Filled composites with decreased thermal conductivity, dielectric constant, and weight

Abstract

To provide a material exhibiting improved insulation while maintaining structural properties of polymeric composites, and a method for producing the same.SOLUTION: A polymeric composite material can include a continuous polymeric matrix and a discontinuous phase that includes a plurality of polymeric aerogel particles dispersed within the continuous polymeric matrix.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Application No. 62 / 733,714, filed September 20, 2018, which is incorporated herein in its entirety without disclaimer.

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

[0003] B. Description of Related Art Polymer-based composites are generally known to exhibit lower thermal conductivity than metal- and / or ceramic-based materials, making them good thermal insulators. Additives can be added to the polymer matrix to modify the thermal conductivity of the polymer. Examples include graphite carbon fiber, ceramics (e.g., aluminum nitride and boron nitride), glass, and aerogel particles. For example, U.S. Patent No. 7,790,787 and U.S. Patent No. 9,777,126 to Williams et al. describe adding aerogel to a thermoplastic polymer at a weight ratio of less than 20:100 to improve the insulating capacity of the polymer composite. The application of thermosetting polymers is somewhat limited by material thickness constraints, as the volume increase of the curable resin tends to cause cracking due to the rapid heating / cooling behavior characteristic of the exothermic peak.

[0004] Although various attempts to create polymer composites have been described, materials that exhibit improved insulating properties while maintaining the textural properties of 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] A discovery has been made that solves some of the problems associated with additive-containing polymer composites. This discovery is based on a polymer composite comprising a polymer matrix having a plurality of polymer aerogel particles (e.g., polyimide aerogel particles) dispersed therein. The resulting polymer composite exhibits improved thermal insulation compared to unfilled polymer composites while maintaining structural properties. In particular, and as non-limitingly illustrated 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 deflection temperature (HDT) of the polymer composition compared to unfilled polymer composites. Furthermore, the resulting polymer composite exhibits reduced dielectric constant and / or thermal conductivity compared to the same polymer composite without the plurality of polymer aerogel particles. Without wishing to be bound by theory, it is believed that 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 polyesters, orthophthalic polyesters, or blends thereof. In some embodiments, the continuous polymer matrix may include polyesters, polyamides, polyepoxides, or any combination or blend thereof. In certain aspects, the continuous polymer matrix includes polyamides such as nylon. Non-limiting examples of nylon include polycaprolactam (nylon 6), poly[imino(1,6-dioxohexamethylene)iminohexamethylene] (nylon 6,6), poly(dodecano-12-lactam) (nylon 12), or any blend thereof. The polymeric aerogel particles can include organic polymer-based aerogel particles. In preferred cases, polyimide aerogel particles can be used. In some aspects, the polymeric aerogel particles can 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. In some cases, the polymeric aerogel particles can exhibit a multimodal particle size distribution (e.g., a bimodal particle size distribution). The polymer composite can 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 may be the same or reduced compared to the same polymer composite without a discrete phase containing multiple polymer aerogel particles, while the compressive yield strength (MPa), compressive elastic strength (GPa), and / or yield strain (%) of the polymer composite may be the same or changed (e.g., reduced, within 5%, comparable, or increased) compared to the same polymer composite without a discrete phase containing multiple polymer aerogel particles. For example, the thermal conductivity of a polymer composite of the present invention may be the same as that of a polymer composite without a discrete phase containing multiple polymer aerogel particles, while the mechanical strength may be reduced but still suitable for a desired application. In another example, the thermal conductivity of a polymer composite may be reduced compared to the same polymer composite without a discontinuous phase containing multiple polymer aerogel particles, while the compressive yield strength (MPa), compressive elastic strength (GPa), and / or yield strain (%) of the polymer composite may be the same or different (e.g., reduced, within 5%, comparable, or increased) compared to the same polymer composite without a discontinuous phase containing multiple polymer aerogel particles. The dielectric constant of the polymer composite may be reduced compared to the same polymer composite without a discontinuous phase containing multiple polymer aerogel particles. One or more additives may be dispersed or solubilized in the continuous polymer matrix. The additives may include inorganic additives, preferably glass particles, glass fibers, glass spheres, hollow glass spheres, ceramic spheres, or polytetrafluoroethylene. The composite material may be in any shape or size. For example, the material may be in the form of a film or fiber (e.g., melt-spun, dry-spun, or wet-spun fiber).

[0008] Also described are articles of manufacture comprising the polymer composites of the present invention. These articles of manufacture may include films, monoliths, wafers, blankets, core composites, substrates for radio frequency antennas, substrates for sunshields, substrates for sunshades, substrates for radomes, insulation for oil and / or gas pipelines, insulation for liquefied natural gas pipelines, insulation for pipelines carrying cryogenic fluids, insulation for apparel, insulation for aerospace applications, insulation for buildings, cars, and other human habitations, insulation for automotive applications, insulation for radiators, insulation for exhaust and ventilation, insulation for air conditioning, insulation for heating and refrigeration equipment and portable air conditioners, insulation for coolers, insulation for packaging, insulation for consumer goods, vibration damping, insulation for wire and cable, insulation for medical devices, supports for catalysts, supports for drugs, pharmaceuticals, and / or drug delivery systems, water filters, oil filters, and solvent filters, or any combination thereof. The articles of manufacture may be injection molded or blow molded.

[0009] Methods of making the polymer composite of the present invention are also described. The methods can include dispersing a plurality of polymeric aerogel particles in a polymer composition to form the polymer composite of the present invention. The dispersing step can include casting, melt blending, or extruding the particles with the polymer composition.

[0010] Methods for altering the viscosity and / or HDT of a polymer composition are also described. A method for altering (e.g., increasing or decreasing) the viscosity of a polymer composition can include dispersing a sufficient amount (e.g., 1% to 50% by weight, preferably 5% to 40% by weight, or 10% to 20% by weight) of a plurality of polymeric aerogel particles in a polymer composition to alter the viscosity of the polymer composition relative to the same polymer composition without the plurality of polymeric 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 polymeric aerogel particles in a polymer composition to alter, preferably increase, the HDT of the polymer composition relative to the same polymer composition without the plurality of polymeric aerogel particles.

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

[0012] In one aspect of the present invention, 33 embodiments are described. Embodiment 1 is a polymer composite comprising a continuous polymer matrix; and a discontinuous phase comprising a plurality of polymer aerogel particles dispersed in the continuous polymer matrix. Embodiment 2 is the polymer composite of Embodiment 1, wherein the continuous polymer matrix comprises a polyester, a polyamide, a polyepoxide, or any combination or blend thereof. Embodiment 3 is the polymer composite of Embodiment 2, wherein the continuous polymer matrix comprises a polyamide, the polyamide being nylon, preferably polycaprolactam, poly[imino(1,6-dioxohexamethylene)iminohexamethylene], poly(dodecano-12-lactam), or any blend thereof. Embodiment 4 is the polymer composite of any one of Embodiments 1-3, wherein the plurality of polymer aerogel particles are organic polymer aerogel, preferably polyimide aerogel particles. A fifth aspect is the polymer composite of 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. A sixth aspect is the polymer composite of 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. A seventh aspect is the polymer composite of 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 the plurality of polymer aerogel particles, based on the total weight of the continuous polymer matrix and the discontinuous phase. Example 8 is the polymer composite of any one of Examples 1-7, comprising 2 to 80 volume %, preferably 5 to 50 volume %, or more preferably 5 to 15 volume %, or about 10 volume %, of a plurality of polymer aerogel particles, based on the total volume of the continuous polymer matrix and the discontinuous phase. Example 9 is the polymer composite of any one of Examples 1-8, wherein the thermal conductivity (W / m·K) of the polymer composite is the same or reduced compared to the same polymer composite without the discontinuous phase comprising a plurality of polymer aerogel particles.Example 10 is the polymer composite of any one of Examples 1-9, wherein the dielectric constant of the polymer composite is reduced relative to the same polymer composite not including a discrete phase containing a plurality of polymer aerogel particles. Example 11 is the polymer composite of any one of Examples 1-10, wherein the compressive yield strength (MPa), compressive elastic strength (GPa), and / or yield strain (%) of the polymer composite is the same or changed relative to the same polymer composite not including a discrete phase containing a plurality of polymer aerogel particles. Example 12 is the polymer composite of any one of Examples 1-11, wherein the polymer matrix comprises a thermoplastic polymer or a blend of thermoplastic polymers, preferably a polyolefin, a fluoropolymer or derivative thereof, or a blend thereof, or more preferably polyethylene or polypropylene, or a blend thereof. Example 13 is the polymer composite of any one of Examples 1-12, wherein the polymer matrix comprises a thermosetting polymer or a blend of thermosetting polymers, preferably a dicyclopentadiene-modified polyester, an isophthalic polyester, an orthophthalic polyester, or a blend thereof. Example 14 is the polymer composite of any one of Examples 1-13, further comprising an additive dispersed or solubilized in the continuous polymer matrix. Example 15 is the polymer composite of Example 14, wherein the additive is an inorganic additive or polytetrafluoroethylene, preferably glass particles, glass fibers, glass spheres, hollow glass spheres, ceramic spheres, or polytetrafluoroethylene. Example 16 is the polymer composite of any one of Examples 1-15, which is in the form of a film. Example 17 is the polymer composite of any one of Examples 1-16, which is in the form of a fiber. Example 18 is the polymer composite of Example 17, wherein the fiber is a melt-spun fiber, a dry-spun fiber, or a wet-spun fiber.

[0013] Example 19 is the polymer composite of any one of Examples 1-18, contained in an article of manufacture. Example 20 is the polymer composite of Example 19, wherein the article is a film, a monolith, a wafer, a blanket, a core composite, a substrate for a radio frequency antenna, a substrate for a sunshield, a substrate for a sunshade, a substrate for a radome, insulation for an oil and / or gas pipeline, insulation for a liquefied natural gas pipeline, insulation for a pipeline carrying cryogenic fluids, insulation for apparel, insulation for aerospace applications, insulation for buildings, cars, and other human habitations, insulation for automotive applications, insulation for radiators, insulation for exhaust and ventilation, insulation for air conditioning, insulation for heating and refrigeration equipment and portable air conditioners, insulation for coolers, insulation for packaging, insulation for consumer goods, vibration damping, insulation for electrical wire and cable, insulation for medical devices, supports for catalysts, supports for drugs, pharmaceuticals, and / or drug delivery systems, storage containers, pipes, tubing, seals, gaskets, water filters, oil filters, and solvent filters, or any combination thereof. Example 21 is the polymer composite of any one of Examples 19-20, wherein the article is an injection molded or blow molded article.

[0014] Example 22 is a method of making the polymer composite material of any one of Examples 1 to 18, comprising dispersing a plurality of polymeric aerogel particles in a polymer composition to form the polymer composite material of any one of Examples 1 to 17. Example 23 is the method of Example 22, wherein the polymeric aerogel particles are dispersed in the polymer composition by casting, melt blending, or extruding the polymeric aerogel particles with the polymer composition.

[0015] Example 24 is a method for altering the viscosity of a polymer composition, comprising dispersing a sufficient amount of polymeric aerogel particles in a polymer composition to alter the viscosity of the polymer composition relative to the same polymer composition without the polymeric aerogel particles. Example 25 is the method of Example 24, wherein the viscosity of the polymer composition is decreased relative to the same polymer composition without the polymeric aerogel particles. Example 26 is the method of Example 25, wherein the viscosity of the polymer composition is increased relative to the same polymer composition without the polymeric aerogel particles.

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

[0017] Example 30 is a method for increasing the heat distortion temperature (HDT) of a polymer composition, comprising dispersing a sufficient amount of the plurality of polymeric aerogel particles in the polymer composition to alter, preferably increase, the HDT of the polymer composition relative to the same polymer composition without the plurality of polymeric aerogel particles. Example 31 is the method of Example 30, wherein the amount of the plurality of polymeric aerogel particles is 1% to 50%, preferably 5% to 40%, or 10% to 20% by weight. Example 32 is the method of any one of Examples 30-31, wherein the aerogel particle size is 10 micrometers to 150 micrometers, preferably 30 micrometers to 125 micrometers. Example 33 is the method of any one of Examples 30-32, 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 the HDT 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 applies equally to other aspects of the invention, and vice versa. It is understood that each aspect described herein is an aspect of the invention that is applicable to other aspects of the invention. It is contemplated that any aspect described herein can be implemented with respect to any method or composition of the invention, and vice versa. Furthermore, compositions of the invention can be used to realize methods of the invention.

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

[0020] The term "aerogel" refers to a class of materials typically produced by forming a gel and removing a mobile interstitial solvent phase from the pores, followed by replacement with a gas or gas-like substance. Controlling the gel and evaporation system can minimize density, shrinkage, and pore collapse. As discussed above, aerogels of the present invention can contain 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, aerogels can contain 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 can be composed of mesopores. In some embodiments, the aerogels of the present invention have low bulk densities (about 0.25 g / cm 3 or less, preferably about 0.01 to 0.5 g / cm 3 ), large surface area (generally about 10 to 1,000 m 2 / g or more, preferably about 50 to 1000m 2 / g), high porosity (greater than about 80%, preferably greater than about 85%), and / or a relatively large pore volume (greater than about 1.0 mL / g, preferably greater than about 1.2 mL / g).

[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 physisorption experiments. In preferred cases, the MIP test used in the Examples section can be used to measure mesopores larger than 5 nm (i.e., American Standard Test Method (ASTM) D4404-10, Standard Test Method for Determination of Pore Volume and Pore Volume Distribution of Soils and Rocks by Mercury Intrusion Porosimetry). In preferred cases, the gas physisorption experiment used in the Examples section can be used to measure mesopores and / or micropores (ASTM D1993-03(2008) Standard Test Method for Precipitated Silicas - Multipoint BET Nitrogen Surface Area).

[0022] The term "impurities" refers to unwanted materials in the feed fluid that differ from the desired filtrate and / or are not desired in the filtrate. In some cases, the impurities can be solids, liquids, gases, or supercritical fluids. In some embodiments, the aerogel can remove some or all of the impurities.

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

[0024] The term "radio frequency (RF)" refers to -4 ~10 7 The term "optical wavelength" refers to the region of the electromagnetic spectrum exhibiting wavelengths in the range of 100 m.

[0025] The term "supercritical fluid" refers to any substance at a temperature and pressure above its critical point. A supercritical fluid can diffuse into solids like a gas and dissolve substances like a liquid. Furthermore, as the critical point is approached, small changes in pressure or temperature produce large changes in density.

[0026] An "aliphatic group" refers to an acyclic or cyclic saturated or unsaturated carbon group, excluding aromatic compounds. Straight-chain aliphatic groups do not contain tertiary or quaternary carbons. Substituents for aliphatic groups include, but are not limited to, halogen, hydroxyl, alkoxyl, haloalkyl, haloalkoxy, carboxylic acid, ester, amine, amide, nitrile, acyl, thiol, and thioether. Branched aliphatic groups contain at least one tertiary and / or quaternary carbon. Substituents for branched aliphatic groups can include alkyl, halogen, hydroxyl, alkoxyl, haloalkyl, haloalkoxy, carboxylic acid, ester, amine, amide, nitrile, acyl, thiol, and thioether. Cycloaliphatic groups contain at least one ring in their 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 on cycloaliphatic groups can include alkyl, halogen, hydroxyl, alkoxy, haloalkyl, haloalkoxy, carboxylic acid, ester, amine, amide, nitrile, acyl, thiol, and thioether.

[0027] An "alkyl group" refers to a saturated hydrocarbon, straight or branched, substituted or unsubstituted. Substituents on the alkyl group can include, but are not limited to, alkyl, halogen, hydroxyl, alkoxy, haloalkyl, haloalkoxy, carboxylic acid, ester, amine, amide, nitrile, acyl, thiol, and thioether.

[0028] An "aryl" or "aromatic" group is a substituted or unsubstituted monocyclic or polycyclic hydrocarbon having alternating single and double bonds in each ring structure. Aryl group substituents can include alkyl, halogen, hydroxyl, alkoxy, 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 TIFF2025128153000002.tif10128. Non-limiting examples of acrylates include acrylates and methacrylates.

[0030] The term "acid" compounds when used in forming unsaturated polyester materials includes carboxylic acid, dicarboxylic acid, and anhydride compounds.

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

[0032] The terms "about" or "approximately" are defined as close to a value as would be understood by one of ordinary skill in the art. In one non-limiting aspect, these terms are defined as within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.

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

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

[0035] The terms "inhibit" or "reduce" or "prevent" or "avoid" or any variation of these terms, as used in the claims and / or specification, include any measurable reduction or complete inhibition to achieve a desired result.

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

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

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

[0039] The polymer 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 "consist essentially of," in one non-limiting aspect, the fundamental and novel properties of the polymer composite materials of the present invention are thermal conductivity and textural 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, while illustrating specific embodiments of the present invention, are given for illustrative purposes only and are not intended to be limiting. Furthermore, it is anticipated that changes and modifications within the spirit and scope of the present invention will become apparent to those skilled in the art from this detailed description. In further embodiments, features from a particular embodiment can be combined with features from other embodiments. For example, features from one embodiment can be combined with features from any of the other embodiments. In further embodiments, additional features can be added to the particular embodiments described herein. [Brief explanation of the drawings]

[0041] Advantages of the present invention will become apparent to those skilled in the art from the following detailed description and by reference to the accompanying drawings.

[0042] [Figure 1] FIG. 1 is a diagram of an aerogel-filled composite of the present invention. [Figure 2] 1A-B are images of aerogel-filled epoxy composites of the present invention. A is a filled high viscosity composite, and B is a filled low viscosity composite. [Figure 3] 1A-C are images of aerogel-filled polyester composites of the present invention. A is a filled unsaturated orthophthalic polyester composite, B is a filled isophthalic polyester composite, and C is a filled vinylester styrene composite. [Figure 4] 1 is an image of an aerogel-filled nylon composite (1 cm diameter) of the present invention. [Figure 5] 1 is an image of (left) an extruded AeroZero® particulate-filled nylon 6 composite film of the present invention and (right) a comparative extruded unfilled nylon 6 composite film. [Figure 6] 1 is an image of an AeroZero® particulate-filled nylon 6 composite before cutting. [Figure 7]1 is compression data for filled epoxy composites of the present invention and comparative unfilled epoxy composites. [Figure 8] 1 is the thermal conductivity of filled epoxy composites of the present invention and comparative unfilled epoxy composites. [Figure 9] 1 is compression data for filled polyester composites of the present invention and comparative unfilled polyester composites. [Figure 10] 1 is the thermal conductivity of a filled polyester composite of the present invention and a comparative unfilled polyester composite. [Figure 11] 1 is compression data for filled nylon 6 composites of the present invention and comparative unfilled nylon 6 composites. [Figure 12] 1 is the thermal conductivity of a filled nylon 6 composite of the present invention and a comparative unfilled nylon 6 composite. [Figure 13] Figure 1 shows the reduction and delayed onset of the exothermic peak during cure of polyester containing 10% v / v / aerogel particles relative to the same unfilled polyester without aerogel particles. [Figure 14] Thermal conductivity versus temperature data is shown for unfilled polyester with no aerogel particles, the same polyester with 10% v / v of 125 micrometer aerogel particles, and the same polyester with 10% v / v of 30 micrometer aerogel particles.

[0043] While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings, which may not be to scale. DETAILED DESCRIPTION OF THE INVENTION

[0044] Detailed Description of the Invention A discovery has been made that provides a solution to some of the problems associated with the insulating and structural properties associated with polymer composites. This discovery is premised on a polymer composite comprising aerogel particles dispersed throughout a polymer matrix. In particular, the polymer composite exhibits good mechanical and insulating properties. These and other non-limiting aspects of the invention are described in further detail in the following sections.

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

[0046] A. Polymer Composites The polymer composites of the present invention comprise a continuous polymer phase and a discontinuous phase dispersed throughout the continuous phase. The discontinuous phase may comprise aerogel particles. In some embodiments, the polymer composites may comprise one or more additives dispersed or solubilized in the continuous polymer matrix. Figure 1 shows a diagram of a polymer composite of the present invention. The polymer composite 10 comprises a polymer continuous phase 12 and a discontinuous particulate phase 14. The polymer composites can be in any shape or form. Non-limiting examples of forms include films, fibers, blocks, sheets, tubes, rolls, etc. Fibers can include melt-spun fibers, dry-spun fibers, or wet-spun fibers. Films and sheets can be of any thickness. The polymer composite can include a plurality of polymer aerogel particles in an amount of 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.%, or equal to or between any two of these, based on the total weight of the continuous polymer matrix and the discontinuous phase. The polymer composite material may contain a plurality of polymer aerogel particles in an amount of 2% to 80% by volume, or at least 2%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, and 80% by volume, based on the total volume of the continuous polymer matrix and the discontinuous phase. The polymer composite material may exhibit improved physical and / or mechanical properties compared to the natural material. The thermal conductivity (W / m·K) of the polymer composite material may be the same or reduced compared to the same polymer composite material without the discontinuous phase containing the plurality of polymer aerogel particles. The composite polymer material may exhibit a thermal conductivity that is at least 5% lower (e.g., less than 95%) than that of the 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 the 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 the dielectric constant of the 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 the natural polymer material. The compressive yield strength (MPa), compressive elastic strength (GPa), and / or yield strain (%) of the polymer composite materials can be the same or can vary. For example, the compressive yield strength (MPa), compressive elastic strength (GPa), and / or yield strain (%) of the polymer composite may be reduced, comparable (e.g., within 5%), or increased compared to the same polymer composite without the plurality of polymer aerogel particles. The HDT of the polymer composite may be 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 the same natural polymer composite. In some embodiments, a polymer aerogel particle is added to the polymer composition to alter the viscosity of the polymer composition compared to the same polymer composition without the plurality of polymer aerogel particles. In some embodiments, to modify the HDT and / or viscosity, 1% to 50% by weight, or at least 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, and 50% by weight of a plurality of polymeric aerogel particles having a particle size of 10-15 micrometers, or at least 10, 25, 50, 75, 100, 125, and 150 micrometers, or at least 10, 25, 50, 75, 100, 125, and 150 micrometers, can be added to the polymer composition.

[0047] B. Material 1. Polymer matrix The polymer matrix can include thermoplastic and / or thermosetting polymers. The polymer matrix can be produced using any known process for making polymers, such as gas-phase processing, solution processing, emulsion processing, or melt processing. Non-limiting examples of thermoplastic polymers include polyethylene terephthalate (PET), polycarbonate (PC) family polymers, 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 polyetherimide (PEI) and their derivatives, thermoplastic polymers, and the like. Examples of the polymer include elastomers (TPE), terephthalic acid (TPA) elastomers, poly(cyclohexanedimethylene terephthalate) (PCT), polyethylene naphthalate (PEN), polyamides (PA), polysulfone sulfonates (PSS), sulfonates of polysulfones, polyether ether ketone (PEEK), polyether ketone ketone (PEKK), acrylonitrile butyldiene styrene (ABS), polyphenylene sulfide (PPS), copolymers thereof, polyesters or derivatives thereof, polyamides or derivatives thereof (e.g., nylon), fluoropolymers or derivatives thereof, or blends thereof. Fluoropolymers include polytetrafluoroethylene (PTFE), perfluoroalkoxy (PFA), fluorinated ethylene-propylene polymer (FEP), ethylene tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polychlorofluoroethylene (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 nylon-type compounds.Non-limiting examples of nylons 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, polyoxybenzyl methylene glycol anhydrides (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 rubber, polyisoprene, polychloroprene, styrene butadiene rubber, nitrile butadiene rubber, ethylene propylene diene monomer rubber (EPDM), butyl rubber (IIR), polybutadiene (BR), epichlorohydrin (ECO), fluorinated hydrocarbons (FKM), copolymers thereof, or blends thereof. Polyimides may also exhibit pseudo-thermoplastic properties. Unsaturated polyesters can be prepared using known polycondensation reactions. The unsaturated polyesters of the present invention may be formed from acid compounds, diols, and alkenyls (e.g., dicyclopentadiene), or may be obtained from commercial sources. 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 thereof, or mixtures thereof. In some embodiments, the unsaturated polyester can have the following general formula: TIFF2025128153000003.tif16128, where R1 can be derived from an acid moiety, R2 can be derived from a diol, and R3 can be an alkenyl moiety. R3 can be formed from an anhydride (e.g., maleic anhydride). R3 can be reacted with a compound having an alkenyl group to form a crosslinked polyester material. The unsaturated polyester can be provided as a solution containing the unsaturated polyester and an alkenyl compound (e.g., styrene or dicyclopentadiene). Unsaturated polyester resins are also commercially available, for example, from Revchem Composites, Inc. (Stockton, California, USA).

[0049] 2. Aerogel The aerogel particles may include organic aerogels. Organic aerogels can be made from polyacrylates, polystyrenes, polyacrylonitriles, polyurethanes, polyimides, polyamides, polyfurfural alcohol, phenol furfuryl alcohol, melamine formaldehyde, resorcinol formaldehyde, cresol formaldehyde, phenol formaldehyde, polyvinyl alcohol dialdehyde, polycyanurates, polyacrylamides, polyesters, cross-linked polyesters, polystyrenes, silicones, various epoxies, agar, agarose, lignin, cellulose, and the like. Organic aerogels can be obtained from Blueshift Materials, Inc., USA. In certain embodiments, the aerogel is a polyimide aerogel. Polyimide-based aerogels may be obtained from commercial suppliers (e.g., Blueshift Materials, Inc., USA, under the trade name AeroZero®) or may be made using known aerogel methodologies. Aerogels can be made using the methodologies described in International Patent Application Publication No. WO 2014 / 189560 to Rodman et al., International Patent Application Publication No. WO 2017 / 07888 to Sakaguchi et al., International Patent Application Publication No. PCT / US2019 / 029191 to Ejaz et al., United States Patent Application Publication No. 2017 / 0121483 to Poe et al., and United States Patent No. 9,963,571 to Sakaguchi et al., all of which are incorporated by reference in their entireties. The aerogel particles can be of any size. In some embodiments, the particle size of the aerogel can be between 5 μm and 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, or equal to 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 between 10 and 100 μm and the other peak between 150 and 300 μm.Aerogel particles can be formed by creating an aerogel film or shape and then reducing the film or shape into particles, for example, by crushing, chopping, or machining the film and / or shape into particles.

[0050] 3. Additives The polymer composite may contain additives. The additives may be dispersed or solubilized in the continuous phase (i.e., the polymer matrix). The additives may include inorganic and organic additives. Inorganic additives include glass particles, glass fibers, glass spheres, hollow glass spheres, and ceramic spheres. Organic additives include polytetrafluoroethylene, antifogging agents, antioxidants, heat stabilizers, light stabilizers, hindered amine light stabilizers, flow improvers, UV absorbers, impact modifiers, coupling agents, colorants, and the like, or any combination thereof. The amount of additive in the polymer matrix may be 0-20 wt.%, or at least, equal to, or between any two of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20 wt.%, based on the total weight of the polymer matrix.

[0051] D. Methods for Fabricating Polymer Composites Polymeric aerogel particles can be dispersed in a polymer matrix using dry or wet blending techniques. Non-limiting examples of dispersion processes include casting, melt blending, or extruding the particles with a polymer composition. In some embodiments, the polymer matrix material (e.g., a pure thermosetting polymer and / or a polymer mixture) can be dry-blended with the aerogel particles to form a dry blend. In another embodiment, the polymer matrix can be premixed and pelletized before being dry-blended with the polymeric aerogel particles. The dry blend can be melt-extruded, preferably in a twin-screw extruder with adjustable temperature zones, such as a conical twin-screw extruder, or solution processed to obtain an organic / inorganic composite. In another embodiment, melt extrusion can be used to mix the polymeric aerogel particles with the polymer matrix. In yet another embodiment, the polymeric 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 can be wet-spun into fibers or cast into a sheet. The polymer composite can then be melt spun into fibers, extruded into tapes, injection molded, blow molded, and / or compression molded into any usable shape or form. The process temperature for making the composite can vary depending on the type of polymer matrix used. The temperature can range from 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 exotherm onset can be 5-50°C, or at least 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, or the equivalent thereof, or between any two of these, or 10%-85%, or at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, and 85%, or the equivalent thereof, or between any two of these.

[0052] E. Products Incorporating Polymer Composites In some aspects, an article can comprise any one of the polymer composite materials of the present invention. In some embodiments, the article is a thin film, a monolith, a wafer, a blanket, a core composite, a substrate for a radio frequency antenna, a sunscreen, a sunshield, a radome, insulation for oil and / or gas pipelines, insulation for liquefied natural gas pipelines, insulation for pipelines carrying cryogenic fluids, insulation for apparel, insulation for aerospace applications, insulation for buildings, cars, and other human habitations, insulation for automotive applications, insulation for radiators, insulation for exhaust and ventilation, insulation for air conditioning, insulation for heating and refrigeration equipment and portable air conditioners, insulation for coolers, insulation for packaging, insulation for consumer goods, vibration damping, insulation for wire and cable, insulation for medical devices, supports for catalysts, supports for drugs, pharmaceuticals, and / or drug delivery systems, storage containers, pipes, tubing, seals, gaskets, water filtration applications, oil filtration applications, and solvent filtration applications.

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

[0054] The polymer composite material of the present invention can be used in or with filtration devices known in the art. Non-limiting examples of filtration devices and applications include gas filters, such as, but not limited to, building air filters, automobile cabin air filters, internal combustion engine air filters, aircraft air filters, satellite air filters, face mask filters, diesel particulate filters, in-line gas filters, cylinder gas filters, soot filters, and pressure swing absorbers. Further non-limiting examples of filtration devices and applications include solvent filtration systems, column filtration, chromatography filtration, vacuum flask filtration, microfiltration, ultrafiltration, reverse osmosis filtration, nanofiltration, centrifugal filtration, gravity filtration, crossflow filtration, dialysis, hemofiltration, hydraulic fluid filtration, and automotive oil filtration. Furthermore, non-limiting examples of filtration purposes include sterilization, separation, purification, and isolation.

[0055] The filtration fluid ("feed") and 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, an inorganic fluid, a biologically-derived fluid, or a mixture thereof. In some cases, the fluid can include solids and / or other fluids. As non-limiting examples, the fluid or a portion thereof can be water, blood, oil, a solvent, air, or a mixture thereof. Water can include water, any form of steam, and supercritical water.

[0056] In some cases, fluids may contain impurities. Non-limiting examples of impurities include solids, liquids, gases, supercritical fluids, objects, compounds, and / or chemicals. The definition of an impurity may vary for the same feed fluid depending on the desired filtrate. 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, nitrite ions, cationic surfactants, and anionic surfactants; metals; heavy metals; suspended, partially dissolved, or dissolved oils; organic solvents; nonionic surfactants; antifoaming agents; chelating agents; microorganisms; particulate matter; and the like. Non-limiting examples of impurities in blood include red blood cells, white blood cells, antibodies, microorganisms, water, urea, potassium, phosphorus, gases, particulate matter, and the like. Non-limiting examples of impurities in oil can include water, particulate matter, heavy and / or light hydrocarbons, metals, sulfur, antifoam agents, etc. Non-limiting examples of impurities in solvent can include water, particulate matter, metals, gases, etc. Non-limiting examples of impurities in air can 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 desired substances include solids, liquids, gases, supercritical fluids, objects, compounds, and / or chemicals. In some embodiments, one or more polymer composite materials can be used to concentrate or capture the desired substance or remove the fluid from the desired substance. Non-limiting examples of desired substances 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, nitrite ions, cationic surfactants, and anionic surfactants, metals, heavy metals, suspended, partially dissolved, or dissolved oils, organic solvents, nonionic surfactants, chelating agents, antifoaming agents, and the like. Non-limiting examples of desired substances in blood include red blood cells, white blood cells, antibodies, lipids, proteins, and the like. Non-limiting examples of desired substances in oil include hydrocarbons of a range of molecular weights, gases, metals, and the like. Non-limiting examples of desired substances in a solvent can include particulate matter, fluids, gases, proteins, lipids, etc. Non-limiting examples of desired substances in air can include water, fluids, gases, particulate matter, etc.

[0058] The filtration system may include a separation zone. Standard engineering techniques can be used to determine the material, size, and shape of the separation zone to achieve the desired flow rate and contact time. The separation zone may be capable of holding and may be made of one or more polymeric composite materials of the present invention. In some cases, the separation zone may be made entirely of one or more polymeric composite materials, or one or more polymeric composite materials within or around a support structure. A feed fluid may be introduced into the separation zone through an inlet or through direct contact with the separation zone. In some embodiments, the feed fluid may be received at a pressure higher or lower than ambient pressure. Introduction of the feed fluid into the separation zone may be at a flow rate sufficient to allow optimal contact between the feed fluid and one or more polymeric composite materials. Contact of the feed fluid with the polymeric composite material may allow the feed fluid to filter through the polymeric composite material, resulting in a filtrate having fewer impurities and / or desired substances than the feed fluid. In certain aspects, the filtrate may be substantially free of impurities and / or desired substances. The filtrate may 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, stored in a storage device, etc. In some cases, one or more polymer composite materials can be removed and / or transferred from the separation zone. In some cases, the filtrate can be collected and / or removed from the separation zone without flowing 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] Filtration conditions within the separation zone can be varied to achieve a desired result (e.g., removal of substantially all impurities and / or desired substances from the feed fluid). Filtration conditions can include temperature, pressure, feed fluid flow, filtrate flow, or any combination thereof. In some cases, filtration conditions are controlled to produce a stream exhibiting specific characteristics. The separation zone may include valves, thermocouples, controllers (automated or manual), 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 flow rates through the separation zone for various dimensions and various polymer composite materials.

[0060] The suitability of a polymer composite for fluid and / or filtration applications can be determined by methods known in the art. Some properties of a polymer composite that can be determined to evaluate its suitability include, but are not limited to, the temperature and / or pressure at which the polymer composite melts, dissolves, oxidizes, reacts, decomposes, or breaks down; the solubility of the polymer composite in materials that come into contact with the polymer composite; the flow rate of fluids passing through the polymer composite; the retention of impurities and / or desired products that form the feed fluid, etc.

[0061] 2. Radio frequency (RF) applications The polymer composite materials of the present invention can be used in radio frequency (RF) applications due to their low density, mechanical robustness, light weight, and low dielectric properties. The use of macroporous polymer composites in RF applications allows for the design of thinner, lighter, and smaller substrates. Non-limiting examples of RF applications include RF antenna substrates, RF antenna sunshields, radomes, and the like. Antennas can include flexible and / or rigid antennas, broadband planar circuit antennas (e.g., patch antennas, E-type broadband patch antennas, elliptically polarized circular patch antennas, monopole antennas, circularly slotted planar antennas, bowtie antennas, inverted-F antennas, and the like). In antenna design, circuits can be attached to substrates containing polymer composite materials and / or combinations of polymer composite materials and other components, such as other polymer materials. The use of polymer composite materials in antennas allows for the design of substrates with higher throughput. Furthermore, polymer composites can have linear thermal expansion coefficients (CTEs) similar to those of aluminum and copper (e.g., CTEs of 23 / K and 17 ppm / K), which can be tailored through the selection of monomers to match the CTE of other desired materials. In some embodiments, the temperature insensitivity and RF transparency of polymer composite materials allow their use in sunshields and / or sunscreens used to protect RF antennas from thermal cycling. In certain embodiments, polymer composite materials can be used as materials in radome applications. A radome is a structural, weatherproof enclosure that protects microwave (e.g., radar) antennas. Polymer composite materials can minimize signal loss due to their low dielectric constant and provide structural integrity due to their rigidity.

[0062] The present invention will be further described in detail by specific examples. The following examples are provided for illustrative purposes only and are not intended to limit the present invention in any way. Those skilled in the art will readily recognize a variety of non-critical parameters that can be changed or modified to produce essentially the same results. [Example]

[0063] The present invention will be further described in detail by specific examples. The following examples are provided for illustrative purposes only and are not intended to limit the present invention in any way. Those skilled in the art will readily recognize a variety of non-critical parameters that can be changed or modified to produce essentially the same results.

[0064] Example 1 (Preparation of polymer composite materials) General Procedure. Filled thermoset resin samples were composites of epoxy or polyester resins filled with AeroZero® (Blueshift Materials, USA) particulate. The AeroZero particulate powder was mixed manually with the liquid resin mixture, after which the curing catalyst was added. The catalyzed thermoset resin mixture was poured into a 12-inch square mold to a thickness of 1 / 4 inch and cured at room temperature. The cured composite was post-cured under vacuum at 125°C for 2 hours.

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

[0066] Polyester Composites: Four filled polyester materials were fabricated and tested for thermal and mechanical properties. These materials were isophthalic 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) TIFF2025128153000004.tif36153

[0068] Nylon: Nylon samples were prepared by anionic polymerization of ε-caprolactam in glass molds. The base 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. For AeroZero-filled nylon 6, AeroZero powder (10 wt%) was added after the components were melted. In both cases, the nylon was polymerized at 140°C after approximately 10 minutes to yield a solid cylinder. Figure 4 shows an image of a polyimide aerogel-nylon composite stock shape. Figure 5 shows an image of a nylon 6 film with 10% v / v / AeroZero® particulate on the left and unfilled nylon 6 on the right. Figure 6 shows an image of an AeroZero® particulate-filled nylon 6 stock shape before cutting.

[0069] Example 2 (Textural characteristics of Example 1 sample and comparative unfilled sample) Figure 7 shows a graphical representation of the compressive yield strength (MPa), compressive modulus (GPa), yield strain (%), filled / unfilled compressive modulus, and filled / unfilled compressive yield strength for filled (10% v / v) and unfilled epoxy resins, obtained according to ASTM D695-15. The horizontal black lines represent values ​​predicted by a finite element analysis model assuming the AeroZero particles were perfect spheres, not bound to the resin. Figure 8 shows thermal conductivity data for 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 / unfilled compressive modulus, and filled / unfilled compressive yield strength for filled (10% v / v) and unfilled polyester resins. The horizontal black lines represent values ​​predicted by a finite element analysis model assuming the AeroZero particles were perfect spheres, not bound to the resin. Figure 10 shows thermal conductivity data for filled and unfilled polymeric materials obtained according to ASTM C518-17. The unfilled sample is represented by a dashed line. Figure 11 shows melt-pressed compaction data for filled and unfilled nylon obtained according to ASTM D695-15. Figure 12 shows thermal conductivity data for filled and unfilled nylon 6 obtained according to ASTM C518-17.

[0070] Example 3 (Reduction of heat generation peak) Decreased and delayed exothermic peak. 100 mL of the Hydrex resin described in Example 1 was manually mixed with AeroZero microparticles at a 20% v / v loading. The catalyst MEKP was added at 2% v / v to this Hydrex / AeroZero mixture and another 100 mL of pure Hydrex resin and manually mixed for 1 minute. These mixtures were simultaneously poured into a beaker equipped with a thermocouple, and the temperature of the mixture was recorded at 1-second intervals for 3 hours. The resulting exothermic data is shown in Figure 13. The unfilled Hydrex exhibited an exothermic peak of 141.6°C, occurring 69 minutes after catalyst addition. In comparison, the Hydrex resin with a 10% v / v loading of AeroZero microparticles exhibited a 20-minute delay in the exothermic peak, with the exothermic peak being 22.5°C lower (reaching 119.1°C).

[0071] Example 4 (Increased HDT in composites) The 10% v / v Ortho A composites prepared in Example 1 exhibited different thermal conductivity trends depending on the size of the AeroZero particulates included in the composite. Figure 14 shows that the heat deflection temperature (HDT), indicated by an inflection point of approximately 40°C in the unfilled and 30 um-filled samples, does not occur within the test temperature range in the 125 um-filled samples. The data determined that the larger particles provide sufficient structural support to offset the effects of the HDT; in other words, the larger the particles, the higher the HDT in the samples. The HDT is the temperature at which the mechanical properties of the material are compromised; therefore, an increase in HDT indicates that the AeroZero particles provide 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 alterations can be made herein without departing from the spirit and scope of the aspects as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular aspects of the processes, machines, manufacture, compositions of matter, means, methods, and steps described herein. As those skilled in the art will readily recognize from the above disclosure, existing or later-developed processes, machines, manufacture, compositions of matter, means, methods, or steps can be utilized that perform substantially the same function or achieve substantially the same result as the corresponding aspects described herein. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.

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:

2. 10. The polymer composite of claim 1, wherein the continuous polymer matrix comprises a polyester, a polyamide, a polyepoxide, or any combination or blend thereof.

3. 3. The polymer composite of claim 2, wherein the continuous polymer matrix comprises a polyamide, and the polyamide is nylon, preferably polycaprolactam, poly[imino(1,6-dioxohexamethylene)iminohexamethylene], poly(dodecano-12-lactam), or any blend thereof.

4. 4. The polymer composite material of claim 1, wherein the plurality of polymer aerogel particles are organic polymer aerogel, preferably polyimide aerogel particles.

5. (delete)

6. 5. The polymer composite of claim 1, wherein the plurality of polymer aerogel particles exhibits a multimodal particle size distribution, preferably a bimodal particle size distribution.

7. 7. The polymer composite of any one of claims 1 to 4 and 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.

8. 8. The polymer composite of any one of claims 1 to 4 and 6 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.

9. (delete)

10. 9. The polymer composite of any one of claims 1-4 and 6-8, wherein the dielectric constant of the polymer composite is reduced compared to the same polymer composite not including the discrete phase comprising the plurality of polymer aerogel particles.

11. 11. The polymer composite of any one of claims 1-4, 6-8, and 10, wherein the compressive yield strength (MPa), compressive elastic strength (GPa), and / or yield strain (%) of the polymer composite is the same or changed compared to the same polymer composite not including a discrete phase comprising the plurality of polymer aerogel particles.

12. 12. The polymer composite of any one of claims 1 to 4, 6 to 8, and 10 to 11, wherein the polymer matrix comprises a thermoplastic polymer or a blend of thermoplastic polymers, preferably a polyolefin, a fluoropolymer or derivatives thereof, or a blend thereof, or more preferably a polyethylene or polypropylene or a blend thereof.

13. 13. The polymer composite of any one of claims 1 to 4, 6 to 8, and 10 to 12, wherein the polymer matrix comprises a thermosetting polymer or a blend of thermosetting polymers, preferably a dicyclopentadiene-modified polyester, an isophthalic-based polyester, an orthophthalic-based polyester, or a blend thereof.

14. 14. The polymer composite of any one of claims 1-4, 6-8, and 10-13, further comprising an additive dispersed or solubilized in the continuous polymer matrix.

15. 15. The polymer composite of claim 14, wherein the additive is an inorganic additive or polytetrafluoroethylene, preferably glass particles, glass fibers, glass spheres, hollow glass spheres, ceramic spheres, or polytetrafluoroethylene.

16. 16. The polymer composite material of any one of claims 1 to 4, 6 to 8, and 10 to 15, in the form of a film.

17. 17. The polymer composite material of any one of claims 1 to 4, 6 to 8, and 10 to 16, in the form of a fiber.

18. 18. The polymer composite of claim 17, wherein the fibers are melt-spun fibers, dry-spun fibers, or wet-spun fibers.

19. 19. The polymer composite material of any one of claims 1 to 4, 6 to 8, and 10 to 18, contained in an article of manufacture.

20. 20. The polymer composite of claim 19, wherein the article is a film, a monolith, a wafer, a blanket, a core composite, a substrate for a radio frequency antenna, a substrate for a sunshield, a substrate for a sunshade, a substrate for a radome, insulation for oil and / or gas pipelines, insulation for liquefied natural gas pipelines, insulation for pipelines carrying cryogenic fluids, insulation for apparel, insulation for aerospace applications, insulation for buildings, cars, and other human habitations, insulation for automotive applications, insulation for radiators, insulation for exhaust and ventilation, insulation for air conditioning, insulation for heating and refrigeration equipment and portable air conditioners, insulation for coolers, insulation for packaging, insulation for consumer goods, vibration damping, insulation for wire and cable, insulation for medical devices, supports for catalysts, supports for drugs, pharmaceuticals, and / or drug delivery systems, storage containers, pipes, tubing, seals, gaskets, water filters, oil filters, and solvent filters, or any combination thereof.

21. 21. The polymer composite of any one of claims 19 to 20, wherein the product is an injection molded or blow molded product.

22. 19. A method of making the polymer composite material of any one of claims 1-4, 6-8, and 10-18, comprising dispersing a plurality of polymer aerogel particles in a polymer composition to form the polymer composite material of any one of claims 1-4, 6-8, and 10-17.

23. 23. The method of claim 22, wherein the polymeric aerogel particles are dispersed in the polymeric composition by casting, melt blending, or extruding the polymeric aerogel particles with the polymeric composition.

24. 1. A method for altering the viscosity of a polymer composition, comprising dispersing a sufficient amount of a plurality of polymeric aerogel particles in a polymer composition to alter the viscosity of the polymer composition compared to the same polymer composition without the plurality of polymeric aerogel particles.

25. 25. The method of claim 24, wherein the viscosity of the polymer composition is reduced compared to the same polymer composition without the plurality of polymeric aerogel particles.

26. 26. The method of claim 25, wherein the viscosity of the polymer composition is increased compared to the same polymer composition without the plurality of polymeric aerogel particles.

27. 1. A method for delaying the onset of exotherm and / or reducing the exotherm peak during curing of a thermosetting polymer, comprising dispersing a sufficient amount of a plurality of polymeric aerogel particles in a polymeric thermosetting composition to delay and / or reduce the exotherm peak of the polymeric thermosetting composition compared to the same polymeric thermosetting composition without the plurality of polymeric aerogel particles.

28. 28. The method of claim 27, wherein the onset of exotherm is delayed by 0.25 hours to 2 hours, preferably 0.3 hours to 0.75 hours.

29. 29. The method of any one of claims 27 to 28, wherein the exothermic peak is reduced by 5 to 50°C, preferably 10 to 30°C, more preferably 15 to 25°C.

30. 1. A method for increasing the heat distortion temperature (HDT) of a polymeric composition, comprising dispersing a sufficient amount of a plurality of polymeric aerogel particles in the polymeric composition to alter, preferably increase, the HDT of the polymeric composition compared to the same polymeric composition without the plurality of polymeric aerogel particles.

31. 31. The method of claim 30, wherein the amount of the plurality of polymer aerogel particles is 1 wt % to 50 wt %, preferably 5 wt % to 40 wt %, or 10 wt % to 20 wt %.

32. 32. The method of any one of claims 30 to 31, wherein the particle size of the aerogel is between 10 micrometers and 150 micrometers, preferably between 30 micrometers and 125 micrometers.

33. 33. The method of any one of claims 30-32, 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 the same natural polymer composite.

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