Filled composite material showing thermal conductivity, dielectric constant, and weight reduction

Abstract

Aerogel-filled polymer composites, methods for making same, and uses thereof are described. The polymer composites can include a continuous polymer matrix and a discontinuous phase including a plurality of polymer aerogel particles dispersed in the continuous polymer matrix.

Description

Technical Field

[0001] Cross - reference to related applications This application claims the benefit of U.S. Provisional Application No. 62 / 733,714, filed Sep. 20, 2018, which is incorporated herein by reference in its entirety without disclaimer.

[0002] A. Field of the Invention The present invention generally relates to polymer composites including a continuous polymer matrix and a discontinuous phase including a plurality of polymer aerogel particles dispersed in the continuous polymer matrix.

Background Art

[0003] B. Description of Related Art Generally, polymer-based composites are known to exhibit lower thermal conductivity compared to metal and / or ceramic-based materials and thus make good thermal insulators. Additives can be added to the polymer matrix to vary the thermal conductivity of the polymer. For example, graphite carbon fibers, ceramics (such as aluminum nitride and boron nitride), glass, aerogel particles, etc. can be used. For example, U.S. Pat. Nos. 7,790,787 (Patent Document 1) and 9,777,126 (Patent Document 2) to Williams et al. describe adding aerogel to a thermoplastic polymer at a weight ratio of less than 20:100 of aerogel to thermoplastic polymer to improve the thermal insulation ability of the polymer composite. The application of thermosetting polymers is somewhat limited by the thickness constraints of the material because the volume increase of the curable resin is likely to cause cracks due to the rapid heating / cooling behavior characteristic of the exothermic peak.

[0004] Although various attempts have been described for making polymer composites, materials that show improved insulation while maintaining the tissue properties of the polymer composites are desired.

Prior Art Documents

Patent Documents

[0005] [Patent Document 1] U.S. Patent No. 7,790,787 [Patent Document 2] U.S. Patent No. 9,777,126 [Summary of the Invention]

[0006] Discoveries have been made to solve several problems related to polymer composites containing additives. This discovery is based on a polymer composite material comprising a polymer matrix in which a plurality of polymer aerogel particles (e.g., polyimide aerogel particles) are dispersed. The resulting polymer composite exhibits improved thermal insulation compared to unfilled polymer composites while maintaining tissue properties. In particular, and as non-limitingly exemplified in the examples, the exothermic peak during curing of the polymer composite can be delayed by the addition of aerogel particles. Surprisingly, it has been found that the addition of polymer aerogel particles increases the heat distortion temperature (HDT) of the polymer composition compared to unfilled polymer composites. Furthermore, the resulting polymer composite exhibits a reduced dielectric constant and / or thermal conductivity compared to the same polymer composite material that does not contain a plurality of polymer aerogel particles. Without wishing to be bound by theory, it is believed that the air trapped in the pores of the aerogel helps to reduce the dielectric constant and / or thermal conductivity.

[0007] In one aspect of the present invention, a polymer composite material is described. The polymer composite material may include a continuous polymer matrix and a discontinuous phase including a plurality of polymer aerogel particles dispersed in the continuous polymer matrix. The polymer matrix may include a thermoplastic polymer or a blend of thermoplastic polymers, a thermosetting polymer, a blend of thermosetting polymers, or any combination thereof. Non-limiting examples of thermoplastic polymers include polyolefins or blends thereof, more preferably polyethylene or polypropylene or blends thereof. Non-limiting examples of thermosetting polymers include dicyclopentadiene-modified polyesters, isophthalic acid-based polyesters, orthophthalic acid-based polyesters, or blends thereof. In some embodiments, the continuous polymer matrix may include a polyester, a polyamide, a polyepoxide, or any combination or blend thereof. In a particular aspect, the continuous polymer matrix includes a polyamide such as nylon. Non-limiting examples of nylon include polycaprolactam (nylon 6), poly[imino(1,6-dioxohexamethylene)iminotrimethylene] (nylon 6,6), poly(dodecano-12-lactam) (nylon 12), or any blend thereof. The plurality of polymer aerogel particles may include organic polymer-based aerogel particles. Preferably, polyimide aerogel particles can be used. In some aspects, the plurality of polymer aerogel particles may have an average diameter of 5 μm to 500 μm, preferably 20 μm to 250 μm, more preferably 25 μm to 150 μm, still more preferably 50 μm to 100 μm. In some cases, the plurality of polymer aerogel particles may exhibit a multimodal particle size distribution (e.g., a bimodal particle size distribution). The polymer composite material may include 0.5 wt% to 10 wt%, preferably 1 wt% to 8 wt%, more preferably 1 wt% to 6 wt%, or about 4 wt% of the plurality of polymer aerogel particles based on the total weight of the continuous polymer matrix and the discontinuous phase, or 2 vol% to 80 vol%, preferably 5 vol% to 50 vol%, more preferably 5 vol% to 15 vol%, or about 10 vol% of the plurality of polymer aerogel particles based on the total volume of the continuous polymer matrix and the discontinuous phase.The thermal conductivity (W / m·K) of the polymer composite material may be the same as or lower than that of the same polymer composite material without a discontinuous phase containing a plurality of polymer aerogel particles. On the other hand, the compressive yield strength (MPa), compressive elastic strength (GPa), and / or yield strain (%) of the polymer composite material may be the same as or different from (e.g., decreased, within 5%, equivalent, or increased) that of the same polymer composite material without a discontinuous phase containing a plurality of polymer aerogel particles. For example, the thermal conductivity of the polymer composite of the present invention can be the same as that of a polymer composite material without a discontinuous phase containing a plurality of polymer aerogel particles, while the mechanical strength is decreased but still suitable for the desired applications. In another example, the thermal conductivity of the polymer composite material may be lower than that of the same polymer composite material without a discontinuous phase containing a plurality of polymer aerogel particles, while the compressive yield strength (MPa), compressive elastic strength (GPa), and / or yield strain (%) of the polymer composite material may be the same as or different from (e.g., decreased, within 5%, equivalent, or increased) that of the same polymer composite material without a discontinuous phase containing a plurality of polymer aerogel particles. The dielectric constant of the polymer composite material may be lower than that of the same polymer composite material without a discontinuous phase containing a plurality of polymer aerogel particles. One or more additives may be dispersed or solubilized in the continuous polymer matrix. Examples of the additives include inorganic additives, preferably glass particles, glass fibers, glass spheres, hollow glass spheres, ceramic spheres, and polytetrafluoroethylene. The composite material can be of any shape or size. For example, the material can be in the form of a film or fiber (e.g., melt-spun fiber, dry-spun fiber, or wet-spun fiber).

[0008] Products containing the polymer composite material of the present invention are also described. Examples of the products include films, monoliths, wafers, blankets, core composite materials, substrates for high-frequency antennas, substrates for sun shields, substrates for sunshades, substrates for radomes, insulators for oil and / or gas pipelines, insulators for liquefied natural gas pipelines, insulators for cryogenic fluid transfer pipelines, insulators for apparel, insulators for aerospace applications, insulators for buildings, vehicles, and other human living environments, insulators for automotive applications, insulators for radiators, insulators for exhaust and ventilation, insulators for air conditioners, insulators for heating and refrigeration devices and portable air conditioners, insulators for coolers, insulators for packaging, insulators for consumer goods, vibration damping materials, insulators for wires and cables, insulators for medical devices, supports for catalysts, supports for drugs, pharmaceuticals, and / or drug delivery systems, water filtration devices, oil filtration devices, and solvent filtration devices, or any combination thereof. The product can be an injection-molded or blow-molded product.

[0009] A method for producing the polymer composite material of the present invention is also described. The method may include a step of dispersing a plurality of polymer aerogel particles in a polymer composition to form the polymer composite material of the present invention. The dispersion step may include casting, melt blending, or extruding the particles together with the polymer composition.

[0010] Methods for changing the viscosity and / or HDT of a polymer composition are also described. A method for changing (e.g., increasing or decreasing) the viscosity of a polymer composition can include dispersing a sufficient amount (e.g., 1 wt% to 50 wt%, preferably 5 wt% to 40 wt%, or 10 wt% to 20 wt%) of a plurality of polymer aerogel particles in the polymer composition to change the viscosity of the polymer composition compared to the same polymer composition without the plurality of polymer aerogel particles. The aerogel particles can have a particle size of 10 to 150 micrometers, or about 30 to 125 micrometers. A method for increasing the HDT of a polymer composition can include dispersing a sufficient amount of a plurality of polymer aerogel particles in the polymer composition to change, preferably increase, the HDT of the polymer composition compared to the same polymer composition without the plurality of polymer aerogel particles.

[0011] A method for reducing the exothermic peak during the curing of a thermosetting polymer is described. The method can include dispersing a sufficient amount of a plurality of polymer aerogel particles in a polymer thermosetting composition to reduce the exothermic peak of the polymer thermosetting composition compared to the same polymer thermosetting composition without the plurality of polymer aerogel particles. The onset of exotherm can be delayed by 0.25 hours to 2 hours, preferably 0.3 hours to 0.75 hours, and / or the exothermic peak can be reduced by 5 to 50 °C, preferably 10 to 30 °C, more preferably 15 to 25 °C.

[0012] In one aspect of the present invention, 33 aspects are described. Aspect 1 is a polymer composite material comprising a continuous polymer matrix; and a discontinuous phase comprising a plurality of polymer aerogel particles dispersed in the continuous polymer matrix. Aspect 2 is the polymer composite material according to Aspect 1, wherein the continuous polymer matrix comprises polyester, polyamide, polyepoxide, or any combination or blend thereof. Aspect 3 is the polymer composite material according to Aspect 2, wherein the continuous polymer matrix comprises polyamide, and the polyamide is nylon, preferably polycaprolactam, poly[imino(1,6-dioxohexamethylene)iminohexamethylene], poly(dodecano-12-lactam), or any blend thereof. Aspect 4 is the polymer composite material according to any one of Aspects 1 to 3, wherein the plurality of polymer aerogel particles are organic polymer aerogels, preferably polyimide aerogel particles. Aspect 5 is the polymer composite material according to any one of Aspects 1 to 4, wherein the plurality of polymer aerogel particles have an average diameter of 5 μm to 500 μm, preferably 20 μm to 250 μm, more preferably 25 μm to 150 μm, and even more preferably 50 μm to 100 μm. Aspect 6 is the polymer composite material according to any one of Aspects 1 to 5, wherein the plurality of polymer aerogel particles exhibit a multimodal particle size distribution, preferably a bimodal particle size distribution. Aspect 7 is the polymer composite material according to any one of Aspects 1 to 6, comprising 0.5 wt% to 10 wt%, preferably 1 wt% to 8 wt%, or more preferably 1 wt% to 6 wt%, or about 4 wt% of a plurality of polymer aerogel particles based on the total weight of the continuous polymer matrix and the discontinuous phase. Aspect 8 is the polymer composite material according to any one of Aspects 1 to 7, comprising 2 vol% to 80 vol%, preferably 5 vol% to 50 vol%, or more preferably 5 vol% to 15 vol%, or about 10 vol% of a plurality of polymer aerogel particles based on the total volume of the continuous polymer matrix and the discontinuous phase. Aspect 9 is the polymer composite material according to any one of Aspects 1 to 8, wherein the thermal conductivity (W / m·K) of the polymer composite material is the same as or lower than that of the same polymer composite material without the discontinuous phase containing a plurality of polymer aerogel particles.Aspect 10 is the polymer composite material according to any one of Aspects 1 to 9, wherein the dielectric constant of the polymer composite material is lower than that of the same polymer composite material not containing a discontinuous phase including a plurality of polymer aerogel particles. Aspect 11 is the polymer composite material according to any one of Aspects 1 to 10, wherein the compressive yield strength (MPa), compressive elastic strength (GPa), and / or yield strain (%) of the polymer composite material are the same as or changed compared to the same polymer composite material not containing a discontinuous phase including a plurality of polymer aerogel particles. Aspect 12 is the polymer composite material according to any one of Aspects 1 to 11, wherein the polymer matrix includes a thermoplastic polymer or a blend of thermoplastic polymers, preferably a polyolefin, a fluoropolymer or a derivative thereof, or a blend thereof, or more preferably polyethylene or polypropylene or a blend thereof. Aspect 13 is the polymer composite material according to any one of Aspects 1 to 12, wherein the polymer matrix includes a thermosetting polymer or a blend of thermosetting polymers, preferably a dicyclopentadiene-modified polyester, an isophthalic acid-based polyester, an orthophthalic acid-based polyester, or a blend thereof. Aspect 14 is the polymer composite material according to any one of Aspects 1 to 13, further including an additive dispersed or solubilized in the continuous polymer matrix. Aspect 15 is the polymer composite material according to Aspect 14, wherein the additive is an inorganic additive or polytetrafluoroethylene, preferably glass particles, glass fibers, glass spheres, hollow glass spheres, ceramic spheres, or polytetrafluoroethylene. Aspect 16 is the polymer composite material according to any one of Aspects 1 to 15, which is in the form of a film. Aspect 17 is the polymer composite material according to any one of Aspects 1 to 16, which is in the form of a fiber. Aspect 18 is the polymer composite material according to Aspect 17, wherein the fiber is a melt-spun fiber, a dry-spun fiber, or a wet-spun fiber.

[0013] Aspect 19 is a polymer composite material according to any one of Aspects 1 to 18, which is included in a product. Aspect 20 is a product that is a film, a monolith, a wafer, a blanket, a core composite material, a substrate for a high-frequency antenna, a substrate for a sun shield, a substrate for a sunshade, a substrate for a radome, an insulator for an oil and / or gas pipeline, an insulator for a liquefied natural gas pipeline, an insulator for a cryogenic fluid transfer pipeline, an insulator for apparel, an insulator for aerospace applications, an insulator for buildings, vehicles, and other human living environments, an insulator for automotive applications, an insulator for a radiator, an insulator for exhaust and ventilation, an insulator for air conditioning, an insulator for heating and refrigeration devices and portable air conditioners, an insulator for a cooler, an insulator for packaging, an insulator for consumer goods, a vibration damping material, an insulator for wires and cables, an insulator for medical devices, a support for a catalyst, a support for drugs, pharmaceuticals, and / or drug delivery systems, a storage container, a pipe, a tube, a seal, a gasket, a water filtration device, an oil filtration device, and a solvent filtration device, or any combination thereof, which is the polymer composite material according to Aspect 19. Aspect 21 is a polymer composite material according to any one of Aspects 19 to 20, wherein the product is an injection-molded or blow-molded product.

[0014] Aspect 22 is a method for producing a polymer composite material according to any one of Aspects 1 to 18, the method including a step of dispersing a plurality of polymer aerogel particles in a polymer composition to form a polymer composite material according to any one of Aspects 1 to 17. Aspect 23 is the method according to Aspect 22, wherein the polymer aerogel particles are dispersed in the polymer composition by casting, melt-blending, or extruding the polymer aerogel particles together with the polymer composition.

[0015] Aspect 24 is a method for changing the viscosity of a polymer composition, the method comprising dispersing a sufficient amount of a plurality of polymer aerogel particles in the polymer composition to change the viscosity of the polymer composition compared to the same polymer composition without the plurality of polymer aerogel particles. Aspect 25 is the method according to aspect 24, wherein the viscosity of the polymer composition is reduced compared to the same polymer composition without the plurality of polymer aerogel particles. Aspect 26 is the method according to aspect 25, wherein the viscosity of the polymer composition is increased compared to the same polymer composition without the plurality of polymer aerogel particles.

[0016] Aspect 27 is a method for delaying the onset of exotherm and / or reducing the exotherm peak during curing of a thermosetting polymer, the method comprising dispersing a sufficient amount of the plurality of polymer aerogel particles in the polymer thermosetting composition to delay and / or reduce the exotherm peak of the polymer thermosetting composition compared to the same polymer thermosetting composition without the plurality of polymer aerogel particles. Aspect 28 is the method according to aspect 27, wherein the onset of exotherm is delayed by 0.25 hour to 2 hours, preferably 0.3 hour to 0.75 hour. Aspect 29 is the method according to any one of aspects 27 to 28, wherein the exotherm peak is reduced by 5 to 50 °C, preferably 10 to 30 °C, more preferably 15 to 25 °C.

[0017] Aspect 30 is a method for increasing the heat deflection temperature (HDT) of a polymer composition, comprising the step of dispersing a sufficient amount of the plurality of polymeric aerogel particles in the polymer composition to change, preferably increase, the HDT of the polymer composition as compared to the same polymer composition without the plurality of polymeric aerogel particles. Aspect 31 is the method according to Aspect 30, wherein the amount of the plurality of polymeric aerogel particles is from 1 wt% to 50 wt%, preferably from 5 wt% to 40 wt%, or from 10 wt% to 20 wt%. Aspect 32 is the method according to any one of Aspects 30 to 31, wherein the particle size of the aerogel is from 10 micrometers to 150 micrometers, preferably from 30 micrometers to 125 micrometers. Aspect 33 is the method according to any one of Aspects 30 to 32, wherein the HDT of the polymer composite is at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, or at least 50% lower than that of the same natural polymer composite.

[0018] Other aspects of the invention are described throughout this application. Any aspect described with respect to one aspect of the invention is equally applicable to other aspects of the invention, and vice versa. Each aspect described herein is understood to be an aspect of the invention applicable to other aspects of the invention. Any aspect described herein is assumed to be practicable with respect to any method or composition of the invention, and vice versa. Further, the compositions of the invention can be used to implement the methods of the invention.

[0019] The following includes definitions of various terms and phrases used throughout this specification.

[0020] The term "aerogel" refers to a class of materials that are generally produced by forming a gel and replacing the interstitial solvent phase of mobility with a gas or gas-like substance after removing it from the pores. By controlling the gel and evaporation systems, density, shrinkage, and pore collapse can be minimized. As described above, the aerogels of the present invention may include micropores and / or mesopores or any combination thereof. The amount of micropores and / or mesopores in any given aerogel of the present invention can be adjusted or regulated as desired. However, in certain preferred aspects, the aerogel may include mesopores such that at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 100% of the pore volume of the aerogel is composed of mesopores. In some embodiments, the aerogels of the present invention have a low bulk density (about 0.25 g / cm 3 Hereinafter, preferably about 0.01 to 0.5 g / cm 3 ), a large surface area (generally about 10 to 1,000 m 2 / g or more, preferably about 50 to 1000 m 2 / g), a high porosity (about 80% or more, preferably more than about 85%), and / or a relatively large pore volume (more than about 1.0 mL / g, preferably about 1.2 mL / g or more).

[0021] The presence of mesopores and / or micropores in the aerogels of the present invention can be determined by mercury intrusion porosimetry (MIP) and / or gas physical adsorption experiments. In a preferred case, MIP tests used in the Examples section can be used to measure mesopores larger than 5 nm (i.e., American Society for Testing and Materials (ASTM) D4404-10, Standard Test Method for Determination of Pore Volume and Pore Volume Distribution of Soils and Rocks by Mercury Intrusion Porosimetry). In a preferred case, gas physical adsorption experiments used in the Examples section can be used to measure mesopores and / or micropores (ASTM D1993-03(2008) Standard Test Method for Precipitated Silica - Multi-Point BET Nitrogen Surface Area).

[0022] The term "impurity" means an undesired substance in the feed fluid that is different from the desired filtrate and / or is not desirable in the filtrate. In some cases, the impurity can be a solid, liquid, gas, or supercritical fluid. In some embodiments, the aerogel can remove some or all of the impurities.

[0023] The term "desired substance" means a desired substance in the feed fluid that is different from the desired filtrate. In some cases, the desired substance can be a solid, liquid, gas, or supercritical fluid. In some embodiments, the aerogel can remove some or all of the desired substance.

[0024] The term "radio frequency (RF)" means the region of the electromagnetic spectrum that exhibits wavelengths in the range of 10 -4 ~10 7 m.

[0025] The term "supercritical fluid" means any substance at a temperature and pressure above the critical point. A supercritical fluid can diffuse into solids like a gas and dissolve substances like a liquid. Further, as it approaches the critical point, a small change in pressure or temperature causes a large change in density.

[0026] "Aliphatic group" refers to an acyclic or cyclic saturated or unsaturated carbon group excluding aromatic compounds. A linear aliphatic group does not contain tertiary or quaternary carbon. Substituents of an aliphatic group include, but are not limited to, halogen, hydroxyl, alkoxyl, haloalkyl, haloalkyl, carboxylic acid, ester, amine, amide, nitrile, acyl, thiol, and thioether. A branched aliphatic group contains at least one tertiary and / or quaternary carbon. Substituents of a branched aliphatic group can include alkyl, halogen, hydroxyl, alkoxyl, haloalkyl, haloalkoxy, carboxylic acid, ester, amine, amide, nitrile, acyl, thiol, and thioether. A cyclic aliphatic group contains at least one ring in its structure. Polycyclic aliphatic groups can include fused polycyclic groups, such as decalin polycyclic groups, and / or spiro polycyclic groups, such as spiro[5.5]undecane polycyclic groups. Substituents of a cyclic aliphatic group can include alkyl, halogen, hydroxyl, alkoxy, haloalkyl, haloalkoxy, carboxylic acid, ester, amine, amide, nitrile, acyl, thiol, and thioether.

[0027] "Alkyl group" refers to a linear or branched substituted or unsubstituted saturated hydrocarbon. Substituents of an alkyl group can include, but are not limited to, alkyl, halogen, hydroxyl, alkoxyl, haloalkyl, haloalkoxy, carboxylic acid, ester, amine, amide, nitrile, acyl, thiol, and thioether.

[0028] "Aryl" group or "aromatic" group refers to a substituted or unsubstituted monocyclic or polycyclic hydrocarbon having alternating single and double bonds in each ring structure. Substituents of an aryl group can include alkyl, halogen, hydroxyl, alkoxyl, haloalkyl, haloalkoxy, carboxylic acid, ester, amine, amide, nitrile, acyl, thiol, and thioether.

[0029] The term "acrylate" includes substituted and unsubstituted vinyl carboxylic acids. The general structure of an acrylate is TIFF0007687948000001.tif10128. Non-limiting examples of acrylates include acrylates and methacrylates.

[0030] The term "acid" compound when used in producing an unsaturated polyester material includes carboxylic acids, dicarboxylic acids, and anhydride compounds.

[0031] The term "alkenyl group" means an unsaturated hydrocarbon (i.e., a double bond).

[0032] The term "about" or "approximately" is defined as being close to a value understood by those skilled in the art. In a non-limiting aspect, these terms are defined as being within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.

[0033] The terms "wt%", "vol%", or "mol%" mean, respectively, the weight percent, volume percent, or mole percent of a component relative to the total weight, total volume, or total moles of a substance containing the component. In a non-limiting example, 10 grams of a component in 100 grams of a substance is 10 wt% of the component.

[0034] The term "substantially" and variations thereof are defined as including ranges within 10%, 5%, 1%, or 0.5%.

[0035] The term "inhibit" or "reduce" or "prevent" or "avoid" or any variation of these terms when used in the claims and / or specification includes any measurable decrease or complete inhibition to achieve the desired result.

[0036] As used in the specification and / or claims, the term "effective" means sufficient to achieve a desired, expected, or intended result.

[0037] When used in combination with any of the terms "comprising", "including", "containing", or "having" in the claims or specification, the use of the word "a" or "an" can mean "one", but is also consistent with the meanings of "one or more", "at least one", and "one or two or more".

[0038] The terms "comprising" (and any form of comprising, such as "comprise" and "comprises"), "having" (and any form of having, such as "have" and "has"), "including" (and any form of including, such as "includes" and "include"), or "containing" (and any form of containing, such as "contains" and "contain") are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.

[0039] The polymeric composite materials of the present invention can "comprise", "consist essentially of", or "consist of" the specific ingredients, components, compositions, etc. disclosed throughout this specification. With respect to the transitional phrase "consisting essentially of", in one non-limiting aspect, the basic and novel properties of the polymeric composite materials of the present invention are thermal conductivity and tissue properties.

[0040] Other objects, features, and advantages of the present invention will become apparent from the following drawings, detailed description, and examples. However, it should be understood that the drawings, detailed description, and examples are shown for illustrative purposes only and are not intended to be limiting, even though they show specific embodiments of the present invention. Furthermore, it is contemplated that modifications and variations within the spirit and scope of the present invention will become apparent to those skilled in the art from this detailed description. In a further aspect, features according to a particular aspect can be combined with features according to other aspects. For example, features according to one aspect can be combined with features according to any of the other aspects. In a further aspect, additional features can be added to the specific aspects described herein.

Brief Description of the Drawings

[0041] The advantages of the present invention may become apparent to those skilled in the art from the following detailed description and by referring to the accompanying drawings.

[0042]

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[0043] The present invention may allow for various modifications and alternative forms, but specific embodiments thereof are shown by way of example in the drawings. The drawings may not be to scale.

Embodiments for Carrying Out the Invention

[0044] Detailed description of the invention Discoveries have been made to provide solutions to several problems related to the insulation and tissue properties associated with polymer composite materials. This discovery is premised on a polymer composite material containing aerogel particles dispersed throughout the polymer matrix. In particular, the polymer composite material exhibits good mechanical properties and insulation. These and other non-limiting aspects of the present invention are described in more detail in the following sections.

[0045] These and other non-limiting aspects of the present invention are described in more detail in the following sections.

[0046] A. Polymeric composite materials The polymer composite material of the present invention includes a continuous polymer phase and a discontinuous phase dispersed throughout the continuous phase. The discontinuous phase can include aerogel particles. In some embodiments, the polymer composite material can include one or more additives dispersed or solubilized in a continuous polymer matrix. FIG. 1 shows a diagram of the polymer composite of the present invention. The polymer composite material 10 includes a polymer continuous phase 12 and a discontinuous particle phase 14. The polymer composite can be of any shape or form. Non-limiting examples of forms include films, fibers, blocks, sheets, tubes, rolls, etc. Examples of fibers can include melt-spun fibers, dry-spun fibers, or wet-spun fibers. The films and sheets can be of any thickness. The polymer composite material can include from 0.5 wt% to 10 wt%, or at least 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, 9 wt%, 9.5 wt%, and 10 wt%, equivalent thereto, or between any two of these, a plurality of polymer aerogel particles based on the total weight of the continuous polymer matrix and the discontinuous phase. The polymer composite material can include from 2 vol% to 80 vol%, or at least 2 vol%, 5 vol%, 10 vol%, 15 vol%, 20 vol%, 25 vol%, 30 vol%, 35 vol%, 40 vol%, 45 vol%, 50 vol%, 55 vol%, 60 vol%, 65 vol%, 70 vol%, 75 vol%, and 80 vol%, equivalent thereto, or between any two of these, a plurality of polymer aerogel particles based on the total volume of the continuous polymer matrix and the discontinuous phase. The polymer composite material can exhibit improved physical and / or mechanical properties compared to natural materials. The thermal conductivity (W / m·K) of the polymer composite material may be the same or decreased compared to the same polymer composite material without the discontinuous phase containing a plurality of polymer aerogel particles. The composite polymer material can exhibit a thermal conductivity that is at least 5% lower (e.g., less than 95%) compared to the thermal conductivity of a natural thermoplastic polymer material.In certain embodiments, the composite material exhibits a thermal conductivity that is at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, or at least 50% lower than that of a natural polymer material. The dielectric constant of the polymer composite material can be reduced compared to the same polymer composite material that does not include a discontinuous phase containing a plurality of polymer aerogel particles. The composite polymer material can exhibit a dielectric constant that is at least 5% lower (e.g., less than 95%) than that of a natural thermoplastic polymer material. In certain embodiments, the composite material exhibits a dielectric constant that is at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, or at least 50% lower than that of a natural polymer material. The compressive yield strength (MPa), compressive elastic modulus (GPa), and / or yield strain (%) of the polymer composite material may be the same or may vary. For example, the compressive yield strength (MPa), compressive elastic modulus (GPa), and / or yield strain (%) of the polymer composite material may be lower, equivalent (e.g., within 5%), or higher compared to the same polymer composite material that does not include a plurality of polymer aerogel particles. The HDT of the polymer composite material is at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, or at least 50% lower than that of the same natural polymer composite material. In some embodiments, into the polymer composition to vary the viscosity of the polymer composition compared to the same polymer composition that does not include a plurality of polymer aerogel particles. In some embodiments, to vary the HDT and / or viscosity, from 1 wt% to 50 wt%, or at least 1 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, and 50 wt%, equivalent to these, or between any two of these, having a particle size of from 10 to 15 micrometers, or at least 10, 25, 50, 75, 100, 125, and 150 micrometers, equivalent to these, or between any two of these, a plurality of polymer aerogel particles can be added to the polymer composition.

[0047] B. Material 1. Polymer Matrix The polymer matrix may include thermoplastic and / or thermosetting polymers. The polymer matrix can be produced using any known process for making polymers (e.g., vapor phase processing, solution processing, emulsion processing, or melt processing, etc.). Non-limiting examples of thermoplastic polymers include polyethylene terephthalate (PET), polymers of the polycarbonate (PC) family, polybutylene terephthalate (PBT), poly(1,4-cyclohexylidene cyclohexane-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 polyetherimide (PEI) and their derivatives, thermoplastic elastomers (TPE), terephthalic acid (TPA) elastomers, poly(cyclohexane dimethylene terephthalate) (PCT), polyethylene naphthalate (PEN), polyamide (PA), polysulfone sulfonate (PSS), sulfonate of polysulfone, polyether ether ketone (PEEK), polyether ketone ketone (PEKK), acrylonitrile butadiene styrene (ABS), polyphenylene sulfide (PPS), its copolymers, polyester or its derivatives, polyamide or its derivatives (e.g., nylon), fluoropolymer or its derivatives, or blends thereof. Examples of fluoropolymers include polytetrafluoroethylene (PTFE), perfluoroalkoxy (PFA), fluorinated ethylene-propylene polymer (FEP), ethylene tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF) and its copolymers (PVDF-TrFE, PVDF-TrFE-CFE), polyvinyl fluoride (PVF), tetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-7-octene sulfonic acid copolymer, or blends thereof. Polyamides can include all types of nylon compounds.Non-limiting examples of nylon include polycaprolactam, poly[imino(1,6-dioxohexamethylene)iminohexamethylene], poly(dodecano-12-lactam), or any blend thereof.

[0048] Non-limiting examples of thermosetting polymers 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, dicyclopentadiene, phenolic resins, benzoxazines, polysiloxanes (e.g., silicones and silicone rubbers), natural rubbers, polyisoprene, polychloroprene, styrene-butadiene rubber, nitrile-butadiene rubber, ethylene-propylene-diene monomer rubber (EPDM), butyl rubber (IIR), polybutadiene (BR), epichlorohydrin (ECO), fluorinated hydrocarbons (FKM), their copolymers, or blends thereof. Polyimides may exhibit pseudo-thermoplasticity. Unsaturated polyesters can be made using known polycondensation reactions. The unsaturated polyesters of the present invention may be formed from acid compounds, diols, alkenyls (e.g., dicyclopentadiene) or obtained from commercial suppliers. Non-limiting examples of acid compounds include isophthalic acid, terephthalic acid, adipic acid, tetrachlorophthalic anhydride and tetrabromophthalic anhydride, phthalic anhydride, maleic anhydride, maleic acid, fumaric acid, or mixtures thereof. Non-limiting examples of diol compounds include 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, dibromoneopentyl glycol, tetrabromobisphenol A, propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, or blends or mixtures thereof. In some embodiments, the unsaturated polyester may have the following general formula: TIFF0007687948000002.tif16128 wherein R 1 is derivable from the acid moiety, R2 is derivable from a diol, and R 3 may be an alkenyl moiety. R 3 is formable from an anhydride (e.g., maleic anhydride). R 3 may be capable of forming a crosslinked polyester material by reacting with a compound having an alkenyl group. The unsaturated polyester can be provided as a solution containing an unsaturated polyester and an alkenyl compound (e.g., styrene or dicyclopentadiene). Also, the unsaturated polyester resin is commercially available from, for example, Revchem Composites, Inc. (Stockton, California, USA).

[0049] 2. Aerogel Aerogel particles can include organic aerogels. Organic aerogels can be made from polyacrylate, polystyrene, polyacrylonitrile, polyurethane, polyimide, polyamide, polyfurfural alcohol, phenol furfuryl alcohol, melamine formaldehyde, resorcinol formaldehyde, cresol formaldehyde, phenol formaldehyde, polyvinyl alcohol dialdehyde, polycyanurate, polyacrylamide, polyester, crosslinked polyester, polystyrene, silicone, various epoxies, agar, agarose, lignin, cellulose, etc. Organic aerogels can be obtained from Blueshift materials, Inc. in the United States. In certain embodiments, the aerogel is a polyimide aerogel. Polyimide-based aerogels may be obtained from commercial suppliers (e.g., the product name AeroZero® from Blueshift Materials, Inc. in the United States), or may be prepared using known aerogel methodologies. Aerogels can be prepared using the methodologies described in Rodman et al.'s International Patent Application Publication No. WO 2014 / 189560, Sakaguchi et al.'s 2017 / 07888, Yang et al.'s 2018 / 078512, Sakaguchi et al.'s 2018 / 140804, Irvin et al.'s 2019 / 006184, Ejaz et al.'s International Patent Application PCT / US2019 / 029191, Poe et al.'s U.S. Patent Application Publication No. 2017 / 0121483, and Sakaguchi et al.'s U.S. Patent No. 9,963,571, all of which are hereby incorporated by reference in their entirety. Aerogel particles can be of any size. In some embodiments, the particle size of the aerogel is 5 μm to 500 μm, or at least 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, 400, 450, and 500 μm, equivalent thereto, or between any two of these. In some embodiments, the particle size distribution can be multimodal (e.g., bimodal, trimodal, etc.). In certain embodiments, the particle size distribution is bimodal, with one peak at 10 - 100 μm and the other peak at 150 - 300 μm.Aerogel particles can be formed by reducing a film or shape of an aerogel to particles after the film or shape of the aerogel is produced. For example, the film and / or shape can be ground, shredded, or machined into particles.

[0050] 3. Additives The polymer composite material may contain additives. The additives may be dispersed or solubilized in the continuous phase (i.e., the polymer matrix). The additives may include inorganic additives and organic additives. Examples of inorganic additives include glass particles, glass fibers, glass spheres, hollow glass spheres, and ceramic spheres. Examples of organic additives include polytetrafluoroethylene, anti-fogging agents, antioxidants, heat stabilizers, light stabilizers, hindered amine light stabilizers, fluidity improvers, ultraviolet absorbers, impact resistance improvers, coupling agents, colorants, etc., or any combination thereof. The amount of the additives in the polymer matrix is 0 to 20% by weight, or at least 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20% by weight, equivalent thereto, or between any two of these.

[0051] D. Method for Producing Polymer Composite Material Polymer aerogel particles can be dispersed in a polymer matrix using dry or wet blending techniques. Non-limiting examples of the dispersion process include casting the particles with the polymer composition, melt blending, or extrusion. In some embodiments, a dry blend can be formed by dry mixing a polymer matrix material (e.g., a pure thermosetting polymer and / or a polymer mixture) with the aerogel particles. In another embodiment, the polymer matrix can be pre-mixed and pelletized and then dry mixed with the polymer aerogel particles. An organic / inorganic composite can be obtained by melt extruding the dry blend, preferably in a twin-screw extruder with an adjustable temperature zone, such as a conical twin-screw extruder, or by solution processing. In another embodiment, melt extrusion can be used to mix the polymer aerogel particles with the polymer matrix. In yet another embodiment, the polymer aerogel particles can be mixed with the polymer material by dissolving the polymer material in a solvent and then adding the aerogel particles to the solution. By dissolving the polymer, the composite material can be wet spun into fibers or cast into sheets. The polymer composite material can then be melt spun into fibers, extrusion molded into tapes, injection molded, blow molded, and / or compression molded into any usable shape or form. The temperature of the process for making the composite material can vary depending on the type of polymer matrix used. The temperature can be in the range of 15°C to 200°C, or any range or value therebetween. The addition of aerogel particles during curing can delay the exotherm by 0.25 hours to 2 hours, preferably 0.3 hours to 0.75 hours. In other embodiments, the decrease in the onset of exotherm can be 5 to 50°C, or at least 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, equivalent thereto, or between any two of these, or 10% to 85%, or at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, and 85%, equivalent thereto, or between any two of these.

[0052] E. Products Comprising Polymer Composite Materials In some situations, the product may include any one of the polymeric composite materials of the present invention. In some embodiments, the product is a thin film, a monolith, a wafer, a blanket, a core composite material, a substrate for high-frequency antennas, a screen, a sun shield, a radome, an insulator for oil and / or gas pipelines, an insulator for liquefied natural gas pipelines, an insulator for cryogenic fluid transfer pipelines, an insulator for apparel, an insulator for aerospace applications, an insulator for buildings, vehicles, and other human living environments, an insulator for automotive applications, an insulator for radiators, an insulator for exhaust and ventilation, an insulator for air conditioning, an insulator for heating and refrigeration devices and portable air conditioners, an insulator for coolers, an insulator for packaging, an insulator for consumer goods, a vibration damper, an insulator for wires and cables, an insulator for medical devices, a support for catalysts, a support for drugs, pharmaceuticals, and / or drug delivery systems, a storage container, a pipe, a tube, a seal, a gasket, for water filtration applications, for oil filtration applications, and for solvent filtration applications.

[0053] 1. Fluid filtration applications In some embodiments, the polymeric composite materials of the present invention can be used in fluid filtration systems and fluid filtration devices. In these applications, the fluid being filtered can be permeable through the polymeric composite material. The feed fluid can be contacted with the polymeric composite material so as to produce a filtrate that is essentially free of impurities and / or desired substances by removing all or substantially all of the impurities and / or desired substances from the feed fluid. The filtrate, impurities, and / or desired substances can be collected, stored, transported, recycled, or further processed. The polymeric composite material can be further processed to release the impurities and / or desired substances from the polymeric composite material.

[0054] The polymeric composite material of the present invention can be used in or with a filtration device known in the art. Non-limiting examples of filtration devices and filtration applications include building air filters, automotive cabin air filters, internal combustion engine air filters, aircraft air filters, satellite air filters, face mask filters, diesel exhaust particulate filters, in-line gas filters, cylinder gas filters, soot filters, pressure swing absorption devices, and other gas filters not limited thereto. Further non-limiting examples of filtration devices and filtration applications include solvent filtration systems, column filtration, chromatography filtration, vacuum flask filtration, microfiltration, ultrafiltration, reverse osmosis filtration, nanofiltration, centrifugal filtration, gravity filtration, cross-flow filtration, dialysis, blood filtration, hydraulic fluid filtration, automotive oil filtration, and the like. Further non-limiting examples of the purposes of filtration include sterilization, separation, purification, isolation, and the like.

[0055] The fluid for filtration ("feed") and the filtrate can be any fluid. The fluid can be a liquid, a gas, a supercritical fluid, or a mixture thereof. In some cases, the fluid can be an aqueous fluid, an organic fluid, a non-organic fluid, a fluid of biological origin, or a mixture thereof. In some cases, the fluid can contain solids and / or other fluids. As non-limiting examples, the fluid or a portion thereof can be water, blood, oil, solvent, air, or a mixture thereof. Water can include water, any form of vapor, and supercritical water.

[0056] In some cases, the fluid may contain impurities. Non-limiting examples of impurities include solids, liquids, gases, supercritical fluids, objects, compounds, and / or chemical substances. What is defined as an impurity may vary depending on the desired filtrate for the same feed fluid. In some embodiments, one or more polymer composite materials can be used to remove impurities. Non-limiting examples of impurities in water include ionic substances such as sodium ions, potassium ions, magnesium ions, calcium ions, fluoride ions, chloride ions, bromide ions, sulfate ions, sulfite ions, nitrate ions, nitrite ions, cationic surfactants, and anionic surfactants, metals, heavy metals, suspended oil, partially dissolved oil, or dissolved oil, organic solvents, non-ionic surfactants, defoamers, chelating agents, microorganisms, particulate matter, etc. Non-limiting examples of impurities in blood include red blood cells, white blood cells, antibodies, microorganisms, water, urea, potassium, phosphorus, gases, particulate matter, etc. Non-limiting examples of impurities in oil include water, particulate matter, heavy and / or light hydrocarbons, metals, sulfur, defoamers, etc. Non-limiting examples of impurities in a solvent include water, particulate matter, metals, gases, etc. Non-limiting impurities in air include water, particulate matter, microorganisms, liquids, carbon monoxide, sulfur dioxide, etc.

[0057] In some cases, the feed fluid may contain a desired substance. Non-limiting examples of the desired substance include solids, liquids, gases, supercritical fluids, objects, compounds, and / or chemical substances. In some embodiments, one or more polymer composite materials can be used to concentrate or capture the desired substance or to remove fluid from the desired substance. Non-limiting examples of the desired substance in water include ionic substances such as sodium ions, potassium ions, magnesium ions, calcium ions, fluoride ions, chloride ions, bromide ions, sulfate ions, sulfite ions, nitrate ions, nitrite ions, cationic surfactants, and anionic surfactants, metals, heavy metals, suspended oil, partially dissolved oil, or dissolved oil, organic solvents, non-ionic surfactants, chelating agents, defoaming agents, etc. Non-limiting examples of the desired substance in blood include red blood cells, white blood cells, antibodies, lipids, proteins, etc. Non-limiting examples of the desired substance in oil include hydrocarbons having a range of molecular weights, gases, metals, etc. Non-limiting examples of the desired substance in a solvent include particulate matter, fluids, gases, proteins, lipids, etc. Non-limiting examples of the desired substance in air include water, fluids, gases, particulate matter, etc.

[0058] The filtration system may include a separation zone. To achieve the desired flow rate and contact time, standard technical methods can be used to determine the material, size, and shape of the separation zone. The separation zone may be capable of holding one or more polymer composite materials of the present invention and may be made thereof. In some cases, the separation zone is entirely made of one or more polymer composite materials or one or more polymer composite materials inside or around a support structure. The feed fluid can be introduced into the separation zone through an inlet or through direct contact with the separation zone. In some embodiments, the feed fluid can be received at a pressure higher or lower than ambient pressure. The introduction of the feed fluid into the separation zone can be carried out at a flow rate sufficient to allow optimal contact between the feed fluid and one or more polymer composite materials. The contact between the feed fluid and the polymer composite material can enable the filtration of the feed fluid with the polymer composite material, thereby obtaining a filtrate having fewer impurities and / or desired substances compared to the feed fluid. In certain aspects, the filtrate may be substantially free of impurities and / or desired substances. The filtrate can exit the separation zone 602 through an outlet or by directly exiting the separation zone 602. In some cases, the filtrate can be recycled to the separation zone, collected, and stored in a storage device, etc. In some cases, one or more polymer composite materials can be removed from and / or moved out of the separation zone. In some cases, the filtrate can be collected and / or removed from the separation zone without flowing out through an outlet. In some cases, impurities and / or desired substances can be removed from the separation zone. As a non-limiting example, impurities and / or desired substances can be removed from the separation zone by flowing a fluid through the separation zone in a direction opposite to the flow of the feed fluid through the separation zone.

[0059] The filtration conditions within the separation zone to achieve the desired result (e.g., removal of substantially all impurities and / or desired substances from the feed fluid) can vary. Filtration conditions include temperature, pressure, the flow of the feed fluid, the flow of the filtrate, or any combination thereof. In some cases, the filtration conditions are controlled to produce a flow exhibiting certain characteristics. The separation zone may include valves, thermocouples, controllers (automatic or manual controllers), computers, or any other equipment deemed necessary to control or operate the separation zone. The flow of the feed fluid can be adjusted and controlled to maintain optimal contact between the feed fluid and one or more polymer composite materials. In some embodiments, computer simulations can be used to determine the flow rates in the separation zones of various dimensions and various polymer composite materials.

[0060] The suitability of the polymer composite material for the fluid and / or filtration application can be determined by methods known in the art. Some of the characteristics of the polymer composite material that can be determined to evaluate its suitability include the temperature and / or pressure at which the polymer composite material melts, dissolves, oxidizes, reacts, decomposes, or breaks; the solubility of the polymer composite material in the materials it contacts; the flow rate of the fluid passing through the polymer composite material; the retention rate of the impurities and / or desired products forming the feed fluid, etc., but is not limited thereto.

[0061] 2. High Frequency (RF) Applications The polymer composite material of the present invention has a low density, is mechanically robust, lightweight, and has low dielectric properties, so it can be used in high-frequency (RF) applications. The use of macroporous polymer composite materials in RF applications enables the design of thinner, lighter, and smaller substrates. Non-limiting examples of high-frequency applications include substrates for RF antennas, RF antenna shields, radomes, etc. Examples of antennas include flexible and / or rigid antennas, broadband planar circuit antennas (such as patch antennas, e-type broadband patch antennas, elliptical polarized circular patch antennas, monopole antennas, planar antennas with circular slots, bowtie antennas, inverted F antennas, etc.). In antenna design, circuits can be attached to substrates containing the polymer composite material and / or combinations of polymer composite materials, as well as other components such as other polymer materials. The use of the polymer composite material in the antenna enables the design of substrates with higher throughput. Furthermore, the polymer composite material can have a coefficient of thermal expansion (CTE) similar to that of aluminum and copper (e.g., CTE 23 / K and 17 ppm / K) and can be adjusted through the selection of monomers that match the CTE of other desired materials. In some embodiments, the polymer composite material can be used in shields and / or screens used to protect RF antennas from thermal cycles because it is temperature-insensitive and RF-transparent. In certain embodiments, the polymer composite material can be used as a material in radome applications. A radome is a structural weatherproof housing that protects microwave (e.g., radar) antennas. The polymer composite material can minimize signal loss due to its low dielectric constant and can achieve structural integrity due to its rigidity.

[0062] The present invention will be described in more detail by way of specific examples. The following examples are shown for illustrative purposes only and are in no way intended to limit the present invention. Those skilled in the art will readily recognize various minor parameters that can be changed or modified to produce essentially the same results.

Examples

[0063] The present invention will be described in more detail by way of specific examples. The following examples are shown for illustrative purposes only and are in no way intended to limit the present invention. Those skilled in the art will readily recognize various less important parameters that can be changed or modified to produce essentially the same results.

[0064] Example 1 (Preparation of Polymer Composite Materials) General procedure. The filled thermosetting resin samples are composites of epoxy resin or polyester resin filled with AeroZero® (Blueshift Materials, USA) microparticles. The AeroZero microparticle powder was manually mixed with the liquid resin mixture, and then a curing catalyst was added. The catalyst-added thermosetting resin mixture was poured into a 12 square inch mold at a thickness of 1 / 4 inch and cured at room temperature. The cured composite was post-cured at 125 °C for 2 hours under reduced pressure.

[0065] Epoxy composites: Two epoxy samples (high viscosity and low viscosity; sold by Smooth-on, Inc., USA under the trade names Tarbender® and EpoxAcast®) with 30 μm AeroZero particles (10% v / v) were prepared and tested for thermal and mechanical properties. These materials are shown in Figures 2A (high viscosity) and 2B (low viscosity).

[0066] Polyester composites: Four filled polyester materials were prepared and tested for thermal and mechanical properties. These materials were isophthalic acid marine resin (Iso), orthophthalic resin 30SS41-G (Ortho A), orthophthalic resin 30SS40-G (Ortho B) (Interplastic Corp., St., USA), and Hydrex 100 33350-99 (Reichhold, USA). Representative examples of these materials are shown in Figures 3A - 3C, and the amounts and particle sizes of AeroZero used are listed in Table 1.

[0067] (Table 1) TIFF0007687948000003.tif36153

[0068] Nylon: The nylon sample was prepared by anionic polymerization of ε-caprolactam in a glass mold. The basic formulation was caprolactam (80 wt%), sodium caprolactamate (18 wt%), and catalyst (2 wt% BRUGGOLEN® C20P, Bruggermann Chemical, Germany). The components were heated to 140 °C and blended by stirring. In the case of AeroZero-filled nylon 6, after melting the components, AeroZero powder (10 wt%) was added. In any case, the nylon was polymerized at 140 °C after about 10 minutes to obtain a solid cylinder. Figure 4 is an image of the polyimide aerogel nylon composite stock shape. Figure 5 is an image of a nylon 6 film with 10% v / v / AeroZero® microparticles on the left and unfilled nylon 6 on the right. Figure 6 is an image of the AeroZero® microparticle-filled nylon 6 stock shape before cutting.

[0069] Example 2 (Microstructural properties of Example 1 samples and comparative unfilled samples) Figure 7 shows a graphical representation of the compressive yield strength (MPa), compressive modulus (GPa), yield strain %, filled compressive modulus / unfilled compressive modulus, and filled resin compressive yield strength / unfilled resin compressive yield strength of filled (10% v / v) and unfilled epoxy resins obtained according to ASTM D695-15. The horizontal black line represents the value predicted by a finite element analysis model assuming that the AeroZero particles were perfect spheres not bonded to the resin. Figure 8 shows the thermal conductivity data of filled and unfilled epoxy composites obtained according to ASTM D695-15. The unfilled sample is represented by a dashed line. Figure 9 shows a graphical representation of the compressive yield strength (MPa), compressive modulus (GPa), yield strain %, filled compressive modulus / unfilled compressive modulus, and filled resin compressive yield strength / unfilled resin compressive yield strength of filled (10% v / v) and unfilled polyester resins obtained according to ASTM D695-15. The horizontal black line represents the value predicted by a finite element analysis model assuming that the AeroZero particles were perfect spheres not bonded to the resin. Figure 10 shows the thermal conductivity data of filled and unfilled polymer materials obtained by ASTM C518-17. The unfilled sample is represented by a dashed line. Figure 11 shows the compression data of melt press filled and unfilled nylon obtained according to ASTM D695-15. Figure 12 shows the thermal conductivity data of filled and unfilled nylon 6 obtained by ASTM C518-17.

[0070] Example 3 (Reduction of exothermic peak) Reduction of the exothermic peak and delay in its occurrence. 100 mL of the Hydrex resin described in Example 1 was manually mixed with AeroZero microparticles at a filling rate of 20% v / v. To this Hydrex / AeroZero mixture and another 100 mL of pure Hydrex resin, 2% v / v of the catalyst MEKP was added and manually mixed for 1 minute. These mixtures were simultaneously poured into beakers equipped with thermocouples, and the temperature of the mixtures was recorded at 1-second intervals for 3 hours. The resulting exothermic data is shown in Figure 13. Unfilled Hydrex showed an exothermic peak of 141.6 °C, which occurred 69 minutes after the addition of the catalyst. In comparison, the Hydrex resin with a 10% v / v filling rate of AeroZero microparticles showed a 20-minute delay in the exothermic peak, and the exothermic peak decreased by 22.5 °C (reaching 119.1 °C).

[0071] Example 4 (Increase in HDT in the composite material) The 10% v / v Ortho A composite material prepared in Example 1 showed different trends in thermal conductivity depending on the size of the AeroZero microparticles contained in the composite material. Figure 14 shows that the heat deflection temperature (HDT), indicated by an inflection point of approximately 40 °C in the unfilled sample and the 30 µm filled sample, did not appear within the test temperature range in the 125 µm filled sample. From the data, it was determined that the larger particles provided sufficient structural support to offset the effect of HDT, in other words, the larger the particles, the higher the HDT in the sample. HDT is the temperature at which the mechanical properties of the material are impaired. Therefore, the increase in HDT indicates that the AeroZero particles achieve structural support and insulation.

[0072] Although the aspects of the present application and their advantages have been described in detail, it should be understood that various changes, substitutions, and modifications can be made herein without departing from the spirit and scope of the aspects defined by the appended claims. Furthermore, the scope of the present application is not intended to be limited to the specific aspects of the processes, machines, manufacturing methods, compositions, means, methods, and steps described herein. As will be readily recognized by those skilled in the art, existing or later-developed processes, machines, manufacturing methods, compositions, means, methods, or steps that perform substantially the same function or achieve substantially the same result as the corresponding aspects described herein can be utilized. Accordingly, the appended claims are intended to include these processes, machines, manufacturing methods, compositions, means, methods, or steps within their scope.

Claims

1. A continuous polymer matrix; and A discontinuous phase comprising a plurality of polymer aerogel particles dispersed in the continuous polymer matrix A polymer composite material comprising: The continuous polymer matrix comprises a polyamide, and the polyamide is polycaprolactam, poly[imino(1,6-dioxohexamethylene)iminohexamethylene], poly(dodecano-12-lactam), or any blend thereof. A polymer composite material.

2. The polymer composite material according to claim 1, wherein the plurality of polymer aerogel particles are organic polymer aerogel particles.

3. The polymer composite material according to claim 1 or 2, wherein the plurality of polymer aerogel particles are polyimide aerogel particles.

4. The polymer composite material according to any one of claims 1 to 3, wherein the plurality of polymer aerogel particles exhibit a multimodal particle size distribution.

5. The polymer composite material according to any one of claims 1 to 4, wherein the plurality of polymer aerogel particles exhibit a bimodal particle size distribution.

6. The polymer composite material according to any one of claims 1 to 5, comprising 0.5 wt% to 10 wt% of a plurality of polymer aerogel particles based on the total weight of the continuous polymer matrix and the discontinuous phase.

7. The polymer composite material according to any one of claims 1 to 6, comprising 2 vol% to 80 vol% of a plurality of polymer aerogel particles based on the total volume of the continuous polymer matrix and the discontinuous phase.

8. The polymer composite material according to any one of claims 1 to 7, wherein the compressive yield strength (MPa), compressive elastic strength (GPa), and / or yield strain (%) of the polymer composite material are the same as or different from those of the same polymer composite material without the discontinuous phase containing a plurality of polymer aerogel particles.

9. The polymer composite material according to any one of claims 1 to 8, further comprising an additive dispersed or solubilized in the continuous polymer matrix.

10. The polymer composite material according to claim 9, wherein the additive is an inorganic additive or polytetrafluoroethylene.

11. The polymer composite material according to claim 9 or 10, wherein the additive is glass particles, glass fibers, glass spheres, hollow glass spheres, ceramic spheres, or polytetrafluoroethylene.

12. The polymer composite material according to any one of claims 1 to 11, which is in the form of a film.

13. The polymer composite material according to any one of claims 1 to 11, which is in the shape of fibers.

14. The polymer composite material according to claim 13, wherein the fiber is a melt-spun fiber, a dry-spun fiber, or a wet-spun fiber.

15. The polymer composite material according to any one of claims 1 to 14, which is included in a product.

16. The product is a film, a monolith, a wafer, a blanket, a core composite material, a substrate for a high-frequency antenna, a substrate for a sunshield, a substrate for a sunshade, a substrate for a radome, an insulator for an oil and / or gas pipeline, an insulator for a liquefied natural gas pipeline, an insulator for a cryogenic fluid transfer pipeline, an insulator for apparel, an insulator for aerospace applications, an insulator for buildings, vehicles, and other human living environments, an insulator for automotive applications, an insulator for a radiator, an insulator for exhaust and ventilation, an insulator for air conditioning, an insulator for heating and refrigeration devices and portable air conditioners, an insulator for a cooler, an insulator for packaging, an insulator for consumer goods, a vibration damper, an insulator for wires and cables, an insulator for medical devices, a support for a catalyst, a support for drugs, pharmaceuticals, and / or drug delivery systems, a storage container, a pipe, a tube, a seal, a gasket, a water filtration device, an oil filtration device, and a solvent filtration device, or any combination thereof. The polymer composite material according to claim 15.

17. The polymer composite material according to claim 15 or 16, wherein the product is an injection-molded or blow-molded product.

18. A method for producing the polymer composite material according to any one of claims 1 to 14, the method including the step of dispersing a plurality of polymer aerogel particles in a polymer composition to form the polymer composite material according to any one of claims 1 to 13.

19. The method according to claim 18, wherein the polymer aerogel particles are dispersed in the polymer composition by casting, melt-blending, or extruding the polymer aerogel particles together with the polymer composition.

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