WO2019006184A1

WO2019006184A1 - Hyperbranched poss-based polymer aerogels

Info

Publication number: WO2019006184A1
Application number: PCT/US2018/040117
Authority: WO
Inventors: David J. Irvin; Muhammad Ejaz; Nicole LAMBDIN; Garrett D. POE; Alan D. SAKAGUCHI
Original assignee: Blueshift Materials, Inc.
Priority date: 2017-06-29
Filing date: 2018-06-28
Publication date: 2019-01-03

Abstract

A hyperbranched polyhedral oligomeric silsesquioxane (POSS) polymer aerogel, and methods for making and using the same, is disclosed. The aerogel can include an open-cell structured POSS polymer matrix of an organically modified POSS polymer.

Description

HYPERBRANCHED POSS-BASED POLYMER AEROGELS

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Application No. 62/526,761 filed June 29, 2017, which is incorporated herein in its entirety without disclaimer. GOVERNMENT SUPPORT CLAUSE

[0002] This invention was made with United States government support under Contract Number DE-AR0000734 awarded by Advanced Research Projects Agency -Energy (ARPA-E) (U.S. Department of Energy). The United States government has certain rights in the invention.

BACKGROUND OF THE INVENTION A. Field of the Invention

[0003] The invention generally concerns hyperbranched polyhedral oligomeric silsesquioxane (POSS) polymer aerogels. In particular the invention concerns a hyperbranched POSS polymer aerogel that includes an open-cell structured POSS polymer matrix of an organically modified POSS polymer. B. Description of Related Art

[0004] A gel by definition is a sponge-like, three-dimensional solid network whose pores are filled with another non-gaseous substance, such as a liquid. The liquid of the gel is not able to diffuse freely from the gel structure and remains in the pores of the gel. Drying of the gel that exhibits unhindered shrinkage and internal pore collapse during drying provides materials commonly referred to as xerogels.

[0005] By comparison, a gel that dries and exhibits little or no shrinkage and internal pore collapse during drying can yield an aerogel. Aerogels are used in a wide variety of applications such as building and construction, aerospace, transportation, catalysts, insulation, sensors, thickening agents, and the like. In instances where transparency and/or minimal haze are desired (e.g., windows, bottles, containers, optics (e.g., ophthalmic lenses), light bulbs, etc.), aerogels have generally failed. For instance, while aerogels made from silica (S1O2) can exhibit high transparency, such silica aerogels are known to be brittle and therefor have low mechanical strength. This limits their use in applications where transparency is desired.

[0006] Efforts to improve the mechanic strength of these silica aerogels have largely focused on the use of organic polymers (e.g., polyimides or silica/polyimide blends) to make the aerogel matrix. While these materials exhibit improved durability, lightweight, and low-density characteristics, they also tend to be opaque and/or have extremely low thicknesses, thereby limiting their use in applications where transparency is desired.

SUMMARY OF THE INVENTION [0007] A discovery has been made that provides a solution to at least some of the aforementioned problems associated with transparent aerogels. The discovery is premised on a hyperbranched POSS polymer aerogel that contains an open-cell structured POSS polymer matrix of an organically modified POSS polymer. The hyperbranched POSS polymer aerogel of the present invention can have good optical properties (e.g., lower haze and high percentage of light transmission). The hyperbranched POSS polymer aerogels can also have good mechanical and thermal properties. Therefore, the aerogels of the present invention can be used in a wide array of applications, especially those that demand high transparency (e.g., windows for transportation vehicles, buildings, houses; ophthalmic lenses, optical devices, etc.).

[0008] In an aspect of the present invention, hyperbranched POSS polymer aerogels are described. A hyperbranched POSS polymer aerogel can include an open-cell structured POSS polymer matrix of an organically modified POSS polymer. The organically modified POSS polymer is derived from an organically modified multi-functionalized POSS material of: [Ri— SiOi.₅]n, where Ri is an organic linker group that has at least 2 carbon atoms and is capable of undergoing a chemical reaction with another identical or similar organic linker group to form a covalent bond between both linker groups, where n is from 6 to 12. In a preferred embodiment, n is 8. Ri can include a C2 to C10 acrylate group, C2 to C10 methacrylate group, a C2 to C10 vinyl group, or a C2 to C10 epoxide group. In some embodiments, a polymerizable organic monomer can be used. In some embodiments, the hyperbranched POSS polymer aerogel can have a specific surface area of 0.15 m²/g to 1500 m²/g, preferably 300 m²/g to 500 m²/g. The hyperbranched POSS polymer aerogel can have a haze value of 0.5 to 10 and/or a total percent light transmission of 10 to 99, or 50 to 99 at 550 nm wavelength as measured by ASTM D1003. In some instance, the hyperbranched POSS polymer aerogel is transparent, translucent, or opaque. In a preferred embodiment, the hyperbranched POSS polymer aerogel is transparent. In certain instances, the aerogels of the present invention can have a thickness of 1 mm to 100 mm or 1 mm to 25 mm and still retain their transparent characteristics, which can be beneficial in applications where transparency and mechanical durability are both desired.

[0009] Still further, and in certain non-limiting aspects, the polymeric matrices of the aerogels of the present invention can include mesopores (pores having a size of 2 nm to 50 nm in diameter) and optionally micropores (pores having a size of less than 2 nm in diameter), and optional macropores (pores having a size of greater than 50 nm) In more preferred instances, the average pore size of the porous aerogel matrices of the present invention is between 1 nm to 50 nm in diameter, preferably 2 nm to 25 nm in diameter, more preferably 3 nm to 15 nm in diameter. Additionally, and in some preferred embodiments, the majority (e.g., more than 50 %) of the pore volume in the aerogels of the present invention can be made up from mesopores. In even further instances, over 55 %, 60 %, 70 %, 80 %, 90 %, 95 %, 99%, or 100% of the pore volume of the aerogels can be made up of mesopores. In instances where less than 100% of the pore volume is made up of mesopores, such aerogels can also include micropores and macropores. This porous architecture along with the incorporation of the aforementioned hyperbranched POSS polymer into the aerogels is believed to contribute to the improved transparency, mechanical, thermal, manufacturability, and/or recyclability properties of the aerogels of the present invention.

[0010] In some aspects of the present invention, the organically modified multi- functionalized POSS material can have the following general structure:

where Ri is an organic linker group having at least 2 carbons and is capable of undergoing a polymerization reaction. In some embodiments, Ri can be a linking group that can independently be a C2 to C10 acrylate group, C2 to C10 vinyl group, or a C2 to C10 epoxide group. In some embodiments, the organically modified multi-functionalized POSS material can be:

[0011] In another aspect of the present invention, methods to produce a hyperbranched POSS polymer aerogel are disclosed. The method can include: (a) obtaining a solution that can include a solvent, a radical initiating agent, an organically modified multi-functionalized POSS material that includes an organic linker group, optionally a chain transfer agent and optionally a polymerizable organic compounds with 1 to 10 functional groups; (b) subjecting the solution to conditions suitable to form an organically modified POSS polymer matrix gel; and (c) subjecting the organically modified POSS polymer matrix gel to conditions suitable to form the hyperbranched POSS polymer aerogel. In some embodiments, a promoter material and/or a chain transfer agent can be added during steps (a) or (b), preferably step (b). The liquid phase of the gel can be the solvent. The solvent can be dimethylformamide, tetrahydrofuran, acetophenone, N-methyl-2-pyrrolidone, xylene, toluene, or blends thereof. In some embodiments, the solution can include at least 5 wt.% to up to 55 wt.% of the organically modified multi-functionalized POSS material, preferably 15 wt.% to 35 wt.%. The organically modified multi-functionalized POSS material can be the material discussed above and throughout the specification. In one preferred instance, this multi-functionalized POSS material is [Ri— SiOi.sjn, where Ri is an organic linker group that has at least 2 carbon atoms and is capable of undergoing a chemical reaction and n is from 6 to 12. Ri can include a C2 to C10 acrylate group, a C2 to C10 vinyl group, or a C2 to C10 epoxide group. In some embodiments, a polymerizable organic monomer can also be added to the solution to extend the linkage and/or to react with Ri. In some embodiments, the organically modified multi-functionalized POSS material can be structures (I) through (V). Step (b) conditions can include heating the solution at 15 °C to 120 °C, or 65 °C to 75 °C form the gel. In some embodiments, step (c) can include subjecting the gel to a drying step to remove the solvent and form the aerogel. Non-limiting examples of a drying step can include supercritical drying, subcritical drying, thermal drying, evaporative drying, ambient drying, or any combination thereof. In some embodiments, evaporative drying and/or ambient drying is preferred. In some embodiments, the drying step can include heating the gel to a temperature of 15 °C to 50 °C, preferably 20 °C to 30 °C, to remove all or most of the solvent. In another instance, the solvent can be removed with or without the use of a gaseous stream. In some instances, step (c) can include subjecting the gel to conditions sufficient to freeze the solvent to form a frozen material. The frozen material can be subjected to a freeze drying or subcritical drying step sufficient to form the aerogel. In some embodiments, the polymer matrix gel can be subjected to at least one solvent exchange with a different solvent (e.g., acetone, tetrahydrofuran, toluene, xylene, hexane, heptane, a methyl siloxane containing material, a hexamethyldisiloxane containing material, a mixture of fluorocarbon and trans- 1,2-dichloroethylene, or combinations thereof) prior to drying the gel. In some instances, no solvent exchange is performed on the formed gel, and the formed gel can be dried such that the original solvent used to make the gel is removed to form the aerogel of the present invention.

[0012] In another aspect of the present invention, articles of manufacture that include the hyperbranched POSS polymer of the present invention are disclosed. Non-limiting examples of articles of manufacture include a thin film, monolith, wafer, blanket, core composite material, insulating material for residential and commercial windows, insulation material for transportation windows, insulation material for transparent light transmitting application, insulation material for translucent light transmitting application, insulation material for translucent lighting applications, insulation material for window glazing, a substrate for radiofrequency antenna, substrate for a sunshield, a substrate for a sunshade, a substrate for radome, insulating material for oil and/or gas pipeline, insulating material for liquefied natural gas pipeline, insulating material for cryogenic fluid transfer pipeline, insulating material for apparel, insulating material for aerospace applications, insulating material for buildings, cars, and other human habitats, insulating material for automotive applications, insulation for radiators, insulation for ducting and ventilation, insulation for air conditioning, insulation for heating and refrigeration and mobile air conditioning units, insulation for coolers, insulation for packaging, insulation for consumer goods, vibration dampening, wire and cable insulation, insulation for medical devices, support for catalysts, support for drugs, pharmaceuticals, and/or drug delivery systems, aqueous filtration apparatus, oil-based filtration apparatus, and solvent- based filtration apparatus, or any combination thereof.

[0013] In the context of the present invention 37 embodiments are described. Embodiment 1 is a hyperbranched polyhedral oligomeric silsesquioxane (POSS) polymer aerogel comprising an open-cell structured POSS polymer matrix of an organically modified POSS polymer. Embodiment 2 is the hyperbranched POSS polymer aerogel of embodiment 1, wherein the organically modified POSS polymer is derived from an organically modified multi- functionalized POSS material of: [Ri— SiOi.s]«, where: Ri is an organic linker group comprising a C2 to Cio acrylate group, a C2 to C10 vinyl group, or a C2 to C10 epoxide group; and n is 6 to 12. Embodiment 3 is the hyperbranched POSS polymer aerogel of embodiment 2, wherein the multi-functionalized POSS material is:

Embodiment 4 is the hyperbranched POSS polymer aerogel of embodiment 2, wherein the functionalized POSS monomer is:

Embodiment 5 is the hyperbranched POSS polymer aerogel of embodiment 2, wherein the functionalized POSS monomer is:

Embodiment 6 is the hyperbranched POSS polymer aerogel of embodiment 2, wherein the functionalized POSS monomer is:

Embodiment 7 is the hyperbranched POSS polymer aerogel of embodiments 1 to 2, wherein organic POSS polymer is derived from a polymerizable organic monomer and a functionalized POSS monomer of: [Ri— SiOi.s]«, where: Ri is organic linker group comprising a C2 to C10 acrylate group, a C2 to C10 vinyl group, or a C2 to C10 epoxide group; and n is 6 to 12. Embodiment 8 is the hyperbranched POSS polymer aerogel of any one of embodiments 1 to 7, having a specific surface area of 0.15 m²/g to 1500 m²/g , preferably 300 m²/g to 500 m²/g. Embodiment 9 is the hyperbranched POSS polymer aerogel of any one of embodiments 1 to 8, having mesopores and optionally micropores, and/or optional macropores. Embodiment 10 is the hyperbranched POSS polymer aerogel of embodiment 9, wherein the pores have an average pore size of 2 to 15 nm. Embodiment 11 is the hyperbranched POSS polymer aerogel of any one of embodiments 1 to 10, having a haze value of 0.5 to 10 as measured by ASTM D1003. Embodiment 12 is the hyperbranched POSS polymer aerogel of any one of embodiments 1 to 10, having a total percent light transmission of 10 to 99 at 550 wavelength as measured by ASTM D1003. Embodiment 13 is the hyperbranched POSS polymer aerogel of any one of embodiments 1 to 10, wherein the aerogel is transparent. Embodiment 14 is the hyperbranched POSS polymer aerogel of any one of embodiments 1 to 10, wherein the aerogel is translucent. Embodiment 15 is the hyperbranched POSS polymer aerogel of any one of embodiments 1 to 10, wherein the aerogel is opaque.

Embodiment 16 is a method to produce a hyperbranched POSS polymer aerogel, the method comprising: obtaining a solution comprising a solvent, a radical initiating agent, a multi- functionalized polyhedral oligomeric silsesquioxane (POSS) material comprising an organic linker group, and optionally a polymerizable organic compound; subjecting the solution to conditions suitable to form a hyperbranched organically modified POSS polymer matrix gel; and subjecting the organically modified POSS polymer matrix gel to conditions suitable to form the hyperbranched POSS aerogel. Embodiment 17 is the method of embodiment 16, wherein subjecting the polymer matrix solution to conditions sufficient to form the polymer matrix comprises adding a sufficient amount of a promoter material and/or a chain transfer material. Embodiment 18 is the method of any one of embodiments 16 to 17, wherein step (b) comprises a temperature of 15 °C to 120 °C, or 65 °C to 75 °C form the gel. Embodiment 19 is the method of any one of embodiments 17 to 18, wherein step (c) comprises subjecting the gel to a drying step to remove a portion of the solvent. Embodiment 20 is the method of embodiment 19, wherein the drying step is supercritical drying, subcritical drying, thermal drying, evaporative drying, ambient drying, or any combination thereof. Embodiment 21 is the method of embodiment 20, wherein the drying step is evaporative drying. Embodiment 22 is the method of embodiment 20, wherein the drying step is ambient drying without the use of a gaseous stream. Embodiment 23 is the method of any one of embodiments 20 to 22, wherein the drying step comprises heating the gel to a temperature of 15 °C to 50 °C, preferably 20 °C to 30 °C. Embodiment 24 is the method of any one of embodiments 16 to 23, wherein step (c) comprises: (i) subjecting the gel to conditions sufficient to freeze the solvent to form a frozen material; and (ii) subjecting the frozen material to a subcritical drying step sufficient to form the aerogel. Embodiment 25 is the method of any one of claims 16 to 24, further comprising subjecting the gel formed in step (b) to at least one solvent exchange to replace the solvent with a second solvent prior to performing step (c). Embodiment 26 is the method of embodiment 25, wherein at least one solvent exchange is performed with acetone, tetrahydrofuran, toluene, xylene, hexane, heptane, a methyl siloxane containing material, a hexamethyldisiloxane containing material, a mixture of fluorocarbon and trans-l,2-dichloroethylene, or combinations thereof. Embodiment 27 is the method of any one of embodiments 16 to 24, wherein no solvent exchange is performed. Embodiment 28 is the method of any one of claims 16 to 27, wherein the solution comprises at least 5 wt.% to up to 55 wt.% of organically modified multi- functionalized POSS material, preferably 15 wt.% to 35 wt.%. Embodiment 29 is the method of any one of embodiments 16 to 28, wherein the organically modified multi-functionalized POSS material has the general formula of is [Ri— SiOi.s]«, where Ri is an organic linker group having at least 2 carbon atoms and is capable of undergoing a chemical reaction, and n is 6 to 12. Embodiment 30 is the method of embodiment 29, wherein Ri is an organic linker group comprising a C2 to C10 acrylate group, a C2 to C10 vinyl group, or a C2 to C10 epoxide group. Embodiment 31 is the method of any one of embodiments 29 to 30, wherein the organically modified multi-functionalized POSS material is:

Embodiment 32 is the method of any one of embodiments 29 to 30, wherein the organically modified functionalized POSS monomer is:

Embodiment 33 is the method of any one of embodiments 29 to 30, wherein the organically modified functionalized POSS material is:

Embodiment 34 is the method of any one of claim 29 to 30, wherein the organically modified functionalized POSS material has the general structure of:

Embodiment 35 is the method of any one of embodiments 16 to 34, wherein the solvent comprises dimethylformamide, tetrahydrofuran, acetophenone or blends thereof.

[0014] Embodiment 36 is an article of manufacture comprising the hyperbranched POSS polymer aerogel of any one of claims 1 to 15. Embodiment 37 is the article of manufacture of claim 35, wherein the article of manufacture is a thin film, monolith, wafer, blanket, core composite material, insulating material for residential and commercial windows, insulation material for transportation windows, insulation material for transparent light transmitting application, insulation material for translucent light transmitting application, insulation material for translucent lighting applications, insulation material for window glazing, core composite material, a substrate for radiofrequency antenna, substrate for a sunshield, a substrate for a sunshade, a substrate for radome, insulating material for oil and/or gas pipeline, insulating material for liquefied natural gas pipeline, insulating material for cryogenic fluid transfer pipeline, insulating material for apparel, insulating material for aerospace applications, insulating material for buildings, cars, and other human habitats, insulating material for automotive applications, insulation for radiators, insulation for ducting and ventilation, insulation for air conditioning, insulation for heating and refrigeration and mobile air conditioning units, insulation for coolers, insulation for packaging, insulation for consumer goods, vibration dampening, wire and cable insulation, insulation for medical devices, support for catalysts, support for drugs, pharmaceuticals, and/or drug delivery systems, aqueous filtration apparatus, oil-based filtration apparatus, and solvent-based filtration apparatus, or any combination thereof

[0015] The following includes definitions of various terms and phrases used throughout this specification.

[0016] The term "aerogel" refers to a class of materials that are generally produced by forming a gel, removing a mobile interstitial solvent phase from the pores, and then replacing it with a gas or gas-like material. By controlling the gel and evaporation system, density, shrinkage, and pore collapse can be minimized. As explained above, aerogels of the present invention can include micropores, macropores and/or mesopores or any combination thereof. The amount of micropores, macropores, and/or mesopores in any given aerogel of the present invention can be modified or tuned as desired. In certain preferred aspects, however, the aerogels can 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 aerogel's pore volume can be made up of mesopores. In some embodiments, the aerogels of the present invention can have low bulk densities (about 0.75 g/cm³ or less, preferably about 0.01 to 0.5 g/cm³), high surface areas (generally from about 0.15 to 500 m²/g and higher, preferably about 300 to 500 m²/g), high porosity (about 20% and greater, preferably greater than about 85%), and/or relatively large pore volume (more than about 3.0 mL/g, preferably about 1.2 mL/g and higher). [0017] The term "hyperbranched" or "hyperbranched polymer" refers to a highly branched macromolecule with three-dimensional dendritic architecture. Hence, the molecular weight of a hyperbranched polymer is not a sufficient parameter that characterizes these polymers. Since the number of possible structures becomes very large as the polymerization degree of macromolecules increases, there is a need to also characterize this aspect of hyperbranched polymers. Thus, the term degree of branching (DB) can be used as a quantitative measure of the branching perfectness for hyperbranched polymers. In some embodiments, the hyperbranched POSS polymer aerogels can include a degree of branching (DB) of at least 2 or more branches per POSS polymer.

[0018] The presence of mesopores, macropores and/or micropores in the aerogels of the present invention can be determined by mercury intrusion porosimetry (MIP) and/or gas physisorption experiments, the MIP can be used to measure the mesopores and macropores above 5 nm (i.e., American Standard Testing Method (ASTM) D4404-10, Standard Test Method for Determination of Pore Volume and Pore Volume Distribution of Soil and Rock by Mercury Intrusion Porosimetry). Gas physisorption experiments can be used to measure mesopores and/or micropores (ASTM D 1993 -03 (2008) Standard Test Method for Precipitated Silica - Surface Area by Multipoint BET Nitrogen).

[0019] The terms "impurity" or "impurities" refers to unwanted substances in a feed fluid that are different than a desired filtrate and/or are undesirable in a filtrate. In some instances, impurities can be solid, liquid, gas, or supercritical fluid. In some embodiments, an aerogel can remove some or all of an impurity.

[0020] The term "desired substance" or "desired substances" refers to wanted substances in a feed fluid that are different than the desired filtrate. In some instances, the desired substance can be solid, liquid, gas, or supercritical fluid. In some embodiments, an aerogel can remove some or all of a desired substance. [0021] The term "radio frequency (RF)" refers to the region of the electromagnetic spectrum having wavelengths ranging from 10^"4 to 10⁷ m.

[0022] The term "supercritical fluid" refers to any substance at a temperature and pressure above its critical point. A supercritical fluid can diffuse through solids like a gas, and dissolve materials like a liquid. Additionally, close to the critical point, small changes in pressure or temperature result in large changes in density.

[0023] An "aliphatic group" is an acyclic or cyclic, saturated or unsaturated carbon group, excluding aromatic compounds. A linear aliphatic group does not include tertiary or quaternary carbons. Aliphatic group substituents include, but are not limited to halogen, hydroxyl, alkyloxy, haloalkyl, haloalkoxy, carboxylic acid, ester, amine, amide, nitrile, acyl, thiol and thioether. A branched aliphatic group includes at least one tertiary and/or quaternary carbon. Branched aliphatic group substituents can include alkyl, halogen, hydroxyl, alkyloxy, haloalkyl, haloalkoxy, carboxylic acid, ester, amine, amide, nitrile, acyl, thiol and thioether. A cyclic aliphatic group is includes at least one ring in its structure. Polycyclic aliphatic groups can include fused, e.g., decalin, and/or spiro, e.g., spiro[5.5]undecane, polycyclic groups. Cyclic aliphatic group substituents can include alkyl, halogen, hydroxyl, alkyloxy, haloalkyl, haloalkoxy, carboxylic acid, ester, amine, amide, nitrile, acyl, thiol and thioether.

[0024] An "alkyl group" is linear or branched, substituted or unsubstituted, saturated hydrocarbon. Alkyl group substituents may include, but are not limited to alkyl, halogen, hydroxyl, alkyloxy, haloalkyl, haloalkoxy, carboxylic acid, ester, amine, amide, nitrile, acyl, thiol and thioether.

[0025] An "aryl" or "aromatic" group is a substituted or unsubstituted, mono- or polycyclic hydrocarbon with alternating single and double bonds within each ring structure. Aryl group substituents can include alkyl, halogen, hydroxyl, alkyloxy, haloalkyl, haloalkoxy, carboxylic acid, ester, amine, amide, nitrile, acyl, thiol and thioether.

[0026] The term "acr late" includes substituted and unsubstituted vinyl carboxylic acids. A general structure

Non-limiting examples of acrylate include aery late and methacrylate.

[0027] The terms "about" or "approximately" are defined as being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment, the terms are defined to be within 10%, preferably within 5%, more preferably within 1%, and most preferably within

0.5%.

[0028] The terms "wt.%", "vol.%", or "mol.%" refers to a weight percentage of a component, a volume percentage of a component, or molar percentage of a component, based on the total weight, the total volume of material, or total moles, that includes the component. In a non-limiting example, 10 grams of component in 100 grams of the material is 10 wt.% of component.

[0029] The term "substantially" and its variations are defined to include ranges within 10%, within 5%, within 1%, or within 0.5%. [0030] The terms "inhibiting" or "reducing" or "preventing" or "avoiding" or any variation of these terms, when used in the claims and/or the specification includes any measurable decrease or complete inhibition to achieve a desired result.

[0031] The term "effective," as that term is used in the specification and/or claims, means adequate to accomplish a desired, expected, or intended result. [0032] The use of the words "a" or "an" when used in conjunction with any of the terms "comprising," "including," "containing," or "having" in the claims, or the specification, may mean "one," but it is also consistent with the meaning of "one or more," "at least one," and "one or more than one."

[0033] The words "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.

[0034] The hyperbranched POSS polymer aerogels of the present invention can "comprise," "consist essentially of," or "consist of particular ingredients, components, compositions, etc. disclosed throughout the specification. With respect to the transitional phase "consisting essentially of," in one non-limiting aspect, a basic and novel characteristic of the hyperbranched POSS polymer aerogels of the present invention is their transparent optical properties.

[0035] Other objects, features and advantages of the present invention will become apparent from the following figures, detailed description, and examples. It should be understood, however, that the figures, detailed description, and examples, while indicating specific embodiments of the invention, are given by way of illustration only and are not meant to be limiting. Additionally, it is contemplated that changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. In further embodiments, features from specific embodiments may be combined with features from other embodiments. For example, features from one embodiment may be combined with features from any of the other embodiments. In further embodiments, additional features may be added to the specific embodiments described herein. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Advantages of the present invention may become apparent to those skilled in the art with the benefit of the following detailed description and upon reference to the accompanying drawings. [0037] FIG. 1A is an image of the acrylate-POSS polymer aerogel of the present invention made from 30 wt.% of structure (IV) in dimethylformamide (DMF).

[0038] FIG. IB is an image of the acrylate-POSS polymer aerogel of the present invention made from 10 wt.% of structure (IV) in DMF.

[0039] FIG. 1C is an image of the acrylate-POSS polymer aerogel of the present invention made from 30 wt.% of structure (IV) in acetophenone (ACP).

[0040] FIG. ID is an image of the methacrylate-POSS polymer aerogel of the present invention made from 30 wt.% of structure (III) in DMF.

[0041] FIGS. IE and IF are images of the methacrylate-POSS polymer aerogel of the present invention made from 10 wt.% of structure (III) in DMF. [0042] FIG. 1G is image of the methacrylate-POSS polymer aerogel of the present invention made from 30 wt.% of structure (III) in acetophenone.

[0043] FIG. 1H is an image of the acrylate-POSS polymer aerogel of the present invention made from 30 wt.% of structure (IV) in ACP.

[0044] FIG. II is an image of the acrylate-POSS polymer aerogel of the present invention made from 30 wt.% of structure (IV) in DMF.

[0045] While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings. The drawings may not be to scale.

DETAILED DESCRIPTION OF THE INVENTION

[0046] A discovery has been made that solves at least some of the problems relating to optical properties of silica aerogels or polymer aerogels. The discovery is premised on a hyperbranched POSS polymer aerogel that that contains an open-cell structured POSS polymer matrix of an organically modified POSS polymer. The hyperbranched POSS polymer aerogel of the present invention can have good optical properties (e.g., low haze and high percentage of light transmission). The hyperbranched POSS polymer aerogels also have good mechanical and thermal properties. These and other non-limiting aspects of the present invention are discussed in further detail in the following sections.

A. Materials

[0047] The materials, solvents, compounds, reagents and the like used to produce the hyperbranched POSS polymer aerogels of the present invention can be made using known synthetic methods or obtained from commercial sources.

1. Organically Modified Multi-Functionalized POSS Materials

[0048] The hyperbranched POSS polymer aerogels of the present invention can be derived from organically modified multi-functionalized POSS materials and optional organic monomers. Organically modified multi-functionalized POSS materials can be made using known synthetic copolymerization by a step growth condensation reaction between hydroxyl or alkoxide groups on the silsesquioxane and the appropriate functionality (e.g., Ri) on the silane or siloxane. Organically modified multi-functionalized POSS materials are also commercially available from Hybrid Plastics (Hattiesburg, MS, USA). The organically modified multi-functionalized POSS materials of the present invention have the general structure of organically modified multi- functionalized POSS material of [Ri— SiOi.s]n, where Ri is an organic linker group that has at least 2 carbon atoms and is capable of undergoing a chemical reaction and n is from 6 to 12 {e.g., 6, 7, 8, 9, 10, 11, or 12 or any value or range there between). Ri can include a reactive group that has 2 to 10 carbon atoms {e.g., 2, 3, 4, 5, 6, 7, 8, 9, or 10). In some embodiments, the reactive group can be a C2 to C10 acrylate group {e.g., methacrylate or methylmethacrylate, butylacrylate groups), a C2 to C10 vinyl group (C2H3 group), or a C2 to C10 epoxide group {e.g., glycidyl isobutyl ether group).

[0049] In a preferred embodiment, the POSS material has 8 repeating units and has the general structure of:

[0050] Ri can be an organic group that includes functionalization that allows Ri to chemically bond with another Ri of structure (I) to link the two structures together. Non- limiting examples of organic groups include olefins, preferably vinyl groups, acrylates, methacrylates, epoxides, or the like. Ri can have 2 to 20 carbon atoms. Non-limiting examples of organically modified multi-functionalized POSS materials include:

2. Optional Reactants

[0051] In some embodiments, additional reactants can be added with the organically modified multi-functionalized POSS materials to produce the aerogels of the present invention. The additional reactants, for example, can be added to the solution that also includes the POSS materials prior to the formation of the gel. The additional reactants can react with the Ri groups of the POSS materials to form covalent bonds. The reactants can be polymerized prior to or after reacting with the Ri groups. The additional reactants can be used to link the POSS materials together form the aerogel matrix. Reactants include compounds having 1 to 10 functional reactive groups. Non-limiting examples of reactants include alpha-olefins (e.g., ethylene propylene, or alpha-olefins have 2 to 20 carbons), dienes, vinyl aromatic monomers (e.g., styrene, vinyl toluene, t-butyl styrene, di-vinyl benzene, vinyl acetates, and all isomers or derivatives of these compounds), acrylates (e.g., methacrylate, methylmethacrylate, 1,6- hexanediol diacrylate, dipentaerythritol pentaacrylate, and the like), unsaturated polyesters, epoxides (e.g. glycidyl compounds) and the like.

3. Radical Initiators, Promoters and Chain Transfer Agents

[0052] Radical initiators, promoters, and chain transfer agents can be used to assist in polymerization of the multi-functionalized POSS materials with each other or other monomers. Radical initiators can produce radical species from Ri of the multi-functionalized POSS material to start the polymerization process. Non-limiting examples of radical initiators can include azobisisobutyronitrile (AIBN), 4,4'-azobis(4-cyanopentanoic acid) (ACPA), 2,2'-azobis(4- methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide (BPO), methyl ethyl ketone peroxide (MEKP), and the like. Promoters or co-catalyst can be used to regulate the reaction rate of the polymerization. Non-limiting examples of promoters include cobalt (Co) compounds such as cobaloximines, cobalt porphyrins, Co(acac)₂, cobalt naphthenate, or combinations thereof. Chain transfer agents are agents that can react with a chain carrier by a reaction in which the original chain carrier is deactivated and a new chain carrier is generated. Chain transfer agents can be multifunctional or monofunctional. Non-limiting examples of chain transfer agents include thiols (e.g., 1-decanethiol, or 1-dodecanethiol, pentaerythritol tetrakis(3- mercaptopropionate) or halogenated hydrocarbons (e.g., carbon tetrachloride). The chain transfer agents can be multifunctional or monofunctional. Monofunctional refers to having one thiol (-SH) group available for free radical transfer. Multifunctional refers to having more than one thiol group (e.g., 1, 2, 3, 4, etc.). In some embodiments, the properties of the aerogel can be tuned depending on the choice of chain transfer agent. By way of example, a higher number sulfur groups per chain transfer agent can improve the strength of the aerogel. For lower haze aerogels, a chain transfer agent having a lower number of sulfur groups can be selected (e.g., 1 to 2 thiol groups). Non-limiting examples of commercial suppliers of promoters, initiators, and chain transfer agents are SigmaMillipore (U.S.A.), Wako Chemical (Japan), and Shepherd (U.S.A.).

4. Solvents

[0053] Solvents used in the polymerization reaction and/or solvent exchange reaction can be low-boiling solvents or solvents with a low vapor pressure. For the polymerization reaction, the solvent can completely or partially solubilize the monomers and multi-functionalized POSS materials. Non-limiting examples of solvents for the polymerization reaction include acetone, tetrahydrofuran, formamide, N-methylformamide, Ν,Ν-dimethylformamide, N,N- diethylformamide, N,N-dimethylacetamide, Ν,Ν-diethylacetamide, 2-pyrrolidone, N-methyl-2- pyrrolidone, l-methyl-2-pyrrolidinone, N-cyclohexyl-2-pyrrolidone, N-vinylacetamide, N- vinylpyrrolidone, hexamethylphosphoramide, and l,13-dimethyl-2-imidazolidinone; organosulfur solvents such as, but not limited to, dimethylsulfoxide, diethylsulfoxide, diethyl sulfoxide, methylsulfonylmethane, and sulfolane; ether solvents including, but not limited to, cyclopentyl methyl ether, di-tert-butyl ether, diethyl ether, diethylene glycol diethyl ether, diglyme, diisopropyl ether, dimethoxy ethane, dimethoxymethane, 1,4-dioxane, ethyl tert-butyl ether, glycol ethers, methoxyethane, 2-(2-methoxyethoxy)ethanol, methyl tert-butyl ether, 2- methyltetrahydrofuran, morpholine, tetraglyme, tetrahydropyran, and triglyme; hydrocarbon solvents including, but not limited to, benzene, toluene, ethylbenzene, cycloheptane, cyclohexane, cyclohexene, cyclooctane, cyclopentane, decalin, dodecane, durene, heptane, hexane, limonene, mesitylene, methylcyclohexane, naphtha, octadecene, pentamethylbenzene, pentane, pentanes, petroleum benzene, petroleum ether, toluene tridecane, and turpentine; nitro solvents including, but not limited to, nitrobenzene, nitroethane, and nitromethane; alcohol solvents including, but not limited to, methanol, ethanol, 1-propanol, 2-propanol, 1 -butanol, 2- butanol, isobutanol, tert-butanol, 3-methyl-2-butanol, 3,3-dimethyl-2-butanol, 2-pentanol, 3- pentanol, 2,2-dimethylpropan-l-ol, cyclohexanol, diethylene glycol, tert-amyl alcohol, phenols, cresols, xylenols, catechol, benzyl alcohol, 1,4-butanediol, 1,2,4-butanetriol, butanol, 2-butanol, N-butanol, tert-butyl alcohol, diethylene glycol, ethylene glycol, 2-ethylhexanol, furfuryl alcohol, glycerol, 2-(2-methoxyethoxy)ethanol, 2-methyl-l -butanol, 2-methyl-l -pentanol, 3- methyl-2-butanol, neopentyl alcohol, 2-pentanol, 1,3 -propanediol, and propylene glycolcycol; ketone solvents including, but not limited to, hexanone, methyl ethyl ketone, methyl isobutyl ketone, disobutyl ketone, acetophenone, butanone, cyclopentanone, ethyl isopropyl ketone, 2- hexanone, isophorone, mesityl oxide, methyl isopropyl ketone, 3-methyl-2-pentanone, 2- pentanone, and 3-pentanoneacetyl acetone; halogenated solvents including, but not limited to, benzotri chloride, bromoform, bromomethane, carbon tetrachloride, chlorobenzene, 1,2- dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, chlorofluorocarbon, chloroform, chloromethane, 1,1-dichloro-l-fluoroethane, 1,1-dichloroethane, 1,2-dichloroethane, 1,1- dichloroethene, 1,2-dichloroethene, di chloromethane, diiodomethane, FC-75, haloalkane, halomethane, hexachlorobutadiene, hexafluoro-2-propanol, parachlorobenzotrifluoride, perfluoro-l,3-dimethylcyclohexane, perfluorocyclohexane, perfluorodecalin, perfluorohexane, perfluoromethylcyclohexane, perfluoromethyldecalin, perfluorooctane, perfluorotoluene, perfluorotripentylamine, tetrabromomethane, 1, 1, 1,2-tetrachloroethane, 1, 1,2,2- tetrachloroethane, tetrachloroethylene, 1, 1, 1-tribromoethane, 1,3,5-trichlorobenzene,, 1, 1, 1- trichloroethane, 1, 1,2-trichloroethane, trichloroethylene, 1,2,3-trichloropropane, 2,2,2- trifluoroethanol, and trihalomethane; ester solvents including, but not limited to, methyl acetate, ethyl acetate, butyl acetate, 2-methoxyethyl acetate, benzyl benzoate, bis(2-ethylhexyl) adipate, bis(2-ethylhexyl) phthalate, 2-butoxyethanol acetate, sec-butyl acetate, tert-butyl acetate, diethyl carbonate, dioctyl terephthalate, ethyl acetate, ethyl acetoacetate, ethyl butyrate, ethyl lactate, ethylene carbonate, hexyl acetate, isoamyl acetate, isobutyl acetate, isopropyl acetate, methyl acetate, methyl lactate, methyl phenyl acetate, methyl propionate, propyl acetate, propylene carbonate, dimethyl carbonate, and triacetin; water, or mixtures thereof.

[0054] Non-limiting examples of the solvents used for the optional solvent exchange include acetone, tetrahydrofuran, toluene, xylene, hexane, heptane, a methyl siloxane containing material, a hexamethyldisiloxane containing material, a mixture of fluorocarbon and trans-1,2- dichloroethylene, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 3-methyl-2-butanol, 3,3-dimethyl-2-butanol, 2-pentanol, 3-pentanol, 2,2- dimethylpropan-l-ol, cyclohexanol, di ethylene glycol, cyclohexanone, acetyl acetone, acetophenone, 1,4-dioxane, diethyl ether, dichloromethane, trichloroethylene, chloroform, carbon tetrachloride, dimethyl carbonate, propylene carbonate, water, or combinations thereof.

B. Preparation of Aerogels [0055] Aerogels of the present disclosure can be made using a multi-step process that includes 1) preparation of the organically modified POSS polymer matrix gel, 2) optional solvent exchange, and 3) drying of the polymeric solution to form the aerogel. These process steps are discussed in more detail below.

1. Hyperbranched Organically Modified POSS Polymer Gels [0056] Processes and methods to produce a multi-functionalized POSS material can include combining an organic linking group Ri and a radical initiator with a solvent to form a reaction mixture. The reaction mixture can be subject to conditions suitable to form a hyperbranched organically modified POSS polymer matrix gel. By way of example, the reaction mixture can be cast with or without agitation at a temperature of 15 °C to 120 °C, or 65 °C to 75 °C, or greater than, equal to, or between any two of 15 °C, 20 °C, 25 °C, 30 °C, 35 °C, 40 °C, 45 °C, 50 °C, 55 °C, 60 °C, 65 °C, 70 °C, 75 °C , 80 °C, 85 °C, 90 °C, 95 °C, 100 °C, 105 °C, 1 10 °C, 1 15 °C and 120 °C for a time sufficient to form a gel (e.g., 1 minute to 24 hours, 2 to 15 hours, 5 to 10 hours). The reaction solvent and other reactants can be selected based on the compatibility with the materials. Non-limiting examples of the reaction solvent are found in the above Solvents section. An amount of multi-functionalized POSS material can range from 5 wt.% to 55 wt.%, 15 wt.% to 35 wt.%, or greater than, equal to, or between any two of 5 wt.%, 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, and 55 wt.%. In a specific embodiment, the reaction solvent is tetrahydrofuran. Radical initiators, promoters, and chain transfer agents can be 0.001 to 0.5 wt.%. In some embodiments, promoter and/or chain transfer agents can be added to the solution. In a preferred embodiment, multi-functionalized POSS material (IV), AIBN, optional cobalt naphthenate and optional dodecane thiol can be solubilized in tetrahydrofuran. The optical properties of the aerogel can be tuned by varying the amount of POSS material used. By way of example, using 15 wt.% to 35 wt.% of a POSS material (IV) can result in a transparent aerogel. In instances where opaque or translucent aerogels are desired, greater than 55 wt.% of the organically modified multi-functionalized POSS material can be added.

[0057] In some embodiments, the organically modified hyperbranched POSS polymer matrix solution can be cast onto a casting sheet covered by a support film for a period of time. In certain embodiments, the casting sheet is a polyethylene terephthalate (PET) casting sheet.

After a passage of time, the polymerized gel can be removed from the casting sheet and prepared for an optional solvent exchange process. Alternatively, the POSS polymer matrix solution can be placed into a mold to obtain a desired shape/stock shape of the gel and prepared for an optional solvent exchange process. In some embodiments, a solvent exchange step is not used, and the initial solvent used to make the gel can be removed by any one of the drying techniques noted below, thereby producing an aerogel of the present invention.

2. Optional Solvent Exchange

[0058] After the organically modified hyperbranched POSS polymer matrix gel is synthesized (polymerized gel), it can be subjected to a solvent exchange where the reaction solvent is exchanged for a more desirable second solvent. The original solvent can be exchanged with a second solvent having a higher volatility than the first solvent and repeated with various solvents. By way of example, the polymerized gel can be placed inside of a pressure vessel and submerged in a mixture that includes the reaction solvent and the second solvent. Then, a high pressure atmosphere can be created inside of the pressure vessel thereby forcing the second solvent into the polymerized gel and displacing a portion of the reaction solvent. Alternatively, the solvent exchange step can be conducted without the use of a high pressure environment. It may be necessary to conduct a plurality of rounds of solvent exchange. [0059] The time necessary to conduct the solvent exchange can vary depending upon the type of polymer undergoing the exchange as well as the reaction solvent and second solvent being used. In one embodiment, each solvent exchange can range from 1 to 170 hours or any period time, or greater than, equal to, or between any two of 1, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 1 10, 1 15, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, and 170 hours. In another embodiment, each solvent exchange can take approximately 1 minute. Exemplary second solvents include those discussed in the Solvents Section. In a specific embodiment, the second solvent can be acetone, tetrahydrofuran, toluene, xylene, hexane, heptane, a methyl siloxane containing material, a hexamethyldisiloxane containing material, a mixture of fluorocarbon and trans- 1,2-dichloroethylene or mixtures thereof. In certain non-limiting embodiments, the second solvent can have a suitable freezing point for performing supercritical or subcritical drying steps. For example, dimethyl carbonate has a freezing point of 2 °C to 4 °C and water has a freezing point of 0 °C under one atmosphere of pressure. Alternatively, and as discussed below, however, the drying can be performed without the use of supercritical or subcritical drying steps, such as by evaporative or ambient drying techniques.

[0060] The temperature and pressure used in the solvent exchange process can be varied. The duration of the solvent exchange process can be adjusted by performing the solvent exchange at a varying temperatures or atmospheric pressures, or both, provided that the pressure and temperature inside the pressure vessel does not cause either the first solvent or the second solvent to leave the liquid phase and become gaseous phase, vapor phase, solid phase, or supercritical fluid. Generally, higher pressures and/or temperatures decrease the amount of time required to perform the solvent exchange, and lower temperatures and/or pressures increase the amount of time required to perform the solvent exchange. 3. Cooling and Drying

[0061] In some embodiments, the polymerized gel can be dried to remove the initial solvent from the gel (e.g., where a solvent exchange step is not used) or to remove the second, third, fourth, or more exchanged solvent from the gel (e.g., where a solvent exchange step is used). In instances where solvent exchange has occurred, the drying step can be performed after the solvent exchange step. Drying techniques can include supercritical drying, subcritical drying, thermal drying, evaporative air-drying, ambient drying, or any combination thereof. In some embodiments, the polymerized gel can be exposed to supercritical drying. In this instance, the solvent in the gel can be removed by supercritical CO2 extraction. [0062] In another embodiment, the polymerized gel can be exposed to subcritical drying. In this instance, the gel can be cooled below the freezing point of the solvent and subjected to a freeze drying or lyophilization process to produce the aerogel. For example, if the solvent in the gel is water, then the polymerized gel is cooled to below 0 °C. After cooling, the polymerized gel is subjected to a vacuum for a period of time wherein the solvent is allowed to sublime.

[0063] In still another embodiment after solvent exchange, the polymerized gel can be exposed to subcritical drying with optional heating after the majority of the second solvent has been removed through sublimation. In this instance, the partially dried gel material is heated to a temperature near, or above, the boiling point of the second solvent for a period of time. The period of time can range from a few hours to several days, although a typical period of time is approximately 4 hours. During the sublimation process, a portion of the second solvent present in the polymerized gel has been removed, leaving a gel that can have macropores, mesopores, or micropores, or any combination thereof or all of such pore sizes. After the sublimation process is complete, or nearly complete, the aerogel has been formed. [0064] In yet another embodiment after solvent exchange or instead of solvent exchange, the polymerized gel can be dried under ambient conditions, for example, by removing the solvent under a stream of gas (e.g. , air, anhydrous gas, inert gas (e.g., nitrogen (N₂) gas), etc. Still further, passive drying techniques can be used such as simply exposing the gel to ambient conditions without the use of a gaseous stream. In this instance, the solvent in the gel is removed by evaporation and pore collapse is prevented by the aerogel network. The drying may also be assisted by heating or irradiating with electromagnetic radiation.

C. Hyperbranched Organically Modified POSS Polymer Aerogels

[0065] The aerogels of the present invention can have an open cell structure and can include at least two multi-functionalized POSS materials linked together through Ri. By way of example, multi-functionalized POSS material (IV) can polymerize with itself such that 1 to 8 POSS materials (IV) are added to an original POSS material (IV). Said another way, every Ri of the POSS material covalently bonds with another Ri of the same or different multi- functionalized POSS material to form a polymer having at least 2 to 9 or greater POSS materials. In some embodiments, the aerogel has a general formula of ([Ri— SiOi.s]n)a, where n is 6 to 12 and a is 2 to infinity or 2 to 2 x 10¹⁰⁰, or 2 x 10³⁵, or 2 x 10²⁵. In some embodiments, the hyperbranched POSS polymer aerogel can have a specific surface area of 0.15 m²/g to 1500 m²/g and higher, preferably 300 m²/g to 500 m²/g. The hyperbranched POSS polymer aerogel can have a haze value of 0.5 to 10, or greater than, equal to or between any two of 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, and 10, and/or a total percent light transmission of 10 to 99 greater than, equal to or between any two of 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, and 99 at 550 wavelength, as measured by ASTM D1003. In some instance, the hyperbranched POSS polymer aerogel is transparent, translucent or opaque. In a preferred embodiment, the hyperbranched POSS polymer aerogel is transparent. In certain instances, the aerogels of the present invention can have a thickness of 1 mm to 100 mm or 1 mm to 25 mm, or greater than, equal to, or between any two of 1 mm 10 mm, 15 mm, 20 mm, 25 mm, 30 mm, 35 mm, 40 mm, 45 mm, 50 mm, 55 mm, 60 mm, 65 mm, 70 mm, 75 mm, 80 mm, 85 mm, 90 mm, 95 mm and 100 mm, and still retain their transparent characteristics. The hyperbranched aerogel can have a degree of branching (DB) of between 0.5 and 0.95, preferably between 0.65 and 0.95, or greater than, equal to, or between 0.5, 0.55, 0.6, 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, and 0.95.

D. Articles of Manufacture

[0066] The open-cell aerogel of the present invention can be included in an article of manufacture. For example, an article of manufacture can include a hyperbranched organically modified POSS polymer matrix. In some embodiments, the article of manufacture is a thin film, monolith, wafer, blanket, core composite material, insulating material for residential and commercial windows, insulation material for transportation windows, insulation material for transparent light transmitting application, insulation material for translucent light transmitting application, insulation material for translucent lighting applications, insulation material for window glazing, core composite material, a substrate for radiofrequency antenna, substrate for a sunshield, a substrate for a sunshade, a substrate for radome, insulating material for oil and/or gas pipeline, insulating material for liquefied natural gas pipeline, insulating material for cryogenic fluid transfer pipeline, insulating material for apparel, insulating material for aerospace applications, insulating material for buildings, cars, and other human habitats, insulating material for automotive applications, insulation for radiators, insulation for ducting and ventilation, insulation for air conditioning, insulation for heating and refrigeration and mobile air conditioning units, insulation for coolers, insulation for packaging, insulation for consumer goods, vibration dampening, wire and cable insulation, insulation for medical devices, support for catalysts, support for drugs, pharmaceuticals, and/or drug delivery systems, aqueous filtration apparatus, oil-based filtration apparatus, and solvent-based filtration apparatus, or any combination thereof. 1. Fluid Filtration Applications

[0067] In some embodiments, the open-cell aerogel with a hyperbranched organically modified POSS polymer ("hyperbranched POSS aerogel") can be used in fluid filtration systems and apparatus. A feed fluid can be contacted with the hyperbranched POSS aerogel such that some, all or, substantially all, of the impurities and/or desired substances are removed from the feed fluid to produce a filtrate essentially devoid of the impurities and/or desired substances. The filtrate, impurities, and/or desired substances can be collected, stored, transported, recycled, or further processed. The hyperbranched POSS aerogel can be further processed to release the impurities and/or desired substances from the aerogel. [0068] The hyperbranched POSS aerogel described herein can be used in or with filtration apparatuses known in the art. Non-limiting examples of filtration apparatuses and applications include gas filters, building air filters, automotive cabin air filters, 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, pressure swing absorption apparatus, etc. Additional non- limiting examples of filtration apparatuses and 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, hemofiltration, hydraulic oil filtration, automotive oil filtration, or the like. Further, non-limiting examples of the purpose of filtration include sterilization, separation, purification, isolation, and the like.

[0069] A fluid for filtration ("feed") and a filtrate can be any fluid. The fluid can be a liquid, gas, supercritical fluid, or a mixture thereof. In some instances, the fluid can be aqueous, organic, non-organic, biological in origin, or a mixture thereof. In some instances, the fluid can contain solids and/or other fluids. As non-limiting examples, the fluid can be or can be partially water, blood, an oil, a solvent, air, or mixtures thereof. Water can include water, any form of steam and supercritical water.

[0070] In some instances, the fluid can contain impurities. Non-limiting examples of impurities include solids, liquids, gases, supercritical fluids, objects, compounds, and/or chemicals, etc. What is defined as an impurity may be different for the same feed fluid depending on the filtrate desired. In some embodiments, one or more aerogels can be used to remove impurities. Non-limiting examples of impurities in water can include ionic substances such as sodium, potassium, magnesium, calcium, fluoride, chloride, bromide, sulfate, sulfite, nitrate, nitrites, cationic surfactants, and anionic surfactants, metals, heavy metals, suspended, partially dissolved, or dissolved oils, organic solvents, nonionic surfactants, defoamants, chelating agents, microorganisms, particulate matter, and the like. Non-limiting examples of impurities in blood can 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 lightweight hydrocarbons, metals, sulfur, defoamants, and the like. Non-limiting examples of impurities in solvents can include water, particulate matter, metals, gases, and the like. Non-limiting impurities in air can include water, particulate matter, microorganisms, liquids, carbon monoxide, sulfur dioxide, and the like.

[0071] In some instances, the feed fluid can contain desired substances. Non-limiting examples of desired substances include solids, liquids, gases, supercritical fluids, objects, compounds, and/or chemicals, and the like. In some embodiments, one or more aerogels can be used to concentrate or capture a desired substance, or remove a fluid from a desired substance. Non-limiting examples of desired substances in water can include ionic substances such as sodium, potassium, magnesium, calcium, fluoride, chloride, bromide, sulfate, sulfite, nitrate, nitrites, cationic surfactants, and anionic surfactants, metals, heavy metals, suspended, partially dissolved, or dissolved oils, organic solvents, nonionic surfactants, chelating agents, microorganisms, particulate matter, etc. Non-limiting examples of desired substances in blood can include red blood cells, white blood cells, antibodies, lipids, proteins, and the like. Non- limiting examples of desired substances in oil can include hydrocarbons of a range of molecular weights, gases, metals, defoamants, and the like. Non-limiting examples of desired substances in solvents can include particulate matter, fluids, gases, proteins, lipids, and the like. Non-limiting examples of desired substances in air can include water, fluids, gases, particulate matter, and the like.

[0072] The hyperbranched POSS aerogel can be used to carry out a filtration of a fluid using an aerogel. A filtration system can include a separation zone. The materials, size, and shape of the separation zone can be determined using standard engineering practice to achieve the desired flow rates and contact time. The separation zone can be capable of holding or may be made of one or more aerogels or the present invention and includes at least one feed fluid inlet and/or at least one filtrate outlet. In some instances, the separation zone is made entirely of one or more hyperbranched POSS aerogel, or one or more hyperbranched POSS aerogel in, or around, a supporting structure. A feed fluid can be introduced to the separation zone through the inlet or through direct contact with the separation zone. In some embodiments, the feed fluid can be received under greater or reduced pressure than ambient pressure. Introduction of the feed fluid into the separation zone can be at a rate sufficient to allow optimum contact of the feed fluid with the one or more aerogels. Contact of the feed fluid with the hyperbranched POSS aerogel can allow the feed fluid to be filtered by the aerogel, which results in the filtrate, which can have less impurity and/or desired substance when compared with the original feed fluid. In certain aspects, the filtrate can be essentially free of the impurity and/or the desired substance. The filtrate can exit the separation zone via the outlet or through directly exiting the separation zone. In some instances, the filtrate can be recycled back to a separation zone, collected, stored in a storage unit, etc. In some instances, one or more hyperbranched POSS aerogels can be removed and/or replaced from the separation zone. In some instances, the filtrate can be collected and/or removed from the separation zone without the filtrate flowing through the outlet. In some instances, the impurities and/or desired substance can be removed from the separation zone. As one non-limiting example, the impurities and/or desired substances can be removed from the separation zone by flowing a fluid through the separation zone in the reverse direction from the flow of the feed fluid through the separation zone.

[0073] The filtration conditions in the separation zone can be varied to achieve a desired result {e.g., removal of substantially all of the impurities and/or desired substance from the feed fluid). The filtration conditions include temperature, pressure, fluid feed flow, filtrate flow, or any combination thereof. Filtration conditions are controlled, in some instances, to produce streams with specific properties. The separation zone can also include valves, thermocouples, controllers (automated 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 optimum contact of the feed fluid with the one or more aerogel. In some embodiments, computer simulations can be used to determine flow rates for separation zones of various dimensions and various aerogels.

[0074] The compatibility of the hyperbranched POSS aerogel with a fluid and/or filtration application can be determined by methods known in the art. Non-limiting properties of the hyperbranched POSS aerogel that can be determined to assess the compatibility of the aerogel include: the temperature and/or pressures that the aerogel melts, dissolves, oxidizes, reacts, degrades, or breaks; the solubility of the aerogel in the material that will contact the aerogel; the flow rate of the fluid through the aerogel; the retention rate of the impurity and/or desired product form the feed fluid; etc.

2. Radiofrequency (RF) Applications

[0075] Due to their low density, mechanical robustness, lightweight, and low dielectric properties, the hyperbranched POSS aerogels can be used in radiofrequency (RF) applications. The use of hyperbranched POSS aerogels in RF applications enables the design of thinner substrates, lighter weight substrates and smaller substrates. Non-limiting examples of radiofrequency applications include a substrate for a RF antenna, a sunshield for a RF antenna, a radome, or the like. Antennas can include flexible and/or rigid antennas, broadband planar- circuited antennas (e.g., a patch antennas, an e-shaped wideband patch antenna, an elliptically polarized circular patch antenna, a monopole antenna, a planar antenna with circular slots, a bow-tie antenna, an inverted-F antenna and the like). In the antenna design, the circuitry can be attached to a substrate that includes the hyperbranched POSS aerogel and/or a combination of the hyperbranched POSS aerogel and other components such as other polymeric materials including adhesives or polymer films, organic and inorganic fibers (e.g., polyester, polyamide, polyimide, carbon, glass fibers, or combinations thereof), other organic and inorganic materials including silica aerogels, polymer powder, glass reinforcement, etc. The use of hyperbranched POSS aerogels in antennas enables the design substrates with higher throughput. In addition, the hyperbranched POSS aerogels can have coefficient of linear thermal expansion (CTE) similar to aluminum and copper (e.g., CTE of about 23/K and about 17 ppm/K), and is tunable through choice of monomer to match CTE of other desirable materials. In some embodiments, the aerogel can be used in sunshields and/or sunscreens used to protect RF antennas from thermal cycles due to their temperature insensitivity and RF transparency. In certain embodiments, the aerogel can be used as a material in a radome application. A radome is a structural, weatherproof enclosure that protects a microwave (e.g., radar) antenna. Hyperbranched POSS aerogels can minimize signal loss due to their low dielectric constant, and can provide structural integrity due to their stiffness.

EXAMPLES

[0076] The present invention will be described in greater detail by way of specific examples. The following examples are offered for illustrative purposes only, and are not intended to limit the invention in any manner. Those of skill in the art will readily recognize a variety of noncritical parameters which can be changed or modified to yield essentially the same results.

Example 1

(Preparation of Hyperbranched POSS Aerogel)

[0077] The reaction vessel was charged with DMF, POSS structure (III) or structure (IV) ("POSS"), 2,2'-azobis(2-methylpropionate) (0.7%, AIBN) in a solvent to POSS ratio of 10- 30:70. After mixing for 2 minutes, agitation was stopped and the reaction vessel was heated to the desired temperature, in this example 70 °C. After 5-30 minutes, the solution had gelled and the gel was allowed to cool to room temperature. The gelled sample was collected and placed into an acetone bath. After immersion for 24 hours, the acetone bath was exchanged for fresh acetone. The soak and exchange process was repeated five times. After the final exchange, the gelled sample was removed and allowed to air dried under flowing air in a fume hood. FIGS. 1 A through II shows images of the cross-linked POSS aerogels of the present invention. Using 10 wt.% and 30 wt.% of the acrylate-POSS material in DMF solvent provided transparent cross- linked POSS aerogels (FIGS. 1A and IB). Using 10 wt.% of methacrylate-POSS in DMF provided a transparent cross-linked POSS aerogel (FIGS. IE and IF). Using 30 wt.% acrylate- POSS in acetophenone (ACP) provided translucent cross-linked POSS aerogels (FIG. 1C). Using 30 wt.%) of methacrylate-POSS in DMF or acetophenone provide translucent cross-linked POSS aerogels (FIGS. ID and 1G). Using 30 wt.% and acrylic-POSS in ACP, followed by a solvent exchange with acetone (5 times) provided a transparent cross-linked POSS aerogel having a surface area of 440 m²/g (FIG. 1H). Using 30 wt.%> and acrylic-POSS in DMF, followed by a solvent exchange with acetone (5 times) provided a transparent cross-linked POSS aerogel (FIG. II) having a specific surface area of 490 m²/g ± 19 as determined by BET, a BJH average pore diameter of 3.2 nm and a DFT pore volume of 0.34 cm³/g. Example 2

(Preparation of Hyperbranched POSS Copolymer Aerogel)

[0078] A solution of AIPN (0.7%) initiator was prepared in N-methyl-2-pyrrolidone ( MP) solvent. Methyacrylopolyhedral oligomeric silsesquioxane (MAPOSS, Hybrid Plastics,

Mississippi, USA) and 1,6-hexanediol diacrylate (HDD A, SigmaMillipore, USA) were mixed at 1 :2 molar ratio and dissolved in the AIBN/NMP solution to produce a monomer/solvent solution having a total monomer: solvent ratio of 30:70 with respect to mass. The above solution was sparged with argon gas for 30 minutes, and sealed. The solution was heated at 90 ^°C for 34 minutes, and the gel was allowed to cool to room temperature. The gelled sample was collected and placed into an acetone bath. After immersion for 24 hours, the acetone bath was exchanged for fresh acetone. The soak and exchange process was repeated four times. After the final exchange, the gelled sample was removed and allowed to air dry in a plastic jar with a 1/8" hole in the lid to produce a semitransparent aerogel having a specific surface area of 400 m²/g ± 3 m²/g as determined by Brunauer-Emmett-Teller (BET) surface area analysis and an average pore diameter of 4.2 nm as determined by Barrett- Joy ner-Halenda (BJH) analysis, and a pore volume of 0.33 cm³/g as determined by density functional theory (DFT) utilizing a Micromeritics Gemini VII 2390 Series Surface Area Analyzer.

Example 3

(Preparation of Hyperbranched POSS Copolymer Aerogel with Chain Transfer Agent)

[0079] A solution of AIBN (0.7%) initiator was prepared with NMP as solvent. MAPOSS, HDDA were mixed at 1 : 1 molar ratio and dissolved in the AIBN/NMP solution to produce a monomer/solvent solution having a total monomer: solvent ratio of 30:70 with respect to mass. To the above solution, 1-decanethiol (31.00 mg, SigmaMillipore, USA) was added, and the solution was sparged with argon gas for 30 minutes, and sealed. The solution was heated at 90 °C for 34 minutes, and allowed to cool to room temperature (20 to 35 °C). The gelled sample was collected and placed into an acetone bath. After immersion for 24 hours, the acetone bath was exchanged for fresh acetone. The soak and exchange process was repeated four times. The gelled sample was removed and allowed to air dry in a plastic jar with a 1/8" hole in the lid to produce a semitransparent aerogel. The aerogel had a specific surface area of 380 m²/g ± 3 m²/g as determined by Brunauer-Emmett-Teller (BET) surface area analysis and an average pore diameter of 3.6 nm as determined by Barrett- Joy ner-Halenda (BJH) analysis, and a pore volume of 0.273 cmVg as determined by density functional theory (DFT) utilizing a Micromeritics Gemini VII 2390 Series Surface Area Analyzer.

Example 4

(Preparation of Hyperbranched POSS Copolymer Aerogel with Multifunctional Chain

Transfer Material)

[0080] A solution of AIBN (0.7%) initiator was prepared with MP as solvent. MAPOSS,

HDDA were mixed at 1 : 1 molar ratio and dissolved in the AIBN/NMP solution to produce a monomer/solvent solution having a total monomer: solvent ratio of 30:70 with respect to mass. .

To the above solution, a multifunctional chain transfer material, pentaerythritol tetrakis(3- mercaptopropionate) (22.40 mg, SigmaMillipore, USA) was added, and the solution was sparged with argon gas for 30 minutes, and sealed. The solution was heated at 90 °C for 34 minutes, and allowed to cool to room temperature (20 to 35 °C). The gelled sample was collected and placed into an acetone bath. After immersion for 24 hours, the acetone bath was exchanged for fresh acetone. The soak and exchange process was repeated four times. The gelled sample was removed and allowed to dry in a plastic jar with a 1/8" hole in the lid to produce a semitransparent aerogel. The recovered aerogel had a specific surface area of 470 m²/g ± 3 m²/g as determined by Brunauer-Emmett-Teller (BET) surface area analysis and an average pore diameter of 3.8 nm as determined by Barrett- Joy ner-Halenda (BJH) analysis, and a pore volume of 0.330 cm³/g as determined by density functional theory (DFT) utilizing a Micromeritics Gemini VII 2390 Series Surface Area Analyzer.

Example 5

(Preparation of Hyperbranched POSS Copolymer Aerogel with THF Solvent Exchange)

[0081] A solution of AIBN (0.7%) initiator was prepared with NMP as solvent. MAPOSS was dissolved in the AIBN/NMP solution to produce a monomer/solvent solution having a total monomer: solvent ratio of 30:70 with respect to mass. Above solution was sparged with argon gas for 30 minutes, and sealed. The solution was heated at 90 °C for 34 minutes, and allowed to cool to room temperature (20 to 35 °C). The gelled sample was collected and placed into a THF bath. After immersion for 24 hours, the THF bath was exchanged for fresh THF. After immersion for 24 hours, the THF bath was exchanged for hexanes. After immersion for 24 hours, the hexanes bath was exchanged for fresh hexanes. The soak and exchange process was repeated five times. The gelled sample was removed and allowed to dry in a plastic jar with a 1/8" hole in the lid to produce a semitransparent aerogel. The recovered aerogel had a specific surface area of 250 m²/g ± 3 m²/g as determined by Brunauer-Emmett-Teller (BET) surface area analysis and an average pore diameter of 3.3 nm as determined by Barrett-Joyner-Halenda (BJH) analysis, and a pore volume of 0.17 cm³/g as determined by density functional theory (DFT) utilizing a Micromeritics Gemini VII 2390 Series Surface Area Analyzer.

Example 6

(Preparation of Hyperbranched POSS Copolymer Aerogel with Chain Transfer Material without Solvent Exchange)

[0082] A solution of AIBN (0.7%) initiator was prepared in xylene as solvent. MAPOSS, HDDA were mixed at 1 : 1 molar ratio and dissolved in the AIBN/xylene solution to produce a monomer/solvent solution having a total monomer: solvent ratio of 30:70 with respect to mass. To the above solution 1-decanethiol (27.00 mg, SigmaMillipore, USA) was added. This solution was sparged with argon gas for 30 minutes, and sealed. The solution was heated at 90 °C for 60 minutes. The polymer gel was dried in air via evaporation to produce a transparent aerogel having a specific surface area of 160 m²/g ± 3 m²/g as determined by Brunauer-Emmett- Teller (BET) surface area analysis and an average pore diameter of 4.0 nm as determined by Barrett-Joyner-Halenda (BJH) analysis, and a pore volume of 0.130 cm³/g as determined by density functional theory (DFT) utilizing a Micromeritics Gemini VII 2390 Series Surface Area Analyzer.

Example 7

(Preparation of Hyperbranched POSS Copolymer Aerogel with a Multifunctional Chain

Transfer Material without Solvent Exchange)

[0083] A solution of AIBN (0.7%) initiator was prepared in xylene as solvent. MAPOSS and HDDA were mixed at 1 : 1 molar ratio and dissolved in the AIBN/xylene solution to produce a monomer/solvent solution having a total monomer: solvent ratio of 30:70 with respect to mass.

To the above solution, the multifunctional chain transfer material pentaerythritol tetrakis(3- mercaptopropionate) (20.00 mg) was added, sparged with argon gas for 30 minutes, and sealed.

The solution was heated at 90 °C for 58 minutes. The polymer gel was dried in air via evaporation to produce a transparent aerogel having a specific surface area of 300 m²/g ± 3 m²/g as determined by Brunauer-Emmett-Teller (BET) surface area analysis and an average pore diameter of 4.8 nm as determined by Barrett- Joy ner-Halenda (BJH) analysis, and a pore volume of 0.314 cm³/g as determined by density functional theory (DFT) utilizing a Micromeritics Gemini VII 2390 Series Surface Area Analyzer.

Example 8

(Preparation of Hyperbranched POSS Terpolymer Aerogel with a Monofunctional Chain

Transfer Material with Solvent Exchange)

[0084] A solution of AIBN (0.65%) initiator was prepared in N-methyl-2-pyrrolidone ( MP) solvent. Methyacrylopolyhedral oligomeric silsesquioxane (MAPOSS, Hybrid Plastics, Mississippi, USA), dipentaerythritol pentaacrylate (SR 399 LV, Sartomer Arkema Group, USA) and 1,6-hexanediol diacrylate (HDD A, SigmaMillipore, USA) were mixed at 1 : 1 :0.25 molar ratio and dissolved in the AIBN/NMP solution to produce a monomer/solvent solution having a total monomer: solvent ratio of 30:70 with respect to mass. To the above solution, the monofunctional chain transfer material 1-decanethiol (44.00 mg, 0.25 mM, SigmaMillipore, USA) was added, and the solution was sparged with argon gas for 30 minutes, and sealed. The solution was heated at 90 ^°C for 34 minutes, and the gel was allowed to cool to room temperature. The gelled sample was collected and placed into an acetone bath. After immersion for 24 hours, the acetone bath was exchanged for fresh acetone. The soak and exchange process was repeated four times. After the final exchange, the gelled sample was removed and allowed to air dry to produce a transparent aerogel having a specific surface area of 184 m²/g ± 3 m²/g as determined by Brunauer-Emmett-Teller (BET) surface area analysis and an average pore diameter of 2.8 nm as determined by Barrett- Joy ner-Halenda (BJH) analysis, and a pore volume of 0.10 cm³/g as determined by density functional theory (DFT) utilizing a Micromeritics Gemini VII 2390 Series Surface Area Analyzer.

[0085] Although embodiments 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 embodiments as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the above disclosure, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein can be utilized. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.

Claims

A hyperbranched polyhedral oligomeric silsesquioxane (POSS) polymer aerogel comprising an open-cell structured POSS polymer matrix of an organically modified POSS polymer.

The hyperbranched POSS polymer aerogel of claim 1, wherein the organically modified POSS polymer is derived from an organically modified multi-functionalized POSS material of:

where:

Ri is an organic linker group comprising a C2 to C10 acrylate group, a C2 to C10 vinyl group, or a C2 to C10 epoxide group; and n is 6 to 12.

The hyperbranched POSS polymer aerogel of claim 2, wherein the multi- functionalized POSS material is:

The hyperbranched POSS polymer aerogel of claim 2, wherein the functionalized POSS monomer is:

5. The hyperbranched POSS polymer aerogel of claim 2, wherein the functionalized POSS monomer is:

6. The hyperbranched POSS polymer aerogel of claim 2, wherein the functionalized POSS monomer is:

7. The hyperbranched POSS polymer aerogel claim 1, wherein organic POSS polymer is derived from a polymerizable organic monomer and a functionalized POSS monomer of:

where: Ri is organic linker group comprising a C2 to C10 acrylate group, a C2 to C10 vinyl group, or a C2 to C10 epoxide group; and n is 6 to 12.

8. The hyperbranched POSS polymer aerogel of claim 1 having a specific surface area of 0.15 m²/g to 1500 m²/g, preferably 300 m²/g to 500 m²/g.

9. The hyperbranched POSS polymer aerogel of claim 1, having mesopores and optional micropores, and/or optional macropores.

10. The hyperbranched POSS polymer aerogel of claim 9, wherein the pores have an average pore size of 2 to 15 nm. 11. The hyperbranched POSS polymer aerogel of claim 1, having a haze value of 0.5 to 10 as measured by ASTM D1003.

12. The hyperbranched POSS polymer aerogel of claim 1, having a total percent light transmission of 10 to 99 at 550 wavelength as measured by ASTM D1003.

13. The hyperbranched POSS polymer aerogel of claim 1, wherein the aerogel is transparent.

14. The hyperbranched POSS polymer aerogel of claim 1, wherein the aerogel is translucent.

15. The hyperbranched POSS polymer aerogel of claim 1, wherein the aerogel is opaque.

16. A method to produce a hyperbranched POSS polymer aerogel, the method comprising: obtaining a solution comprising a solvent, a radical initiating agent, a multi- functionalized polyhedral oligomeric silsesquioxane (POSS) material comprising an organic linker group, and optionally a polymerizable organic compound; subjecting the solution to conditions suitable to form a hyperbranched organically modified POSS polymer matrix gel; and subjecting the organically modified POSS polymer matrix gel to conditions suitable to form the hyperbranched POSS aerogel.

17. The method of claim 16, wherein subjecting the polymer matrix solution to conditions sufficient to form the polymer matrix comprises adding a sufficient amount of a promoter material and/or a chain transfer material.

18. The method of claim 16, wherein step (b) comprises a temperature of 15 °C to 120 °C, or 65 °C to 75 °C form the gel.

19. The method of clam 16, wherein step (c) comprises subjecting the gel to a drying step to remove a portion of the solvent.

20. The method of claim 19, wherein the drying step is supercritical drying, subcritical drying, thermal drying, evaporative drying, ambient drying, or any combination thereof.

21. The method of claim 20, wherein the drying step is evaporative drying.

22. The method of claim 20, wherein the drying step is ambient drying without the use of a gaseous stream.

23. The method of claim 20, wherein the drying step comprises heating the gel to a temperature of 15 °C to 50 °C, preferably 20 °C to 30 °C.

24. The method of claim 16, wherein step (c) comprises:

(i) subjecting the gel to conditions sufficient to freeze the solvent to form a frozen material; and

(ii) subjecting the frozen material to a subcritical drying step sufficient to form the aerogel.

25. The method of claim 16, further comprising subjecting the gel formed in step (b) to at least one solvent exchange to replace the solvent with a second solvent prior to performing step (c).

26. The method of claim 25, wherein at least one solvent exchange is performed with acetone, tetrahydrofuran, toluene, xylene, hexane, heptane, a methyl siloxane containing material, a hexamethyldisiloxane containing material, a mixture of fluorocarbon and trans- 1,2-dichloroethylene, or combinations thereof.

27. The method of claim 16, wherein no solvent exchange is performed.

28. The method of claim 16, wherein the solution comprises at least 5 wt.% to up to 55 wt.% of organically modified multi-functionalized POSS material, preferably 15 wt.% to 35 wt.%.

29. The method of claim 16, wherein the organically modified multi-functionalized POSS material has the general formula of is [Ri— SiOi.s]«, where Ri is an organic linker group having at least 2 carbon atoms and is capable of undergoing a chemical reaction, and n is 6 to 12.

30. The method of claim 29, wherein Ri is an organic linker group comprising a C2 to C10 acrylate group, a C2 to C10 vinyl group, or a C2 to C10 epoxide group.

31. The method of claim 29, wherein the organically modified multi-functionalized POSS material is:

The method of claim 29, wherein the organically modified functionalized POSS monomer is:

The method of claim 29, wherein the organically modified functionalized POSS material is:

The method of claim 29, wherein the organically modified functionalized POSS material has the general structure of:

The method of claim 16, wherein the solvent comprises dimethylformamide, tetrahydrofuran, acetophenone or blends thereof.

An article of manufacture comprising the hyperbranched POSS polymer aerogel of claim 1.

The article of manufacture of claim 36, wherein the article of manufacture is a thin film, monolith, wafer, blanket, core composite material, insulating material for residential and commercial windows, insulation material for transportation windows, insulation material for transparent light transmitting application, insulation material for translucent light transmitting application, insulation material for translucent lighting applications, insulation material for window glazing, core composite material, a substrate for radiofrequency antenna, substrate for a sunshield, a substrate for a sunshade, a substrate for radome, insulating material for oil and/or gas pipeline, insulating material for liquefied natural gas pipeline, insulating material for cryogenic fluid transfer pipeline, insulating material for apparel, insulating material for aerospace applications, insulating material for buildings, cars, and other human habitats, insulating material for automotive applications, insulation for radiators, insulation for ducting and ventilation, insulation for air conditioning, insulation for heating and refrigeration and mobile air conditioning units, insulation for coolers, insulation for packaging, insulation for consumer goods, vibration dampening, wire and cable insulation, insulation for medical devices, support for catalysts, support for drugs, pharmaceuticals, and/or drug delivery systems, aqueous filtration apparatus, oil-based filtration apparatus, and solvent-based filtration apparatus, or any combination thereof.