobing, is carried out as part of a surface modification or hydrophobing of the airgel. The hydrophobic properties are retained even when the composite particles are used as binders or binder components of a geopolymer and enable the production of moldings from inorganic foams having hydrophobic surfaces.
  • the surface of the porous carrier or airgel is changed so that the interaction between the surface and polar substances, such as alcohols or water, is minimized.
  • polar substances such as alcohols or water
  • all measures known and suitable from the prior art can be used.
  • a surface modification by means of silanes or siliconates or polysiloxanes a particularly effective hydrophobization of the porous support material can be achieved.
  • the surface modification, in particular the surface, preferably the outer surface, of the porous support materials is formed by polysiloxanes.
  • the polysiloxanes can be applied or formed by direct treatment of the surface with polysiloxanes or preferably by treatment with silanes and / or siliconates, which react by condensation reactions to form polysiloxanes.
  • the porous support material is in the form of particles. If the porous carrier material is already present in particle form, it is possible to fill the pores of the porous carrier material with the airgel as uniformly as possible.
  • the carrier material is in particle form, then it has proven useful if the particles of the porous carrier material have absolute particle sizes in the range of 10 to 5,000 ⁇ m, in particular 20 to 4,000 ⁇ m, preferably 30 to 3,000 ⁇ m, preferably 40 to 2,000 ⁇ m, particularly preferably 50 to 1, 500 ⁇ m.
  • the particle size of the porous carrier material is thus preferably smaller than the particle size of the composite particles, d. H. the airgel is located both in the pores of the porous support material and on its surface.
  • a finely divided carrier material is used, since as complete as possible penetration of the pores of the porous carrier material with the aerogels or their precursors used is possible.
  • the insulating properties, in particular the thermal conductivities, of the composite particles are decisively improved.
  • Pores with sizes in the aforementioned ranges play a major role in particular in the thermal conductivity of the materials, which is why it is important that just these pores are filled with airgel.
  • the airgel used to be incorporated into the pores of the porous support material virtually any airgel can be used. However, it has proven to be useful when silica aerogels are used, especially since they can build particularly good and durable bonds to the porous support materials. Aerogels having the properties described below can also be used as silicate starting material in the form of particles for the production of inorganic foams or geoploymeren.
  • the airgel usually has a bulk density of 0.025 to 0.30 g / cm 3 , in particular 0.03 to 0.25 g / cm 3 , preferably 0.04 to 0.22 g / cm 3 , preferably 0.05 to 0 , 15 g / cm 3 , on.
  • the bulk density of the airgel refers to an airgel, which was not formed directly on the porous support material, but under otherwise comparable conditions, but without support material.
  • the pore diameter of the airgel used can naturally vary within wide ranges. However, it has proven useful if the airgel has an average pore diameter of 1 to 300 nm, in particular 5 to 200 nm, preferably 10 to 150 nm, preferably 15 to 100 nm. In this connection, it may likewise be provided that the airgel has an average pore diameter of less than 300 nm, in particular less than 200 nm, preferably less than 150 nm, preferably less than 100 nm. Aerogels with average pore diameters in the aforementioned ranges have particularly good thermal insulation properties and at the same time are sufficiently mechanically stable.
  • the airgel is hydrophobized. It is thus preferred in the context of the present invention if both the airgel and the porous support material or the porous composite material are hydrophobized in order to avoid water absorption as possible.
  • the airgel has a contact angle with water of 100 to 170 °, in particular 130 to 165 °, preferably 140 to 165 °. It has proven useful if the airgel is formed on the porous carrier material and / or in the pores of the porous carrier material, preferably in the pores of the porous carrier material.
  • the airgel By forming the airgel on or in the porous carrier material, a particularly good penetration of the pores of the carrier material with the airgel is achieved, whereby on the one hand the thermal insulation properties of the resulting composite particles are optimized and on the other hand the airgel embedded in the pores is optimally protected and particularly good bonded to the surface of the porous support material.
  • the airgel is obtained by means of a sol-gel process.
  • the composite particles are obtainable by carrying out a sol-gel process for the preparation of silica aerogels in the presence of the porous support material.
  • the porous support material in a first process step, is subjected to a treatment to increase the open pore volume, and
  • Pores of the porous support material an airgel, in particular a silica airgel is formed.
  • the formation or production of the airgel on or in the porous carrier material permits a particularly intimate bond between carrier material and airgel, which is associated with particularly good heat-insulating properties of the resulting composite particles on the one hand and particularly good protection of the airgel on the other hand.
  • the formation of the airgel on or in the porous carrier material also achieves the greatest possible penetration of the porous carrier material with the airgel. It has been found that in the production of porous composite particles whose pores contain an airgel, significantly better results are obtained when the porous support material is subjected to a treatment to increase the open pore volume, ie the volume of pores which are in contact with the environment. is subjected. In this way, it becomes possible to reproducibly produce porous composite particles whose pores contain an airgel for improved thermal insulation, even on a technical and industrial scale.
  • the open pore volume of the porous support material in the context of this embodiment of the present invention is increased by mechanical and / or chemical, preferably mechanical, treatment of the porous support material.
  • porous support material in process step (a) is subjected to a grinding process, in particular in a ball mill.
  • the grinding of the porous support material, in particular in a ball mill represents a very simple and cost-effective variant for increasing the open pore volume. It has been shown that the grinding process not only crushes the particles of the porous support material and thus the specific surface area is increased, but that also by the mechanical action, a larger proportion of open pores for the subsequent formation of the airgel is available.
  • the porous support material in process step (a) is usually treated with a caustic, in particular an aqueous solution of an alkali metal and / or alkaline earth metal hydroxide, preferably an alkali metal hydroxide.
  • a caustic in particular an aqueous solution of an alkali metal and / or alkaline earth metal hydroxide, preferably an alkali metal hydroxide.
  • the alkali metal hydroxide is selected from sodium hydroxide and / or potassium hydroxide.
  • sodium hydroxide solution or potassium hydroxide solution are thus preferably used for the chemical treatment of the porous support material.
  • the solution comprises the alkali metal and / or alkaline earth metal hydroxide in amounts of 50 to 60 wt .-%, in particular 10 to 40 wt .-%, preferably 10 to 30 wt .-%, based on the solution.
  • the porous support material with the liquor at elevated temperature, in particular at temperatures in the range of 30 to 80 ° C, in particular 35 to 70 ° C, preferably 40 to 60 ° C, treated.
  • the treatment to increase the open pore volume of the porous support material is carried out chemically, it has proven useful if, following the actual process step (a), the chemical treatment agent, in particular the lye, is removed without residue. This is preferably done by repeated washing with demineralized water. In this connection, it has proven useful to carry out 1 to 10 washing operations, in particular 2 to 7 washing operations, preferably 3 to 5 washing operations.
  • a thorough removal of residues of the reagent used in the chemical treatment, in particular of potassium or sodium hydroxide is often necessary, since in the formation of airgel compliance with a certain pH range is critical. Alkaline residues not removed from the system prevent the setting of a stable pH value and can thus hinder or prevent the formation of the airgel.
  • porous carrier material is impregnated with the hydrosol.
  • the sol penetrates consequently in all (Open) pores of the porous support material and fills it as completely as possible.
  • the sol is converted to a gel.
  • This process is also referred to as "aging" and describes the process of polymerization or condensation reactions of the individual molecules of the sol to macromolecules, the so-called gel.
  • the gel obtained, in particular hydrogel must then be dried to airgel. This can be done, for example, in an autoclave under supercritical conditions. It is also possible to convert hydrogels into alkogels by solvent exchange, in particular of water to alcohol, which permits removal of the solvent under gentler conditions, but also in the supercritical region. The replacement of the solvent or the solvent mixtures by carbon dioxide and subsequent supercritical drying is possible. These variants are all technically possible, but expensive in terms of apparatus. In the context of the present invention, a simple removal of the solvent or dispersant at elevated temperature is possible, with very good results being obtained as well.
  • hydrogel is rendered hydrophobic.
  • the hydrogel is rendered hydrophobic by treatment, in particular chemical reaction, with at least one hydrophobizing agent.
  • a hydrophobing of the airgel allows an exchange of polar solvents, in particular water, for less polar solvents, which can then be removed under elevated temperature and / or reduced pressure, without drying in the supercritical region would be necessary.
  • supercritical drying of the hydrophobized airgel with carbon dioxide is also possible and represents a particularly rapid and gentle drying process.
  • a hydrophobing, in particular an in-situ hydrophobization, of the gel is carried out.
  • In-situ hydrophobization of the gel makes it possible to form the surface or the pore structure of the airgel in such a way that the interaction with polar substances, in particular water, is weakened such that removal of these polar substances by heating or use of vacuum becomes possible without destroying the airgel structure.
  • This makes it possible, when selecting suitable hydrophobizing agents, to perform the entire airgel synthesis in an aqueous medium.
  • a simultaneous hyrophobization of the surface of the porous support material is achieved by in-situ hydrophobing of the airgel.
  • the hydrophobizing agent is selected from phosphonates, sulfonates, substituted amines, silanes, polysiloxanes, siliconates, carboxylic acid derivatives, ethoxylates, polyethers, in particular silanes, polysiloxanes and siliconates, and mixtures thereof.
  • silanes, siliconates and polysiloxanes, preferably silanes and siliconates as a hydrophobing agent is a particularly uniform incorporation into the forming gel material, especially in silica hydrogels, possible, whereby an effective surface modification of all, ie, internal, surfaces of the gel can be achieved. This effect is especially pronounced in the case of silanes and siliconates.
  • silanes, siliconates and polysiloxanes are also outstandingly suitable for surface modification, in particular hydrophobing, of mineral or silicate-based porous support materials which are preferably used in the context of the present invention.
  • a polysiloxane when used as a hydrophobing agent, its chemical nature may vary widely. In this context, it is preferred if a polysiloxane having reactive functional groups, in particular selected from hydroxy functions, amines and / or carboxylic acids, is used.
  • silane is used as a hydrophobing agent for the hydrophobization of the gel, its chemical nature may likewise vary widely. However, particularly good results are obtained when a silane of the general formula I
  • n is 1 to 3, in particular 1 or 2, preferably 1;
  • Halide in particular chloride, bromide and / or iodide
  • OX with X hydrogen, alkyl, aryl, polyether and / or carboxylic acid derivative, in particular alkyl, preferably C to Cs-alkyl, preferably C 2 - to C 4 -alkyl; is used.
  • R 2 corresponds to OX, in particular ethoxy.
  • n 1 to 6, in particular 1 to 3, preferably 1;
  • R d- to Cio-alkyl and / or C 6 - to C15-A17I
  • alkali metal preferably sodium or potassium
  • the hydrophobing agent is selected from sodium methylsiliconate, Kaliummethylsiliko- nat, Natriumpropylsilikonat and Kaliumpropylsilikonat and mixtures thereof.
  • the hydrophobizing agent is potassium methyl silicate.
  • a solvent or dispersion medium is used.
  • the use of only one solvent in the course of the process greatly simplifies the process, since in the production of aerogels, in particular of silica aerogels, often several solvent changes must be made. On the one hand, a repeated solvent change leads to a greater expense in terms of process engineering, and on the other hand, the disposal of the solvent residues or dispersion agent residues is also made considerably more difficult since they often have to be collected and disposed of separately.
  • a single solvent in particular water is used.
  • solutions or dispersions which are used in process step (b) always have one and the same solvent, preferably water.
  • a polar solvent or dispersant in particular a polar protic solvent or dispersant, is used as the solvent or dispersant.
  • the solvent or dispersant is selected from the group of alcohols, in particular C 1 to C 8 alcohols, amines and water, in particular methanol, ethanol, propanol and water, preferably ethanol and water. It is particularly preferred if the solvent or dispersant is water.
  • An advantage of using water is that it is neither toxic nor environmentally objectionable. In addition, water is non-combustible and easy to dispose of.
  • process step (b) is preferably carried out in a plurality of process stages, wherein
  • the sol is converted to a gel, in particular a hydrogel.
  • the sol is prepared in a preparatory process stage upstream of process stage (i).
  • the sol is prepared from a solution or dispersion of at least one precursor.
  • the solution or dispersion contains the precursor in amounts of from 0.01 to 20% by weight, in particular from 0.1 to 15% by weight, preferably from 0.5 to 10% by weight, preferably 0.75 to 8 wt .-%, based on the solution or dispersion contains.
  • concentration ranges a particularly uniform polymerization or condensation of the sol molecules or particles is achieved, so that a particularly homogeneous gel, in particular hydrogel, is obtained.
  • the sol in particular the hydrosol, can be prepared from a large number of possible precursor compounds.
  • a hydrosol based on monosilicic acid and / or colloidal silica from an alkali metal silicate solution, in particular sodium silicate solution is prepared as a precursor.
  • the hydrosol is prepared from an alkali metal silicate solution, it has proven useful if the hydrosol is prepared by reacting the alkali metal silicate solution with mineral acids, in particular hydrochloric acid, nitric acid and / or sulfuric acid, or by ion exchange, preferably by ion exchange ,
  • ion exchange with a strongly acidic cation exchange resin in particular a sulfonated polystyrene resin, preferably a sulfonated divinylbenzene cross-linked polystyrene resin is performed.
  • a strongly acidic cation exchange resin in particular a sulfonated polystyrene resin, preferably a sulfonated divinylbenzene cross-linked polystyrene resin
  • ion exchangers in particular based on sulfonated divinylbenzene crosslinked polystyrene resins, leads to particularly pure hydrosols which are virtually free of salts, in particular interfering ions, which hinder the polymerization of the airgel or lead to defects in the gel.
  • the sol has a pH in the range of 1 to 6, in particular 2 to 4, preferably 2 to 3 after its preparation.
  • good results are obtained if the sol has a pH of less than 6, in particular less than 4, in particular less than 3.
  • the sol has a conductivity at 20 ° C. of at most 1 500 ⁇ / ⁇ , in particular at most 1 000 ⁇ / ⁇ , preferably at most 800 ⁇ / ⁇ .
  • particularly good results are obtained if the sol has a conductivity at 20 ° C.
  • process step (i) is carried out at room temperature or in a temperature range from 15 to 30 ° C, in particular from 20 to 25 ° C.
  • process step (i) under elevated pressure, in particular at an absolute pressure of 2 to 12 bar, in particular 3 to 10 bar, preferably 4 to 9 bar, preferably 6 to 8 bar.
  • step (i) is not performed permanently under elevated pressure.
  • the pressure is increased at intervals, in particular at 2 to 50 intervals, preferably 5 to 40 intervals, preferably 8 to 30 intervals, particularly preferably 10 to 20 intervals.
  • the pressure is increased starting from the ambient pressure or from normal pressure.
  • process step (i) is then carried out for a period of 1 to 60 minutes, in particular 5 to 50 minutes, preferably 10 to 40 minutes, preferably 20 to 30 minutes, at normal pressure or ambient pressure, in particular wherein the mixture of sol and porous particles is allowed to rest at normal pressure or ambient pressure.
  • the pH of the sol, in particular for gel formation is preferably in the range from 3.5 to 7, in particular 3.5 to 6.5, preferably 4 to 6, preferably 4 to 5 set.
  • a particularly uniform and controlled polymerization or condensation of the sol to gel, in particular of silica hydrosols to hydrogels takes place.
  • the adjustment of the pH in particular in process step (i) so this can be done in many ways.
  • particularly good results are obtained in the context of the present invention if the pH is adjusted by adding a base, in particular by adding sodium hydroxide solution, potassium hydroxide solution and / or aqueous ammonia solution, preferably aqueous ammonia solution.
  • the use of ammonia solution has the particular advantage that the resulting ammonium ions do not adversely affect the polymerization or condensation of the sol to the gel and, moreover, are not incorporated into the gel structure, for example sodium or potassium ions.
  • the pH is adjusted by adding acid, in particular a mineral acid, preferably hydrochloric acid. Adjustment of the pH by addition of acids may be necessary in particular if strongly basic hydrophobing agents are used.
  • the sol is brought into contact, in particular offset, with at least one hydrophobizing agent.
  • the hydrophobizing agent is used to hydrophobize the sol in the form of a solution or dispersion, in particular an aqueous solution or dispersion.
  • concentration of the hydrophobing agent in the solution or dispersion is concerned, this can vary within wide limits.
  • the solution or dispersion contains the hydrophobizing agent in amounts of 1 to 90% by weight, in particular 10 to 80% by weight, preferably 30 to 70% by weight, preferably 40 to 60% by weight. %, based on the solution or dispersion of the hydrophobing agent contains.
  • the sol is brought into contact with the hydrophobizing agent before the porous support material is brought into contact with the sol. It has been found that best results are achieved when the reaction mixture for the preparation of the gel, in particular the hydrogel is completed so far that only by raising the temperature and aging, the formation of the gel remains to wait before the prepared sol with the porous support material in Contact is brought.
  • the addition of the hydrophobing agent to the sol is preferably carried out for several minutes with slight shearing.
  • the adjustment of the pH takes place after the sol has been brought into contact with the hydrophobizing agent.
  • the adjustment of the pH is effected for 0.1 to 60 minutes, preferably 0.5 to 30 minutes, preferably 0.5 to 15 minutes, after the sol has been brought into contact with the hydrophobizing agent has been.
  • the porous support material is added to the sol, in particular with stirring.
  • the sol it is also possible to carefully add the sol to the porous support material.
  • the weight-related ratio of porous carrier material to hydrosol usually lies in the range from 5: 1 to 1:20, in particular from 3: 1 to 1:15, preferably from 1: 1 to 1:10, preferably from 1: 1 to 1: 5.
  • the duration in which the sol in process step (i) and the porous support material are brought into contact can vary in many areas. However, particularly good results are obtained when the sol and the porous support material are brought into contact for at least 1 hour, in particular at least 2 hours, preferably at least 3 hours, preferably at least 6 hours. Likewise, it has been proven, if the sol and the porous support material are brought into contact for at most 24 hours, in particular at most 18 hours, preferably at most 15 hours, preferably at most 12 hours. In this connection it can likewise be provided that the sol and the porous carrier material are brought into contact for a period of 1 to 24 hours, in particular 2 to 18 hours, preferably 3 to 15 hours, preferably 6 to 12 hours.
  • the duration of the contacting is dependent inter alia on the nature of the hydrophobizing agent used, the grain size of the porous support material and the pore structure, in particular the pore size distribution, the porous support materials.
  • the temperature at which - in particular in process step (i) - the sol and the porous carrier material are brought into contact this naturally can vary within wide ranges. However, particularly good results are obtained when the sol and the porous support material are brought into contact at room temperature. In this context, it has proven useful when the sol and the porous support material in the temperature range of 15 to 30 ° C, in particular 20 to 25 ° C, are brought into contact.
  • the contacting of the sol and the porous support material at room temperature has the advantage that the gelation proceeds only very slowly, so that the porous support material can be completely penetrated by the hydrosol. Too rapid gelation would prevent the sol or gel from penetrating far into the pores or filling smaller pores.
  • the sol and the porous carrier material are brought into contact under elevated pressure, in particular in process stage (i), in particular where the increased pressure is applied at intervals and preferably repeated pressure buildup is undertaken becomes. This ensures in particular that the porous carrier material is penetrated rapidly and completely by the sol.
  • the mixture is particularly preferred at temperatures in the range from 30 to 90.degree. C., in particular 35 to 85.degree. C., preferably 40 to 80.degree. C., particularly preferably 50 to 75.degree 60 to 70 ° C, is heated. Heating in process step (ii) enables rapid gel formation, in particular in the pores of the porous support material.
  • the mixture is kept at the elevated temperature for 1 to 100 hours, in particular 5 to 85 hours, preferably 10 to 70 hours, preferably 20 to 60 hours, particularly preferably 24 to 48 hours. It is also possible that the mixture is kept at the elevated temperature for less than 100 hours, in particular less than 85 hours, preferably less than 70 hours, preferably less than 60 hours, more preferably less than 48 hours.
  • the aforementioned reaction times are usually sufficient to achieve complete conversion of the sol to the gel.
  • the hydrogel obtained in process step (ii) is processed to an airgel, in particular wherein the obtained in process step (ii) a gel containing particles and then dried.
  • the drying of the gel to an airgel is concerned, this can - as stated above - be done in many ways.
  • the hydrogel-containing particles at temperatures in the range of 20 to 200 ° C, in particular 30 to 150 ° C, preferably 40 to 120 ° C, preferably 50 to 100 ° C, dried.
  • particularly good results are obtained when the hydrogel-containing particles are dried for a period of 8 to 72 hours, in particular 12 to 60 hours, preferably 24 to 48 hours. This is possible in particular even when using water as the sole solvent or dispersant, if a suitable hydrophobing of the airgel is carried out.
  • the thermal drying described above is carried out at normal or ambient pressure.
  • the particles having a hydrogel are particularly preferably subjected to supercritical drying with carbon dioxide.
  • the supercritical drying is compared to the purely ther- mix drying much less time consuming and faster to carry out, whereby the increased equipment cost can be compensated in economic terms.
  • the solvent or dispersing agent in particular water, is successively displaced or dissolved in the aerogels by carbon dioxide from the pores of the airgel and the carbon dioxide is converted into the gas phase after complete saturation of the gel with carbon dioxide.
  • the silicate-containing material is selected from expanded perlite, a mixture of expanded perlite and a silica airgel, the composite particles based on Perlite, ie expanded perlite whose pores have a silica airgel, and mixtures thereof.
  • the silicate-containing material is rendered hydrophobic, preferably by treatment with water repellents.
  • hydrophobizing agents based on silanes, siliconates or siloxanes, in particular silanes or siloxanes it is possible in this way to produce hydrophobicized inorganic foams, in particular geopolymer foams, with an extremely low proportion of organic, and thus combustible, radicals.
  • the solid inorganic foams or geopolymer foams obtained are nevertheless rendered hydrophobic in such a way that they can be used outdoors without any further treatment since, in contrast to other purely mineral-based systems, they have no capillary activity with regard to liquid water.
  • the same water repellents are used as previously described in connection with the composition particles.
  • the amount in which the composition contains the silicate-containing material can vary within wide ranges. However, it has proven useful if the composition contains the silicate-containing material in amounts of 10 to 70 wt .-%, in particular 15 to 60 wt .-%, preferably 20 to 50 wt .-%, based on the composition.
  • the composition according to the invention contains at least one alkaline activator.
  • the alkaline activator selected from inorganic hydroxides, alkali metal silicates and mixtures thereof.
  • the alkaline activator is an inorganic hydroxide
  • the inorganic hydroxide is selected from the group of lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide and mixtures thereof, preferably sodium hydroxide, potassium hydroxide and mixtures thereof. Particularly preferred in this context is when sodium hydroxide is used.
  • the alkaline activator is an alkali metal silicate
  • the alkali metal silicate is selected from lithium silicate, sodium silicate and / or potassium silicate, especially lithium silicate and / or potassium silicate.
  • the alkali metal silicate is present in the form of an aqueous solution of an alkali metal silicate, in particular as lithium water glass, sodium water glass and / or potassium water glass.
  • Particularly good results are obtained when the alkaline activator is lithium water glass and / or potassium water glass.
  • the alkaline activator is an aqueous solution of an alkali metal silicate
  • the aqueous solution of the alkali metal silicate in amounts of 10 to 50 wt .-%, in particular 15 to 40 wt .-%, in particular 20 to 30 wt .-%, based on the solution of the alkali metal silicate.
  • the alkaline activator has a weight ratio of inorganic hydroxide to aqueous solution of an alkali metal silicate in amounts of 10: 1 to 1:10, in particular 5: 1 to 1: 5, preferably 2: 1 to 1: 2 , preferably 1: 1, on.
  • alkaline activator preferably in the form of sodium hydroxide solution.
  • an inorganic hydroxide in particular sodium hydroxide
  • alkaline activator preferably in the form of sodium hydroxide solution.
  • the amount in which the composition contains the alkaline activator this may also vary widely depending on the particular conditions of use and the composition of the alkaline activator.
  • the Setting the alkaline activator in amounts of 0.1 to 35 wt .-%, in particular 0.5 to 30 wt .-%, preferably 1 to 28 wt .-%, preferably 1 to 25 wt .-%, based on the composition contains.
  • the composition of the invention has fibers, which in particular increased mechanical stability of the cured inorganic foam, in particular the Geopolymerschaums, can be achieved and beyond the foam stability of the uncured inorganic foam, in particular geopolymer foam, is improved. Particularly good results are obtained in this context when the fibers are inorganic, especially inorganic, mineral fibers.
  • the mechanical properties of the resulting inorganic foam, in particular of the geopolymer foam can be specifically improved by the use of inorganic or mineral fibers, while on the other hand the combustibility and the resistance of the cured foam are retained.
  • the fibers are selected from calcium silicate fibers, glass fibers, wollastonite fibers, carbon fibers, carbon nanotubes and mixtures thereof. Particularly good results are obtained in the context of the present invention, when the fibers are calcium silicate fibers.
  • the composition usually contains the fibers in amounts of from 0.1 to 20% by weight, in particular from 0.2 to 15% by weight, in particular from 0.5 to 12% by weight, preferably from 1 to 10% by weight, based on the composition.
  • the solvent or dispersant in the composition according to the invention is a water-containing solvent or dispersion medium, in particular water or a mixture of water and an organic solvent. In the context of the present invention, however, it is preferred if the solvent or dispersion medium is water.
  • the solvent or dispersing agent is a water-containing solvent and has an organic solvent
  • the organic solvent is selected from alcohols, in particular methanol, ethanol and / or isopropanol, acetone, dimethylformamide, ethyl acetate and mixtures thereof. Particularly good results are obtained in this context when the organic solvent is selected from methanol, ethanol, isopropanol and mixtures thereof.
  • the abovementioned organic solvents are miscible with water over a wide range and are also outstandingly suitable for dispersing or dissolving polar substances.
  • the solvent or dispersion medium is a mixture of water and an organic solvent
  • the solvent or dispersion medium contains water and organic solvent in a weight-based ratio of water to organic solvent in the range from 20: 1 to 1: 1, in particular from 18: 1 to 5: 1, preferably 15: 1 to 10: 1.
  • the composition to use the solvent or dispersion agent in amounts of from 10 to 90% by weight, in particular from 20 to 85% by weight, preferably from 30 to 80% by weight 35 to 75 wt .-%, based on the composition contains.
  • the composition contains at least one filler. If the composition contains a filler, then the filler is usually selected from hollow microspheres, expanded glass, magnesium oxide, titanium dioxide, quartz powder, inorganic pigments and mixtures thereof.
  • the composition contains the filler in amounts of 1 to 40% by weight, in particular 1 to 30% by weight, preferably 5 to 25% by weight, preferably 10 to 20% by weight on the composition, contains.
  • the composition contains, in addition to the silicate-containing material which forms part of the binder, no further fillers, the density of the obtained inorganic foam, in particular geopolymer foam, not to increase.
  • the composition contains at least one additive. If the composition contains an additive, this is usually selected from accelerators, retardants, complexing agents and mixtures thereof. Thus, additives used in the present invention are used primarily to adjust the curing rate of the binder.
  • the composition usually contains the additive in amounts of from 0.01 to 5% by weight, in particular from 0.05 to 2% by weight, preferably from 0.1 to 2% by weight on the composition.
  • the composition contains at least one surfactant.
  • surfactants enable the most even and gentle dispersion of, in particular, hydrophobicized materials, in particular hydrophobized silicate-containing materials.
  • the hydrophobized materials such as hydrophobized silicate-containing materials, are not completely and uniformly wetted by the usually aqueous solvent or dispersant.
  • the surfactant is selected from nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants and mixtures thereof. In this context, it is particularly preferred if the surfactant is selected from anionic surfactants, amphoteric surfactants and mixtures thereof.
  • the composition contains a surfactant
  • the composition contains the surfactant in amounts of 0.01 to 15 wt .-%, in particular 0.1 to 15 wt .-%, preferably 0.2 to 10 wt. -%, preferably 0.4 to 8 wt .-%, based on the composition contains.
  • the composition further comprises at least one hydrophobizing agent.
  • hydrophobizing agents makes it possible to obtain hydrophobic inorganic foams, in particular geopolymer foams, which have the advantageous properties of inorganic foams, in particular high mechanical stability and low thermal conductivity, but on the other hand avoid the typical detection of mineral-based materials, in particular high capillary water absorption ,
  • hydrophobizing agent is selected from silanes, siloxanes, silicates and mixtures thereof.
  • hydrophobizing agent is selected from silanes and siloxanes and mixtures thereof.
  • siloxane When a siloxane is used as a hydrophobing agent in this embodiment, its chemical nature may vary widely. In this context, it is preferred if a polysiloxane having reactive functional groups, in particular selected from hydroxy functions, amines and / or carboxylic acids, is used.
  • a siloxane having a weight average molecular weight M w in the range of 250 to 5,000 g / mol, in particular 300 to 3,000 g / mol, preferably 450 to 2,000 g / mol, particularly preferably 500 to 1 .500 g / mol is used.
  • silane is used as a hydrophobing agent in the context of the present invention, its chemical nature can likewise vary within wide limits. However, particularly good results are obtained when a silane of the general formula I
  • n is 1 to 3, in particular 1 or 2, preferably 1;
  • C 2 - to C 2 o-alkyl and / or C 6 - to C 20 -aryl preferably C 3 - to C 2 o-alkyl and / or C 6 - to C 2 o-aryl, preferably C 4 - to C 5 -alkyl and / or C 6 - to C 5 -aryl,
  • R 2 halide, in particular chloride, bromide and / or iodide,
  • OX with X hydrogen, alkyl, aryl, polyether and / or carboxylic acid derivative, in particular alkyl, preferably C to Cs-alkyl, preferably C 2 - to C 4 -alkyl;
  • R 2 corresponds to OX, in particular ethoxy.
  • composition comprises a siliconate as hydrophobing agent
  • hydrophobing agent is selected from sodium methylsiliconate, potassium methylsiliconate, sodium propylsiliconate and potassium propylsiliconate and mixtures thereof. Preference is given in this connection to the use of potassium methylsiliconate.
  • the composition contains the hydrophobizing agent in amounts of from 0.01 to 5% by weight, in particular from 0.02 to 2% by weight, preferably from 0.03 to 1% by weight. , in particular 0.04 to 0.5 wt .-%, based on the composition comprises.
  • the composition has at least one foam stabilizer.
  • a foam stabilizer in particular, the size of the individual foam bubbles can be adjusted and their stability can be improved. In this way it is prevented that the not yet cured foam collapses again and the foam bubbles are destroyed before the binder hardens.
  • the foam stabilizer is selected from olefin sulfonates, olefin sulfates, alkyl polyglycosides, cellulose derivatives and mixtures thereof. It is particularly preferred in this Context, when the foam stabilizer is an olefin sulfate, in particular lauryl sulfate.
  • the composition contains a foam stabilizer
  • good results are obtained if the composition contains the foam stabilizer in amounts of 0.001 to 5% by weight, in particular 0.001 to 2% by weight, preferably 0.002 to 1% by weight, preferably 0.003 to 0.5 wt .-%, based on the composition having.
  • the foam stabilizer very small amounts are usually sufficient in the context of the present invention in order to obtain sufficient stabilization of the as yet uncured inorganic foams.
  • the composition contains at least one foaming agent.
  • a foaming agent usually generates gas bubbles by chemical reaction, causing foam bubbles in the foam.
  • the foam is formed by introducing a gas, in particular an inert gas, such as, for example, argon or nitrogen, into the composition, i. without the use of a foaming agent.
  • a foaming agent is used, since especially by a uniform distribution of the foaming agent in the composition, a particularly homogeneous foaming can be achieved.
  • the composition contains a foaming agent
  • a foaming agent particularly good results are obtained when the foaming agent is selected from hydrogen peroxide, in particular 30% aqueous hydrogen peroxide solution, percarbonates, perborates and metals, in particular iron, zinc and aluminum and mixtures thereof.
  • the aforementioned metals are oxidized at the high pH values usually present in the composition with the formation of hydrogen.
  • the metals in particular iron, zinc and / or aluminum are present in the form of fine powders.
  • the composition contains a foaming agent, it has proven useful if the composition contains the foaming agent in amounts of from 0.1 to 20% by weight, in particular from 0.5 to 10% by weight, preferably from 1 to 8% by weight. , preferably 2 to 5 wt .-%, based on the composition contains.
  • the composition contains
  • (C) fibers in amounts of from 0.1 to 20% by weight
  • (H) at least one foaming agent in amounts of from 0.1 to 20 wt .-%, each based on the composition.
  • the silicate-containing material contains at least one aluminosilicate, in particular based on perlite, in particular expanded perlite.
  • the expanded perlite is hydrophobicized and / or in combination with an airgel, wherein it is particularly preferred if the airgel is present in the pores of the expanded perlite.
  • it is also particularly preferred according to this embodiment when the airgel is present in the pores of the expanded perlite and both the airgel and the perlite are hydrophobic.
  • FIG. 1 is a side view of a plate of a geopolymer foam prepared from the composition of the invention.
  • Fig. 2 is a perspective view of a plate of a geopolymer foam prepared with a composition of the invention.
  • Another object of the present invention - according to a z w e t e an aspect of the present invention - is the use of the above-described composition for producing an inorganic foam, in particular geopolymer foam.
  • Another object of the present invention - according to an aspect of the present invention - is the use of a previously described composition for producing a shaped body of an inorganic foam, in particular a geopolymer foam.
  • Another object of the present invention - according to one aspect of the present invention - is a process for the production of a shaped body of an inorganic foam, in particular a geopolymer foam, wherein
  • the composition prepared in process step (a) is converted into a mold and foamed.
  • Particularly good results are obtained in the context of the present invention, when the above-described inventive composition is prepared for the production of the inorganic foam.
  • it is preferred in this context if in a first process stage (i) of the first process step (a)
  • (V) optionally at least one surfactant, in particular in amounts of from 0.01 to 15% by weight,
  • (VI) optionally at least one hydrophobing agent, in particular in amounts of 0.01 to 5 wt .-%, and
  • the individual components are processed to form a homogeneous paste, in particular with the aid of a kneader.
  • the individual components are mixed as uniformly as possible in order to obtain the most homogeneous possible inorganic foam.
  • the mixture is treated with a foaming agent .
  • the foaming agent in amounts of 0.1 to 20 wt .-%, in particular 0.5 to 10 wt .-%, preferably 1 to 8 wt .-%, preferably 2 to 5 wt. %, based on the mixture is used.
  • the composition in the second process step (b) is foamed under the action of the foaming agent for a period of 10 minutes to 5 hours, in particular 30 minutes to 3 hours, preferably 1 to 2 hours or is allowed to foam.
  • the composition is not foamed with the aid of a foaming agent, but by the introduction of gases, in particular of inert gases, such as nitrogen and / or argon.
  • gases in particular of inert gases, such as nitrogen and / or argon.
  • the foaming is usually at ambient temperature, in particular at room temperature, d. H. in the temperature range of 20 to 25 ° C, carried out.
  • a foaming agent in process step (a)
  • the foam formation begins already in process step (a), but the complete formation of the foam takes place only after conversion into the mold for the production of the shaped body.
  • the foamed composition may additionally be cured in a third method step (c) following the second method step (b).
  • the inorganic foam obtainable with the composition according to the invention in particular geopolymer foam, experiences its final properties. particular its good thermal insulation properties and excellent mechanical strength.
  • composition is cured for a period of 1 to 96 hours, in particular 10 to 80 hours, preferably 15 to 70 hours, preferably 20 to 60 hours, preferably 24 to 48 hours.
  • temperatures at which the composition is cured can vary within wide ranges depending on the respective mixtures. However, it has proven useful when the composition at temperatures in the range of 40 to 120 ° C, in particular 50 to 100 ° C, preferably 60 to 90 ° C, cured. In this way, the curing can be accelerated significantly without the not yet fully cured foam is destroyed.
  • the shaped body is a plate, in particular an insulating board.
  • the plate has a thickness of 0.5 to 20 cm, in particular 1 to 15 cm, preferably 1, 5 to 12 cm, preferably 2 to 10 cm.
  • excellent thermal insulation materials can be provided, which moreover have excellent fire protection properties.
  • the foamed composition is transferred into a still liquid state, in particular by spraying or pouring.
  • Another object of the present invention - according to a fifth aspect of the present invention - a molding comprising an inorganic foam, in particular a Geopolymerschaum, available after the method described above and / or from the previously described composition.
  • the shaped body usually has a specific thermal conductivity at 25 ° C. in the range of 0.020 to 0.045 W / mK, in particular 0.022 to 0.043 W / mK, preferably 0.024 to 0.042 W / mK, preferably 0.025 to 0.040 W / mK, on.
  • the moldings obtainable with the composition according to the invention of the process according to the invention thus have excellent heat-insulating properties.
  • the density, in particular the dry density, of the molding according to the invention can naturally vary within wide ranges.
  • the shaped body has a dry density in the range of 50 to 250 g / l, in particular 70 to 220 g / l, preferably 80 to 200 g / l.
  • the shaped bodies according to the invention thus have a density which allows manual processing and handling even of larger plates.
  • the foamable mass prepared in step 1 is filled into open containers having a base area of 20 ⁇ 20 cm and a height of 5 cm. It is set to a filling height of 2 cm.
  • the composition can continue to foam in the containers.
  • the containers are placed in an oven for 1 hour at 40 ° C. While At this time, a stable foam is formed and a first crosslinking takes place.
  • the filled with the prepared inorganic foam containers are dried for 36 hours at 90 ° C in the oven. In this case, the final cross-linking takes place and dimensionally stable inorganic foams are obtained, which can easily be dissolved out of the molds.
  • the plates which are insulated from the molds and have a diameter of 20 x 20 x 2 to 5 cm, have lambda values of 28 mW / mK and a dry bulk density of 105 g / l.
  • FIG. 1 shows a side view of a previously prepared inorganic foam after curing and leaching from the mold. It is very nice to see a foam structure of closed-cell pores.
  • Fig. 2 shows a perspective view of another sample in which the inorganic foam has grown beyond the edge of the mold during resting in step 2. Again, the pore structure of the foam can be seen well.

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Abstract

La présente invention concerne une composition pour la préparation d'une mousse minérale, notamment d'une mousse géopolymère, et son utilisation pour la réalisation de corps moulés, notamment de plaques isolantes.
EP18716615.2A 2017-04-10 2018-04-10 Procédé de préparation de mousse minérale et son utilisation Withdrawn EP3609855A1 (fr)

Applications Claiming Priority (2)

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DE102017107732 2017-04-10
PCT/EP2018/059113 WO2018189151A1 (fr) 2017-04-10 2018-04-10 Procédé de préparation de mousse minérale et son utilisation

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CN109516730B (zh) * 2018-12-07 2021-07-16 华北理工大学 粉煤灰基矿物聚合物发泡自保温材料的制备装置和方法
CN110302422B (zh) * 2019-08-01 2020-07-07 山东大学 一种硅酸钙镁纳米空心微球改性的温敏水凝胶及其制备方法与应用
EP3950636A1 (fr) * 2020-08-06 2022-02-09 Zavod za Gradbenistvo Slovenije Composites légers activés par des alcalis à base de mousses activées par des alcalis et procédé de fabrication
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