EP3253818A1 - Procédé de production d'un matériau aérogel - Google Patents

Procédé de production d'un matériau aérogel

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Publication number
EP3253818A1
EP3253818A1 EP16703515.3A EP16703515A EP3253818A1 EP 3253818 A1 EP3253818 A1 EP 3253818A1 EP 16703515 A EP16703515 A EP 16703515A EP 3253818 A1 EP3253818 A1 EP 3253818A1
Authority
EP
European Patent Office
Prior art keywords
gel
sol
solvent
airgel
mold
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Withdrawn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
EP16703515.3A
Other languages
German (de)
English (en)
Inventor
Matthias Koebel
Lukas Huber
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.)
Eidgenoessische Materialprufungs und Forschungsanstalt EMPA
Original Assignee
Eidgenoessische Materialprufungs und Forschungsanstalt EMPA
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 Eidgenoessische Materialprufungs und Forschungsanstalt EMPA filed Critical Eidgenoessische Materialprufungs und Forschungsanstalt EMPA
Publication of EP3253818A1 publication Critical patent/EP3253818A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/20—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored
    • B29C67/202—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored comprising elimination of a solid or a liquid ingredient
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0004—Preparation of sols
    • B01J13/0026—Preparation of sols containing a liquid organic phase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0004—Preparation of sols
    • B01J13/0039—Post treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0052—Preparation of gels
    • B01J13/0065—Preparation of gels containing an organic phase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0091—Preparation of aerogels, e.g. xerogels
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/145—Preparation of hydroorganosols, organosols or dispersions in an organic medium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/155—Preparation of hydroorganogels or organogels
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/157—After-treatment of gels
    • C01B33/158—Purification; Drying; Dehydrating
    • C01B33/1585—Dehydration into aerogels
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/16—Preparation of silica xerogels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/30—Materials not provided for elsewhere for aerosols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0058—Liquid or visquous
    • B29K2105/0061—Gel or sol
    • 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
    • C01P2006/16—Pore diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
    • C08J2205/026—Aerogel, i.e. a supercritically dried gel
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
    • C08J2205/028—Xerogel, i.e. an air dried gel
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/042—Nanopores, i.e. the average diameter being smaller than 0,1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08J2361/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • the invention relates to a method for the simplified production of an airgel material according to the preamble of claim 1, depending on a precursor product according to the preamble of claim 13 or 14, and an airgel plate according to the preamble of claim 15th
  • Aerogels are increasingly being used in highly specialized niche markets, such as in building technology as high-insulation materials or in the aerospace and marine industries, as well as in high-tech applications. Aerogels are available in various designs and materials. The industrialization of aerogels and xerogels has been experiencing a significant boom since the turn of the millennium.
  • silicate-based aerosols Si0 2
  • the best-known forms include granules and monolithic plates.
  • airgel based on at least partially crosslinked polymers are well known, such as the resin-based resorcinol-Formalhedyd [Pekala et. al, J. Mater.
  • a critical step in the production of airgel materials is the drying of a wet gel.
  • previously used for silicate-based gels only supercritical drying, ie drying from a supercritical fluid (typically lower alcohols or later C0 2 ).
  • a supercritical fluid typically lower alcohols or later C0 2
  • solvent drying subcritical drying of hydrophobic gels materials with quasi-identical properties as the supercritically dried aerogels can be produced.
  • WO 1998/005591 A1 relates to a production process for organically modified, permanently hydrophobic aerogels.
  • the SiO 2 gel is formed starting from a waterglass solution by means of neutralization by acid or after the formation of a silica sol by ion exchange and subsequent base additions.
  • the pH during gelation is typically in the range between 4 and 8.
  • the wet gel is washed in an organic solvent until the water content is below 5% and then hydrophobed. Drying under atmospheric pressure by evaporation of the solvent leaves the airgel material as granules back.
  • the dimension or shape of the gel bodies are not further described in this publication. Also not further described are the washing and hydrophobing times wherein the grinding of the solidified gel is mentioned by name.
  • aerogels are prepared either as granules or thin mats or plates having a shortest dimension or thickness of less than 2 cm and then glued in one or more refining steps.
  • thicker insulation boards or other, partly functional composite materials can be produced.
  • US 2014/0004290 A1 and US 2014/0287641 A1 describe such production methods of composite materials starting from airgel as a base material by means of adhesive technology, the main focus being on improved mechanical properties and processability.
  • WO 2012/062370 A1 describes a similar process, wherein the adhesive component used is a resorcinol-formaldehyde resin system in xerogel form.
  • the dimensionality of the gel is caused by fragmentation before the solvent exchange by mechanical processes or by gelling in drop form in the drop tower.
  • the first method has become established in the industry, as it allows a significantly better space utilization in the system.
  • the state of the art is the gelation of a gel carpet on a moving belt and dismemberment of the aged gel carpet over a rather.
  • the shearing forces occurring there have the consequence that in addition to the desired granules in the size range of 1 to 5 mm, a considerable amount of the gel remains as fine fraction ⁇ 1 mm. This fine fraction can amount to up to 30% of the total yield and is produced in the production as an inferior product.
  • the object of the invention is to provide an improved process for the production of airgel materials. Further objects are to provide precursor products for the production of an airgel plate as well as a new airgel plate.
  • the process according to the invention for producing an airgel material having a porosity of at least 0.55 and an average pore size of 10 nm to 500 nm comprises the following steps:
  • the mold used in step b) is provided with a plurality of channel-forming elements, which are designed so that the sol filled in the mold over a predetermined, defined in channel direction of the elements minimum length L everywhere a maximum of a distance X of one Channel-forming element is removed, with the proviso that X ⁇ 15 mm and L / X> 3.
  • the sol filled in the mold is - over a predetermined, defined in channel direction of the elements minimum length L - anywhere a maximum of a distance X from a channel-forming Element removed. Considering a cross-section perpendicular to the channel direction, this means that no point in the sol is further than X from the nearest channel-forming element.
  • maximum distance should not be misunderstood as absolute maximum distance. Rather, it is the maximum of all shortest distances. Stated another way, the “maximum distance” in the sense of the present invention is the shortest distance between the innermost point of a cross-sectional area and the interface defined by the channel-forming element.
  • the maximum distance X depends on the shape and in certain cases also on the mutual spacing of the channel-forming elements.
  • the corresponding relations result from known relationships of planar geometry. For complicated and / or irregular shapes, the maximum distance must be determined numerically, if necessary.
  • the formation of an airgel starting from a sol is basically known and includes in particular a step of solvent exchange and / or a step of chemical modification.
  • the inventive arrangement a much better accessibility of the gel is ensured for supplied solvent and / or reagent. This results in a shortening of the process duration and, consequently, an improvement of the process economy.
  • the diffusion-limited solvent exchange processes can be greatly accelerated.
  • a silicate-based gel slab of 50 nm average pore size and 5 mm thickness can be mixed in one Alcohol-based solvent mixture at room temperature within a few hours completely (ie to the depth of the plate) replace.
  • the inventive method allows a much simpler and faster production of airgel materials compared to the previously known methods by controlled structuring of the gel body, whereby process efficiency and throughput can be significantly increased.
  • various materials come into question for the production of the casting mold, ie for the outer housing as well as for any pipe or rod elements that may be used. These include, for example, polyolefins, in particular polypropylene or polyethylene, but also glass or ceramic and metals such as stainless steel. In any case, the choice of materials will require compatibility with the media used (acids, bases, solvents).
  • the channel-forming elements are configured as a bundle of mutually parallel tubes, wherein the mold for the sol is formed by the interiors of the tubes, and wherein the solvent exchange d) and / or the chemical modification of the gel e) by a gap formed between the gel and the channel-forming element as a result of shrinkage during the aging of the gel c) is carried out directly in the casting mold, preferably by forced convection of supplied solvent or reaction agent.
  • the maximum distance X is to be determined by considering the distance of a point located inside the tube from the inner surface of the respective tube element.
  • different shapes of the pipe cross-section can be used.
  • these are tubes with a circular or quadrangular, in particular square inner profile.
  • all tubes have an identical cross section, which is preferably hexagonal. This makes it possible to build compact tube bundles with little dead volume between the individual tubes.
  • the optionally solvent-exchanged and optionally chemically modified gel is removed in the form of gel bars from the mold and then the drying f) is carried out by means of subcritical drying.
  • the individual tie rods disintegrate into smaller fragments, advantageously an airgel or xerogel granules with minimal fines.
  • the channel-forming elements are configured as a bundle of mutually parallel rod elements, wherein the mold for the sol is formed by a space located between the rod elements, and wherein the rod elements after gelation and aging in the channel direction from the The mold can be pulled out in such a way that a plate-shaped gel body with continuous channels is formed.
  • the solvent exchange d) and / or the chemical modification of the gel e) is carried out by applying solvent or reagent. It is understood that in this type of arrangement, the rod elements act as placeholders for subsequently formed channels in the aged gel. Accordingly, the maximum distance X is to be determined by considering the distance of a point lying between the rod elements from the outer surface of the nearest rod element.
  • rod elements In principle, different cross-sectional shapes can be used for the rod elements.
  • these are rods with a circular or quadrangular, in particular square or hexagonal outer profile.
  • the application of solvent or reagent to a previously formed plate-shaped gel body after removal of the same is carried out of the mold.
  • the rod elements are attached to one end of a removable bottom surface or top surface of the mold and can be easily pulled out of the gel body after aging of the gel.
  • a chemical modification of the aged gel is performed, wherein the chemical modification is a hydrophobing initiated by the release or addition of at least one hydrophobizing catalyst co-operating with the hydrophobizing agent;
  • the drying of the gel is carried out by subcritical drying.
  • Activation of the hydrophobing agent in this case can be triggered by the addition of a small amount, typically of the order of 10-20% of the gel volume, of an acidic hydrophobing catalyst dissolved in a compatible solvent mixture.
  • a small amount typically of the order of 10-20% of the gel volume
  • the hydrophobizing agent must also diffuse into the depth of the gel material, wherein the shape and shape of the gel body affect the time required for the hydrophobing step sensitively.
  • the introduction of small amounts of hydrophobing catalyst, measured on the gel volume is significantly easier and more economical to implement by targeted structuring of the gel.
  • the hydrophobicization is an acid-catalyzed process, ie by H + and H 3 0 + ions is catalyzed
  • the process running under slightly basic conditions gelling process and the process running under acidic conditions hydrophobicity can approximately process clean time in one and the same organogel be carried out separately from each other.
  • the process is characterized by a significantly reduced solvent consumption.
  • the prior art typically requires more than 2 times the gel volume of solvents.
  • Alcoholic solvent mixture is understood in the present context to mean a mixture which consists essentially of one or optionally several their alcohols (especially ethanol, methanol, n-propanol, isopropanol, butanols) and a suitable proportion of water repellents. It is understood that the mixture may also contain a small amount of water, unavoidable impurities, and optionally, as explained elsewhere, certain additives.
  • a hydrophobizing agent is understood in a manner known per se to mean a component which makes a surface hydrophobic, ie. gives water-repellent properties.
  • the hydrophobing agent or the hydrophobing process refers primarily to the silicate gel and the modifications of its properties.
  • the advantageous embodiment comprises the gelling of an alkoxide-based silicate sol in an alcoholic solvent mixture which contains at least one catalytically activatable hydrophobizing agent.
  • the gelation process is initiated by adding a dilute base such as ammonia.
  • a dilute base such as ammonia.
  • the gel thus formed which may also be referred to as "organogel” is subjected to an aging process.
  • the optionally aged gel now contains all the components required for hydrophobicization and subcritical drying according to WO 2013/053951 A1 or, more precisely, a pore liquid with the main components alcohol and activatable hydrophobizing agent, with the exception of the hydrophobizing catalyst.
  • HMDSO hexamethyldisiloxane
  • the volume fraction of the hydrophobizing agent in the sol is from 20 to 50%, in particular from 25% to 40% and in particular from 34% to 38%.
  • the hydrophobing catalyst trimethylchlorosilane (TMCS) and / or HCl in alcoholic solution or a mixture of these two components, which is dissolved in a dilute solvent mixture consisting of a similar or identical composition as the pore liquid and in the Liquid phase is brought into contact with the gel.
  • TMCS trimethylchlorosilane
  • HCl alcoholic solution or a mixture of these two components, which is dissolved in a dilute solvent mixture consisting of a similar or identical composition as the pore liquid and in the Liquid phase is brought into contact with the gel.
  • the amount of catalyst-loaded solution measured in terms of gel volume should be kept as small as possible in order to maintain the advantage of the lowest possible solvent balance.
  • the catalyst-containing solution in a batch process or continuous process makes up a volume fraction or volume flow rate fraction of not more than 30%, in particular not more than 10%.
  • HCl nitric acid
  • the gel is a polymer-based gel, preferably a polyisocyanate-based gel.
  • a first precursor product for producing an airgel plate which consists of an airgel plate provided with slots according to the invention.
  • the elongated holes can as perpendicular through the plane of the plate extending through channels or as corresponding blind holes with only one-sided opening.
  • the elongated holes can in particular be produced by a method described above (claim 5), wherein the hole dimension is essentially defined by the external dimensions of the rod elements used. However, the shrinkage during aging of the gel should be taken into account.
  • a second precursor product for producing an airgel plate which consists of a plurality of airgel rods.
  • These rods can be produced in particular by a method described above (claim 2), wherein the outer mass of the airgel rods in the way is significantly defined by the internal dimensions of the pipe elements used.
  • the shrinkage during aging of the gel must also be taken into account here.
  • an airgel plate which comprises a first precursor product in the form of an airgel plate, in the slots of which appropriately shaped airgel rods of a second precursor product are inserted or pressed.
  • the same material can be used for the airgel plate and for the airgel rods.
  • the plate element with the advantages of the method according to the invention can first be produced.
  • the ultimately undesirable in the produced airgel plate slots, which would result in a significant reduction in heat insulation capacity, can be eliminated by the airgel rods used.
  • the airgel rods used are made of a different material, which in particular allows an improvement of the mechanical and thermal properties of the final product.
  • formed from a silicate-based gel, provided with continuous slots airgel plate with airgel rods are made of a Polyurethanangel.
  • Fig. 1 is a schematic representation of distance relations in different
  • Fig. 1 illustrates some basic geometric shapes and relations.
  • the innermost point furthest from the next channel-forming element is represented by a cross.
  • the maximum distance X defined in the sense explained above, ie the shortest distance of the innermost point from the next channel-forming element, is also shown.
  • FIGS. 1 a to 1 e show a situation in which the tube components 2 used as channel-forming elements as well as a sol or a gel 4 formed therefrom, still unaged, can be seen.
  • these figures also show a solvent or a reaction agent 5 for the steps d) or e) described at the outset, which after penetration of the pipe components is to penetrate into the previously aged gel.
  • Figures 1f and 1g show another situation in which channeling in an aged gel material 6 has already been accomplished by rod members; the rod elements were removed and circular channels 7 were formed into which the reagent 5 was filled.
  • FIGS. 2a to 2d initially shows in FIG. 2a a bundle of circular cylindrical tubes 2, which initially is still empty and in particular stands on the bottom of a boundary shell (not shown).
  • the tube bundle is filled with a sol or an unaged gel 4 formed therefrom.
  • aging of the gel has occurred with concomitant shrinkage, whereby between the cylindrical rods 6 of aged gel and the tubes 2 a filled with Synereseorganizkeit gap-like gap 8 has arisen.
  • the tie rods 6 are shown with partially pulled up tubes 2. These are now ready for further processing.
  • FIGS. 3 a to 3 e initially shows in FIG. 3 a a cuboid boundary shell 10 with a bottom plate 12 which is provided with a nail rod arrangement with an arrangement of cylindrical rods 14.
  • the boundary shell contains a filled sol or a gel 4 which is still unaged, and whose level is just below the rod tips.
  • Fig. 3c an aging of the gel with concomitant shrinkage has occurred, whereby between the cylindrical rods 14 and the plate-shaped body 16 of aged gel each have a gap 8 is formed.
  • FIG. 3 a cuboid boundary shell 10 with a bottom plate 12 which is provided with a nail rod arrangement with an arrangement of cylindrical rods 14.
  • all rods are about the same length.
  • the boundary shell contains a filled sol or a gel 4 which is still unaged, and whose level is just below the rod tips.
  • Fig. 3c an aging of the gel with concomitant shrinkage has occurred, whereby between the cylindrical rods 14 and the plate-shaped body 16 of aged
  • a cover part 18 of the boundary shell has been lifted up, whereby a bottom part 20 of the boundary shell with the gelatinous gel body 16 located therein is exposed.
  • the aged gel body 16 provided with through-holes 22 has been lifted out of the bottom part 20 provided with the rods 14 and is ready for further processing.
  • a silica sol in alcohol is activated by adding dilute ethanolic ammonia solution at room temperature.
  • the sol contains as secondary component 2% aminopropyltnethoxysilane (APTES) which is added together with the ammonia.
  • APTES aminopropyltnethoxysilane
  • APTES aminopropyltnethoxysilane
  • a silica sol is produced in a continuous process and diluted with HMDSO from a 10% Si0 2 content to 6.6%.
  • this sol is activated at a temperature of 35 ° C. by admixing dilute ammonia solution.
  • 200 I container already which are provided with a cavity fully filling, honeycomb-like insert.
  • the honeycomb shape has a wall thickness of 0.5 mm and a cell diameter of 8mm.
  • the containers are now filled individually and hermetically sealed by means of a lid, after which they are stored for 18 h at 70 ° C. During this time, the mixture gels and gel bodies formed in the honeycomb channels age, shrinking slightly.
  • the density of the aerogranular granules thus obtained is 0.096 g / cm 3 and the heat conductivity of the bed 17.8 mW / m K.
  • the inserts are used in a large-scale process not in individual containers but in an elongated process tunnel, and thus pass through the entire production process on a conveyor belt drive with the gel, whereby the syneresis liquid is removed from the bottom in a certain area and shortly thereafter the hydrophobizing catalyst is metered from the ceiling through an injection system.
  • the gel body is then removed from the mold and transferred to an autoclave.
  • the pore liquid contained in the gel body is then extracted in this autoclave by means of supercritical C0 2 and the gel is then dried supercritically.
  • a polyurethane orogel perforated plate of 273 mm thickness remains.
  • mixtures 1 and 2 consist of a solution of resorcinol with a small addition of acid catalyst and a dilute, aqueous formaldehyde solution.
  • a suitable solvent medium such as acetone or ethanol
  • an airgel plate A prepared in a continuous flow reactor silica sol is adjusted to a silicate content of 5.7% (measured as Si0 2 ).
  • the sol is provided with ammonia as a gelation catalyst and placed in a dish form containing a nail-board-like insert.
  • the filling height H of the mixed solution is also 70 mm so that the tips of the bars are barely covered.
  • the sol is covered with a second plate (cover plate, not shown).
  • cover plate After gelation and aging of the gel, the cover plate is removed, the gel plate removed from the mold and the insert carefully dissolved out.
  • the through holeed gel plate is transferred to a slow speed (7.3 m / h) conveyor belt.
  • This gel body is sprayed from above with a mixture of fresh hydrophobing agent mixture consisting of 85% HMDSO and 15% hydrochloric acid dilute ethanol, wherein the build-up on the plate excess liquid sucked continuously through the gas and liquid permeable conveyor belt membrane material by means of pump at low vacuum becomes.
  • the plate After 6 hours of exchange and hydrophobization time at 75 ° C., the plate is dried by means of solvent drying at 150 ° C.
  • the replacement and hydrophobicization time to be expected under otherwise identical conditions is approximately 25 times longer, ie. 150 h, which is unsustainable for an industrial process.
  • the airgel plate produced in the above example and produced according to the method according to the invention is filled with aerosol cylinders suitable for the holes.
  • the gel cylinders required for this purpose were previously prepared specifically from a suitably selected polyurethane gel formulation and then dried overcored from C0 2 .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Mechanical Engineering (AREA)
  • Silicon Compounds (AREA)
  • Colloid Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

L'invention concerne un procédé de production d'un matériau aérogel ayant une porosité d'au moins 0,55 et une taille moyenne de pores de 10 nm à 500 nm. Le procédé comprend les étapes suivantes: a) préparation et éventuellement activation d'un sol ; b) introduction du sol dans un moule (10) ; c) gélification du sol de façon à former un gel, puis vieillissement du gel ; au moins une des étapes d) et e) suivantes : d) remplacement du fluide des pores par un solvant ; et e) modification chimique du gel (6) vieilli et dont le fluide des pores a été éventuellement remplacé par un solvant, au moyen d'un réactif ; puis f) séchage du gel, de façon à former le matériau aérogel. Le moule utilisé à l'étape b) est muni d'une pluralité d'éléments formant des canaux (2) qui sont conçus de telle sorte que le sol introduit dans le moule est éloigné en tous points au maximum d'une distance X d'un élément formant un canal, sur une longueur minimale L donnée, définie dans la direction des canaux des éléments, avec X < 15 mm et L/X > 3.
EP16703515.3A 2015-02-04 2016-02-04 Procédé de production d'un matériau aérogel Withdrawn EP3253818A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP15153869.1A EP3053952A1 (fr) 2015-02-04 2015-02-04 Procédé de production d'un matériau aérogel
PCT/EP2016/052359 WO2016124680A1 (fr) 2015-02-04 2016-02-04 Procédé de production d'un matériau aérogel

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EP3253818A1 true EP3253818A1 (fr) 2017-12-13

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EP16703515.3A Withdrawn EP3253818A1 (fr) 2015-02-04 2016-02-04 Procédé de production d'un matériau aérogel

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EP (2) EP3053952A1 (fr)
JP (1) JP6936147B2 (fr)
KR (1) KR20170113606A (fr)
CN (1) CN107428545B (fr)
AU (1) AU2016214370B2 (fr)
WO (1) WO2016124680A1 (fr)

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KR20190020748A (ko) * 2016-06-17 2019-03-04 헨켈 아게 운트 코. 카게아아 폴리실록산 기반 에어로겔
CA3030383C (fr) 2016-07-29 2023-02-21 Evonik Degussa Gmbh Procede pour la fabrication d'un materiau hydrophobe, thermo-isolant
EP3529301B1 (fr) 2016-10-24 2023-11-29 Blueshift Materials, Inc. Aérogel polymère organique renforcé par des fibres
JP7050810B2 (ja) 2017-01-18 2022-04-08 エボニック オペレーションズ ゲーエムベーハー 造粒体状断熱材およびその製造方法
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DE102017209782A1 (de) 2017-06-09 2018-12-13 Evonik Degussa Gmbh Verfahren zur Wärmedämmung eines evakuierbaren Behälters
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EP3758921A1 (fr) * 2018-03-01 2021-01-06 Basf Se Procédé de fabrication d'un corps constitué d'un matériau poreux
EP3762137A1 (fr) 2018-03-05 2021-01-13 Evonik Operations GmbH Procédé de production d'un matériau aérogel
EP3597615A1 (fr) 2018-07-17 2020-01-22 Evonik Operations GmbH Matériau d'oxyde mixte granulaire et composition d'isolation thermique sur sa base
MX2021000623A (es) 2018-07-17 2021-04-13 Evonik Operations Gmbh Composicion de aislamiento termico a base de granulados de silice, procesos para su preparacion y usos de la misma.
JP7086266B2 (ja) 2018-07-18 2022-06-17 エボニック オペレーションズ ゲーエムベーハー シリカをベースとする成形断熱体を周囲圧力で疎水化する方法
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CN112976432B (zh) * 2021-01-26 2023-03-31 广东千大新材料有限公司 一种自脱落补形式气凝胶复合材料的制备方法

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CN107428545B (zh) 2023-04-14
US20180001576A1 (en) 2018-01-04
JP6936147B2 (ja) 2021-09-15
EP3053952A1 (fr) 2016-08-10
JP2018511663A (ja) 2018-04-26
WO2016124680A1 (fr) 2016-08-11
AU2016214370A1 (en) 2017-08-31
KR20170113606A (ko) 2017-10-12
CN107428545A (zh) 2017-12-01
AU2016214370B2 (en) 2020-04-09

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