High-temperature insulating laminate containing an aerogel layer

Abstract

The present disclosure includes high temperature thermal insulation laminates. Some laminates have a front surface; a rear surface; one or more heat spreading layers, each comprising at least 90% by weight of a metal or graphite having a melting point of at least 1,300°C and a thermal conductivity of at least 15 W / Km; and one or more thermal insulating layers coupled to the heat spreading layer, each comprising a layer of polymer aerogel, wherein at least a majority of the front surface is defined by one of the heat spreading layers. TIFF2023525572000006.tif79131

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority to U.S. Provisional Patent Application No. 63 / 025,953, filed on 15 May 2020, which is incorporated herein by reference in its entirety without waiver of rights.

[0002] A. Field of Invention The present invention generally relates to thermal insulation materials for use in high-temperature environments (e.g., above 1,000°C), and more specifically, to flexible (e.g., can be arranged in a roll) and / or thin (e.g., with a thickness of 6 × 1 / 1000 inch (mil) to 125 mil) such materials. [Background technology]

[0003] B. Description of related technologies In many cases, it is desirable to protect components from high-temperature environments and / or to insulate them. Traditionally, ceramic fiber-based materials, such as those containing fiberglass, silica fibers, or alumina fibers, have been used, which can be placed around components in high-temperature environments or used to cover high-temperature environments. However, such materials are relatively brittle, inflexible, and prone to cracking, which reduces their effectiveness. [Overview of the project]

[0004] Aerogel is another material that can be used for thermal insulation and, in contrast to the materials mentioned above, can be relatively flexible. However, when aerogel is exposed to high-temperature environments (e.g., above 1,000°C), such as flames, it can burn or carbonize, shortening its service life. Nevertheless, some of the laminates of the present invention enable the use of one or more aerogel layers as thermal insulation in such high-temperature environments by including at least one or more heat-dispersing layers, each comprising a high-temperature resistant and thermally conductive material, which can help shield the aerogel layers from the high-temperature environment. Such heat-dispersing layers can reduce the occurrence of hot spots along the aerogel layers and the resulting burning or carbonization of the aerogel layers by, for example, diffusing heat from the environment along the laminate. Suitable high-temperature resistant and thermally conductive materials may be, for example, graphite or metal having: (1) a melting point of at least 1,300°C (e.g., at least 1,600°C, at least 1,900°C, at least 2,200°C, at least 2,400°C, at least 2,700°C, at least 3,000°C, or at least 3,300°C); and (2) a thermal conductivity of at least 15 W / Km (e.g., at least 30 W / Km, at least 40 W / Km, at least 50 W / Km, at least 75 W / Km, at least 100 W / Km, at least 125 W / Km, at least 150 W / Km, or at least 175 W / Km).

[0005] Some of the laminates of the present invention are also relatively thin, which can enhance their usefulness. For example, in some laminates, the thermal dispersion layer may each have a thickness of 1.0 mil to 10.0 mil (e.g., 1.0 mil to 5.0 mil, or about 2.0 mil), and the aerogel layer may each have a thickness of 1.5 mil to 800 mil (e.g., 1.5 mil to 400 mil, 1.5 mil to 200 mil, 1.5 mil to 80 mil, 1.5 mil to 40 mil, 1.5 to 20 mil, 1.5 mil to 10 mil, 1.5 to 7.0 mil, 3.0 mil to 7.0 mil, about 6.5 mil, or about 5.0 mil). To further illustrate, such a laminate may have a total thickness of 6.0 mil to 150 mil (e.g., 6.0 mil to 75 mil, 6.0 mil to 50 mil, or 6.0 mil to 25 mil). In some laminates, the aerogel layers may have thermal conductivity values ​​of 0.001–0.5 W / mK, 0.005–0.2 W / mK, 0.01–0.1 W / mK, 0.01–0.5 W / mK, or approximately 0.03 W / mK, measured using steady-state thermal transfer from flat slab specimens with a Netzsch HFM 436 / 3 / 1E Lamda heat flow meter device in accordance with ASTM C518-10.

[0006] To further enhance their usefulness, some of the laminates of the present invention may be relatively flexible. For example, some laminates can be arranged in a roll shape with an inner diameter of 10 cm or less (e.g., 8 cm, 5 cm, 4 cm, 2 cm, or 1 cm or less) without undergoing permanent deformation. Such flexibility can be provided, even if not to the level of this example, by the relatively thinness of the materials of the thermal dispersion layer, aerogel layer, and other (if any) layers of the laminate, and / or by the relatively thinness of those layers (e.g., those mentioned above).

[0007] Some of the laminates of the present invention include a front surface; a rear surface; one or more heat dispersing layers, each containing at least 90% by weight of a metal or graphite having a melting point of at least 1,300°C and a thermal conductivity of at least 15 W / Km; and one or more insulating layers bonded to the heat dispersing layers, wherein at least a large portion of the front surface is defined by one of the heat dispersing layers. In some laminates, the heat dispersing layer includes two or more heat dispersing layers, wherein at least a large portion of the front surface of the laminate is defined by one of the first heat dispersing layers, and at least a large portion of the rear surface of the laminate is defined by one of the second heat dispersing layers. In some laminates, the insulating layer includes two or more insulating layers, wherein no heat dispersing layer is located between adjacent insulating layers.

[0008] In some laminates, at least one of the heat-dispersing layers contains at least 90% by weight of metal. In some laminates, the melting point of the metal is at least 1,600°C, at least 1,900°C, at least 2,200°C, at least 2,400°C, at least 2,700°C, at least 3,000°C, or at least 3,300°C. In some laminates, the melting point of the metal is less than 3,800°C or less than 3,600°C. In some laminates, the thermal conductivity of the metal is greater than 15 W / Km, greater than 30 W / Km, greater than 40 W / Km, greater than 50 W / Km, greater than 75 W / Km, greater than 100 W / Km, greater than 125 W / Km, greater than 150 W / Km, or greater than 175 W / Km. In some laminates, the thermal conductivity of the metal is less than 200 W / Km. In some laminates, the metals include molybdenum, tungsten, rhenium, tantalum, niobium, stainless steel, or alloys thereof.

[0009] In some laminates, at least one of the heat-dispersing layers contains at least 90% by weight of graphite.

[0010] In some laminates, at least one of the heat-dispersing layers has a thickness of 1.0 to 10.0 mils or 1.0 to 5.0 mils. In some laminates, at least one of the heat-dispersing layers has a thickness of approximately 2.0 mils.

[0011] In some aspects, at least one of the insulating layers may contain a porous material. In some aspects, each insulating layer may independently contain a porous material. In certain aspects, the porous material may be an open-cell porous material. In certain other aspects, the porous material may be a closed-cell porous material. In certain aspects, the porous material may be a foam. In certain aspects, the foam may be an organic or silicone foam. Non-limiting examples of organic foams may include polyurethane, polystyrene, polyvinyl chloride, (meth)acrylic polymer, polyamide, polyimide, polyaramid, polyurea, polyester, polyolefin (e.g., polyethylene, polypropylene, ethylene propylene diene monomer (EPDM) foam), polyethylene terephthalate, polybutylene terephthalate, polyvinyl chloride, polyvinyl acetate, ethyl vinyl alcohol (EVOH), ethylene vinyl acetate (EVA), polymethyl methacrylate, polyacrylate, polycarbonate, polysulfonate, or synthetic rubber foam, or any combination thereof. In certain aspects, the foam may be a polyurethane foam. In certain aspects, the porous material may be an aerogel. In some laminates, each insulating layer may contain a layer of polymer aerogel. In some laminates, at least one of the insulating layers contains an open-cell structure of polymer aerogel. In some laminates, at least one of the insulating layers contains micropores, mesopores, and / or macropores. In some laminates, at least one of the insulating layers has a pore volume in which micropores occupy at least 10%, at least 50%, at least 75%, or at least 95% of the pore volume. In some laminates, at least one of the insulating layers has a pore volume in which mesopores occupy at least 10%, at least 50%, at least 75%, or at least 95% of the pore volume.In some laminates, for at least one of the insulating layers, the polymer aerogel layer has pore volume, with macropores accounting for at least 10%, at least 50%, at least 75%, or at least 95% of the pore volume. In some laminates, for at least one of the insulating layers, the polymer aerogel layer has pore volume, with micropores and / or mesopores accounting for at least 10%, at least 50%, at least 75%, or at least 95% of the pore volume. In some laminates, for at least one of the insulating layers, the polymer aerogel layer has an average pore diameter of 2.0 nm to 50 nm. In some laminates, for at least one of the insulating layers, the polymer aerogel layer has an average pore diameter of 50 nm to 5,000 nm. In some laminates, the average pore diameter is 100 nm to 800 nm, 100 nm to 500 nm, 150 nm to 400 nm, 200 nm to 300 nm, or 225 nm to 275 nm.

[0012] In some laminates, the polymer aerogel layer in at least one of the insulating layers contains at least 90% by weight of an organic polymer. In some laminates, the polymer aerogel layer in at least one of the insulating layers contains at least 90% by weight of polyimide, polyamide, polyaramid, polyurethane, polyurea, polyester, or a mixture thereof. In some laminates, the polymer aerogel layer in at least one of the insulating layers contains at least 90% by weight of polyimide.

[0013] In some aspects, at least one or more insulation layers may include fibers without the porous material of the present invention. In other aspects, at least one or more insulation layers may include a combination of the porous material of the present invention and fibers (e.g., fibers dispersed or aligned within the porous material). The fibers may be natural, synthetic, semi-synthetic fibers, or a combination thereof. The fibers may include plant, woody, animal, mineral, biofibers, or a combination thereof. In some specific examples, the fibers may include rayon, bamboo, diacetate, triacetate fibers, polyester fibers, aramid fibers, or a combination thereof. In some embodiments, the fibers may include metal fibers, carbon fibers, carbide fibers, glass fibers, mineral fibers, basalt fibers, or a combination thereof. In some embodiments, the fibers may include thermoplastic polymer fibers, thermosetting polymer fibers, or a combination thereof. Non-limiting examples of thermoplastic fibers include polyethylene terephthalate (PET), polymers of the polycarbonate (PC) family, polybutylene terephthalate (PBT), poly(1,4-cyclohexylidenecyclohexane-1,4-dicarboxylate) (PCCD), glycol-modified polycyclohexyl terephthalate (PCTG), poly(phenylene oxide) (PPO), polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), polystyrene (PS), polymethyl methacrylate (PMMA), polyethyleneimine, or polyethere. This includes fibers made from luimide (PEI) and its derivatives, thermoplastic elastomers (TPE), terephthalic acid (TPA) elastomers, poly(cyclohexanedimethylene terephthalate) (PCT), polyethylene naphthalate (PEN), polyamide (PA), polysulfone sulfonate (PSS), polysulfone sulfonate, polyether ether ketone (PEEK), polyether ketone ketone (PEKK), acrylonitrile butyldiene styrene (ABS), polyphenylene sulfide (PPS), copolymers thereof, or mixtures thereof.Non-limiting examples of thermosetting fibers include fibers of unsaturated polyester resins, polyurethanes, polyoxybenzylmethylene glycol anhydride (e.g., Bakelite), urea formaldehyde, diallyl phthalate, epoxy resins, epoxy vinyl esters, polyimides, cyanate esters of polycyanurates, dicyclopentadienes, phenols, benzoxazines, copolymers thereof, or mixtures thereof. In some embodiments, the fibers are polyaramids, polyimides, polybenzoxazoles, polyurethanes, or mixtures thereof. In some embodiments, the fibers are vinylon. In some embodiments, the fibers are polyester fibers. In some embodiments, the fibers are nonwoven fabrics. In some embodiments, the fibers form a fiber matrix. In some embodiments, the fibers are 5 μm thick. 2 ~40,000 μm 2 The average filament cross-sectional area and average length are 20 mm to 100 mm. In some embodiments, the cross-sectional area is 5, 10, 15, 20, 25, 50, 100, 150, 200, 250, 300, 350, 400, 450, or 500 μm. 2, or any two of those values. In some embodiments, the fibers have an average length of about 0.1, 0.2, 0.3, 0.4, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900, 1000, 1500, 2000, 3000, 4000, 5000 mm, or any two of those values. Bundles of various types of fibers can be used depending on the intended application of the internally reinforced aerogel. For example, the bundle may be of carbon fiber or ceramic fiber, or of fiber that is a precursor of carbon or ceramic, glass fiber, aramid fiber, or a mixture of different types of fibers. The bundle may contain any number of fibers. For example, a bundle may contain 400, 750, 800, 1375, 1000, 1500, 3000, 6000, 12000, 24000, 50000, or 60000 filaments. The fibers may have filament diameters of 5–24 microns, 10–20 microns, or 12–15 microns, or any range in between, or filament diameters of 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 microns, or any value in between. The fibers in a bundle of fibers may be 7 μm in diameter. 2 ~800μm 2 The average filament cross-sectional area may be such that the average diameter of the circular fibers is 3 to 30 microns. In some embodiments, the fiber matrix includes felt, padding, nonwoven fabric, or mat.

[0014] In some laminates, for at least one of the thermal insulation layers, the polymer aerogel layer has a thickness of 1.5 mil to 800 mil, 1.5 mil to 400 mil, 1.5 mil to 200 mil, 1.5 mil to 80 mil, 1.5 mil to 40 mil, 1.5 to 20 mil, 1.5 mil to 10 mil, 1.5 mil to 7.0 mil, 3.0 mil to 7.0 mil, about 6.5 mil, or about 5.0 mil; and / or has a thermal conductivity of 0.001 to 0.5 W / mK, 0.005 to 0.2 W / mK, 0.01 to 0.1 W / mK, 0.01 to 0.5 W / mK, or about 0.03 W / mK, where the thermal conductivity is measured using steady-state heat transfer through a flat slab specimen by a Netzsch HFM 436 / 3 / 1E Lambda, heat flow meter device in accordance with ASTM C518-10.

[0015] Some laminates include one or more adhesive layers disposed between adjacent layers of the thermal dispersion layer and the thermal insulation layer, respectively. In some laminates, at least one of the adhesive layers includes silicone. In some laminates, the silicone includes polydimethylsilicone. In some laminates, the silicone includes biphenyl silicone. In some laminates, at least one of the adhesive layers has a thickness of 0.5 mil to 5.0 mil, 0.5 mil to 3.0 mil, 0.5 mil to 2.0 mil, or 1.0 mil to 2.0 mil.

[0016] In some laminates, the laminate has a thickness of 6.0 mil to 150 mil, 6.0 mil to 75 mil, 6.0 mil to 50 mil, or 6.0 mil to 25 mil.

[0017] In some laminates, the laminate can maintain mechanical integrity when exposed to a temperature of at least 800 °C, at least 1,000 °C, at least 1,300 °C, at least 1,600 °C, at least 1,900 °C, or at least 2,200 °C for at least 30 seconds, at least 1 minute, at least 1.5 minutes, or at least 2 minutes.

[0018] In some laminates, the laminate does not contain fibers. In some laminates, the laminate does not contain ceramics.

[0019] In some laminates, the laminate is arranged in a roll shape such that a part of the front surface of the laminate faces a part of the rear surface of the laminate. Some of the devices of the present invention include one of the laminates of the present invention and a protective film removably disposed on at least one of the front and rear surfaces.

[0020] Some of the methods of the present invention include exposing one of the laminates of the present invention to a temperature of at least 800 °C, at least 1,000 °C, at least 1,300 °C, at least 1,600 °C, at least 1,900 °C, or at least 2,200 °C for at least 30 seconds, at least 1 minute, at least 1.5 minutes, or at least 2 minutes, where during the exposure, the laminate maintains mechanical integrity.

[0021] Similarly, a method for producing a layer of a polymeric aerogel suitable for use in at least some of the laminates of the present invention is also disclosed. The method may include: (a) providing a monomer or combination of monomers in a solvent to form a solution; (b) polymerizing the monomers in the solution to form a polymer gel matrix; and (c) subjecting the polymer gel matrix to conditions sufficient to remove liquid from the polymer gel matrix to form an aerogel having a polymer matrix with an open cell structure. Step (b) may further include adding a curing agent to the solution to reduce the solubility of the polymer formed in the solution and to form macropores in the gel matrix, and the macropores formed contain liquid from the solution. The process may include flowing the polymer gel matrix in step (b) onto a support such that a layer of the polymer gel matrix is formed on the support, where the aerogel in step (c) is in the form of a film.

[0022] The porous structure of aerogels, including the amount and volume of macroporous, mesoporous, and microporous cells, can be controlled primarily by controlling the polymer / solvent dynamics during the formation of the polymer gel matrix. As an example, a curing agent can be added to the solution in step (b) to reduce the solubility of the polymer formed in the solution and to form macropores in the gel matrix, the formed macropores containing liquid from the solution. Such a curing agent could be, for example, 1,4-diazabicyclo[2.2.2]octane. Alternatively, to improve the solubility of the polymer formed in the solution, adding a curing agent such as triethylamine to the solution in step (b) will result in the formation of a relatively small number of macropores in the gel matrix. In another example, when forming a polyimide aerogel, increasing the ratio of rigid amines (e.g., p-phenylenediamine (p-PDA)) to more flexible diamines (e.g., 4,4'-oxydianiline (4,4'-ODA)) in the polymer backbone may favor the formation of macropores compared to smaller mesopores and micropores.

[0023] More detailed information regarding monomers, solvents, and processing conditions is broadly described below, but the following can be adjusted to control the porous structure of the aerogel: (1) polymerization solvent; (2) polymerization temperature; (3) polymer molecular weight; (4) molecular weight distribution; (5) copolymer composition; (6) branching amount; (7) crosslinking amount; (8) branching method; (9) crosslinking method; (10) method used for gel formation; (11) type of catalyst used for gel formation; (12) chemical composition of the catalyst used for gel formation; (13) amount of catalyst used for gel formation; (14) gel formation temperature; (15) type of gas flowing over the material during gel formation; (16) velocity of gas flowing over the material during gel formation; (17) atmospheric pressure during gel formation; (18) removal of dissolved gases during gel formation; (19) presence of solid additives in the resin during gel formation; (20) duration of the gel formation process; (21) substrate used for gel formation; (22) at each stage of any solvent exchange process. (23) the type of solvent used; (24) the composition of the solvent used in each stage of any solvent exchange process; (25) the time used in each stage of any solvent exchange process; (26) the residence time of the portion in each stage of the solvent exchange process; (27) the flow rate of any solvent exchange solvent; (28) the stirring speed of any solvent exchange solvent; (29) the temperature used in each stage of any solvent exchange process; (30) the ratio of the volume of any solvent exchange solvent to the volume of the portion; (31) the drying method; (32) the temperature at each stage of the drying process; (33) the pressure at each stage of the drying process; (34) the composition of the gas used in each stage of the drying process; (35) the gas flow rate in each stage of the drying process; (36) the gas temperature in each stage of the drying process; (37) the temperature of the portion in each stage of the drying process; (38) the presence of an enclosure around the portion in each stage of the drying process; (39) the type of enclosure around the portion during drying; and / or (40) the solvent used in each stage of the drying process.

[0024] The term "aerogel" generally refers to a class of materials produced by forming a gel, removing the mobile interstitial solvent phase from the pores, and then replacing it with a gas or gaseous material. By controlling the gel and evaporation system, density, shrinkage, and pore collapse can be minimized. The aerogels of the present invention can include macropores, mesopores, and / or micropores. In a preferred aspect, macropores can occupy most (e.g., more than 50%) of the pore volume of the aerogel. In other alternative aspects, most of the pore volume of the aerogel can be occupied by mesopores and / or micropores such that less than 50% of the pore volume of the aerogel is occupied by macropores. In some embodiments, the aerogels of the present invention have a low bulk density (about 0.75 g / cm 3 preferably about 0.01 g / cm 3 ~0.5 g / cm 3 ), a high surface area (generally about m 2 / g 10 - 1,000 m 2 / g or more, preferably about 50 m 2 / g - 1000 m 2 / g), a high porosity (about 20% or more, preferably more than about 85%), and / or a relatively large pore volume (more than about 0.3 mL / g, preferably about 1.2 mL / g or more).

[0025] The presence of macropores, mesopores, and / or micropores in the aerogel of the present invention can be determined by mercury intrusion porosimetry (MIP) and / or gas physicoadsorption experiments. MIP testing can be used to measure mesopores and macropores (i.e., American Standard Testing Method (ASTM) D4404-10, Standard Test Method for Determination of Pore Volume and Pore Volume Distribution of Soil and Rock by Mercury Intrusion Porosimetry). Gas physicoadsorption experiments can be used to measure micropores (i.e., ASTM D1993-03 (2008) Standard Test Method for Precipitated Silica - Surface Area by Multipoint BET Nitrogen).

[0026] The term "combined" is defined as being linked, but not necessarily directly or mechanically. Two "combined" items may be single entities or linked to each other through one or more intermediate components or elements.

[0027] The terms “a” and “an” are defined as one or more unless the disclosure expressly requires otherwise.

[0028] The term “substantially” is defined as being largely but not entirely the specified (and including the specified; for example, substantially 90 degrees includes 90 degrees, and substantially parallel includes parallel). In any disclosed embodiment, the terms “substantially,” “approximately,” and “about” may be replaced with “within [a certain percentage]” of the specified, where the percentage is 0.1, 1, 5, or 10%.

[0029] The phrase "and / or" means "and or." For example, A, B, and / or C include: A only, B only, C only, a combination of A and B, a combination of A and C, a combination of B and C, or a combination of A, B, and C. In other words, "and / or" functions as an inclusive or.

[0030] The terms “comprise” (and any form of “comprises” and “comprising”), “have” (and any form of “has” and “having”), “include” (and any form of “includes” and “including”), and “contain” (and any form of “contains” and “containing”) are open-ended linking verbs. As a result, a device that “comprises,” “has,” “includes,” or “contains” one or more elements has, but is not limited to having only, those one or more elements. Similarly, a method that “comprises,” “has,” “includes,” or “contains” one or more stages has, but is not limited to having, those one or more stages.

[0031] Any aspect of any apparatus and method may consist of or essentially consist of any described elements, features, and / or steps, rather than comprise / have / include / contain them. Accordingly, in any of the claims, the phrase "consists of" or "essentially consists of" can be used in place of any of the aforementioned open-ended linking verbs to modify a given claim from one which otherwise used an open-ended linking verb.

[0032] Unless expressly prohibited by the nature of this disclosure or the aspects thereof, features of one aspect may be applied to other aspects, even if not described or illustrated.

[0033] [Invention 1001] Front and; Rear and; One or more heat dispersing layers, each of which is A metal having a melting point of at least 1,300°C and a thermal conductivity of at least 15 W / Km, or Graphite One or more heat dispersing layers containing at least 90% by weight of; One or more insulating layers bonded to a heat dissipation layer, each comprising a polymer aerogel layer, and A laminate containing, At least a large portion of the front surface is defined by one of the heat dissipation layers. Laminated structure. [Invention 1002] The heat dispersing layer includes two or more heat dispersing layers. At least a large portion of the front surface of the laminate is defined by one of the first heat-dispersing layers, and At least a large portion of the rear surface of the laminate is defined by one of the second heat-dispersing layers. A laminate according to the present invention 1001. [Invention 1003] A laminate according to the present invention 1001 or 1002, wherein at least one of the heat dispersing layers contains at least 90% by weight of metal. [Invention 1004] A laminate according to the present invention 1003, wherein the metal comprises molybdenum, tungsten, rhenium, tantalum, niobium, stainless steel, or an alloy thereof. [Invention 1005] A laminate according to the present invention 1003 or 1004, wherein the melting point of the metal is at least 1,600°C, at least 1,900°C, at least 2,200°C, at least 2,400°C, at least 2,700°C, at least 3,000°C, or at least 3,300°C. [Invention 1006] A laminate according to any of the present invention 1003 to 1005, wherein the melting point of the metal is less than 3,800°C or less than 3,600°C. [Invention 1007] A laminate according to any of the present invention 1003 to 1006, wherein the thermal conductivity of the metal is greater than 15 W / Km, greater than 30 W / Km, greater than 40 W / Km, greater than 50 W / Km, greater than 75 W / Km, greater than 100 W / Km, greater than 125 W / Km, greater than 150 W / Km, or greater than 175 W / Km. [Invention 1008] A laminate according to any of the present invention 1003 to 1007, wherein the thermal conductivity of the metal is less than 200 W / Km. [Invention 1009] A laminate according to any one of the inventions 1001 to 1008, wherein at least one of the heat dispersing layers contains at least 90% by weight of graphite. [Invention 1010] A laminate according to any one of the invention 1001 to 1009, wherein at least one of the heat-dispersing layers has a thickness of 1.0 to 10.0 mils or 1.0 to 5.0 mils. [Invention 1011] A laminate of the present invention 1010, wherein at least one of the heat-dispersing layers has a thickness of about 2.0 mils. [Invention 1012] A laminate according to any one of the invention 1001 to 1011, wherein at least one of the insulating layers includes a polymer aerogel layer with an open-cell structure. [Invention 1013] A laminate according to any one of the invention 1001 to 1012, wherein at least one of the insulating layers comprises a polymer aerogel layer containing micropores, mesopores, and / or macropores. [Invention 1014] For at least one of the insulation layers, The polymer aerogel layer has pore volume, Micropores occupy at least 10%, at least 50%, at least 75%, or at least 95% of the pore volume. A laminate according to the present invention 1013. [Invention 1015] For at least one of the insulation layers, The polymer aerogel layer has pore volume, Mesopores occupy at least 10%, at least 50%, at least 75%, or at least 95% of the pore volume. A laminate according to the present invention 1013. [Invention 1016] For at least one of the insulation layers, The polymer aerogel layer has pore volume, Macropores occupy at least 10%, at least 50%, at least 75%, or at least 95% of the pore volume. A laminate according to the present invention 1013. [Invention 1017] For at least one of the insulation layers, The polymer aerogel layer has pore volume, Micropores and / or mesopores occupy at least 10%, at least 50%, at least 75%, or at least 95% of the pore volume. A laminate according to the present invention 1013. [Invention 1018] A laminate according to any one of the invention 1001 to 1012, wherein at least one of the insulating layers is a polymer aerogel layer having an average pore diameter of 2.0 nm to 50 nm. [Invention 1019] A laminate according to any one of the invention 1001 to 1012, wherein at least one of the insulating layers is a polymer aerogel layer having an average pore diameter of 50 nm to 5,000 nm. [Invention 1020] A laminate according to the present invention 1019, wherein the average pore diameter is 100nm to 800nm, 100nm to 500nm, 150nm to 400nm, 200nm to 300nm, or 225nm to 275nm. [Invention 1021] A laminate according to any one of the present invention 1001 to 1020, wherein at least one of the insulating layers is a polymer aerogel layer containing at least 90% by weight of an organic polymer. [Invention 1022] A laminate according to any one of the present inventions 1001 to 1020, wherein at least one of the insulating layers comprises a polymer aerogel layer containing at least 90% by weight of polyimide, polyamide, polyaramid, polyurethane, polyurea, polyester, or a mixture thereof. [Invention 1023] A laminate according to the present invention 1022, wherein at least one of the insulating layers is a polymer aerogel layer containing at least 90% by weight of polyimide. [Invention 1024] A laminate according to any of the present invention 1001 to 1023, wherein at least one of the insulating layers is a polymer aerogel layer having a thickness of 1.5 to 800 mils, 1.5 to 400 mils, 1.5 to 200 mils, 1.5 to 80 mils, 1.5 to 40 mils, 1.5 to 20 mils, 1.5 to 10 mils, 1.5 to 7.0 mils, 3.0 to 7.0 mils, about 6.5 mils, or about 5.0 mils. [Invention 1025] One or more adhesive layers are placed between adjacent layers of the heat dissipation layer and the insulation layer, respectively. A laminate according to any of the present invention 1001 to 1024, including the above. [Invention 1026] A laminate according to the present invention 1025, wherein at least one of the adhesive layers contains silicone. [Invention 1027] A laminate according to the present invention 1026, wherein the silicone contains polydimethylsilicone. [Invention 1028] A laminate according to the present invention 1026, wherein the silicone contains biphenyl silicone. [Invention 1029] A laminate according to any one of the present invention 1026 to 1028, wherein at least one of the adhesive layers has a thickness of 0.5 mil to 5.0 mil, 0.5 mil to 3.0 mil, 0.5 mil to 2.0 mil, or 1.0 mil to 2.0 mil. [Invention 1030] The insulation layer includes two or more insulation layers, There is no heat dissipation layer between adjacent layers of the insulation layer. A laminate according to any of the present invention 1001 to 1029. [Invention 1031] A laminate according to any of the present invention 1001 to 1030, which does not contain fibers. [Invention 1032] A laminate according to any of the present invention 1001 to 1031, which does not contain ceramics. [Invention 1033] A laminate according to any of the present invention 1001 to 1032, having a thickness of 6.0 mil to 150 mil, 6.0 mil to 75 mil, 6.0 mil to 50 mil, or 6.0 mil to 25 mil. [Invention 1034] A laminate according to any one of the present invention 1001 to 1033, wherein a part of the front surface of the laminate is arranged in a roll shape so as to face a part of the rear surface of the laminate. [Invention 1035] A laminate according to any one of the present invention 1001 to 1034, which can maintain mechanical integrity when exposed to a temperature of at least 800°C, at least 1,000°C, at least 1,300°C, at least 1,600°C, at least 1,900°C, or at least 2,200°C for at least 30 seconds, at least 1 minute, at least 1.5 minutes, or at least 2 minutes. [Invention 1036] A laminate according to any of the invention 1001 to 1035, wherein at least one of the insulating layers is a polymer aerogel layer having a thermal conductivity of 0.001 to 0.5 W / mK, 0.005 to 0.2 W / mK, 0.01 to 0.1 W / mK, 0.01 to 0.5 W / mK, or about 0.03 W / mK, where the thermal conductivity is measured using steady-state heat transfer on a flat slab specimen with a Netzsch HFM 436 / 3 / 1E Lamda, heat flow meter apparatus in accordance with ASTM C518-10. [Invention 1037] A method comprising the step of exposing a laminate of any of the present invention 1001 to 1036 to a temperature of at least 800°C, at least 1,000°C, at least 1,300°C, at least 1,600°C, at least 1,900°C, or at least 2,200°C for at least 30 seconds, at least 1 minute, at least 1.5 minutes, or at least 2 minutes, During exposure, the laminate maintains its mechanical integrity. method. [Invention 1038] A laminate according to any of invention 1001 to 1036, A protective film is detachably disposed on the surface of at least one of the front and rear surfaces. A device including a device. Some details and other information related to the aforementioned aspects are described below. [Brief explanation of the drawing]

[0034] The following drawings are illustrative and not limiting. For brevity and clarity, not all features of a given structure are always labeled in every drawing in which that structure appears. The same reference number does not necessarily refer to the same structure. Rather, the same reference number may be used to indicate similar features or features with similar functions, just as it may not refer to identical reference numbers.

[0035] [Figure 1] Figure 1A is a top view of one of the laminates of the present invention, including a heat dissipation layer and three insulating layers. Figure 1B is a cross-sectional side view of the laminate of Figure 1A, obtained along line 1B-1B in Figure 1A. [Figure 2] Figure 2A is a cross-sectional side view of one of the thermal insulation layers of the laminate shown in Figure 1A. Figure 2B is a cross-sectional side view of a thermal insulation layer that may be suitable for use in some of the laminates of the present invention. [Figure 3] Figure 1A is a cross-sectional side view of the heat-dispersing layer of the laminate. [Figure 4] Figures 4A to 4C show the laminates of the present invention, each having a different number of heat dissipation layers and / or different number of heat insulating layers than the laminate in Figure 1A. [Figure 5] This shows one example of the laminated structure of the present invention arranged in a roll shape. [Figure 6] This is the distribution of pore diameters for the first non-restrictive aerogel of the present invention. [Figure 7] This is the distribution of pore diameters for the second non-limiting aerogel of the present invention. [Figure 8] This is the distribution of pore diameters for the third non-limiting aerogel of the present invention. [Modes for carrying out the invention]

[0036] Detailed explanation A. High-temperature insulating laminate Referring here to Figures 1A and 1B, the laminate shown is a first embodiment 10a of the laminate of the present invention. Laminate 10a includes a heat dispersing layer 14 and three insulating layers 18a bonded to the heat dispersing layer. However, the laminate of the present invention may include any suitable number of heat dispersing layers (e.g., 1, 2, 3, or more heat dispersing layers) and any suitable number of insulating layers (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or more insulating layers). Generally, the heat dispersing layer helps to shield the insulating layer from a high-temperature environment, allowing the use of the insulating layer which otherwise could burn or carbonize prematurely in that environment. To illustrate using laminate 10a, the laminate has a front surface 22a, the heat dispersing layer 14 defines at least a large portion (e.g., at least 90%, or at most all) of the front surface of the laminate (e.g., the planar area of ​​the front surface), and each of the insulating layers 18a is located beneath the heat dispersing layer. Thus, the heat-dispersing layer can help dissipate heat from the environment along the laminate, reducing the exposure of the insulation layer to hot spots that could otherwise burn or carbonize the insulation layer. Through at least such a configuration, the laminate 10a, and others described later, can withstand exposure to temperatures of at least 800°C, at least 1,000°C, at least 1,300°C, at least 1,600°C, at least 1,900°C, or at least 2,200°C for at least 30 seconds, at least 1 minute, at least 1.5 minutes, or at least 2 minutes, while maintaining its mechanical shape and integrity.

[0037] Turning to Figure 2A, the thermal insulation layer 18a is shown. In some aspects, the thermal insulation layer 18a may contain a porous material. In certain aspects, the porous material may be an open-cell porous material. In certain other aspects, the porous material may be a closed-cell porous material. In certain aspects, the porous material may be a foam. In certain aspects, the foam may be an organic or silicone foam. In certain aspects, the organic foam may be polyurethane, polystyrene, polyvinyl chloride, (meth)acrylic polymer, polyamide, polyimide, polyaramid, polyurea, polyester, polyolefin (e.g., polyethylene, polypropylene, ethylene propylene diene monomer (EPDM) foam, etc.), polyethylene terephthalate, polybutylene terephthalate, polyvinyl chloride, polyvinyl acetate, ethyl vinyl alcohol (EVOH), ethylene vinyl acetate (EVA), polymethyl methacrylate, polyacrylate, polycarbonate, polysulfonate, or synthetic rubber foam, or any combination thereof. In certain aspects, the foam may be a polyurethane foam. In certain aspects, the porous material may be an aerogel. In certain aspects, the insulating layer 18a includes a layer of polymer aerogel. The polymer aerogel layer includes an open-cell structure. Provided for illustrative purposes, at least 10%, at least 50%, at least 75%, or at least 95% of the pore volume of the polymer aerogel layer are occupied by micropores, mesopores, and / or macropores. The polymer aerogel layer has an average pore diameter of 50 nm to 5,000 nm (e.g., 100 nm to 800 nm, 100 nm to 500 nm, 150 nm to 400 nm, 200 nm to 300 nm, or 225 nm to 275 nm). In the thermal insulation layer 18a, the polymer aerogel layer has a thickness 26 of 1.5 mil to 800 mil, 1.5 mil to 40 mil, 1.5 to 20 mil, 1.5 mil to 7.0 mil, 3.0 mil to 7.0 mil, approximately 6.5 mil, or approximately 5.0 mil.In some aspects, the polymer aerogel layer in the insulating layer 18a has a thermal conductivity of 0.001–0.5 W / mK, 0.005–0.2 W / mK, 0.01–0.1 W / mK, 0.01–0.5 W / mK, or about 0.03 W / mK, where the thermal conductivity is measured using steady-state heat transfer on a flat slab specimen with a Netzsch HFM 436 / 3 / 1E Lambda heat flow meter apparatus in accordance with ASTM C518-10. In some aspects, the insulating layer 18a may include fibers without the porous material of the present invention. In other aspects, the insulating layer 18a may include a combination of the porous material and fibers of the present invention (e.g., fibers dispersed or aligned within the porous material). The fibers may be natural, synthetic, semi-synthetic fibers, or a combination thereof. The fibers may include plant, woody, animal, mineral, biofibers, or a combination thereof. In some specific examples, the fibers may include rayon, bamboo, diacetate, triacetate fibers, polyester fibers, aramid fibers, or combinations thereof. In some embodiments, the fibers may include metal fibers, carbon fibers, carbide fibers, glass fibers, mineral fibers, basalt fibers, or combinations thereof. In some embodiments, the fibers may include thermoplastic polymer fibers, thermosetting polymer fibers, or combinations thereof.Non-limiting examples of thermoplastic fibers include polyethylene terephthalate (PET), polymers of the polycarbonate (PC) family, polybutylene terephthalate (PBT), poly(1,4-cyclohexylidenecyclohexane-1,4-dicarboxylate) (PCCD), glycol-modified polycyclohexyl terephthalate (PCTG), poly(phenylene oxide) (PPO), polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), polystyrene (PS), polymethyl methacrylate (PMMA), polyethyleneimine, or polyethere. Fibers of luimide (PEI) and its derivatives, thermoplastic elastomers (TPE), terephthalic acid (TPA) elastomers, poly(cyclohexanedimethylene terephthalate) (PCT), polyethylene naphthalate (PEN), polyamide (PA), polysulfone sulfonate (PSS), polysulfone sulfonate, polyether ether ketone (PEEK), polyether ketone ketone (PEKK), acrylonitrile butyldiene styrene (ABS), polyphenylene sulfide (PPS), copolymers thereof, or mixtures thereof. Non-limiting examples of thermosetting fibers include fibers of unsaturated polyester resins, polyurethanes, polyoxybenzylmethylene glycol anhydride (e.g., Bakelite), urea formaldehyde, diallyl phthalate, epoxy resins, epoxy vinyl esters, polyimides, cyanate esters of polycyanurates, dicyclopentadiene, phenols, benzoxazines, copolymers thereof, or mixtures thereof. In some embodiments, the fiber is polyaramid, polyimide, polybenzoxazole, polyurethane, or a mixture thereof. In some embodiments, the fiber is vinylon. In some embodiments, the fiber is polyester fiber. In some embodiments, the fiber is a nonwoven fabric. In some embodiments, the fiber forms a fiber matrix. In some embodiments, the fiber is 5 μm thick. 2 ~40,000 μm 2The average filament cross-sectional area and average length are 20 mm to 100 mm. In some embodiments, the cross-sectional area is 5, 10, 15, 20, 25, 50, 100, 150, 200, 250, 300, 350, 400, 450, or 500 μm. 2 , or any two of those values. In some embodiments, the fibers have an average length of about 0.1, 0.2, 0.3, 0.4, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900, 1000, 1500, 2000, 3000, 4000, 5000 mm, or any two of those values. Bundles of various types of fibers can be used depending on the intended application of the internally reinforced aerogel. For example, the bundle may be of carbon fiber or ceramic fiber, or of fiber that is a precursor of carbon or ceramic, glass fiber, aramid fiber, or a mixture of different types of fibers. The bundle may contain any number of fibers. For example, a bundle may contain 400, 750, 800, 1375, 1000, 1500, 3000, 6000, 12000, 24000, 50000, or 60000 filaments. The fibers may have filament diameters of 5–24 microns, 10–20 microns, or 12–15 microns, or any range in between, or filament diameters of 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 microns, or any value in between. The fibers in a bundle of fibers may be 7 μm in diameter. 2 ~800μm 2 The average filament cross-sectional area may be such that the average diameter of the circular fibers is 3 to 30 microns. In some embodiments, the fiber matrix includes felt, padding, nonwoven fabric, or mat.

[0038] The materials and processes for preparing the polymer aerogel layer are described in sections B and C below.

[0039] In some embodiments, the laminate may include reinforcement, such as multiple fibers, to increase strength and / or stiffness. For example, referring to Figure 2B, an insulating layer 18b is shown which includes a reinforcing layer 38. While insulating layer 18b includes a single reinforcing layer 38, other insulating layers may have two, three, four, five, or more reinforcing layers. Such reinforcing layers may include one or more unidirectional sheets, woven sheets, and / or nonwoven sheets made of fibers, dispersed within a layer of polymer aerogel, or optionally in a thermoplastic or thermosetting resin (e.g., non-porous) that differs in structure and / or composition from the layer of polymer aerogel. If multiple sheets are included, the reinforcing layer may be a reinforced laminate. The sheets of the reinforcing layer 38 may be substantially fiberless (e.g., polymer films, such as fluoropolymer films). In addition, or alternatively, at least one (e.g., each) of the reinforcing layers 38 may include a paper sheet, which optionally contains cellulose fibers, vinylon fibers, polyester fibers, polyolefin fibers, and / or polypropylene fibers. Paper suitable for such a reinforcing layer 38 is commercially available from Hirose Paper Mfg. Co. (Kochi, Japan) or Hirose Paper North America (Macon, Georgia, USA).

[0040] In the thermal insulation layer 18b, the reinforcing layer 38 may be embedded in the polymer aerogel layer and / or bonded to the polymer aerogel layer (or between the layers) via, for example, one or more adhesive layers (e.g., 62 described later). In some embodiments, the reinforcing layer 38 may be located outside the thermal insulation layer of the laminate. The reinforcing or supporting layer 38 may be embedded in or bonded to the aerogel layer as described in section C. In some embodiments, for at least one (e.g., each) thermal insulation layer, reinforcing fibers may be dispersed throughout the polymer aerogel layer (e.g., not in the aforementioned sheets) such that the volume of the fibers is optionally greater than or equal to any one value of 0.1%, 10%, 20%, 30%, 40%, or 50% of the volume of the polymer aerogel layer, or between any two values. However, in some embodiments, the laminate does not contain fibers (e.g., to increase flexibility).

[0041] Suitable fibers include glass fibers, carbon fibers, aramid fibers, thermoplastic fibers, thermosetting fibers, ceramic fibers, basalt fibers, rock wool fibers, steel fibers, and cellulose fibers. The average filament cross-sectional area of ​​the fibers used for reinforcement is 7, 15, 30, 60, 100, 200, 300, 400, 500, 600, 700, or 800 μm. 2 It can be any one or more of the following values, or between any two values; for example, for a fiber having a circular cross-section, the average diameter of the fiber can be any one or more of the following values, or between any two values ​​(e.g., 5-24 μm, e.g., 10-20 μm or 12-15 μm).

[0042] Non-limiting examples of thermoplastic polymers that can be used as a material in which fibers are dispersed in the reinforcing layer 38 and / or for polymer reinforcing fibers include polyethylene terephthalate (PET), polycarbonate (PC), polybutylene terephthalate (PBT), poly(1,4-cyclohexylidenecyclohexane-1,4-dicarboxylate) (PCCD), glycol-modified polycyclohexyl terephthalate (PCTG), poly(phenylene oxide) (PPO), polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), polystyrene (PS), polymethyl methacrylate (PMMA), polyethyleneimine, or polyetheric acid. This includes polyamides (PEI) and their derivatives, thermoplastic elastomers (TPE), terephthalic acid (TPA) elastomers, poly(cyclohexanedimethylene terephthalate) (PCT), polyethylene naphthalate (PEN), polyamides (PA), polysulfone sulfonates (PSS), polysulfone sulfonates, polyether ether ketones (PEEK), polyether ketone ketones (PEKK), acrylonitrile butyldiene styrene (ABS), polyphenylene sulfide (PPS), copolymers thereof, polyesters or derivatives thereof, polyamides or derivatives thereof (e.g., nylon), or mixtures thereof.

[0043] Non-limiting examples of thermoplastic fibers that can be used as materials in which fibers are dispersed in the reinforcing layer 38 and / or for polymer reinforcing fibers include unsaturated polyester resins, polyurethanes, polyoxybenzylmethylene glycol anhydride (e.g., Bakelite), urea formaldehyde, diallyl phthalate, epoxy resins, epoxy vinyl esters, polyimides, cyanate esters of polycyanurates, dicyclopentadienes, phenols, benzoxazines, copolymers thereof, or mixtures thereof.

[0044] Such reinforcement can increase the strength and stiffness of the laminate. For example, each of the insulating layers (e.g., 18b) reinforced with a polymer aerogel layer (e.g., by one or more embedded sheets and / or fiber reinforcement dispersed throughout the aerogel) may have a tensile strength of any one value greater than or equal to 5, 10, 15, 20, or 25 MPa, or between any two values, and / or a Young's modulus of any one value greater than or equal to 200, 225, 250, 275, 300, 325, or 350 MPa, or between any two values. Each of the reinforced layers 38 may also be stiffer than the other laminate layers; for example, the bending stiffness of each reinforced layer may be greater than the bending stiffness of each of the polymer aerogel layers of the heat dissipation layer 14 and the insulating layers (18a, 18b) by any one value greater than or equal to 10%, 20%, 30%, or 40%, or between any two values.

[0045] A further description of appropriate reinforcement of the aerogel layer (e.g., in the insulating layer 18b) is provided in U.S. Patent No. 10,500,557 by Sakaguchi et al., which is incorporated herein by reference in its entirety.

[0046] Figure 3 shows the thermal dispersion layer 14. The thermal dispersion layer 14 may contain a metal or graphite in any one or more of 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, 95 wt%, 96 wt%, 97 wt%, 98 wt%, or 99 wt%, or between any two of these values. A suitable metal may be one that is stable at high temperatures and has relatively high thermal conductivity. For example, such a metal may have a melting point of at least 1,300°C, at least 1,600°C, at least 1,900°C, at least 2,200°C, at least 2,400°C, at least 2,700°C, at least 3,000°C, or at least 3,300°C (e.g., and less than 3,800°C or less than 3,600°C). Such metals may also have thermal conductivity greater than 15 W / Km, 30 W / Km, 40 W / Km, 50 W / Km, 75 W / Km, 100 W / Km, 125 W / Km, 150 W / Km, or 175 W / Km (for example, but less than 200 W / Km). Non-limiting examples of such metals include molybdenum, tungsten, rhenium, tantalum, niobium, stainless steel, or alloys thereof. Commercially available materials that can be used as the thermal dispersion layer 14 (including graphite and the aforementioned metals) are shown in Table 2 below.

[0047] [Table 2]

[0048] The metal layer 14 may have any suitable thickness 50, such as 1.0 mil to 10.0 mil or 1.0 mil to 5.0 mil. As an example, the metal layer 14 may have a thickness of approximately 2.0 mil.

[0049] Returning to Figure 1B, optionally, the heat dispersive layer 14 and the heat insulating layer 18a are joined to each other by an adhesive layer 62. Such an adhesive layer may include, for example, silicone (e.g., polydimethyl silicone, biphenyl silicone, etc.). The adhesive layer 62 may have a thickness of 0.5 to 5.0 mil, 0.5 to 3.0 mil, 0.5 to 2.0 mil, or 1.0 to 2.0 mil. In some embodiments, at least two layers of the laminate are joined to each other without an adhesive layer. For example, a polymer aerogel layer of the heat insulating layer (e.g., 18) can be formed on a heat dispersive layer (e.g., 14, which may be a substrate as described later) and optionally subsequently pressed into the heat dispersive layer (e.g., by arranging the laminate in a roll shape).

[0050] The laminate 10a may have a thickness 74 of 6.0 mil to 150 mil, 6.0 mil to 75 mil, 6.0 mil to 50 mil, or 6.0 mil to 25 mil, measured between its front and rear surfaces, 22a and 22b. The laminate 10a may also have any suitable length 78 and width 82. For example, the length 78 may be greater than or equal to any one of 0.1 m, 1.0 m, 10 m, 100 m, 500 m, and 1000 m, or between any two of these values, and the width 82 may be 0.01 m, 0.05 m, 0.10 m, 0.15 m, 0.20 m, 0.25 m, 0.30 m, 0.35 m, 0.40 m, 0.45 m, 0.50 m, 0 The values ​​may be one or more of any of 0.55m, 0.60m, 0.65m, 0.70m, 0.75m, 0.80m, 0.85m, 0.90m, 0.95m, 1.0m, 1.5m, 2.0m, 2.5m, 3.0m, 3.5m, 4.0m, 4.5m, 5.0m, 5.5m, 5.5m, and 6.0m, or between any two of these values. Similarly, the laminate 10a may have any suitable shape, including, for example, a rectangle, square, triangle, or other polygon, or a circle, ellipse, or other round shape.

[0051] The laminate 10a may include a plurality of passages 90, each extending through one or more of its layers, such as through one or more of its adhesive layers 62 (up to each including each of them), one or more of its thermal insulation layers 18a (up to each including each of them), and / or its heat dissipation layer 14 (or, in the case of a laminate having two or more heat dissipation layers, one or more of the heat dissipation layers (up to each including each of them)). Such passages may facilitate the ventilation of material (e.g., gas) from the laminate because their layers decompose when exposed to high temperatures. The passages 90 may be relatively small; for example, a passage may be characterized as a pinhole and / or may have a maximum cross-sectional dimension of any one value less than or equal to 5.0 mm, 4.0 mm, 3.0 mm, 2.0 mm, 1.0 mm, 0.5 mm, or 0.25 mm, or between any two of these values. The ventilation facilitated by the passages 90 may, in addition or alternatively, be facilitated by the open-cell structure of the polymer aerogel of the thermal insulation layer.

[0052] Figures 4A to 4D show further embodiments, 10b to 10d, of the laminate of the present invention. As shown, in some embodiments, the laminate (e.g., 10b to 10d) may include at least two heat dissipation layers 14, one defining at least a large portion (e.g., at least 90%, at most all) of the front surface 22a (e.g., the planar area of ​​the front surface) of the laminate, and the other defining at least a large portion (e.g., at least 90%, at most all) of the rear surface 22b (e.g., the planar area of ​​the rear surface) of the laminate. In some embodiments, the laminate (e.g., 10a to 10d) may not include any heat dissipation layer (e.g., 14) positioned between two insulating layers (e.g., 18a); in other words, the laminate may include heat dissipation layers (e.g., 14) only on its front and rear surfaces (e.g., 22a, 22b).

[0053] The laminate (e.g., 10a-10d) can be rigid or flexible. For example, referring to Figure 5, the laminate (whether reinforced as described above or not) can be placed in a roll shape 94 having an inner diameter 98 of any one value less than or equal to 10 cm, 8 cm, 5 cm, 4 cm, 2 cm, or 1 cm, or between any two of those values, without undergoing permanent deformation. Such flexibility may be provided by the materials of the thermal dispersive layer, insulating layer, and other (if any) layers of the laminate, and / or the relatively thin thickness of those layers (e.g., as described above), even if not to the level of this example. A more flexible laminate may be easier to use and less prone to cracking than a less flexible laminate. However, in other embodiments, the laminate may have higher rigidity (e.g., so that it cannot be placed in such a roll shape without undergoing permanent deformation), which may be provided by the aforementioned reinforcement, the materials and thickness of one or more layers of the laminate, etc.

[0054] Also disclosed, as shown in Figure 5, is a laminate (e.g., 10a-10d) having a protective film 110 detachably disposed on at least one of its front and rear surfaces (e.g., 22a and 22b, respectively). The protective film 110 can be removed from the laminate, for example, by peeling it off. Such a protective film does not form part of the laminate.

[0055] The laminates of the present invention (e.g., 10a-10d) can be used in a variety of applications where it is desirable to shield components from high-temperature environments. One or more of the laminates of the present invention can be used, for example, to shield a rocket motor. For illustrative purposes, such a rocket motor may include a casing that defines an internal volume for storing propellant, and one or more of the laminates of the present invention can be placed along and / or inside the casing. As another example, one or more of the laminates of the present invention can be placed along the wings or fins (or other surfaces) of an aircraft, spacecraft, missile, rocket, etc., to protect the wings, fins, or other surfaces (or components they contain) from the heat generated by drag. As yet another example, the laminates of the present invention can be used in ammunition. For illustrative purposes, tracer rounds contain a composition that burns so that the trajectory of the projectile is visible. However, the composition often burns at high temperatures, which can damage the projectile. To mitigate this, one or more of the laminates of the present invention can be placed to shield the rest of the projectile from the composition. These specific examples are provided for illustrative purposes only, and the laminates of the present invention can, of course, be used in general to protect components (e.g., electronic components, wires, cables, etc.) from high-temperature environments.

[0056] B. Materials for polymer aerogel layers The polymer aerogel layer may contain organic materials, inorganic materials, or mixtures thereof. Organic aerogels can be made from polyacrylate, polystyrene, polyacrylonitrile, polyurethane, polyurea, polyimide, polyamide, polyaramid, polyfurfural alcohol, phenol furfuryl alcohol, melamine formaldehyde, resorcinol formaldehyde, cresol formaldehyde, phenol formaldehyde, polyvinyl alcohol dialdehyde, polycyanurate, polyacrylamide, various epoxies, agar, agarose, etc. In certain embodiments, the aerogel is a polyimide aerogel.

[0057] Polyimides are a type of polymer with many desirable properties. Polyimide polymers contain a nitrogen atom in their polymer backbone, where the nitrogen atom is linked to two carbonyl carbons so that it is somewhat stabilized by adjacent carbonyl groups. The carbonyl group contains a carbon atom called the carbonyl carbon, which is double-bonded to an oxygen atom. Since polyimide polymers are usually produced using two different types of monomers, polyimides are typically considered AA-BB type polymers. Polyimides can also be prepared from AB type monomers. For example, aminodicarboxylic acid monomers can be polymerized to form AB type polyimides. Monoamines and / or monoanhydrides can be used as end-capping agents as needed.

[0058] One class of polyimide monomers is typically diamines, or diamine monomers. Diamine monomers may also be diisocyanates, and it should be understood that isocyanates may be substituted for amines as appropriate in this description. As is well known to those skilled in the art, there are other types of monomers that can be used instead of diamine monomers. These other types of monomers are called acid monomers and are typically in the form of dianhydrides. In this description, the term “diacid monomer” is defined to include dianhydrides, tetraesters, diesteric acids, tetracarboxylic acids, or trimethylsilyl esters, all of which can react with diamines to produce polyimide polymers. Dianhydrides should be understood to be tetraesters, diesteric acids, tetracarboxylic acids, or trimethylsilyl esters, which may be substituted as appropriate. As is well known to those skilled in the art, there are other types of monomers that can be used instead of diacid monomers.

[0059] Since one diamino acid monomer has two anhydride groups, different diamino monomers can react with each anhydride group, and therefore a diamino acid monomer can be located between two different diamino monomers. A diamine monomer contains two amine functional groups; therefore, after the first amine functional group is bonded to one diamino acid monomer, the second amine functional group is still available to bond to another diamino acid monomer, which then bonds to another diamine monomer, and so on. In this way, a polymer skeleton is formed. The resulting polycondensation reaction product forms a polyamic acid.

[0060] Polyimide polymers are typically formed from two different types of monomers, and it is possible to mix different variants of each type of monomer. Therefore, one, two, or more diacid monomers can be included in the reaction vessel, as can one, two, or more diamino monomers. When long polymer chains are desired, the total molar amount of diacid monomers is maintained to be approximately the same as the total molar amount of diamino monomers. Because multiple types of diamines or diacids can be used, the monomer composition of each polymer chain can be varied to produce polyimides with different properties. For example, a single diamine monomer AA can be reacted with two diacid comonomers B1B1 and B2B2 to produce a polyimide of the general formula (AA-B1B1). x -(AA-B2B2) y A polymer chain of the following can be formed, where x and y are determined by the relative incorporation of B1B1 and B2B2 into the polymer backbone. Alternatively, the diamine comonomers A1A1 and A2A2 can be reacted with a single diacid monomer BB to form a polymer of the general formula (A1A1-BB). x -(A2A2-BB) y A polymer chain of the general formula (A1A1-B1B1) can be formed by reacting two diamine comonomers A1A1 and A2A2 with two diacid comonomers B1B1 and B2B2. w -(A1A1-B2B2) x -(A2A2-B1B1) y -(A2A2-B2B2) zPolymer chains can be formed, where w, x, y, and z are determined by the relative incorporation of A1A1-B1B1, A1A1-B2B2, A2A2-B1B1, and A2A2-B2B2 into the polymer backbone. Three or more diacid comonomers and / or three or more diamine comonomers can also be used. Thus, one or more diamine monomers can be polymerized with one or more diacids, and the general formula of the polymer is determined by varying the amount and type of monomers used.

[0061] There are many examples of monomers that can be used to prepare polymer aerogels containing polyamic acid amide polymers. In some embodiments, the diamine monomer is a substituted or unsubstituted aromatic diamine, a substituted or unsubstituted alkyl diamine, or a diamine that may contain both aromatic and alkyl functional groups. A non-restrictive list of possible diamine monomers includes 4,4'-oxydianiline (ODA), 3,4'-oxydianiline, 3,3'-oxydianiline, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, diaminobenzanilide, 3,5-diaminobenzoic acid, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 1,3-bis-(4-aminophenoxy)benzene, 1,3-bis-(3-aminophenoxy)benzene, 1,4-bis-(4-aminophenoxy)benzene, 1,4-bis-(3-aminophenoxy)benzene, 2,2-bis[4-( 4-aminophenoxy)phenyl]-hexafluoropropane, 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 4,4'-isopropylidenedianiline, 1-(4-aminophenoxy)-3-(3-aminophenoxy)benzene, 1-(4-aminophenoxy)-4-(3-aminophenoxy)benzene, bis-[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(3-aminophenoxy)phenyl]sulfone, bis(4-[4-aminophenoxy]phenyl) ether, 2,2'-bis-(4-aminophenyl)-hexafluoropropane (6F-diamine), 2,2'-bis-(4-phenoxyaniline)isopropylidene, meta-phenylenediamine, para-phenylenediamine, 1,2-diaminobenzene, 4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 2,6-diaminopyridine, bis(3-aminophenyl)diethylsilane, 4,4'-diaminodiphenyldiethylsilane, benzidine, dichlorobenzidine, 3,3'-dimethoxybenzidine, 4,4'-Diaminobenzophenone, N,N-bis(4-aminophenyl)-n-butylamine, N,N-bis(4-aminophenyl)methylamine, 1,5-diaminonaphthalene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4-aminophenyl-3-aminobenzoate, N,N-bis(4-aminophenyl)aniline, bis(p-beta-amino-t-butylphenyl)ether, p-bis-2-(2-methyl-4-aminopentyl)benzene, p-bis(1,1-dimethyl-5-aminopentyl)benzene, 1,3-bis(4-aminophenoxy)benzene, m-xylenediamine, p-xylenediamine, 4,4'-diaminodiphenyl etherphosphine oxide, 4,4'-diaminodiphenyl N-methylamine, 4,4'- Diaminodiphenyl N-phenylamine, amino-terminated polydimethylsiloxane, amino-terminated polypropylene oxide, amino-terminated polybutylene oxide, 4,4'-methylenebis(2-methylcyclohexylamine), 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, and 4,4'-methylenebisbenzeneamine, 2,2'-dimethylbenzidine (also known as 4,4'-diamino-2,2'-dimethylbiphenyl (DMB)), bisaniline-p-xylidene, 4,4'-bis(4-aminophenoxy)biphenyl, 3,3'-bis(4 This includes aminophenoxy)biphenyl, 4,4'-(1,4-phenylenediisopropylidene)bisaniline, and 4,4'-(1,3-phenylenediisopropylidene)bisaniline, or combinations thereof. In certain embodiments, the diamine monomer is ODA, 2,2'-dimethylbenzidine, or both.

[0062] An unrestricted list of possible dianhydride ("diacid") monomers includes hydroquinone dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), pyromellitic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid anhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 4,4'-(4,4'-isopropylidene diphenoxy)bis(phthalic acid anhydride), 2,2-bis(3, 4-Dicarboxyphenyl)propane dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic acid anhydride, bis(3,4-dicarboxyphenyl) sulfoxide dianhydride, polysiloxane-containing dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid dianhydride, 2,3,2',3'-benzophenonetetracarboxylic acid dianhydride, naphthalene-2,3,6,7-tetracarboxylic acid dianhydride, naphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 4, 4'-Oxydiphthalic acid dianhydride, 3,3',4,4'-biphenylsulfonetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, bis(3,4-dicarboxyphenyl)sulfide dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 2,6-dichloronaphthalene-1,4 These include ,5,8-tetracarboxylic dianhydride, 2,7-dichloronaptalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene, 8,9,10-tetracarboxylate dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, and thiophene-2,3,4,5-tetracarboxylic dianhydride. In certain embodiments, the dianhydride monomer is BPDA, PMDA, or both.

[0063] In some cases, the molar ratio of the anhydride to the total diamine is 0.4:1–1.6:1, 0.5:1–1.5:1, 0.6:1–1.4:1, 0.7:1–1.3:1, or in particular 0.8:1–1.2:1. In further cases, the molar ratio of the dianhydride to the polyfunctional amine (e.g., triamine) is 2:1–140:1, 3:1–130:1, 4:1–120:1, 5:1–110:1, 6:1–100:1, 7:1–90:1, or in particular 8:1–80:1. Monoanhydride groups can also be used. Non-limiting examples of monoanhydride groups include 4-amino-1,8-naphthalic anhydride, endo-bicyclo[2.2.2]octa-5-ene-2,3-dicarboxylic acid anhydride, citraconic acid anhydride, trans-1,2-cyclohexanedicarboxylic acid anhydride, 3,6-dichlorophthalic acid anhydride, 4,5-dichlorophthalic acid anhydride, tetrachlorophthalic acid anhydride, 3,6-difluorophthalic acid anhydride, 4,5-difluorophthalic acid anhydride, tetrafluorophthalic acid anhydride, maleic acid anhydride, 1-cyclopentene-1,2-dicarboxylic acid anhydride, and 2,2-dimethylglutaric acid anhydride. This includes 3,3-dimethylglutaric anhydride, 2,3-dimethylmaleic anhydride, 2,2-dimethylsuccinic anhydride, 2,3-diphenylmaleic anhydride, phthalic anhydride, 3-methylglutaric anhydride, methylsuccinic anhydride, 3-nitrophthalic anhydride, 4-nitrophthalic anhydride, 2,3-pyrazinedicarboxylic acid anhydride, or 3,4-pyridinedicarboxylic acid anhydride. In particular, one anhydride group may be a phthalic anhydride.

[0064] In another embodiment, the polymer composition used to prepare the polymer aerogel layer comprises a polyfunctional amine monomer having at least three primary amine functional groups. The polyfunctional amine may be a substituted or unsubstituted aliphatic polyfunctional amine, a substituted or unsubstituted aromatic polyfunctional amine, or a polyfunctional amine comprising a combination of an aliphatic group and two aromatic groups, or a combination of an aromatic group and two aliphatic groups.A non-restrictive list of possible polyfunctional amines includes propane-1,2,3-triamine, 2-aminomethylpropane-1,3-diamine, 3-(2-aminoethyl)pentane-1,5-diamine, bis(hexamethylene)triamine, N',N'-bis(2-aminoethyl)ethane-1,2-diamine, N',N'-bis(3-aminopropyl)propane-1,3-diamine, 4-(3-aminopropyl)heptane-1,7-diamine, N',N'-bis(6-A Minohexyl)hexane-1,6-diamine, benzene-1,3,5-triamine, cyclohexane-1,3,5-triamine, melamine, N-2-dimethyl-1,2,3-propanetriamine, diethylenetriamine, 1-methyl or 1-ethyl or 1-propyl or 1-benzyl-substituted diethylenetriamine, 1,2-dibenzyldiethylenetriamine, lauryldiethylenetriamine, N-(2-hydroxypropyl)diethylenetriamine N,N-bis(l-methylheptyl)-N-2-dimethyl-1,2,3-propanetriamine, 2,4,6-tris(4-(4-aminophenoxy)phenyl)pyridine, N,N-dibutyl-N-2-dimethyl-l,2,3-propanetriamine, 4,4'-(2-(4-aminobenzyl)propane-1,3-diyl)dianiline, 4-((bis(4-aminobenzyl)amino)methyl)aniline, 4-(2-(bis(4-aminophenethyl)amino)eth These include 1,3,5-tris(4-aminophenethyl)pentane-1,5-diyl)dianiline, 1,3,5-tris(4-aminophenoxy)benzene (TAPOB), 4,4',4''-methanetriyltrianiline, N,N,N',N'-tetrakis(4-aminophenyl)-1,4-phenylenediamine, polyoxypropylene triamines, octa(aminophenyl) polyhedral oligomer silsesquioxanes, or combinations thereof. A specific example of a polyoxypropylene triamine is JEFFAMINE® T-403 from Huntsman Corporation, The Woodlands, TX, USA. In certain embodiments, the aromatic polyfunctional amine may be 1,3,5-tris(4-aminophenoxy)benzene or 4,4',4''-methanetriyltrianiline.In some embodiments, the polyfunctional amine comprises three primary amine groups and one or more secondary and / or tertiary amine groups, such as N',N'-bis(4-aminophenyl)benzene-1,4-diamine.

[0065] Non-limiting examples of capping agents or groups include those derived from reagents, particularly amines, maleimides, nadiimides, acetylenes, biphenylenes, norbornene, cycloalkyls, and N-propargyls, as well as reagents containing 5-norbornene-2,3-dicarboxylic acid anhydride (nadic anhydride, Na), methylnadic anhydride, hexachloronadic anhydride, cis-4-cyclohexene-1,2-dicarboxylic acid anhydride, 4-amino-N-propargylphthalimide, 4-ethynylphthalic anhydride, and maleic anhydride.

[0066] The characteristics or properties of the final polymer are greatly influenced by the selection of monomers used to produce the polymer. Factors to consider when selecting monomers include the properties of the final polymer, such as flexibility, thermal stability, coefficient of thermal expansion (CTE), coefficient of water absorption expansion (CHE), and any other properties that are particularly desirable, as well as cost. Often, certain important properties of the polymer can be identified for a particular application. Other properties of the polymer may be less important or may have a wide range of acceptable values; therefore, many different monomer combinations can be used.

[0067] In some examples, the polymer backbone may contain further substituents. Substituents (e.g., oligomers, functional groups, etc.) may be directly bonded to the backbone or linked to it through linking groups (e.g., tethers or flexible tethers). In other embodiments, compounds or particles may be incorporated into the polyimide structure (e.g., by mixing and / or encapsulation) without covalent bonding to the polyimide structure. In some examples, the incorporation of compounds or particles may be carried out during a polyamic reaction step. In some examples, particles may aggregate, thereby producing a polyimide having domains containing different concentrations of non-covalently bonded compounds or particles.

[0068] Certain properties of polyimides can be influenced by incorporating specific compounds into them. Monomer selection is one way to influence specific properties. Another way to influence properties is by adding compounds or property-modifying molecules to the polyimide.

[0069] C. Preparation of polymer aerogel layers Polymer aerogel films that can be used in at least some of the laminates of the present invention are commercially available. Non-limiting examples of such films include Blueshift AeroZero® rolled thin films (available from Blueshift Materials, Inc. (Spencer, Massachusetts)) and Airloy® films (available from Aerogel Technologies, LLC), with Blueshift AeroZero® rolled thin films being preferred in some aspects.

[0070] Furthermore, in addition to the processes described later, polymer aerogels (such as films, stock shapes, or monoliths) can be prepared using the methods described in International Publication No. 2014 / 189560 by Rodman et al., No. 2017 / 07888 by Sakaguchi et al., No. 2018 / 078512 by Yang et al., No. 2018 / 140804 by Sakaguchi et al., and No. 2019 / 006184 by Irvin et al., International Application PCT / US2019 / 029191 by Ejaz et al., U.S. Patent Application Publication No. 2017 / 0121483 by Poe et al., and / or U.S. Patent No. 9,963,571 by Sakaguchi et al., all of which are incorporated herein by reference in their entirety.

[0071] The following provides non-limiting steps that can be used to produce a polymer aerogel layer suitable for use in the laminate of the present invention. These steps may include (1) preparation of the polymer gel, (2) optional solvent exchange, (3) drying the polymer solution to form an aerogel, and (4) bonding the polymer aerogel film onto a substrate.

[0072] 1. Formation of polymer gel The first stage in the synthesis of aerogels may be the synthesis of a polymerized gel. For example, if a polyimide aerogel is desired, at least one acid monomer can be reacted with at least one diamino monomer in a reaction solvent to produce a polyamic acid. As mentioned above, many acid monomers and diamino monomers may be used to synthesize polyamic acids. In one aspect, the polyamic acid is brought into contact with an imidation catalyst in the presence of a chemical dehydrating agent to produce a polymerized polyimide gel via an imidation reaction. "Imidation" is defined as the conversion of a polyimide precursor to imide. Any imidation catalyst suitable for driving the conversion of the polyimide precursor to the polyimide state is appropriate. Non-limiting examples of chemical imidation catalysts include pyridine, methylpyridine, quinoline, isoquinoline, 1,8-diazabicyclo[5.4.0]undeca-7-ene (DBU), triethylenediamine, lutidine, N-methylmorpholine, triethylamine, tripropylamine, tributylamine, other trialkylamines, 2-methylimidazole, 2-ethyl-4-methylimidazole, imidazole, other imidazoles, and combinations thereof. Any dehydrating agent suitable for use in the formation of imide rings from amic acid precursors is suitable for use in the methods of the present invention. Preferred dehydrating agents include at least one compound selected from the group consisting of acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, trifluoroacetic anhydride, phosphorus trichloride, and dicyclohexylcarbodiimide.

[0073] In one aspect of the present invention, one or more diamino monomers and one or more polyfunctional amine monomers are pre-mixed in one or more solvents, and then one or more dianhydrides (e.g., diacid monomers) are added sequentially in small amounts at predetermined time increments while monitoring the viscosity. The desired viscosity of the polymerization solution may be in the range of 50 to 20,000 cP, or particularly 500 to 5,000 cP. Non-crosslinked aerogels can be prepared by carrying out the reaction using the gradual addition of dianhydrides while monitoring the viscosity. For example, a triamine monomer (23 equivalents) can be added to the solvent to obtain a 0.0081 molar solution. A first diamine monomer (280 equivalents) can be added to the solution, followed by a second diamine monomer (280 equivalents). Next, dianhydrides (552 equivalents in total) can be added sequentially in small amounts at predetermined time increments while monitoring the viscosity. Dianhydrides can be added until the viscosity reaches 1,000 to 1,500 cP. For example, the first part of the dianhydride can be added, the reaction can be stirred (e.g., for 20 minutes), the second part of the dianhydride can be added, and then a sample of the reaction mixture can be analyzed for viscosity. After stirring for a further time (e.g., 20 minutes), the third part of the dianhydride can be added, and a sample can be taken for viscosity analysis. After stirring for a desired period (e.g., 10 to 12 hours), one anhydride (96 equivalents) can be added. After reaching the target viscosity, the reaction mixture can be stirred for a desired period (e.g., 10 to 12 hours) or until the reaction is considered complete.

[0074] The reaction temperature for gel formation can be determined by routine experimentation depending on the starting materials. In a preferred embodiment, the temperature may be one or more of any one of 15°C, 20°C, 30°C, 35°C, 40°C, and 45°C, or between any two of these values. After a desired time (e.g., about 2 hours), the product can be isolated (e.g., filtered), and then nitrogen-containing hydrocarbons (828 equivalents) and a dehydrating agent (1214 equivalents) can be added. The addition of nitrogen-containing hydrocarbons and / or dehydrating agents can be done at any temperature. In some embodiments, nitrogen-containing hydrocarbons and / or dehydrating agents are added to the solution at 20°C to 28°C (e.g., room temperature) and stirred at that temperature for a desired time. In some examples, after adding nitrogen-containing hydrocarbons and / or dehydrating agents, the solution temperature is raised to 150°C.

[0075] The reaction solvent may include dimethyl sulfoxide (DMSO), diethyl sulfoxide, N,N-dimethylformamide (DMF), N,N-diethylformamide, N,N-dimethylacetamide (DMAc), N,N-diethylacetamide, N-methyl-2-pyrrolidone (NMP), 1-methyl-2-pyrrolidinone, N-cyclohexyl-2-pyrrolidone, 1,13-dimethyl-2-imidazolidinone, diethylene glycol dimethoxy ether, o-dichlorobenzene, phenol, cresol, xylenol, catechol, butyrolactone, hexamethylphosphoramide, and mixtures thereof. The reaction solvent and other reactants can be selected based on their suitability with the materials and methods applied; that is, based on whether the polymerized polyamic acid amide gel is cast onto a support film, injected into a moldable portion, or poured into a shape for further processing into a workpiece. In certain embodiments, the reaction solvent is DMSO.

[0076] With the above in mind, the incorporation of macropores into the aerogel polymer matrix, as well as the amount of such macropores present, can be carried out in the manner outlined. In one non-limiting manner, the formation of macropores, compared to small mesopores and micropores, can be controlled primarily by controlling the polymer / solvent dynamics during gel formation. In this way, the pore structure can be controlled, and the amount and volume of macroporous, mesoporous, and microporous cells can be controlled. For example, curing additives that reduce the solubility of the polymer produced during polymerization, such as 1,4-diazabicyclo[2.2.2]octane, may produce polymer gels containing more macropores compared to other curing additives that improve the solubility of the resulting polymer, such as trimethylamine. In another specific non-limiting example, when producing polyimide aerogels, the formation of macropores can be favored over small mesopores and micropores by increasing the ratio of rigid amines (e.g., p-phenylenediamine (p-PDA)) incorporated into the polymer backbone to more flexible diamines (e.g., -ODA).

[0077] The polymer solution may be cast onto a cast sheet covered with a support film for a certain period of time. Casting techniques may include spin casting, gravure coating, three-roll coating, roll knife coating, slot die extrusion, dip coating, Meyer rod coating, or other techniques. In one embodiment, the cast sheet is a polyethylene terephthalate (PET) cast sheet. After the time has elapsed, the polymerization-reinforced gel is removed from the cast sheet and prepared for a solvent exchange step. In some embodiments, the cast film can be heated stepwise to high temperatures to remove the solvent and convert the amic acid functional groups in the polyamic acid to polyimide by a dehydration cyclization reaction also known as imidization. In some examples, the polyamic acid may be converted to polyimide in solution by adding a chemical dehydrating agent, a catalyst, and / or heat.

[0078] In some embodiments, polyimide polymers can be produced by preparing polyamic acid polymers in a reaction vessel. The polyamic acid is then formed into a sheet or film and subsequently treated with a catalyst or heat and catalyst to convert the polyamic acid into polyimide.

[0079] The wet gel used to prepare the aerogel may be prepared by any known gel-forming technique, for example, by adjusting the pH and / or temperature of a diluted metal oxide solution to the point at which gelation occurs.

[0080] 2. Any solvent exchange After synthesizing the polymer gel, in certain cases, it may be desirable to perform a solvent exchange, replacing the reaction solvent with a more desirable second solvent. Therefore, in one embodiment, a solvent exchange can be performed by placing the polymer gel inside a pressure vessel and depositing it in a mixture containing the reaction solvent and the second solvent. A high-pressure atmosphere is then created inside the pressure vessel, thereby forcing the second solvent into the polymer gel and replacing part of the reaction solvent. Alternatively, the solvent exchange step may be carried out without using a high-pressure environment. Multiple solvent exchanges may be necessary. In some embodiments, solvent exchange is not essential.

[0081] The time required for solvent exchange will vary depending on the type of polymer being exchanged and the reaction solvent and second solvent used. In one embodiment, each solvent exchange may take 1 to 168 hours, or any period between those, including 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, or 23, 24, 25, 50, 75, 100, 125, 150, 155, 160, 165, 166, 167, or 168 hours. In another embodiment, each solvent exchange may take approximately 1 to 60 minutes, or about 30 minutes. Exemplary second solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 3-methyl-2-butanol, 3,3-dimethyl-2-butanol, 2-pentanol, 3-pentanol, 2,2-dimethylpropan-1-ol, cyclohexanol, diethylene glycol, cyclohexanone, acetone, acetylacetone, 1,4-dioxane, diethyl ether, dichloromethane, trichloroethylene, chloroform, carbon tetrachloride, water, and mixtures thereof. In certain non-limiting embodiments, the second solvent may have a freezing point suitable for carrying out supercritical or subcritical drying steps. For example, at 1 atmosphere, tert-butyl alcohol has a freezing point of 25.5°C and water has a freezing point of 0°C. Alternatively, drying may be carried out without using supercritical or subcritical drying steps, such as by evaporative drying techniques, as described below.

[0082] The temperature and pressure used in the solvent exchange process may be varied. The duration of the solvent exchange process can be adjusted by performing the solvent exchange at various temperatures, atmospheric pressures, or both, provided that the pressure and temperature in the pressure vessel do not cause either the first or second solvent to separate from the liquid phase into a gas, vapor, solid, or supercritical fluid. In general, higher pressure and / or temperature reduces the amount of time required for the solvent exchange, while lower temperature and / or pressure increases the amount of time required for the solvent exchange.

[0083] 3. Cooling and drying In one embodiment, the polymerized gel can be exposed to supercritical drying after solvent exchange. In this example, the solvent in the gel can be removed by supercritical CO2 extraction.

[0084] In another embodiment, after solvent exchange, the polymerized gel can be subjected to subcritical drying. In this example, the gel can be cooled to below the freezing point of the second solvent and subjected to a freeze-drying or lyophilization process to produce an aerogel. For example, if the second solvent is water, the polymerized gel is cooled to below 0°C. After cooling, the polymerized gel is subjected to reduced pressure for a certain period of time to sublimate the second solvent.

[0085] In yet another embodiment, after solvent exchange, the polymerized gel may be subjected to subcritical drying with optional heating after most of the second solvent has been removed by sublimation. In this example, the partially dried gel material is heated for a certain period of time to a temperature close to or above the boiling point of the second solvent. The period can range from several hours to several days, but a typical period is about 4 hours. During the sublimation process, some of the second solvent present in the polymerized gel is removed, leaving a gel that may have macropores, mesopores, or micropores, or any combination thereof, or all of such pore sizes. After the completion or near completion of the sublimation process, an aerogel is formed.

[0086] In yet another embodiment, after solvent exchange, the polymerized gel can be dried under ambient conditions by removing the solvent, for example, under a flow of gas (e.g., air, anhydrous gas, or an inert gas (e.g., nitrogen (N2) gas)). Furthermore, passive drying techniques can also be used, such as simply exposing the gel to ambient conditions without using an airflow.

[0087] Once cooled or dried, the film and stock shape can be configured for use in the laminate of the present invention. For example, the film or stock shape can be processed into any desired shape (e.g., by cutting or polishing) such as a square, rectangle, circle, triangle, irregular shape, or random shape. Alternatively, as described above, the film or stock shape can be attached to a support material with an adhesive or the like. In an alternative embodiment, the support material can be incorporated into a matrix of polymer aerogel, as described later.

[0088] 4. Incorporation of support material into polymer aerogel matrix In addition to the methods described above regarding the use of adhesives for bonding polymer aerogels to support materials, any aspect of the present invention may include incorporating support materials into a polymer matrix to produce reinforced polymer aerogels without the use of adhesives. Notably, during the production of unreinforced polymer aerogels, a reinforcing support film can be used as a carrier to support the gelled film during processing. During unwinding, the gelled film can be irreversibly pressed into the carrier film. Pressing the gelled film into the carrier film can provide a substantial improvement in durability. In another example, during the solution casting step described above, the polymer solution can be cast into the reinforcing or support material.

[0089] Substrate selection and direct casting may enable optimization (e.g., minimization) of the thickness of the resulting reinforced aerogel material. This process can also be extended to the production of fiber-reinforced polymer aerogels, providing internally reinforced polyimide aerogels as an example. The process may include (a) forming a polyamic acid solution from a mixture of dianhydride and diamine monomers in a polar solvent such as DMSO, DMAc, NMP, or DMF; (b) contacting the polyamic acid solution with the chemical curing agents and chemical dehydrating agents mentioned above to initiate chemical imidation; (c) casting the polyamic acid solution onto a fiber support before gelation and allowing it to permeate; (d) gelling the catalytic polyamic acid solution around and within the fiber support during chemical imidation; (e) optionally performing solvent exchange to facilitate drying; and (f) removing the transient liquid phase contained within the gel by supercritical, subcritical, or ambient drying to obtain an internally reinforced aerogel. [Examples]

[0090] The present invention will be described in detail with specific examples. The following examples are provided for illustrative purposes only and are not intended to limit the invention in any way. Those skilled in the art will readily recognize non-material parameters that can be changed or modified to obtain essentially the same results.

[0091] Table 2 shows the acronyms of the compounds used in the following examples.

[0092] [Table 2]

[0093] The structure of the starting material is shown below. TIFF0007893573000003.tif41158

[0094] Example 1 (Preparation of highly branched BPDA / DMB-ODA polyimide) A reaction vessel equipped with a stirrer and a water jacket was used. The temperature was maintained in the range of 18–35°C by adjusting the water flow rate through the reaction vessel jacket. DMSO (108.2 lbs. 49.1 kg) was added to the reaction vessel, and the stirrer speed was adjusted to 120–135 rpm. TAPOB (65.13 g) was added to the solvent. To this solution, DMB (1081.6 g) was added, followed by ODA (1020.2 g). Next, the first part of BPDA (1438.4 g) was added. After stirring for 20 minutes, the viscosity of the reaction mixture sample was analyzed using a Brookfield DV1 viscometer (Brookfield, AMETEK, USA). The second part of BPDA (1407.8 g) was added, and the reaction mixture was stirred for a further 20 minutes. The third part of BPDA (138.62 g) was added, and the reaction mixture was stirred for 20 minutes. The viscosity of the reaction mixture sample was analyzed. After stirring for 8 hours, PA (86.03 g) was added. The resulting reaction mixture was stirred until no more solids were visible. After 2 hours, the product was removed from the reaction vessel, filtered, and weighed.

[0095] Example 2 (Preparation of highly branched polyimide aerogel monoliths by freeze-drying) The resin prepared in Example 1 (approximately 10,000 g) was mixed with triethylamine (approximately 219 g) and acetic anhydride (approximately 561 g) for 5 minutes. After mixing, the resulting solution was poured into a square 15" x 15" mold and left for 48 hours. The gelled product was removed from the mold and placed in an acetone bath. After immersion for 24 hours, the acetone bath was replaced with fresh acetone. The immersion and replacement process was repeated 5 times. After the final replacement, the bath was replaced with tertiary butyl alcohol. After immersion for 24 hours, the tertiary butyl alcohol bath was replaced with fresh tertiary butyl alcohol. The immersion and replacement process was repeated 3 times. Subsequently, the portion was flash-frozen and subjected to subcritical drying at 5°C for 96 hours, followed by drying under reduced pressure at 50°C for 48 hours. The final recovered aerogel portion was observed using scanning electron microscopy (SEM) with a Phenom Pro Scanning Electron Microscope (Phenom-World, the Netherlands) and showed an open-cell structure. It was measured according to ASTM D4404-10 using a Micromeritics® AutoPore V 9605 Automatic Mercury Penetrometer (Micromeritics® Instrument Corporation, USA) and measured at 0.22 g / cm³. 3 The density and porosity of 88.5% were determined by ASTM D395-16, the compressive modulus was 2.2 MPa, and the compressive strength at 25% strain was 3.5 MPa, also determined by ASTM D395-16. The pore diameter distribution was measured according to ASTM D4404-10 using a Micromeritics® AutoPore V 9605 Automatic Mercury Penetrometer (Micromeritics® Instrument Corporation, USA), and the pore diameter distribution is shown in Figure 6. From the data, it was determined that 100% of the pores were macropores and the average pore diameter was approximately 1,200 nm, thus confirming the formation of a macroporous aerogel structure.

[0096] Example 3 (Preparation of highly branched polyimide aerogel monoliths by heat drying) The resin prepared in Example 1 (approximately 10,000 g) was mixed with triethylamine (approximately 219 g) and acetic anhydride (approximately 561 g) at a temperature of 10-35°C for 5 minutes. After mixing, the resulting solution was poured into a square 15" x 15" mold and left for 48 hours. The gelled product was removed from the mold and placed in an acetone bath. After immersion for 24 hours, the acetone bath was replaced with fresh acetone. The immersion and replacement process was repeated five times. After the final replacement, the portion was dried in an ambient air drying process (approximately 20-30°C) over 48 hours to evaporate most of the acetone, followed by heat drying at 50°C for 4 hours, 100°C for 2 hours, 150°C for 1 hour, and then 200°C for 30 minutes. The final recovered aerogel had similar properties to those observed in Example 2.

[0097] Example 4 (Preparation of highly branched polyimides) As described in Example 1, approximately 2.86 g of TAPOB was added to a reaction vessel containing approximately 2,523.54 g of DMSO at a temperature of 18-35°C. To this solution, the first part of DMB (approximately 46.75 g) was added, followed by the first part of ODA (approximately 44.09 g). After stirring for approximately 20 minutes, the first part of BPDA (approximately 119.46 g) was added. After stirring for approximately 20 minutes, TAPOB (approximately 2.86 g), DMB (approximately 46.75 g), and ODA (approximately 44.09 g) were added. After stirring for approximately 20 minutes, BPDA (approximately 119.46 g) was added. After stirring for approximately 20 minutes, TAPOB (approximately 2.86 g), DMB (approximately 46.75 g), and ODA (approximately 44.09 g) were added. After stirring for approximately 20 minutes, BPDA (approximately 119.46 g) was added. After stirring for approximately 8 hours, PA (approximately 50.12 g) was added. The resulting reaction mixture was stirred until no more solids were visible. After approximately 2 hours, the product was removed from the reaction vessel, filtered, and weighed.

[0098] Example 5 (Preparation of highly branched polyimide aerogel monoliths by freeze-drying) The resin prepared in Example 4 (approximately 400 g) was mixed with 2-methylimidazole (approximately 53.34 g) at a temperature of 18-35°C for 5 minutes, and then mixed with benzoic anhydride (approximately 161.67 g) for 5 minutes. After mixing, the resulting solution was poured into a square 3" x 3" mold and placed in a 75°C oven for 30 minutes, then left at room temperature overnight. The gelled product was removed from the mold and placed in an acetone bath. After immersion for 24 hours, the acetone bath was replaced with fresh acetone. The immersion and replacement process was repeated 5 times. After the last replacement, the bath was replaced with tertiary butyl alcohol. After immersion for 24 hours, the tertiary butyl alcohol bath was replaced with fresh tertiary butyl alcohol. The immersion and replacement process was repeated 3 times. Subsequently, the portion was frozen in a shelf freezer and subjected to subcritical drying at 5°C for 96 hours, followed by drying under reduced pressure at 50°C for 48 hours. The final recovered aerogel portion was observed using scanning electron microscopy (SEM) with a Phenom Pro Scanning Electron Microscope (Phenom-World, the Netherlands) and was found to have an open-cell structure. It was measured according to ASTM D4404-10 using a Micromeritics® AutoPore V 9605 Automatic Mercury Penetrometer (Micromeritics® Instrument Corporation, USA) and measured at 0.15 g / cm³. 3 The density and porosity of 92.2% were observed. The pore size distribution was measured according to ASTM D4404-10 using a Micromeritics® AutoPore V 9605 Automatic Mercury Penetrometer (Micromeritics® Instrument Corporation, USA), and the pore size distribution is shown in Figure 7. From the data, it was determined that 96.3% of the pore volume of the molded aerogel was occupied by pores with an average pore diameter greater than 50 nm, and therefore a macroporous aerogel structure was formed.

[0099] Example 6 (Preparation of highly branched polyimides) As described in Example 1, approximately 2,776.57 g of DMSO was added to a reaction vessel, to which approximately 2.05 g of TAPOB was added at a temperature of 18-35°C. To this solution, approximately 33.54 g of DMB was added, followed by approximately 31.63 g of ODA. After stirring for approximately 20 minutes, approximately 67.04 g of PMDA was added. After stirring for approximately 20 minutes, approximately 2.05 g of TAPOB, approximately 33.54 g of DMB, and approximately 31.63 g of ODA were added. After stirring for approximately 20 minutes, approximately 67.04 g of PMDA was added. After stirring for approximately 20 minutes, approximately 2.05 g of TAPOB, approximately 33.54 g of DMB, and approximately 31.63 g of ODA were added. After stirring for approximately 20 minutes, approximately 67.04 g of PMDA was added. After stirring for approximately 8 hours, PA (approximately 18.12 g) was added. The resulting reaction mixture was stirred until no more solids were visible. After approximately 2 hours, the product was removed from the reaction vessel, filtered, and weighed.

[0100] Example 7 (Preparation of highly branched polyimide aerogel monoliths by freeze-drying) The resin prepared in Example 6 (approximately 400 g) was mixed with 2-methylimidazole (approximately 40.38 g) at a temperature of 18-35°C for 5 minutes, and then mixed with benzoic anhydride (approximately 122.38 g) for 5 minutes. After mixing, the resulting solution was poured into a square 3" x 3" mold and placed in a 75°C oven for 30 minutes, then left at room temperature overnight. The gelled product was removed from the mold and placed in an acetone bath. After immersion for 24 hours, the acetone bath was replaced with fresh acetone. The immersion and replacement process was repeated 5 times. After the last replacement, the bath was replaced with tertiary butyl alcohol. After immersion for 24 hours, the tertiary butyl alcohol bath was replaced with fresh tertiary butyl alcohol. The immersion and replacement process was repeated 3 times. Subsequently, the portion was frozen in a shelf freezer and subjected to subcritical drying at 5°C for 96 hours, followed by drying under reduced pressure at 50°C for 48 hours. The final recovered aerogel portion was observed using scanning electron microscopy (SEM) with a Phenom Pro Scanning Electron Microscope (Phenom-World, the Netherlands) and showed an open-cell structure. It was measured according to ASTM D4404-10 using a Micromeritics® AutoPore V 9605 Automatic Mercury Penetrometer (Micromeritics® Instrument Corporation, USA) and measured at 0.23 g / cm³. 3 The density and porosity of 82.7% were observed. The pore size distribution was measured according to ASTM D4404-10 using a Micromeritics® AutoPore V 9605 Automatic Mercury Penetrometer (Micromeritics® Instrument Corporation, USA), and the pore diameter distribution is shown in Figure 8. From the data, it was determined that pores with an average pore diameter greater than 50 nm occupied 90.6% of the pore volume of the aerogel.

[0101] Example 8 (Preparation of highly branched polyamic film) A reaction vessel equipped with a stirrer and a water jacket was used. The temperature was maintained in the range of 20-28°C by adjusting the water flow rate through the reaction vessel jacket. DMSO (108.2 lbs. 49.1 kg) was added to the reaction vessel, and the stirrer speed was adjusted to 120-135 rpm. TAPOB (65.03 g) was added to the solvent. To this solution, DMB (1,080.96 g) and then ODA (1,018.73 g) were added. The first part of BPDA (1,524.71 g) was added. After stirring for 20 minutes, the viscosity of the sample of the reaction mixture was analyzed. The second part of BPDA (1,420.97 g) was added, and the reaction mixture was stirred for a further 20 minutes. The viscosity of the sample of the reaction mixture was analyzed. The third part of BPDA (42.81 g) was added, and the reaction mixture was stirred for a further 20 minutes. The viscosity of the sample of the reaction mixture was analyzed. After stirring for 8 hours, PA (77.62 g) was added. The resulting reaction mixture was stirred until no more solids were visible. After 2 hours, the resin was removed from the reaction vessel, filtered, and weighed.

[0102] 10,000 g of resin was mixed with 250 g of 2-methylimidazole for 5 minutes. 945 g of benzoic anhydride was added, and the solution was mixed for another 5 minutes. After mixing, the resulting solution was poured onto a mobile polyester substrate and heated in a 100°C oven for 30 seconds. The gelled film was collected and placed in an acetone bath. After immersion for 24 hours, the acetone bath was replaced with fresh acetone. The immersion and replacement process was repeated six times. After the final replacement, the gelled film was removed. The acetone solvent was evaporated at room temperature under a flow of air, followed by drying at 200°C for 2 hours. The final recovered aerogel portion was observed using scanning electron microscopy (SEM) with a Phenom Pro Scanning Electron Microscope (Phenom-World, the Netherlands) and showed an open-cell structure. It was measured according to ASTM D4404-10 using a Micromeritics® AutoPore V 9605 Automatic Mercury Penetrometer (Micromeritics® Instrument Corporation, USA) and measured at 0.20 g / cm³. 3The film exhibited a density and porosity of >80%. The final recovered film, measured according to ASTM D882-12, showed a tensile strength of 1200 psi (8.27 MPa) and elongation of 14% at room temperature. The film had an average pore diameter of 400 nm.

[0103] Example 9 (Polyimide aerogel films laminated with graphite (single-layer and multi-layer)) A 6-inch x 12-inch laminate sample was assembled using polyimide aerogel film AeroZero® (Blueshift Materials, Inc. (Spencer, Massachusetts)), 2.0 mil thick silicone adhesive transfer tape, and 4.0 mil thick N-100 NeoNxGen® graphite film (NeoGraf Solutions, LLC, Lakewood, Ohio). For a single AeroZero® layer stack, one side of the release liner was removed from the silicone adhesive layer and placed on the AeroZero® film. Pressure was applied using a hand roller. The release liner was peeled off from the other side of the adhesive layer, and the graphite layer was placed on top. Pressure was applied again using a hand roller. For bonding the laminate to a given substrate, an additional sheet of silicone adhesive transfer tape was placed on the bare AeroZero® surface.

[0104] For the multilayer AeroZero® laminate, the assembly was constructed by stacking additional sheets of silicone adhesive transfer tape on a bare AeroZero® surface, followed by stacking additional AeroZero® sheets on top, repeating the addition of three layers of AeroZero®, and then placing a graphite layer.

[0105] The polyimide aerogel film AeroZero® (Blueshift Materials, Inc. (Spencer, Massachusetts)) had a thickness of 6.5 mils and a thermal conductivity of 0.03 W / mK (measured using steady-state heat transfer on flat slab specimens with a Netzsch HFM 436 / 3 / 1E Lambda heat flow meter in accordance with ASTM C518-10).

[0106] Example 10 (Polyimide aerogel films laminated with molybdenum (single-layer and multi-layer)) A 6-inch x 12-inch laminate sample was assembled using polyimide aerogel film AeroZero® (Blueshift Materials, Inc. (Spencer, Massachusetts)) and 2.0 mil thick molybdenum foil (Elmet Technoloiges, Lewiston, Maine, USA). For a single AeroZero® layer stack, one side of the release liner was removed from the silicone adhesive layer and placed on the AeroZero® film. Pressure was applied using a hand roller. The release liner was peeled off from the other side of the adhesive layer, and the molybdenum foil was placed on top. Pressure was applied again using a hand roller. For bonding the laminate to a given substrate, an additional sheet of silicone adhesive transfer tape was placed on the bare AeroZero® surface.

[0107] For the multilayer AeroZero® laminate, the assembly was constructed by stacking additional sheets of silicone adhesive transfer tape on a bare AeroZero® surface, followed by stacking additional AeroZero® sheets on top, repeating the addition of three layers of AeroZero®, and then placing a molybdenum layer.

[0108] The polyimide aerogel film AeroZero® (Blueshift, Inc.) had a thickness of 6.5 mils and a thermal conductivity of 0.03 W / mK (measured using steady-state heat transfer on a flat slab specimen with a Netzsch HFM 436 / 3 / 1E Lambda heat flow meter in accordance with ASTM C518-10).

[0109] Example 11 (Polyimide aerogel films laminated with steel (single-layer and multi-layer)) A 6-inch x 12-inch laminate sample was assembled using polyimide aerogel film AeroZero® (Blueshift Materials, Inc. (Spencer, Massachusetts)) and 2.0 mil thick stainless steel 304 (McMaster-Carr, Douglassville, Georgia). For a single AeroZero® layer stack, one end of the release liner was removed from the silicone adhesive layer and placed on the AeroZero® film. Pressure was applied using a hand roller. The release liner was peeled from the other side of the adhesive layer, and a steel sheet was placed on top. Pressure was applied again using a hand roller. For bonding the laminate to a given substrate, an additional sheet of silicone adhesive transfer tape was placed on the bare AeroZero® surface.

[0110] For the multilayer AeroZero® laminate, the assembly was constructed by stacking additional sheets of silicone adhesive transfer tape on a bare AeroZero® surface, followed by stacking additional AeroZero® sheets on top, repeating the addition of three layers of AeroZero®, and then placing a steel layer.

[0111] The polyimide aerogel film AeroZero® (Blueshift Materials, Inc. (Spencer, Massachusetts)) had a thickness of 6.5 mils and a thermal conductivity of 0.03 W / mK (measured using steady-state heat transfer on flat slab specimens with a Netzsch HFM 436 / 3 / 1E Lambda heat flow meter in accordance with ASTM C518-10).

[0112] Example 12 (Tungsten-laminated polyimide aerogel film (single layer)) A 6-inch x 12-inch laminate sample was assembled using polyimide aerogel film AeroZero® (Blueshift Materials, Inc. (Spencer, Massachusetts)) and 5.0 mil thick tungsten (Elmet Technoloiges, Lewiston, Maine, USA). For a single AeroZero® layer stack, one end of the release liner was removed from the silicone adhesive layer and placed on the AeroZero® film. Pressure was applied using a hand roller. The release liner was peeled off from the other side of the adhesive layer, and the tungsten sheet was placed on top. Pressure was applied again using a hand roller. For bonding the laminate to a given substrate, an additional sheet of silicone adhesive transfer tape was placed on the bare AeroZero® surface.

[0113] The polyimide aerogel film AeroZero® (Blueshift Materials, Inc. (Spencer, Massachusetts)) had a thickness of 6.5 mils and a thermal conductivity of 0.03 W / mK (measured using steady-state heat transfer on flat slab specimens with a Netzsch HFM 436 / 3 / 1E Lambda heat flow meter in accordance with ASTM C518-10).

[0114] Example 13 (Polyimide aerogel film laminated with niobium (single layer)) A 6-inch x 12-inch laminate sample was assembled using polyimide aerogel film AeroZero® (Blueshift Materials, Inc. (Spencer, Massachusetts)) and 2.0 mil thick niobium foil (Fine Metals Corporation, Ashland, Virginia). For a single AeroZero® layer stack, one end of the release liner was removed from the silicone adhesive layer and placed on the AeroZero® film. Pressure was applied using a hand roller. The release liner was peeled off from the other side of the adhesive layer, and the niobium sheet was placed on top. Pressure was applied again using a hand roller. For bonding the laminate to a given substrate, an additional sheet of silicone adhesive transfer tape was placed on the bare AeroZero® surface.

[0115] The polyimide aerogel film AeroZero® (Blueshift Materials, Inc. (Spencer, Massachusetts)) had a thickness of 6.5 mils and a thermal conductivity of 0.03 W / mK (measured using steady-state heat transfer on flat slab specimens with a Netzsch HFM 436 / 3 / 1E Lambda heat flow meter in accordance with ASTM C518-10).

[0116] Example 14 Laminate peel strength test The peel strength tests of the single-layer Aerozero laminates described in Examples 10-13 were performed using a Testometric M250-2.5CT (Testometric, UK) and the 180° peel strength test according to ASTM D3330. The results are shown in Table 1.

[0117] [Table 1]

[0118] Example 15 (Flame test of graphite laminate) Several laminates were prepared, each containing three 6.5 mil thick AeroZero® films (Blueshift Materials, Inc., Spencer, Massachusetts) for the thermal insulation layer and an approximately 4.0 mil thick N-100 NeoNxGen® (NeoGraf Solutions, LLC, Lakewood, Ohio) graphite layer for the heat dissipation layer. In each laminate, the heat dissipation layer defined the front and rear surfaces of the laminate, and the heat dissipation layer and the thermal insulation layer were bonded together using a silicone adhesive layer approximately 2.0 mil thick. The laminates had a width and length of 6 inches.

[0119] For each laminate, the front surface of the laminate was exposed for 60 to 120 seconds to a flame generated by a MAPP gas torch with a flame temperature of approximately 2,050°C. The laminates maintained their mechanical integrity.

[0120] Example 16 (Flame test of a molybdenum laminate with two heat-dispersing layers) Several laminates were prepared, each containing three 6.5 mil thick AeroZero® films (Blueshift Materials, Inc., Spencer, Massachusetts) for the thermal insulation layer and approximately 2.0 mil thick molybdenum foil (Elmet Technologies, Lewiston, Maine, USA) for the heat dissipation layer. In each laminate, the heat dissipation layer defined the front and rear surfaces of the laminate, and the heat dissipation layer and the thermal insulation layer were bonded together using a silicone adhesive layer approximately 2.0 mil thick. The laminates had a width and length of 6 inches.

[0121] For each laminate, the front surface of the laminate was exposed for 60 to 120 seconds to a flame generated by a MAPP gas torch with a flame temperature of approximately 2,050°C. The laminate maintained its mechanical integrity throughout the test.

[0122] Example 17 (Flame test of a molybdenum laminate with one heat dispersing layer) Several laminates were prepared, each containing three 6.5 mil thick AeroZero® films (Blueshift Materials, Inc., Spencer, Massachusetts) for the thermal insulation layer and approximately 2.0 mil thick molybdenum foil (Elmet Technologies, Lewiston, Maine, USA) for the heat dissipation layer. In each laminate, the heat dissipation layer defined only the front surface of the laminate, and the heat dissipation layer and the thermal insulation layer were bonded to each other using a silicone adhesive layer approximately 2.0 mil thick. The laminates had a width and length of 6 inches.

[0123] For each laminate, the front surface of the laminate was exposed for 60 to 120 seconds to a flame generated by a MAPP gas torch with a flame temperature of approximately 2,050°C. The laminate maintained its mechanical integrity throughout the test.

[0124] The aforementioned specification and examples provide a complete description of the structure and use of exemplary embodiments. While certain embodiments have been described in some detail, or with respect to one or more individual embodiments, those skilled in the art will be able to make many modifications to the disclosed embodiments without departing from the scope of the invention. Therefore, there is no intention to limit the various exemplary embodiments of the apparatus and methods to any particular form disclosed. Rather, they include all modifications and substitutions within the scope of the claims, and embodiments other than those shown may include some or all of the features of the embodiments shown. For example, elements may be omitted or combined as a single structure and / or connections may be substituted. Furthermore, where appropriate, aspects of any embodiment described above may be combined with aspects of any other embodiment described above to form further embodiments having equivalent or different characteristics and / or functions and addressing the same or different problems. Similarly, it will be understood that the advantages and merits described above may relate to one embodiment or to several embodiments.

[0125] Unless such a limitation is explicitly referenced in the given claims using the terms “means” or “step,” the claims are not intended to include, and should not be construed to include, a means-plus or step-plus-function limitation.

Claims

1. Front and; Rear and; One or more heat dispersing layers, each of which is A metal having a melting point of at least 1,300°C and a thermal conductivity of at least 15 W / Km, or Graphite One or more heat-dispersing layers containing at least 90% by weight of; A plurality of insulating layers, wherein at least one of the plurality of insulating layers is bonded to a heat dissipation layer, and each of the plurality of insulating layers includes a polymer aerogel layer. A laminate containing, The first adhesive layer bonds the first insulation layer among the plurality of insulation layers to the second insulation layer among the plurality of insulation layers. The second adhesive layer bonds the first thermal insulation layer of the thermal insulation layer to the first thermal dispersion layer of the thermal dispersion layer. At least 90% of the aforementioned front surface is defined by the first heat dispersive layer of the heat dispersive layer, The rear surface is defined by one of the plurality of insulating layers, or at least 90% of the rear surface is defined by a second heat dissipation layer among the heat dissipation layers. Laminated structure.

2. The laminate according to claim 1, wherein at least one of the heat-dispersing layers contains at least 90% by weight of metal.

3. The laminate according to claim 2, wherein the metal comprises molybdenum, tungsten, rhenium, tantalum, niobium, stainless steel, or an alloy thereof.

4. The laminate according to claim 2 or 3, wherein the melting point of the metal is at least 1,600°C, at least 1,900°C, at least 2,200°C, at least 2,400°C, at least 2,700°C, at least 3,000°C, or at least 3,300°C.

5. The laminate according to any one of claims 2 to 4, wherein the melting point of the metal is less than 3,800°C or less than 3,600°C.

6. The laminate according to any one of claims 2 to 5, wherein the thermal conductivity of the metal is greater than 15 W / Km, greater than 30 W / Km, greater than 40 W / Km, greater than 50 W / Km, greater than 75 W / Km, greater than 100 W / Km, greater than 125 W / Km, greater than 150 W / Km, or greater than 175 W / Km.

7. A laminate according to any one of claims 2 to 6, wherein the thermal conductivity of the metal is less than 200 W / Km.

8. The laminate according to any one of claims 1 to 7, wherein at least one of the heat dispersing layers contains at least 90% by weight of graphite.

9. The laminate according to any one of claims 1 to 8, wherein at least one of the heat-dispersing layers has a thickness of 1.0 to 10.0 mils or 1.0 to 5.0 mils.

10. The laminate according to claim 9, wherein at least one of the heat-dispersing layers has a thickness of about 2.0 mils.

11. The laminate according to any one of claims 1 to 10, wherein at least one of the plurality of thermal insulation layers includes an open-cell structure of polymer aerogel.

12. The laminate according to any one of claims 1 to 11, wherein at least one of the plurality of insulating layers comprises a polymer aerogel layer with micropores, mesopores, and / or macropores.

13. With respect to at least one of the plurality of thermal insulation layers, The polymer aerogel layer has pore volume, Micropores occupy at least 10%, at least 50%, at least 75%, or at least 95% of the pore volume. The laminate according to claim 12.

14. With respect to at least one of the plurality of thermal insulation layers, The polymer aerogel layer has pore volume, Mesopores occupy at least 10%, at least 50%, at least 75%, or at least 95% of the pore volume. The laminate according to claim 12.

15. With respect to at least one of the plurality of thermal insulation layers, The polymer aerogel layer has pore volume, Macropores occupy at least 10%, at least 50%, at least 75%, or at least 95% of the pore volume. The laminate according to claim 12.

16. With respect to at least one of the plurality of thermal insulation layers, The polymer aerogel layer has pore volume, Micropores and / or mesopores occupy at least 10%, at least 50%, at least 75%, or at least 95% of the pore volume. The laminate according to claim 12.

17. The laminate according to any one of claims 1 to 11, wherein at least one of the plurality of thermal insulation layers has a polymer aerogel layer having an average pore diameter of 2.0 nm to 50 nm.

18. The laminate according to any one of claims 1 to 11, wherein at least one of the plurality of thermal insulation layers has a polymer aerogel layer having an average pore diameter of 50 nm to 5,000 nm.

19. The laminate according to claim 18, wherein the average pore diameter is 100 nm to 800 nm, 100 nm to 500 nm, 150 nm to 400 nm, 200 nm to 300 nm, or 225 nm to 275 nm.

20. The laminate according to any one of claims 1 to 19, wherein at least one of the plurality of thermal insulation layers contains at least 90% by weight of an organic polymer in the polymer aerogel layer.

21. The laminate according to any one of claims 1 to 19, wherein at least one of the plurality of insulating layers comprises at least 90% by weight of a polymer aerogel layer of polyimide, polyamide, polyaramid, polyurethane, polyurea, polyester, or a mixture thereof.

22. The laminate according to claim 21, wherein at least one of the plurality of thermal insulation layers contains at least 90% by weight of a polymer aerogel layer of polyimide.

23. The laminate according to any one of claims 1 to 22, wherein at least one of the plurality of insulating layers has a polymer aerogel layer having a thickness of 1.5 to 800 mils, 1.5 to 400 mils, 1.5 to 200 mils, 1.5 to 80 mils, 1.5 to 40 mils, 1.5 to 20 mils, 1.5 to 10 mils, 1.5 to 7.0 mils, 3.0 to 7.0 mils, about 6.5 mils, or about 5.0 mils.

24. One or more adhesive layers are placed between adjacent layers of the heat dissipation layer and the insulation layer, respectively. A laminate according to any one of claims 1 to 23, including the laminate.

25. The laminate according to claim 24, wherein at least one of the adhesive layers contains silicone.

26. The laminate according to claim 25, wherein the silicone comprises polydimethylsilicone.

27. The laminate according to claim 25, wherein the silicone comprises biphenyl silicone.

28. The laminate according to any one of claims 25 to 27, wherein at least one of the adhesive layers has a thickness of 0.5 to 5.0 mils, 0.5 to 3.0 mils, 0.5 to 2.0 mils, or 1.0 to 2.0 mils.

29. There is no heat dissipation layer between adjacent layers of the insulation layer. A laminate according to any one of claims 1 to 28.

30. A laminate according to any one of claims 1 to 29, which does not contain fibers.

31. A laminate according to any one of claims 1 to 30, which does not contain ceramics.

32. A laminate according to any one of claims 1 to 31, having a thickness of 6.0 mil to 150 mil, 6.0 mil to 75 mil, 6.0 mil to 50 mil, or 6.0 mil to 25 mil.

33. The laminate according to any one of claims 1 to 32, wherein a part of the front surface of the laminate is arranged in a roll shape so as to face a part of the rear surface of the laminate.

34. A laminate according to any one of claims 1 to 33, which can maintain its mechanical shape when exposed to a temperature of at least 800°C, at least 1,000°C, at least 1,300°C, at least 1,600°C, at least 1,900°C, or at least 2,200°C for at least 30 seconds, at least 1 minute, at least 1.5 minutes, or at least 2 minutes.

35. The laminate according to any one of claims 1 to 34, wherein at least one of the plurality of insulating layers has a polymer aerogel layer having a thermal conductivity of 0.001 to 0.5 W / mK, 0.005 to 0.2 W / mK, 0.01 to 0.1 W / mK, 0.01 to 0.5 W / mK, or about 0.03 W / mK, where the thermal conductivity is measured using steady-state heat transfer with a flat slab test specimen using a Netzsch HFM 436 / 3 / 1E Lamda, heat flow meter apparatus in accordance with ASTM C518-10.

36. A method comprising the step of exposing a laminate according to any one of claims 1 to 35 to a temperature of at least 800°C, at least 1,000°C, at least 1,300°C, at least 1,600°C, at least 1,900°C, or at least 2,200°C for at least 30 seconds, at least 1 minute, at least 1.5 minutes, or at least 2 minutes, During exposure, the laminate maintains its mechanical shape. method.

37. A laminate according to any one of claims 1 to 35, A protective film is detachably disposed on the surface of at least one of the front and rear surfaces. A device including a device.

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