A complex containing aerogel particles

Abstract

The present invention relates to a composite comprising two or more layers, the composite comprising a layer (LA) having a thickness in the range of 0.1 to 4 mm and mainly comprising aerogel particles having a diameter in the range of 0.1 to 4 mm before compression, one adjacent binder layer (LB) having a thickness in the range of 0.01 to 1 mm, optionally a support layer (LC) adjacent to the binder layer (LB) and having a thickness in the range of 0.01 to 3 mm, and optionally a second adjacent binder layer (LB') and a support or coating layer (LC') located on the second side of the particle layer (LA), wherein the aerogel particle layer (LA) comprises both binder particles and aerogel particles, and optionally a portion of the support layer (LC), and includes a layer section (LA-1) located adjacent to the binder layer (LB) and having a thickness in the range of 0.01 to 1 mm, and the aerogel particle layer (LA) further comprises a binder-free layer section (LA-2) having a thickness of 0.05 mm or more. The present invention further relates to a method for manufacturing the composite, and to a method for using the composite according to the present invention as an insulating material in buildings and construction, home appliances, thermologistics, cryogenic applications, automotive applications, infrastructure applications, marine applications, oil and gas applications, clothing, or as a heat shield or heat transfer inhibitor in batteries.

Description

[Technical Field]

[0001] The present invention relates to a composite comprising two or more layers, the composite comprising a layer (LA) having a thickness in the range of 0.1 to 4 mm and mainly comprising aerogel particles having a diameter in the range of 0.1 to 4 mm before compression, one adjacent binder layer (LB) having a thickness in the range of 0.01 to 1 mm, optionally a support layer or coating layer (LC) having a thickness in the range of 0.01 to 3 mm, adjacent to the binder layer (LB) and located on its second side, and optionally a second adjacent binder layer (LB') and support layer or coating layer (LC') located on the second side of the aerogel particle layer (LA), wherein the aerogel particle layer (LA) comprises both binder particles and aerogel particles, and optionally a portion of the support layer (LC), and includes a layer section (LA-1) located adjacent to the binder layer (LB) and having a thickness in the range of 0.01 to 1 mm, and the aerogel particle layer (LA) further includes a binder-free layer section (LA-2) having a thickness of 0.05 mm or more. The present invention further relates to a method for manufacturing the composite, and to a method for using the composite according to the present invention as an insulating material in buildings and construction, home appliances, thermologistics, cryogenic applications, automotive applications, infrastructure applications, marine applications, oil and gas applications, clothing, or as a heat shield or heat transfer inhibitor in batteries. [Background technology]

[0002] Aerogel materials are known in the prior art due to their superior thermal insulation properties. Commercially available aerogel materials are used as super-thermal insulation materials in fields such as construction and transportation.

[0003] Almost all aerogel materials currently on the market are based on inorganic silica aerogels in the form of aerogel fiber blankets, aerogel particles, or aerogel powders. Aerogels typically require hydrophobicization, such as with silane additives, to achieve sufficient resistance to water and moisture in their applications. Inorganic silica aerogels, especially those dried using supercritical CO2, and particularly hydrophobic silica aerogels, have low mechanical strength and cause dust generation and release throughout all stages of use, including transportation, installation, use, and disposal. This dust release makes handling and integration of silica aerogels difficult.

[0004] Some applications require aerogel composites or blankets of varying thicknesses. Electric vehicle (EV) batteries, in particular, require extremely thin composites or blankets, often less than 2 mm thick. While aerogel blankets can be cut into thin layers, the minimum thickness is limited by the fiber carrier. If the aerogel is not adequately retained within the fiber structure, excessively thin layers will result in loss of contained aerogel. An alternative method involves mixing and compressing aerogel powder with fibers to form a composite. One solution at the current level of technology is to encapsulate the resulting composite or blanket to prevent dust release into the surrounding environment. This avoids handling difficulties or adverse effects on the overall system function. Especially in transportation applications, typical vibrations during use can cause dust generation and release. Whether encapsulated or not, vibrations can displace the aerogel material within the blanket or composite, potentially leading to material inhomogeneity within the composite and impairing its function. This is a particular problem in thermal shielding used for cell connections in electric vehicle batteries. This is because such malfunctions could compromise the safety of electric vehicles in the event of thermal runaway.

[0005] For example, EP0850206B1 describes a composite made from small diameter (<0.5 mm) aerogel particles and different physical or reactive binder systems. The binder and aerogel are mixed, and the mixture is compression molded. The binder forms a continuous phase, reducing thermal conductivity through thermal bridges. EP0854892B1 describes an aerogel sheet based on a wet process requiring a drying step.

[0006] EP0963358B1 describes a composite in which aerogel particles compressed with a thermoplastic binder are combined in a sandwich structure. The binder and aerogel are mixed, and the mixture is compression molded. The binder forms a continuous phase, reducing thermal conductivity through thermal bridges. WO2016053399A2 describes a thin aerogel blanket based on a typical aerogel manufacturing process based on supercritical drying using a thin aerogel blanket. This process requires supercritical drying of the aerogel inside the blanket.

[0007] US9097377B2 describes a thin aerogel composite based on a thin aerogel blanket encapsulated in a laminate foil layer to prevent dust release. This requires the manufacture of the aerogel blanket, cutting into thinner blankets, and lamination processes.

[0008] Another drawback of existing aerogel materials, such as silica aerogel blankets, stems from their costly manufacturing processes. Most aerogel materials require a supercritical drying process to maintain the desired pore structure of the material in the wet gel stage during the dry aerogel stage. Supercritical drying requires a pressure vessel and the use of a supercritical drying medium such as CO2 or ethanol, which demands high pressure and high temperature. Aerogel blankets are supercritically dried in an autoclave, but a sufficient inner diameter (often over 0.5m, sometimes over 1m) and length are required to accommodate the rolled blankets, thus increasing manufacturing and operating costs. Furthermore, increasing the thickness of the aerogel blanket increases the supercritical drying time due to diffusion limitations; for a typical aerogel blanket with a thickness of 5-20mm, the drying time is exponentially longer compared to minute aerogel particles with a diameter of less than 3-4mm. Charging and uncharging the autoclave is more difficult than with aerogel blankets, requiring high-pressure, high-speed opening and closing lids. Alcogel particles and aerogel particles, on the other hand, can be pumped as slurries or moved using pneumatic systems. Furthermore, silica aerogel materials disclosed in conventional technologies generally tend to generate dust. [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] EP0850206B1 [Patent Document 2] EP0854892B1 [Patent Document 3] EP0963358B1 [Patent Document 4] WO2016053399A2 [Patent Document 5] US9097377B2 [Overview of the project] [Problems that the invention aims to solve]

[0010] Accordingly, there is a need for an aerogel material that combines the advantages of time- and cost-efficient aerogel production with the easy production of blankets or composites that do not release any dust during use.

Means for Solving the Problem

[0011] According to the present invention, this object is (a) a layer (LA) which comprises aerogel particles having a diameter before compression in the range of 0.1 to 4 mm and has a thickness in the range of 0.1 to 4 mm, (b) one adjacent binder layer (LB) having a thickness in the range of 0.01 to 1 mm, (c) optionally a support layer (LC) having a thickness in the range of 0.01 to 3 mm, adjacent to the binder layer (LB) and located on the second side thereof, (d) optionally a second adjacent binder layer (LB') and a support layer or covering layer (LC') located on the second side of the aerogel particle layer (LA) achieved by a composite comprising two or more layers comprising

[0012] wherein the aerogel particle layer (LA) comprises both binder particles and aerogel particles, and optionally a part of the support layer (LC), and comprises a layer section (LA-1) located adjacent to the binder layer (LB) and having a thickness in the range of 0.01 to 1 mm, the aerogel particle layer (LA) further comprises a binder-free layer section (LA-2) having a thickness of 0.05 mm or more.

Brief Description of the Drawings

[0013] [Figure 1]Figure 1 shows possible schematic cross-sections of composites with different layer structures. Figure 1(a) shows a schematic cross-section of a composite with layers (LA), (LB), and (LC). This composite has a total thickness (LT) according to the following equation: (LT)-(LC)-(LB)=(LA)=(LA-1)+(LA-2). Figure 1(b) shows a schematic cross-section of a composite with layers (LA), (LB), (LC), (LB'), and (LC'). This composite has a total thickness (LT) according to the following equation: (LT)-(LC)-(LC')-(LB)-(LB')=(LA)=(LA-1)+(LA-2). Figure 1(c) shows a schematic cross-section of a composite having layers (LA), (LB), and (LC) and sections 1, 2, and 3 with different thicknesses, where the average thickness is obtained for layers (LA) and (LA-2). [Figure 2] Figure 2 shows a schematic cross-sectional view of a composite having layers (LA), (LB), and (LC), where the thickness of layer (LB) or the thickness of layers (LB) and (LC) varies. [Figure 3] Figure 3 shows a schematic cross-sectional view of a composite having layers (LA), (LB), and (LC). Layer LC is a fibrous layer containing a binder covering the fibers, which gives the average thickness of layers (LA), (LB), and (LC). [Modes for carrying out the invention]

[0014] Surprisingly, it was discovered that by adjusting the composition of aerogel particles, it is possible to control the ductility or brittleness of the particles and obtain ductile aerogel particles. As a result, the ductile aerogel particles do not break or release dust even under compression or vibration. Furthermore, it was found that by arranging such ductile aerogel particles in a densely packed layer, and preferably by simply compressing the aerogel particle layer, an aerogel layer suitable for heat insulation is formed. By combining a surface material and a binder layer on both sides of the aerogel particle layer, a dust-free laminated aerogel composite material can be obtained that does not release dust during use or under vibration.

[0015] The thickness can be measured, for example, by measuring the cross-sectional distance with an optical microscope or by X-ray tomography. For thicknesses less than 10 μm, imaging techniques such as scanning electron microscopy or micro-X-ray tomography are preferred. For thicknesses greater than 10 μm, optical microscopes or scanning electron microscopes can also be used. The composite is cut to produce cross-sections in which the thickness of each layer can be measured. In some cases, it may be necessary to separate the layers before measurement.

[0016] Methods for measuring the thickness of thin films on a surface include techniques using oblique sections and optical microscopy, as described in ASTM D 4138, for example. A method using thickness gauges is described in ASTM D 6988.

[0017] The layer (LA) has a thickness in the range of 0.1 to 4 mm and mainly contains aerogel particles with a diameter in the range of 0.1 to 4 mm before compression, and may contain further particles. Furthermore, according to the present invention, the layer (LA) may also contain more than 35 volume%, for example more than 50 volume%, or more than 60 volume%, of the layer (LA) aerogel particles with a diameter in the range of 0.1 to 4 mm before compression. According to the present invention, the layer (LA) may also contain aerogel particles of different diameters or aerogel particles of different compositions.

[0018] It is also possible for the layer (LA) to not contain other particles. It is also possible to intentionally create voids between the aerogel particles of the layer (LA), or to fill the voids with fillers or other materials, but the layer (LA) preferably contains more than 35 volume% of aerogel particles.

[0019] The thickness of a layer (LA) can be determined by measuring the thickness of each layer, for example, by measuring the thickness of each sample using its cross-section. According to the present invention, the thickness can be determined by measuring multiple samples and using the average value obtained. To measure the thickness of a layer (LA), the distance between the upper and lower surfaces of the layer (LA) parallel to the layer (LC) is measured. Each surface is defined by two planes formed by the largest aerogel particles of the layer (LA) from which the upper and lower boundary of the layer (LA) can be derived. The surfaces of the upper and lower planes are not flat and vary depending on the variation in aerogel particle size across the entire composite surface.

[0020] A layer (LA) is defined as the sum of two aerogel layers, namely layer (LA-1), which contains both aerogel and binder from a binder layer (LB), and layer (LA-2), which is an aerogel layer that does not contain binder from the binder layer (LB).

[0021] The thicknesses of layers (LA-1) and (LA-2) can be determined by measuring their respective thicknesses, for example, by measuring the thickness of each layer using the cross-section of each sample. According to the present invention, the thickness can be determined using the average value obtained by measuring multiple samples. To measure the thickness of layers (LA-1) and (LA-2), the distance between the surface of the layer, defined by the aerogel particles constituting the layer, and the surface formed by the binder between the aerogel particles is measured. If the composite includes layers (LB) and (LB'), the thickness of layer (LA-2) is the average distance between the surfaces formed by the binder layers (LB) and (LB') between the aerogel particles.

[0022] The binders used in this invention can be classified into solid binders, such as thermoplastic binders, or liquid binders, such as thermosetting binders. In either case, to produce adhesive properties, the binder is converted into an incompressible liquid (within the maximum compression range of this invention). In the case of thermoplastic binders, the solid polymer becomes molten as the temperature rises. Since the final composite is in a dry state, the binder thickness should also be measured in its final form, i.e., the solid binder layer. This means that the binder thickness should be measured after cooling in the case of thermoplastic binders, and after drying or curing in the case of thermosetting plastic binders.

[0023] The thickness of a layer (LB) can be determined by measuring its thickness, for example, by measuring the thickness of each layer using the cross-section of each sample. According to the present invention, the thickness can be determined using the average value obtained by measuring multiple samples. To measure the thickness of a layer (LB), the distance between the upper and lower surfaces of the layer (LB) parallel to the layer (LC) is measured. Each surface is defined by two planes formed by upper and lower points at a predetermined point in the composite from which the boundary of the layer (LB) can be derived. Planar surfaces may differ across the surface of the composite depending on the change in the thickness of the layer (LB). Also, gaps may exist in the layer (LB), for example, when it contains fibers coated with a binder.

[0024] For incompressible support layers (LC), the coating thickness of the binder layer (LB) can be determined according to ISO 2808:2019, which specifies procedures for measuring the wet film thickness, dry film thickness, and uncured powder layer thickness.

[0025] The thickness of the support layer can be measured using, for example, a caliper or thickness gauge. Various ASTM or ISO standards exist depending on the material of the layer (LC). According to the present invention, the thickness can be determined using the average value obtained by measuring multiple samples. If the layer (LC) is coated with layer (LB) at the measurement point, the actual thickness of the layer (LC) is obtained by subtracting the thickness of (LB) from the measured thickness. Alternatively, layers (LB) and (LA) can be removed from the layer (LC) using methods known in the prior art before thickness measurement.

[0026] The support layer is either compressible (thickness changes upon compression) or incompressible. To determine whether the support layer (LC) is compressible or not, the (LC) laminate is compressed to 5 MPa for 5 minutes using a bench press, and then the thickness is measured after removing the compressive force. If the average thickness of the support layer after compression is within 10 μm of the average thickness of the (LC) laminate before compression, the support layer is considered incompressible.

[0027] The layer (LC) may be composed of fibers, nonwoven fabrics, or similar materials.

[0028] The composite according to the present invention comprises a layer (LA), a layer (LB), and optionally layers (LC), (LB'), and (LC'). According to the present invention, layer (LB) is adjacent to layer (LA) and is usually adhered to layer (LA). In particular, layer (LB) adheres to at least partially, preferably 60% or more, of the aerogel particles of layer (LA).

[0029] In a further embodiment, the present invention relates to the composite disclosed above, wherein the binder layer (LB) adheres to more than 60% of the aerogel particles of the layer (LA) to support the support layer (LC).

[0030] According to the present invention, the binder layer (LB) and the support layer (LC) can also be bonded together.

[0031] In a further embodiment, the present invention relates to the composite disclosed above, wherein a binder layer (LB) and a support layer (LC) or a binder layer (LB') and (LC') are bonded together.

[0032] Aerogel particles can be organic materials based on synthetic polymers such as polyurethane and polyimide, inorganic materials based on silica, or hybrids of two or more polymers or systems. Suitable aerogel particles and methods for producing them are, in principle, well known to those skilled in the art.

[0033] Aerogels can be hydrophobicized or coated to impart water repellency and moisture resistance. Coatings can also impart functionality to aerogels. Binders can be incorporated into the coatings. An example of coating an aerogel substrate is shown in the following document: https: / / doi.org / 10.1007 / s10570-021-04032-0.

[0034] To improve water resistance and moisture resistance, the final composite material can be hydrophobized, preferably in the gas phase, using hydrophobic agents known in the art, such as silane-based hydrophobic agents like TMCS, HMDSO, and HMDZ.

[0035] The aerogel particle size is determined by the final desired composite thickness, surface thickness, desired aerogel content in the laminated composite, and compression level. Smaller aerogel particles are faster to manufacture, but in the case of mainly organic aerogels, very small aerogel particles can pose an explosion hazard or become difficult to handle during manufacturing and handling. Preferably, the aerogel particle size is <4 mm, <3 mm, <2 mm, <1 mm and greater than 0.1 mm, more preferably greater than 0.5 mm, and even more preferably greater than 1 mm. Fine aerogel particles can be manufactured directly or obtained by grinding and polishing larger aerogel particles. By using a mixture of two or more particle sizes, the air gaps between spherical particles of a given size can be replaced with fine particles that fit directly, with or without a compression process. This makes it possible to form an aerogel particle layer that does not contain aerogel powder smaller than 0.1 mm that would cause dust to be released from the composite, and that is substantially free of air gaps.

[0036] The density of aerogel particles depends on the desired aerogel properties and is usually determined by a specific formulation. Ductile aerogel particles are obtained using organic polymers containing biopolymers, and hybrids of organic polymers containing biopolymers and inorganic precursors, as reported in PCT / EP2023 / 955870. Bio-based polymers are selected for green composites. For fire-resistant and high-temperature resistant composites, a high inorganic content is selected while avoiding brittleness and dust generation.

[0037] In further embodiments, the present invention also relates to the composite disclosed above, wherein the uncompressed aerogel particles of layer (LA) have one or more of the features (α) to (γ): (α) Porosity of 80-99.6%, (β) 15-200 kg / m 3 Particle bulk density, (γ) Thermal conductivity measured in a buffer-packed particle layer at 10°C, with a thermal conductivity of 16-30 mW / mK.

[0038] It has been found that the aerogel particles used allow for the preparation of composites with advantageous properties. Aerogel particles are compressible, and stable composite materials can be obtained. Accordingly, according to further embodiments, the present invention also relates to the composites disclosed above, wherein individual aerogel particles can be compressed to 5-98% of their original thickness without visible damage when compressed at a compression rate of 0.01-5 mm / sec, or the force reduction due to primary damage during compression is less than 1 N.

[0039] Stable composites can be obtained from aerogel particles. It has been found that particularly stable composites are obtained when using aerogel particles with a diameter in the range of 0.1 to 4 mm before compression. Preferably, the particle size distribution of the aerogel is monodisperse, polydisperse, or partially monodisperse, and the roundness of the individual aerogel particles is preferably in the range of 25% to 100%.

[0040] In yet another embodiment, the present invention relates to the composite material disclosed above, and hereby, (I) The particle size distribution of the aerogel is monodisperse, polydisperse, or partially monodisperse, and / or (II) The sphericity of individual aerogel particles is in the range of 25% to 100%.

[0041] According to the present invention, silica-based aerogels have been found to have particularly excellent properties for the preparation of composites. Preferably, the aerogel is a silica-based aerogel.

[0042] In particular, hybrid aerogels containing biopolymers selected from ion-crosslinkable polycarboxylate polymers, alginates, pectin, or modified cellulose.

[0043] The polarity of aerogels can also be adjusted by further processing steps applied to the aerogel itself. For example, appropriate treatments such as hydrophobic treatment are generally known.

[0044] In yet another embodiment, the present invention also relates to the composite disclosed above, wherein the aerogel is (A) Containing 20-80% by mass of silica and 20% by mass of ion-crosslinkable polycarboxylate polymer, provided that the ion-crosslinkable polycarboxylate polymer is at least 25 kg / m³ 3 is, or (B) Contains 20-90% by mass of silica and 10% by mass of alginate, but with at least 15 kg / m³ of alginate. 3 is, or (C) Contains 20-85% by mass of silica and 15% by mass of pectin, but with pectin at least 20 kg / m³ 3 is, or (D) Contains 20-80% by mass of silica and 20% by mass of CMC, but with at least 25 kg / m³ of CMC. 3 is, or (E) Containing 20-85% by mass of silica and 7.5% by mass of alginate, with alginate at least 15 kg / m³ 3 And the non-alginate ion crosslinkable polycarboxylate polymer is at least 10 kg / m³ 3 That is It is a silica-based aerogel.

[0045] The aerogel particles may also include further materials to modify the properties of the material, such as lignin, tannin, polysaccharides, proteins, synthetic polymers, fillers, opacifiers, or materials that impart high temperature stability, fire resistance, or elasticity. According to another embodiment, the present invention also relates to the composite disclosed above, wherein the aerogel particles include lignin, tannin, polysaccharides, proteins, synthetic polymers, fillers, opacifiers, or materials that impart high temperature stability, fire resistance, or elasticity.

[0046] To avoid the adverse effects of binders on the thermal insulation performance of the composite, binders may be necessary to bond aerogel particles to the surface material or to each other, but only if a binder-free layer (LA-2) is present. The binder must not penetrate the aerogel layer beyond the depth set by layer (LA-1), but at least layer (LA-2) must be binder-free to form thermal bridges. Reactive binders such as acrylates, polyurethanes, epoxy, and silicones, or thermoplastic binders such as PE, PP, PA, TPU, and silicones are available. Bio-based binders are selected for green composites. Binders are supplied in liquid formulations, powders, sheets, nonwovens, fibers, or other appropriate forms. The binder formulation should be selected to avoid penetration and damage to the aerogel particle pores and degradation of thermal insulation performance, for example, by using aqueous binder formulations with hydrophobic aerogel particles, or high-viscosity binder formulations. The binder must exhibit good adhesion to the aerogel particles and surface material to ensure the mechanical integrity of the layered composite and prevent delamination or release of aerogel particles from the composite. At the same time, the binder layer should be as thin as possible to avoid adverse effects on the thermal insulation performance of the composite. The binder should be selected based on the operating temperature of the application. For example, a thermoplastic binder with a sufficiently high melting point should be used. The temperature should not be so high as to damage the aerogel particles or surface material. Such binders are known in the prior art.

[0047] In yet another embodiment, the present invention also relates to the composites disclosed above, wherein the binder is selected from reactive binders based on acrylates, polyurethanes, epoxy resins, silicones, water glass, and other inorganic binder systems, or from thermoplastic binders based on PE, PP, PA, TPU, PLA, and other bio-based polymers, silicones, or mixtures thereof.

[0048] In the production of layered aerogel particle composites, instead of mixing or coating the aerogel particles with a binder, it is possible to first form a binder layer and a surface layer, and then add aerogel particles for bonding.

[0049] In the context of the present invention, it is also possible to use the binder itself, or a binder composition comprising the binder and appropriate additives (e.g., fillers, particularly fibrous fillers or refractory fillers).

[0050] Surprisingly, it was discovered that by adjusting the composition of aerogel particles, it is possible to obtain fire-resistant, ductile aerogel particles that do not generate dust. From such fire-resistant, ductile aerogel particles, a dust-free, fire-resistant, layered aerogel composite can be formed.

[0051] Aerogel particle composites can be manufactured from aerogel particles using discontinuous or continuous processes. In principle, cost-effective and rapid roll-to-roll processes are possible.

[0052] The surface material may be a nonwoven fabric, woven fabric, or sheet, and is generally known from the prior art. The surface material may consist of or incorporate woven fabrics or nonwoven fabrics, glass fibers, ceramic fibers, mica, cellulose, hemp, paper or coated paper, other bio-based materials, synthetic polymers, or biopolymers. Bio-based materials are selected for green composites. To obtain a thin surface material or flexible composite material having a relatively high aerogel content within the composite, a surface material with a thickness of less than 2 mm, preferably less than 1 mm, more preferably less than 0.5 mm, and particularly less than 0.1 mm is advantageous.

[0053] In another embodiment, the present invention also relates to the composite disclosed above, wherein the composite comprises an elastic frame surrounding an elastic nonwoven fabric or blanket, elastic particles, or an aerogel layer (LA) that imparts elasticity to the composite when mechanically compressed.

[0054] When a thermoplastic binder layer is used as the base, the layered aerogel particle composite can be temporarily softened by heating.

[0055] In the manufacture of aerogel particle composites, compression may be necessary to improve the bonding between the aerogel particle layer, the binder layer, and the surface material, or to reduce air gaps between aerogel particles, or to reduce the thickness of the composite. Preferably, the aerogel particles should not be compressed by more than 80%, and more preferably more than 50%. This is to avoid excessively increasing the density and potentially adversely affecting the thermal insulation performance.

[0056] The thermal conductivity of the aerogel particle bed was found to be within the same range as that of the composite. For example, the lambda value remained constant above 5 mW / m·K, preferably above 2 mW / m·K. The lambda value of such a composite depends on the lambda value of the aerogel particles and the relative thickness of the aerogel particle layer to the binder layer and surface layer, but is expected to be less than 30 mW / m·K, preferably less than 25 mW / m·K, and more preferably less than 23 mW / m·K.

[0057] By stacking multiple compressed aerogel particle layers, thicker aerogel composites can be formed. These aerogel particle layers can be joined using binders known in the prior art, or by stitching together fibrous surface materials, as also known in the prior art. Furthermore, by stacking multiple aerogel particle layers and compressing this multilayer aerogel particle structure, thicker aerogel composites can be formed. In such multilayer aerogel particle arrangements, binders may be required to bond the particles together or between the aerogel particles and the surface material. Additionally, to achieve specific properties of the aerogel composite, it is possible to form multilayer arrangements of different types of aerogel particles, or to manufacture mixed layers such as organic / organic, synthetic polymer / biopolymer, organic / inorganic, or inorganic / inorganic.

[0058] Furthermore, to impart additional functionality to the aerogel particle composite, other types of layers or surface materials can be introduced, such as an electrical insulating layer, a thermal conductive layer, a phase change material, a mechanical shock resistant layer, a waterproof layer, or a fire-resistant layer.

[0059] Elastic properties can be imparted to a composite by introducing an elastic layer. This is advantageous in electric vehicle batteries for compensating for the expansion and contraction of battery cells during operation and throughout the battery life. For example, one or more binder layers can be elasticized by using thermoplastic elastomers or elastomer sheets, webs, powders, molded shapes, particles, and similarly, TPU. It is also possible to introduce elastic particles or molded shapes, such as elastomer beads, 3D printed parts, or molded parts, into an aerogel particle layer (LA). In the gelation process of the manufacturing process, it is also possible to increase and adjust the elasticity of the aerogel particles in the layer (LA) by incorporating minute elastic particles. Furthermore, the elastic behavior of aerogel particles can be modified by changing the biopolymer content and type.

[0060] Typically, the composite according to the present invention has a thickness in the range of 0.1 to 20 mm, for example, in the range of 0.2 to 15 mm, preferably in the range of 0.3 to 10 mm or 0.5 to 5 mm.

[0061] Layers (LA) and (LB) typically account for at least 20%, preferably at least 30%, and especially at least 50% of the complex. If the complex contains multiple layers (LA) and / or (LB), the combined total of layers (LA) and (LB) typically accounts for at least 20%, preferably at least 30%, and especially at least 50% of the complex.

[0062] Appropriate processes for preparing aerogel powder or aerogel beads are, in principle, well known to those skilled in the art.

[0063] A suitable process may include, for example, gel preparation, solvent replacement, and drying steps.

[0064] In a further embodiment, the present invention also relates to a method for preparing the composite disclosed above, wherein the aerogel beads are obtained by solvent exchange and supercritical drying or freeze-drying.

[0065] In the production of aerogel particles, the costly and time-consuming supercritical drying of silica aerogel blankets can be avoided. Supercritical drying of aerogel particles is known in principle and can be carried out in small-diameter tubes that function as autoclaves for aerogel particles, in contrast to the large and expensive autoclaves used for silica aerogel blankets. Processes suitable for the production of aerogel particle gel precursors are, in principle, well known to those skilled in the art. Suitable processes include ionic crosslinking or pH-induced crosslinking.

[0066] In yet another embodiment, the present invention also relates to the composite disclosed above, in which the aerogel particles are prepared by ion crosslinking or pH-induced crosslinking.

[0067] Typically, a gel is formed from the components of mixture (M1) and at least one polyvalent metal ion. Mixture (M1) needs to have suitable components, particularly suitable functional groups, that enable gel formation with the polyvalent metal ion.

[0068] Typically, a gel (A) is prepared by contacting a mixture (M1) with an aqueous solution of polyvalent metal ions. Appropriate mixing procedures are, in principle, well known to those skilled in the art. For example, spherical aerogel particles can be prepared by adding the mixture (M1) dropwise to an aqueous solution of polyvalent metal ions. Alternatively, the mixture (M1) can be provided either by filling the pores of a carrier material or by mixing it with fibers before contacting the aqueous solution of polyvalent metal ions to prepare the gel (A). Furthermore, the mixture (M1) can be brought into contact with polyvalent metal ions in an emulsion or during a spraying process.

[0069] Gelation itself is well known to those skilled in the art, and is described, for example, on page 21, line 19 to page 23, line 13 of WO 2009 / 027310.

[0070] Preferably, the conditions are adjusted so that the hydrogel, alcohol gel and / or aerogel exhibit a spherical shape. Preferably, according to step b), spherical beads with an average diameter in the range of 0.1 to 4 mm, preferably 1 to 2 mm, are obtained.

[0071] Preferably, no crosslinking or hydrophobicization occurs due to covalent chemical reactions.

[0072] Preferably, the temperature and pressure in the gelation step are adjusted to conditions under which a gel is formed. A suitable temperature is in the range of 5 to 40°C, preferably in the range of 15 to 35°C. According to a further embodiment, the present invention relates to the method described above, wherein step b) is carried out at a temperature in the range of 5 to 40°C.

[0073] The formation rate of insoluble gels can be controlled very precisely and easily by selecting appropriate conditions.

[0074] Gel (A) is typically a water-containing gel, i.e., a hydrogel. Usually, gel (A) is exposed to a water-miscible solvent (L) to obtain gel (B), i.e., an organogel.

[0075] In the present invention, water miscibility means that the solvent is at least partially miscible with water in order to enable solvent exchange within the gel.

[0076] Solvent exchange is performed either by directly immersing the gel in a new solvent (single step) or by sequentially immersing it in different water-new solvent mixtures (multi-step). In the latter case, the content of the new solvent is increased after a certain period of time (exchange frequency) has elapsed since the previous immersion step (Robitzer et al., 2008, Langmuir, 24(21), 12547-12552). The solvent used for water replacement should not dissolve the gel structure, be completely miscible with the preceding solvent (water), and be approved for pharmaceutical manufacturing. Furthermore, if a supercritical drying step is included, the solvent (L) should be at least partially miscible with the supercritical medium.

[0077] The solvent (L) can, in principle, be any suitable compound or mixture of several compounds that meets the above requirements and is liquid under the temperature and pressure conditions of the process in which it is used.

[0078] Examples of suitable solvents (L) include alcohols, ketones, aldehydes, alkyl alkanoates, organic carbonates, amides such as formamides and N-methylpyrrolidone, sulfoxides such as dimethyl sulfoxide, aliphatic and alicyclic halogenated or non-halogenated hydrocarbons, halogenated or non-halogenated aromatic compounds, and fluorine-containing ethers. Mixtures of two or more of the above compounds can also be used.

[0079] In many cases, a particularly suitable solvent (L) can be obtained by using two or more perfectly miscible compounds selected from the solvents mentioned above. Particularly suitable solvents include alcohols and ketones, such as C1-C6 alcohols and C1-C6 ketones, and mixtures thereof.

[0080] Particularly suitable are alcohols such as methanol, ethanol, and isopropanol, and ketones such as acetone and methyl ethyl ketone.

[0081] Solvent exchange can be carried out in one, two, three, or more stages while varying the solvent concentration. According to a preferred embodiment, the gel (A) is sequentially immersed in ethanol / water mixtures of concentrations of, for example, 30, 60, 90, and 100% by mass, for 5 minutes to 12 hours, depending on the particle size and porosity. Solvent exchange can also be carried out continuously.

[0082] A gel (B) is obtained by solvent substitution, which is then dried.

[0083] Drying is usually carried out by known methods. Drying under supercritical conditions is preferred, and is particularly carried out after substitution with CO2 or other solvents suitable for the purpose of removing the gelling solvent. Such drying methods are well known to those skilled in the art. A supercritical state is characterized by the temperature and pressure at which the CO2 or any solvent used to remove the gelling solvent is in a supercritical state. This method can reduce the shrinkage of the gel during solvent removal.

[0084] Furthermore, the resulting gel can be dried by converting the liquid contained within the gel into a gaseous state at a temperature and pressure below its critical temperature and critical pressure.

[0085] Preferably, the resulting gel is dried by converting the solvent (L) to a gaseous state at a temperature and pressure below the critical temperature and critical pressure of the solvent (L). Therefore, it is preferable to dry the gel by removing the solvent (L) that was present during the reaction without replacing it with an additional solvent.

[0086] Such methods are also known to those skilled in the art and are described in WO 2009 / 027310, page 26, line 22 to page 28, line 36.

[0087] Drying can be performed by converting the liquid contained in the gel into a gaseous state at a temperature and pressure below the critical temperature and pressure of the liquid contained in the gel. It is also possible to perform drying under supercritical conditions.

[0088] This method may also include one or more further modification steps, such as a molding step involving fibers and / or adhesives and / or thermoplastic materials, a compression step, a lamination step, a hydrophobic step, or a carbonization step. For example, one or more of these steps can be combined, such as a post-drying step and a hydrophobic step.

[0089] According to the present invention, hybrid aerogels, in particular, have been found to have good properties for preparing the composites according to the present invention. In particular, hybrid aerogels comprising a secondary material and a biopolymer selected from ion-crosslinkable polycarboxylate polymers, alginic acid, pectin, or modified cellulose are suitable.

[0090] Appropriate processes for producing biopolymer-based aerogels are, in principle, well known to those skilled in the art. Typically, aerogels are obtained by a process comprising gel formation, solvent replacement, and drying. In further embodiments, the present invention also relates to the liquid or paste-like compositions disclosed above, where aerogel beads are obtained by solvent replacement and supercritical drying or freeze-drying.

[0091] For example, a suitable aerogel involves at least the following steps: a) A step of providing a mixture (M1) comprising at least one compound (C1) selected from water-soluble biopolymers and inorganic precursors, at least one water-soluble polysaccharide having a carboxylic acid group as component (C2), and water. b) A step of preparing a gel (A) by contacting the mixture (M1) with an aqueous solution of polyvalent metal ions, c) A step of exposing the gel (A) obtained in step b) to a water-miscible solvent (L) to obtain gel (B), d) A step of drying the gel (B) obtained in step c) It is prepared by a method that includes [a specific method].

[0092] In the context of the present invention, a suitable inorganic precursor is soluble or at least partially soluble in the mixture (M1) and needs to solidify in the gelation step.

[0093] In this invention, "gel" refers to a polymer-based crosslinking system that exists in contact with a liquid (known as a sorbogel or ryogel) or water as a liquid (known as an aquagel or hydrogel). Here, the polymer phase forms a continuous three-dimensional network.

[0094] In this invention, water solubility means having sufficient solubility in water to form a solution that can be used for gel preparation. Furthermore, in this invention, a water-swelled dispersion can also be used for gel preparation.

[0095] The properties of aerogels can be customized by adjusting the composition of the mixture (M1), the hydrogel (gel (A)) formation stage, the solvent exchange, and the reaction conditions during the drying process. According to the present invention, the properties of hydrogels and / or aerogels can be influenced by changing the ratio of components, controlling the parameters of step b), and introducing a wide range of organic and inorganic materials into the gel matrix.

[0096] In a further embodiment, the present invention comprises the following steps: (i) A step of forming a binder layer (LB), (ii) A process of forming a layer (LA) mainly containing aerogel particles, (iii) The process of forming a composite including layer (LA) and layer (LB) by applying conditions suitable for achieving a stable bond between layer (LA) and layer (LB). The present invention also relates to a method for preparing a complex comprising two or more layers, Here, the uncompressed aerogel particles of layer (LA) preferably have characteristics (α)~(γ): (α) Porosity of 80-99.6%, (β) 15-200 kg / m 3 Particle bulk density, (γ) Thermal conductivity measured in a buffer-packed particle layer at 10°C, with a value of 16-30 mW / mK. It has one or more of the following.

[0097] In particular, the present invention also relates to a method for preparing a composite comprising two or more layers, comprising the following steps: (i) a step of forming a binder layer (LB), (ii) a step of forming a layer (LA) containing aerogel particles having a diameter before compression in the range of 0.1 to 4 mm, (iii) forming a composite comprising the layer (LA) and the layer (LB) by applying conditions suitable for achieving stable bonding between the layer (LA) and the layer (LB), and formation of a layer section (LA-1) having a thickness of 0.01 to 1 mm containing a binder and the aerogel particles, and a layer section (LA-2) having a thickness of 0.05 mm or more containing no binder, , wherein the uncompressed aerogel particles in the layer (LA) preferably have one or more of the following features (α) to (γ): (α) a porosity of 80 to 99.6%, (β) 15 to 200 kg / m 3 of particle bulk density, (γ) a thermal conductivity measured on a loosely packed particle layer at 10°C of 16 to 30 mW / mK .

[0098] The method of the present invention comprises steps (i), (ii), and (iii), and may further comprise additional steps in addition thereto.

[0099] For the preferred aerogel particles used, reference is made to the above disclosure.

[0100] According to a further embodiment, the present invention also relates to the method disclosed above, wherein the aerogel is a silica-based aerogel.

[0101] According to a further embodiment, the present invention also relates to the method disclosed above, wherein the aerogel comprises (A) 20 to 80% by mass of silica and 20% by mass of an ionically crosslinkable polycarboxylate polymer, provided that the ionically crosslinkable polycarboxylate polymer has a bulk density of at least 25 kg / m 3is, or (B) Contains 20-90% by mass of silica and 10% by mass of alginate, but with at least 15 kg / m³ of alginate. 3 is, or (C) Contains 20-85% by mass of silica and 15% by mass of pectin, but with pectin at least 20 kg / m³ 3 is, or (D) Contains 20-80% by mass of silica and 20% by mass of CMC, but with at least 25 kg / m³ of CMC. 3 is, or (E) Containing 20-85% by mass of silica and 7.5% by mass of alginate, with alginate at least 15 kg / m³ 3 And the non-alginate ion crosslinkable polycarboxylate polymer is at least 10 kg / m³ 3 That is It is a silica-based aerogel.

[0102] It has been found that applying pressure to the composite yields a particularly stable composite. In a further embodiment, the present invention also relates to the method disclosed above, wherein the method comprises the following steps: (iv) A step of compressing the composite so that the aerogel is compressed to 5-98% of its original thickness. (v) A step of applying a compression speed preferably in the range of 0.01 to 1 mm / second. Includes.

[0103] The composite may also include further layers, such as a coating layer or a further layer containing aerogel particles. According to another embodiment, the present invention also relates to the method disclosed above, wherein a further layer containing aerogel particles is formed as part of the composite.

[0104] Furthermore, for preferred embodiments of the composite, refer to the above disclosure. In a further embodiment, the present invention also relates to the method disclosed above, wherein the thickness of the composite is in the range of 0.1 to 20 mm.

[0105] In a further embodiment, the present invention also relates to the method disclosed above, wherein the thickness of the layer (LA) containing the aerogel particles is in the range of 0.1 to 4 mm.

[0106] In a further embodiment, the present invention also relates to the method disclosed above, wherein the diameter of the uncompressed aerogel particles is in the range of 0.1 to 4 mm.

[0107] In a further embodiment, the present invention also relates to the method disclosed above, wherein the binder is selected from acrylates, polyurethanes, epoxy resins, silicones, or thermoplastic binders such as PE, PP, PA, TPU, and PLA.

[0108] In a further embodiment, the present invention also relates to composites obtained according to the methods disclosed above.

[0109] This composite material has been found to possess excellent stability and thermal insulation properties, making it suitable for use as thermal insulation in buildings and construction, home appliances, thermologistics, cryogenic applications, oil and gas applications, clothing, or as a heat shield or heat transfer inhibitor in batteries.

[0110] In a further embodiment, the present invention relates to a method for using the composite disclosed above as an insulating material in buildings and construction, home appliances, thermologistics, cryogenic applications, automotive applications, infrastructure applications, marine applications, oil and gas applications, or clothing, or as a heat shield or heat transfer inhibitor in batteries.

[0111] Preferred embodiments are described in the claims and description. Combinations of preferred embodiments do not depart from the scope of the invention. Preferred embodiments of the components used are described below.

[0112] The present invention includes the following embodiments, which include specific combinations of embodiments as indicated by their respective defined interdependencies.

[0113] The present invention is further described by the following series of embodiments and combinations of embodiments arising from the described dependencies and backreferences. In particular, where the scope of an embodiment is referred to in the context of terms such as "the composite described in any one of Embodiments 1 to 4," it is intended that all embodiments within that scope are expressly disclosed to those skilled in the art; that is, the wording of this term should be understood by those skilled in the art as synonymous with "the composite described in any one of Embodiments 1, 2, 3, and 4." Furthermore, it is explicitly stated that the following series of embodiments represent appropriately configured portions of the general description of preferred aspects of the present invention and therefore appropriately support the claims of the present invention, but do not represent the claims of the present invention.

[0114] 1. (a) A layer (LA) containing aerogel particles with a diameter in the range of 0.1 to 4 mm before compression and having a thickness in the range of 0.1 to 4 mm. (b) One adjacent binder layer (LB) having a thickness in the range of 0.01 to 1 mm, (c) A support layer (LC) having a thickness of any size in the range of 0.01 to 3 mm, adjacent to the binder layer. (d) A second adjacent binder layer (LB') and a support or coating layer (LC') optionally located on the second side of the particle layer (LA). A complex comprising two or more layers, The aerogel particle layer (LA) includes both the binder and aerogel particles, and optionally a portion of the support layer (LC), and includes a layer section (LA-1) located adjacent to the binder layer (LB) and having a thickness in the range of 0.01 to 1 mm. The allogel particle layer (LA) is a composite further comprising a binder-free layer section (LA-2) having a thickness of 0.05 mm or more.

[0115] 2. The composite according to Embodiment 1, wherein the binder layer (LB) has more than 60% of the aerogel particles of the layer (LA) attached to the support layer (LC).

[0116] 3. The composite according to Embodiment 1 or 2, wherein a binder layer (LB) and a support layer (LC) or a binder layer (LB') and (LC') are combined.

[0117] 4. Uncompressed aerogel particles of layer (LA) are characterized from (α) to (γ): (α) Porosity of 80-99.6%, (β) 15-200 kg / m 3 Particle bulk density, (γ) Thermal conductivity measured in a buffer-packed particle layer at 10°C, with a value of 16-30 mW / mK. A composite according to any one of embodiments 1 to 3, having one or more of the above.

[0118] 5. Individual aerogel particles can be compressed to 5-98% of their original thickness without visible damage during compression at a compression rate of 0.01-5 mm / second, or The composite according to any one of Embodiments 1 to 4, wherein the force reduction due to primary failure during compression is less than 1 N.

[0119] 6. (I) The particle size distribution of the aerogel is monodisperse, polydisperse, or partially monodisperse, and / or (II) The composite according to any one of Embodiments 1 to 5, wherein the sphericity of the individual aerogel particles is in the range of 25% to 100%.

[0120] 7. The aerogel is a silica-based aerogel, preferably the aerogel is (A) Containing 20-80% by mass of silica and 20% by mass of an ion-crosslinkable polycarboxylate polymer, provided that the ion-crosslinkable polycarboxylate polymer is at least 25 kg / m³ 3 is, or (B) Contains 20-90% by mass of silica and 10% by mass of alginate, but with at least 15 kg / m³ of alginate. 3 is, or (C) Contains 20-85% by mass of silica and 15% by mass of pectin, but with pectin at least 20 kg / m³ 3 is, or (D) Contains 20-80% by mass of silica and 20% by mass of CMC, but with at least 25 kg / m³ of CMC. 3 is, or (E) Containing 20-85% by mass of silica and 7.5% by mass of alginate, with alginate at least 15 kg / m³ 3 And the non-alginate ion crosslinkable polycarboxylate polymer is at least 10 kg / m³ 3 That is A silica-based aerogel composite according to any one of Embodiments 1 to 6.

[0121] 8. The composite according to any one of Embodiments 1 to 7, wherein the aerogel particles include lignin, tannin, polysaccharide, protein, synthetic polymer, filler, opacifier, or a material that imparts high temperature stability, fire resistance, or elasticity.

[0122] 9. The composite according to any one of Embodiments 1 to 8, wherein the aerogel particles are prepared by ionic crosslinking or pH-induced crosslinking.

[0123] 10. The composite according to any one of Embodiments 1 to 9, wherein the binder is selected from reactive binders based on acrylates, polyurethanes, epoxy resins, silicones, water glass, or other inorganic binder systems, or from thermoplastic binders based on PE, PP, PA, TPU, PLA, or other bio-based polymers, silicones, or mixtures thereof.

[0124] 11. The composite according to any one of embodiments 1 to 10, wherein the composite comprises an elastic nonwoven fabric or blanket, elastic particles, elastic shapes, or an elastic frame surrounding an aerogel layer (LA) that imparts elasticity to the composite when mechanically compressed.

[0125] 12. The following steps, (i) A step of forming a binder layer (LB), (ii) A step of forming a layer (LA) containing aerogel particles with a diameter in the range of 0.1 to 4 mm before compression, (iii) The process of forming a composite including layer (LA) and layer (LB) by applying conditions suitable for achieving a stable bond between layer (LA) and layer (LB). A method for preparing a complex comprising two or more layers, including Uncompressed aerogel particles in layer (LA) have the following characteristics: (α)~(γ): (α) Porosity of 80-99.6%, (β) 15-200 kg / m 3 Particle bulk density, (γ) Thermal conductivity measured in a buffer-packed particle layer at 10°C, with a value of 16-30 mW / mK. A method having one or more of the following.

[0126] 13. The following steps, (i) A step of forming a binder layer (LB), (ii) A step of forming a layer (LA) containing aerogel particles with a diameter in the range of 0.1 to 4 mm before compression, (iii) A step of forming a composite including layer (LA) and layer (LB) by applying conditions suitable for achieving stable bonding between layer (LA) and layer (LB), and the formation of layer sections (LA-1) with a thickness of 0.01 to 1 mm including the binder and aerogel particles, and layer sections (LA-2) with a thickness of 0.05 mm or more that do not include the binder. A method for preparing a complex comprising two or more layers, including Uncompressed condensed aerogel particles of layer (LA) preferably have characteristics (α)~(γ): (α) Porosity of 80-99.6%, (β) 15-200 kg / m 3 Particle bulk density, (γ) Thermal conductivity measured in a buffer-packed particle layer at 10°C, with a value of 16-30 mW / mK. A method having one or more of the following.

[0127] 14. The method according to Embodiment 12 or 13, wherein the aerogel is a silica-based aerogel.

[0128] 15. Aerogel, (A) Containing 20-80% by mass of silica and 20% by mass of an ion-crosslinkable polycarboxylate polymer, provided that the ion-crosslinkable polycarboxylate polymer is at least 25 kg / m³ 3 is, or (B) Contains 20-90% by mass of silica and 10% by mass of alginate, but with at least 15 kg / m³ of alginate. 3 is, or (C) Contains 20-85% by mass of silica and 15% by mass of pectin, but with pectin at least 20 kg / m³ 3 is, or (D) Contains 20-80% by mass of silica and 20% by mass of CMC, but with at least 25 kg / m³ of CMC. 3 is, or (E) Containing 20-85% by mass of silica and 7.5% by mass of alginate, with alginate at least 15 kg / m³ 3 And the non-alginate ion crosslinkable polycarboxylate polymer is at least 10 kg / m³ 3 That is The method according to any one of embodiments 12 to 14, wherein the material is a silica-based aerogel.

[0129] 16. (iv) A step to compress the composite so that the aerogel is compressed to 5-98% of its original thickness. The method according to any one of embodiments 12 to 15, including the method described in any one of embodiments 12 to 15.

[0130] 17. (iv) A step of compressing the composite so that the aerogel is compressed to 5-98% of its original thickness. (v) A process in which a compression speed in the range of 0.01 to 1 mm / second is applied. The method according to any one of embodiments 12 to 16, including the method described in any one of embodiments 12 to 16.

[0131] 18. The method according to any one of embodiments 12 to 17, wherein a further layer containing aerogel particles is formed as part of the composite.

[0132] 19. The method according to any one of embodiments 12 to 18, wherein the thickness of the composite is in the range of 0.1 to 20 mm.

[0133] 20. The method according to any one of embodiments 12 to 19, wherein the thickness of the layer (LA) containing aerogel particles is in the range of 0.1 to 4 mm.

[0134] 21. The method according to any one of Embodiments 12 to 20, wherein the binder is selected from acrylate, polyurethane, epoxy resin, silicone, or thermoplastic binders such as PE, PP, PA, TPU, and PLA.

[0135] 22. The method according to any one of embodiments 12 to 21, wherein the thickness of the binder layer (LB) is in the range of 0.01 to 1 mm.

[0136] 23. The method according to any one of embodiments 12 to 22, wherein the composite comprises a support layer (LC) adjacent to a binder layer having a thickness in the range of 0.01 to 3 mm.

[0137] 24. The aerogel particle layer (LA) includes both the binder and aerogel particles, and optionally a portion of the support layer (LC), and includes a layer section (LA-1) located adjacent to the binder layer (LB) and having a thickness in the range of 0.01 to 1 mm. The method according to any one of embodiments 12 to 23, wherein the allogel particle layer (LA) further comprises a binder-free layer section (LA-2) having a thickness of 0.05 mm or more.

[0138] 25. The method according to any one of embodiments 12 to 24, wherein the binder layer (LB) has more than 60% of the aerogel particles of the layer (LA) attached to the support layer (LC).

[0139] 26. The method according to any one of embodiments 12 to 25, wherein a binder layer (LB) and a support layer (LC) or a binder layer (LB') and (LC') are combined.

[0140] 27. Uncompressed aerogel particles of layer (LA) are characterized from (α) to (γ): (α) Porosity of 80-99.6%, (β) 15-200 kg / m 3 Particle bulk density, (γ) Thermal conductivity measured in a buffer-packed particle layer at 10°C, with a value of 16-30 mW / mK. The method according to any one of embodiments 12 to 26, having one or more of the above.

[0141] 28. Individual aerogel particles can be compressed to 5-98% of their original thickness without visible damage during compression at a compression rate of 0.01-5 mm / second, or The method according to any one of embodiments 12 to 27, wherein the force reduction due to primary failure during compression is less than 1 N.

[0142] 29. (I) The particle size distribution of the aerogel is monodisperse, polydisperse, or partially monodisperse, and / or (II) The method according to any one of Embodiments 12 to 28, wherein the sphericity of the individual aerogel particles is in the range of 25% to 100%.

[0143] 30. The method according to any one of Embodiments 12 to 29, wherein the aerogel particles include lignin, tannin, polysaccharide, protein, synthetic polymer, filler, opacifier, or a material that imparts high temperature stability, fire resistance, or elasticity.

[0144] 31. The method according to any one of embodiments 12 to 30, wherein the aerogel particles are prepared by ion crosslinking or pH-induced crosslinking.

[0145] 32. The method according to any one of Embodiments 12 to 31, wherein the binder is selected from reactive binders based on acrylates, polyurethanes, epoxy resins, silicones, water glass, or other inorganic binder systems, or from thermoplastic binders based on PE, PP, PA, TPU, PLA, or other bio-based polymers, silicones, or mixtures thereof.

[0146] 33. The method according to any one of embodiments 12 to 32, wherein the composite comprises an elastic nonwoven fabric or blanket, elastic particles, elastic shapes, or an elastic frame surrounding an aerogel layer (LA) that imparts elasticity to the composite when mechanically compressed.

[0147] 34. A composite obtained by the method described in any one of Embodiments 12 to 33.

[0148] 35. A method for using a composite according to any one of Embodiments 1 to 11 or 34, or a composite obtained or obtainable by the method described in any one of Embodiments 12 to 33, as thermal insulation in building and construction, home appliances, thermologistics, cryogenic applications, automotive applications, infrastructure applications, marine applications, oil and gas applications, or apparel, or as a heat shield or heat transfer inhibitor in batteries.

[0149] The present invention will be explained below using examples. [Examples]

[0150] 1. Preparation of aerogel Aerogel particles were prepared by the following method: Colloidal silica (CS, Levasil CS15-340P, Nouryon) and sodium alginate (SA, Protanal LF120, IFF) were mixed with water to obtain a precursor solution at a predetermined target concentration. One liter of the precursor solution was added dropwise to five liters of calcium chloride bath (20 g / l) at room temperature to form hydrogel particles. The particle size of the hydrogel particles was controlled to a range of 0.1 mm to 4 mm by the dropwise method. The water in the hydrogel particles was replaced with approximately 98% ethanol in 10 steps by immersion in 98% ethanol in an amount 10 times the volume of the particles at room temperature for approximately 3 hours. The resulting alcohol gel particles were dried with supercritical CO2 to obtain aerogel particles. If necessary, the aerogel particles were pulverized in a kitchen blender for approximately 60 seconds to obtain a powder (particle size 10-100 μm).

[0151] 2. Preparation of the complex 2.1 Materials Aerogel particles as described above. Glass fiber facing material (approximately 0.2 mm thick). Hot melt web (copolyester, 100 g / m²). 2 ).

[0152] 2.2 Monolayer composite Aerogel particles were laminated onto a first fiberglass surface (20 × 20 cm) and a first hot-melt web layer (20 × 20 cm), and covered with a second layer of hot-melt web and fiberglass surface. This assembly was compressed to the target thickness while being heated for approximately 30 seconds at a temperature exceeding the melting point of the hot-melt web, obtaining an aerogel particle laminated composite sheet with both sides bonded together by the hot-melt web between two fiberglass surfaces. The hot-melt did not penetrate to the center of the composite, forming a binder-free aerogel particle layer.

[0153] 2.3 Multilayer composites Aerogel particles were laminated onto a glass fiber surface with a hot-melt web layer, and after covering with another hot-melt web layer, layers of ductile aerogel particles and hot-melt web were further laminated alternately. This assembly was covered with a final glass fiber surface and compressed to the target thickness while heating at a temperature above the melting point of the hot-melt web for approximately 30 seconds to obtain a thick laminated aerogel composite. The overall thickness of the thick aerogel composite was controlled by the number of layers.

[0154] 3. Testing of the composite

[0155] [Table 1]

[0156] CS: Colloidal silica, SA: Sodium alginate, TC: Thermal conductivity (measured with Fox 200) *:-: The complex was easily separated; +: The complex was not easily separated.

[0157] **:-: Combustion;+: May not combust, but may carbonize.

[0158] References: EP 0850206 B1 EP 0854892 B1 EP 0963358 B1 WO 2016053399 A2 US 9097377 B2 PCT / EP2023 / 955870 Robitzer et al., 2008, Langmuir, 24(21), 12547-12552. WO 2009 / 027310

Claims

1. A complex comprising two or more layers, (a) A layer (LA) having a diameter in the range of 0.1 to 4 mm before compression and a thickness in the range of 0.1 to 4 mm, (b) One adjacent binder layer (LB) having a thickness in the range of 0.01 to 1 mm, (c) Optionally, a support layer (LC) having a thickness in the range of 0.01 to 3 mm, adjacent to the binder layer. (d) Optionally, a second adjacent binder layer (LB') and a support or coating layer (LC') located on the second side of the particle layer (LA). Includes, The aerogel particle layer (LA) contains both a binder and aerogel particles, and includes a layer section (LA-1) adjacent to the binder layer (LB) having a thickness in the range of 0.01 to 1 mm. The composite comprises an allogel particle layer (LA) having a thickness of 0.05 mm or more and containing a binder-free layer section (LA-2).

2. The composite according to claim 1, wherein the binder layer (LB) adheres to more than 60% of the aerogel particles of the layer (LA), preferably to the support layer (LC).

3. The composite according to claim 1 or 2, wherein a binder layer (LB) and a support layer (LC) or a binder layer (LB') and (LC') are combined.

4. Uncompressed aerogel particles in layer (LA) are characterized from (α) to (γ): (α) Porosity of 80-99.6%, (β) 15-200kg / m ３ Particle bulk density, (γ) Thermal conductivity measured in a buffer-filled particle layer at 10°C, with a conductivity of 16–30 mW / mK. A composite according to claim 1 or 2, having one or more of the above.

5. The composite according to claim 1 or 2, wherein the individual aerogel particles can be compressed to 5-98% of their original thickness without visible damage during compression at a compression rate of 0.01-5 mm / second, or the force reduction due to primary damage during compression is less than 1 N.

6. (i) The particle size distribution of the aerogel is monodisperse, polydisperse, or partially monodisperse, and / or (II) The composite according to claim 1 or 2, wherein the sphericity of the individual aerogel particles is in the range of 25% to 100%.

7. Aerogel is, (A) Containing 20 to 80% by mass of silica and 20% by mass of an ion-crosslinkable polycarboxylate polymer, the ion-crosslinkable polycarboxylate polymer is present in a concentration of at least 25 kg / m³ ３ is, or (B) Containing 20-90% by mass of silica and 10% by mass of alginate, but with at least 15 kg / m³ of alginate. ３ is, or (C) Contains 20-85% by mass of silica and 15% by mass of pectin, but with pectin at least 20 kg / m³ ３ is, or (D) Containing 20-80% by mass of silica and 20% by mass of CMC, but with at least 25 kg / m³ of CMC. ３ is, or (E) Containing 20-85% by mass of silica and 7.5% by mass of alginate, with alginate at least 15 kg / m³ ３ And the non-alginate ion crosslinkable polycarboxylate polymer is at least 10 kg / m ３ That is The composite according to claim 1 or 2, wherein the composite is a silica-based aerogel.

8. The composite according to claim 1 or 2, wherein the binder is selected from reactive binders based on acrylate, polyurethane, epoxy resin, silicone, or water glass, or other inorganic binder systems, or from thermoplastic binders based on PE, PP, PA, TPU, PLA, or other bio-based polymers, silicone, or mixtures thereof.

9. The following steps, (i) A step of forming a binder layer (LB), (ii) A step of forming a layer (LA) containing aerogel particles having a diameter in the range of 0.1 to 4 mm before compression, (iii) A process for forming a composite including layer (LA) and layer (LB) by applying conditions suitable for achieving stable bonding between layer (LA) and layer (LB), and the formation of layer sections (LA-1) with a thickness of 0.01 to 1 mm including the binder and aerogel particles, and layer sections (LA-2) with a thickness of 0.05 mm or more that do not include the binder. A method for preparing a complex comprising two or more layers, including Uncompressed aerogel particles of layer (LA) preferably have characteristics (α) to (γ): (α) Porosity of 80-99.6%, (β) 15-200kg / m ３ Particle bulk density, (γ) Thermal conductivity measured in a buffer-filled particle layer at 10°C, with a conductivity of 16–30 mW / mK. A method having one or more of the following.

10. The method according to claim 9, wherein the aerogel is a silica-based aerogel.

11. The aforementioned method, (iv) A step of compressing the composite so that the aerogel is compressed to 5-98% of its original thickness. (v) A process of applying a compression speed in the range of 0.01 to 1 mm / second. The method according to claim 9 or 10, including the method described in claim 9 or 10.

12. The method according to claim 9 or 10, wherein the thickness of the composite is in the range of 0.1 to 20 mm.

13. The method according to claim 9 or 10, wherein the thickness of the layer (LA) containing aerogel particles is in the range of 0.1 to 4 mm.

14. The method according to claim 9 or 10, wherein the binder is selected from the group consisting of acrylate, polyurethane, epoxy resin, silicone, or thermoplastic binders such as PE, PP, PA, TPU, and PLA.

15. A method for using the composite according to claim 1 or 2, or a composite obtained or obtainable by the method of claim 9 or 10, as thermal insulation in buildings and construction, home appliances, thermologistics, cryogenic applications, automotive applications, infrastructure applications, marine applications, oil and gas applications, or apparel, or as a heat shield or heat transfer inhibitor in batteries.

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