WO2020247743A2

WO2020247743A2 - Aerogels having a core-spoke polymeric matrix, methods of making, and uses thereof

Info

Publication number: WO2020247743A2
Application number: PCT/US2020/036313
Authority: WO
Inventors: David J. Irvin; Garrett D. Poe; Muhammad Ejaz; Marisa SNAPP-LEO
Original assignee: Blueshift Materials, Inc.
Priority date: 2019-06-06
Filing date: 2020-06-05
Publication date: 2020-12-10
Also published as: WO2020247743A3

Abstract

A hyperbranched organic aerogel, and methods for making and using the same, are disclosed. The aerogel can include a core/flexible spoke type structure. The aerogel can include flexible spokes that can include 3 to 8 flexible hydrocarbon-containing materials bonded to a core material. The core and flexible hydrocarbon-containing spacer material can include 1 to 3 A-X functional groups, where A is silicon (Si), phosphorous (P), or sulfur (S), and X is oxygen (O) or nitrogen (N).

Description

AEROGELS HAVING A CORE-SPOKE POLYMERIC MATRIX, METHODS OF

MAKING, AND USES THEREOF

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims benefit to U.S. Provisional Patent Application No. 62/858,180 filed June 6, 2019, which is incorporated herein by reference in its entirety.

BACKGROUND OF THE INVENTION

A. Field of the Invention

[0002] The invention generally concerns hyperbranched polymer aerogels that have a core/spoke structure. In particular, the invention concerns hyperbranched polymer aerogels that include a core bound to 3 to 8 flexible hydrocarbon spacers. The core, flexible hydrocarbon spacers, or both, can include 1 to 3 A-X functional groups, where A is silicon (Si), phosphorous (P), or sulfur (S), and X is oxygen (O) or nitrogen (N).

B. Description of Related Art

[0003] A gel 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.

[0004] By comparison, a gel that dries and exhibits little or no shrinkage and no 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 therefore have low mechanical strength. This limits their use in applications where transparency is desired.

[0005] Efforts to improve the mechanic strength of these silica aerogels have largely focused on the use of organic polymers (e.g., polyurethane or silica/polyurethane 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

[0006] A discovery has been made that provides a solution to at least some of the aforementioned problems associated with attempts to make transparent organic aerogels. The discovery is focused on core/spoke structured hyperbranched aerogels that do not have a cage-like structure (e.g., do not have a polyoctahedral silsesquioxane like structure). The combination of the hyperbranched aerogel structure and the pore sizes can allow the transparency and toughness (e.g., a compression strength of at least 1 MPa) to be tuned to fit desired applications. By way of example, hyperbranched polymer aerogels of the present invention can be designed to be transparent, translucent, or opaque, and exhibit toughness.

[0007] In a particular aspect of the invention, the aerogel can include a hyperbranched polymer matrix that includes a core bound to 3 to 8 flexible hydrocarbon-containing spacers. In this way, the structure of the aerogel polymer matrix can resemble a hub (i.e., core) that has spokes (e.g., flexible spacers) extending from the hub. The core and/or flexible hydrocarbon-containing spacers can have 1 to 3 A-X functional groups where A is silicon (Si), phosphorous (P), or sulfur (S), and X is oxygen (O) or nitrogen (N). The flexible spacer can include an aliphatic group, a substituted aliphatic group having 2 to 20 carbon atoms, or an aromatic group having 2 to 20 carbon atoms. The hyperbranched polymer aerogel of the present invention can have a haze value of 0.1 to 25, 0.3 to 25, or 0.5 to 25, and/or a total percent light transmission of 1 to 99, 5 to 99, or 10 to 99, at a 550 wavelength as measured using known methodology (e.g., ASTM D1003). In some aspects of the present invention, the core can be rigid.

[0008] 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 optionally macropores (pores having a size of greater than 50 nm). In some instances, the average pore size of the porous aerogel matrices of the present invention can be less than 50 nm in diameter, preferably 1 nm to 50 nm in diameter. Additionally, 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 aforementioned hyperbranched polymer core/spoke structure is believed to contribute to the improved transparency, mechanical, thermal, manufacturability, and/or recyclability properties of the aerogels of the present invention.

[0009] In some aspects of the present invention, the core can have the general formula of [Ri-A-

X-A-R₂], where R¹ and R² are each independently, an aliphatic group, a substituted aliphatic group, an aromatic group, a substituted aromatic group, or a carbon based polymer; A can be Si, P, or S; and X is O or N. In another aspect, the core can have a formula of [(Ri)(R₂)(R₃)-[A-X-A]_n] where: Ri, R₂, and R₃ can each be independently, an aliphatic group, a substituted aliphatic group, an aromatic group, a substituted aromatic group, and at least one of Ri, R₂, and R₃ is bound to the flexible spacer; A can be Si, P, or S; and X is O or N; and n is 1 to 8, preferably 3. In certain aspects, Ri and R₂, Ri and R₃, or R₂ and R₃, are aliphatic groups. In a preferred aspect, A is Si and X is O or N. In some aspects, the core can have a structure of:

where a, b, and c are each independently 0 to 10, Ri, R₂, and R₃ are each independently methyl, ethyl, or propyl, and X is O or N, and

represents the bond to the core. In a preferred aspect, the core can have the structure

represents the bond to the core. In another aspect of the present invention, the core can have a structure of

can be an aliphatic group, preferably methyl or ethyl, and

represents the bond to the core. In yet another aspect of the present invention, the core can have a structure of

bond to the spacer.

[0010] Flexible hydrocarbon-containing spacers of the present invention can include carbon and/or heteroatoms (e.g., Si, O, S, N, and the like). In some aspects, the flexible hydrocarbon- containing spacer can include a substituted aromatic group, an aliphatic hydrocarbon chain, an ester, a substituted ester, an ether, a polyether, a polyester, a silane, a polysilane, a siloxane, a polysiloxane, or any combination thereof. In one aspect, the flexible hydrocarbon containing spacer can have the structure of:

can include CH2, Si, O, S, N, or P, and w is 1 to 20, preferably 4 to 7, or 6, and

represents the bond to the core. In some aspects, Y can be a linear hydrocarbon chain, a branched hydrocarbon chain, a multi-branched hydrocarbon chain, an ethylene oxide chain, a silicone based linker, a sulfide based linker, a sulfoxide based linker, a sulfone based linker, an amine based linker, a phosphorous based linker, or combinations thereof. Non-limiting examples of a linear hydrocarbon chain include -CH2-, -C2H4-, -C3H6-, - C4H8-, -C5H10-, {etc.). Non limiting examples of a branched hydrocarbon chain include -(C2H3-)- CH3, -(C₃H₅-)-CH₃, -(C₄H₇-)-CH₃, -(C₂H₃-)-Rl, -(C₃H₅-)-Rl, where R1 is a linear or branched hydrocarbon chain from 1-10 carbons including but not limited to 2-propyl, 2-butyl, 2-pentyl, 3- pentyl, 2-hexyl, 3-hexyl, 2-heptyl, 3-heptal, 4-heptyl. Non limiting examples of a multi-branched hydrocarbon chain include -(C2H2-)-(CH₃,)2, -(C₃H4-)-(CH₃,)2, -(C4H6-)-(CH₃,)2. Non-limiting examples of an ethylene oxide chain include -(CH2-CH2-O)-, -(CH₂-CH₂-0)₂-,-(CH₂-CH₂-0)₃-,- (CH₂-CH₂-0)₄- and/or -(Ct -Ct -C s-. Non-limiting examples of a silicone-based linker include - (Si(-CH₃)2-0-Si(-CH₃)₂)-, -(Si(-CH₃)2-0-Si(-CH₃)₂)2-, -(Si(-CH₃)2-0-Si(-CH₃)₂)₃-, -(Si(-C₆H₅)₂-0-

Si(-C₆H₅)₂)-, -(Si(-C₆H5)2-0-Si(-C₆H5)2)2-, -(Si(-CH₃)(-C6H5)-0-Si(-CH₃)(-C₆H5)-)-, -(Si(-CH₃)(- C₆H5)-0-Si(-CH₃)(-C6H₅)-)2-, -(Si(-CH₃)(-C6H5)-0-Si(-CH₃)(-C6H₅)-)₃-. Non-limiting examples of a sulfide based linker include -(CH₂-CH₂-S=0)-, -(CH₂-CH₂-S=0)₂-,-(CH₂-CH₂-S=0)₃-,-(CH₂- CH₂-S=0)₄-. Non-limiting examples of a sulfoxide based linker include -(CH₂-CH₂-S=0)-, -(CH2- CH2-S=0)2-,-(CH2-CH2-S=0)₃-,-(CH2-CH2-S=0)4-. Non-limiting examples of a sulfone based linker include -(CH₂-CH₂-S(=0)₂)-, -(CH₂-CH2-S(=0)2)2-,-(CH2-CH2-S(=0)2)₃-,-(CH2-CH₂-

S (=0)2)4-· Non-limiting examples of an amine based linker include -(CH₂-CH₂-N(-R1))-, -(CH2- CH₂-N(-R1))2-,-(CH2-CH2-N(-R1))₃-,-(CH2-CH₂- N(-R1))₄-, where R1 is a linear or branched hydrocarbon chain from 1-10 carbons including but not limited to 2-propyl, 2-butyl, 2-pentyl, 3- pentyl, 2-hexyl, 3-hexyl, 2-heptyl, 3-heptal, 4-heptyl, (etc.), a multi-branched hydrocarbon chain - (C2H2-)-(CH₃,)2, -(C₃H₄-)-(CH₃,)₂, -(C4H6-)-(CH₃,)2. Non-limiting examples of a phosphorous based linker include -(0=P(-CH₃))-, -(0=P(-C6H₅)- , -(CH₂-CH₂-0-(0=P(CH₃)-0-CH₂-CH₂)-,-

(C₆H4-0-(0=P(CH₃)-0-C6H₄-)-, -(CH₂-CH2-0-(0=P(C6H5)-0-CH2-CH₂)-, -(C6H4-0-(0=P(C₆H₅)-

O-C6H4-)-. Combinations of such linkers can also be used, non-limiting examples of which can include -(CH2-CH2-SMCH2-CH2-O)-, -(CH2-CH2-OMCH2-CH2-SMCH2-CH2-O)-, or -(CH2-CH2- 0)-(CH₂-CH₂-S)₂-(CH₂-CH₂-0). In some embodiments, the flexible hydrocarbon-containing spacer can have the structure

can each be independently an aliphatic group or an aromatic group, preferably methyl, ethyl, or phenyl, and

represents the bond to the core. In some aspects, structures (I), (II), and (III) can be used as flexible spacers with

representing the bond to the core.

[0011] In another aspect of the present invention, methods to produce a hyperbranched polymer aerogel of the present invention include subjection a solution that includes a solvent, gel forming agent, a core precursor material, and a spoke precursor material to conditions suitable to form a hyperbranched organic polymer matrix gel; and (b) subjecting the organically modified organic polymer matrix gel to conditions suitable to form the hyperbranched organic polymer aerogel of the present invention. The core precursor material, the spoke, or both can include at least one A-X functional group, where A is silicon (Si), phosphorous (P), or sulfur (S) and X is X is oxygen (O) or nitrogen (N). In some embodiments, the core does not include a caged or cage-like structure (e.g., does not include a polyoctahedral silsesquioxane like structure, adamantane like structure, dicyclopentadiene like structure, norbomene like structure). In other instances, however, the core can include a caged or cage-like structure (e.g., polyoctahedral silsesquioxane like structure, adamantane like structure, dicyclopentadiene like structure, norbornene like structure). Conditions of step (a) can include a temperature of -50 °C to 120 °C, -25 °C to 120 °C, 0 °C to 120 °C, 15 °C to 120 °C, or 65 °C to 95 °C form the gel. Step (b) of the method can include subjecting the organically modified organic polymer matrix gel to conditions suitable to form the hyperbranched organic polymer aerogel of the present invention. Conditions of step (a) and/or step (b) can include adding a sufficient amount of a promoter material and/or a chain transfer material and/or subjecting the gel to a drying step to remove a portion of the solvent. The drying step can include supercritical drying, subcritical drying, thermal drying, evaporative drying, ambient drying, or any combination thereof. In some aspects, the drying step can include evaporative drying. In another aspect, the drying step can include ambient drying without the use of a gaseous stream. In yet another aspect, the drying can include heating the gel to a temperature of 15 °C to 50 °C, preferably 20 °C to 30 °C. Step (b) can also include (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. In some embodiments, the dried gel can be heated under vacuum at 20 to 90 °C, preferably 60 to 80 °C, or any range or value there between for a period of time (e.g., 1 to 80 hours, or any range or value there between). In some embodiments, in step (a) the precursors to the core and the flexible hydrocarbon spacer of the aerogels can be the same material (e.g., 1,3,5-trivinyl- 1,3,5-trimethylcyclotrisiloxane (TVMS) or dimethoxymethylvinylsilane) and can be polymerized under solvent radical conditions under an inert gas atmosphere. In these instances, the conditions for step (a) can include a monomer to solvent ratio of 50:50, 40:60, 35:65, 30:70, 25:75, 20:80, 15:85, 10:90, or 5:95, or any range or value there between. The solution can be heated at 110 to 130 °C, or 115 to 125 °C or about 120 °C for a desired amount of time (e.g., about 20 hours) to form a hard transparent gel. The gelled sample can be processed a described in step (b) above.

[0012] In some aspects, the gel formed in step (a) can be subjected to at least one solvent exchange to replace the solvent with a second solvent prior to performing step (b). At least one solvent exchange can be performed with acetone, tetrahydrofuran, toluene, xylene, hexane, heptane, methanol, ethanol, isopropanol, a methyl siloxane containing material, a hexamethyldisiloxane containing material, a mixture of fluorocarbon and trans-l,2-dichloroethylene, or combinations thereof. In some embodiments, no solvent exchange is performed.

[0013] In certain aspects of the present invention, the core precursor material, or the flexible spacer silicon precursor material, can have the structure:

where a, b, and c are each independently 0 to 10, Ri, R2, and R3 are each independently methyl, ethyl, or propyl, and X is O or N. By way of example, the core precursor material or a flexible hydrocarbon spacer precursor material can have the structure:

[0014] In another aspect of the present invention, the core precursor material or hydrocarbon flexible spacer can have the structure of:

[0015] The flexible hydrocarbon precursor material can include alpha-olefins, preferably, ethylene propylene, or alpha-olefins have 2 to 20 carbons, dienes, vinyl aromatic monomers, preferably styrene, vinyl toluene, t-butyl styrene, di-vinyl benzene, vinyl acetates, and all isomers or derivatives of these compounds, acrylates preferably, methacrylate, methylmethacrylate, hexane diol diacrylate, unsaturated polyesters, epoxides, preferably glycidyl compounds, siloxane compounds, silane compounds, divinyldimethyl silane, and any combination thereof.

[0016] In another aspect of the present invention, articles of manufacture that include the hyperbranched 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.

[0017] In the present invention 53 embodiments are described. Embodiment 1 is hyperbranched polymer aerogel comprising a core bound to 3 to 8 flexible hydrocarbon-containing spacers, wherein the core, flexible hydrocarbon-containing spacers, or both, comprise 1 to 3 A-X functional groups, where A is silicon (Si), phosphorous (P), or sulfur (S) and X is oxygen (O) or nitrogen (N). Embodiment 2 is the hyperbranched polymer aerogel of embodiment 1, wherein the core does not include a caged or cage-like structure. Embodiment 3 is the hyperbranched polymer aerogel of embodiment 2, wherein the core does not include a polyoctahedral silsesquioxane like structure, an adamantane like structure, a dicyclopentadiene like structure, or a norbornene like structure. Embodiment 4 is the hyperbranched polymer aerogel of any one of embodiments 1 to 3, wherein in the flexible spacer is an aliphatic group, a substituted aliphatic group having 2 to 20 carbon atoms, or an aromatic group having 2 to 20 carbon atoms. Embodiment 5 is the hyperbranched polymer aerogel of any one of embodiments 1 to 4, wherein the aerogel has a compression strength of at least 1 or at least 5 MPa. Embodiment 6 is the hyperbranched polymer aerogel of any one of embodiments 1 to 5, having mesopores and optional micropores, and/or optional macropores. Embodiment 7 is the hyperbranched polymer aerogel of embodiment 6, wherein the mesopores have an average pore size of less than 50 nm, preferably 2 to 50 nm. Embodiment 8 is the hyperbranched polymer aerogel of embodiment 1, having a haze value of 0.5 to 25 as measured by ASTM D1003. Embodiment 9 is the hyperbranched polymer aerogel of any one of embodiments 1 to 8, having a total percent light transmission of 10 to 99 at 550 wavelength as measured by ASTM D1003. Embodiment 10 is the hyperbranched polymer aerogel of embodiment 1, wherein the aerogel is transparent. Embodiment 11 is the hyperbranched polymer aerogel of embodiment 1, wherein the aerogel is translucent. Embodiment 12 is the hyperbranched polymer aerogel of embodiment 1, wherein the aerogel is opaque. Embodiment 13 is the hyperbranched polymer aerogel of embodiment 1, wherein the core has a formula of [R1-A-X-A-R2], where: R¹ and R² are each independently, an aliphatic group, a substituted aliphatic group, an aromatic group, a substituted aromatic group, or a carbon based polymer; A is silicon (Si), phosphorous (P), or sulfur (S); and X is oxygen (O) or nitrogen (N), wherein Ri and R2 are bound to the flexible hydrocarbon- containing spacer. Embodiment 14 is the hyperbranched polymer aerogel of embodiment 1, wherein the core has a formula of: [(Ri)(R2)(R3)-[A-X-A]_n] where: Ri, R2, and R3 are each independently, an aliphatic group, a substituted aliphatic group, an aromatic group, a substituted aromatic group, and at least one of Ri, R2, and R3 is bound to the flexible spacer; A is silicon (Si), phosphorous (P), or sulfur (S); X is oxygen (O) or nitrogen (N); and n is 1 to 8. Embodiment 15 is the aerogel of embodiment 14, wherein Ri and R2, Ri and R3, or R2 and R3, are aliphatic groups. Embodiment 16 is the aerogel of any one of embodiments 14 to 15, wherein A is Si. Embodiment 17 is the aerogel of any embodiment 16, wherein X is O or N. Embodiment 18 is the aerogel of any one of embodiments 14 to 17, wherein n is 3. Embodiment 19 is the aerogel of embodiment 18, wherein the core has the structure:

where a, b, and c are each independently 0 to 10, Ri, R2, and R3 are each independently methyl, ethyl, or propyl, and X is O or N, and

represents the bond to the flexible hydrocarbon- containing spacer. Embodiment 20 is the aerogel of embodiment 19, wherein the core has the structure:

represents the bond to the flexible hydrocarbon- containing spacer. Embodiment 21 is the aerogel of embodiment 1, wherein the core has a structure of:

are an aliphatic group, preferably methyl or ethyl, and

represents the bond to the flexible hydrocarbon-containing spacer, preferably having at least three extended chains. Embodiment 22 is the aerogel of embodiment 1, wherein the core has the structure of:

represents the bond to the flexible hydrocarbon-containing spacer. Embodiment 23 is the aerogel of any one of embodiments 1 to 22, wherein the flexible hydrocarbon-containing spacer comprises a substituted aromatic group, an aliphatic hydrocarbon chain, an ester, a substituted ester, an ether, a polyether, a polyester, a silane, a polysilane, a siloxane, a polysiloxane, a thiol, or any combination thereof. Embodiment 24 is the aerogel of embodiment 23, wherein the flexible hydrocarbon-containing spacer has the structure of

(V) where Y comprises CH2, Si, O, S, N, or combinations thereof and w is 1 to 20, preferably 4 to 7, or 6, and

represents the bond to the core. Embodiment 25 is the aerogel of embodiment 23, wherein the flexible hydrocarbon- containing spacer has the structure of

are each independently an aliphatic group or an aromatic group, preferably methyl, ethyl, or phenyl, and

represents the bond to the core. Embodiment 26 is the aerogel of any one of embodiments 1 to 25, wherein the core is rigid.

[0018] Embodiment 27 is a hyperbranched polymer aerogel comprising a polyoctahedral silsesquioxane (POSS) core bound to a flexible hydrocarbon spacer comprising an ester functional group and a silicon containing group. Embodiment 28 is the hyperbranched polymer aerogel of embodiment 27, wherein the ester functional group is positioned between the POSS core and the silicon containing group. Embodiment 29 is the hyperbranched polymer aerogel of embodiment 28, wherein 3 to 4 aliphatic groups separate the POSS core and the ester functional group. Embodiment 30 is the hyperbranched polymer aerogel of any one of embodiments 27 to 29, wherein the silicon containing group has structure of compounds (I) or (II) bound to the ester functional group. Embodiment 31 is the hyperbranched polymer aerogel of any one of embodiments 27 to 30, wherein the silicon containing flexible hydrocarbon spacer comprises three methyl groups. Embodiment 32 is the hyperbranched polymer aerogel of any one of embodiments 27 to 31, wherein the POSS cage further comprises a flexible spacer comprising a second ester functionality, the second ester functionality having the structure of compound (IV) bound to the ester functional group of the core or the silane containing group.

[0019] Embodiment 33 describes a method to produce a hyperbranched organic polymer aerogel of any one of embodiments 1 to 32, the method comprising: (a)(i) subjecting a solution comprising a solvent, a gel forming agent, a core precursor material, and a flexible spacer precursor material to conditions suitable to form a hyperbranched organic polymer matrix gel, the core precursor material, the flexible spacer precursor material, or both comprise at least one A-X functional group, where A is silicon (Si), phosphorous (P), or sulfur (S) and X is X is oxygen (O) or nitrogen (N); or

(a)(ii) subjecting a solution comprising a solvent, a gel forming agent, a POSS material and a flexible spacer precursor material to conditions suitable to form a hyperbranched organic polymer matrix gel, the flexible spacer precursor material comprises a functionalized silicon material; and

(b) subjecting the organically modified organic polymer matrix gel to conditions suitable to form the hyperbranched organic polymer aerogel of embodiment 1 or 32. Embodiment 34 is the method of embodiment 33, 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 35 is the method of any one of embodiments 33 to 34, wherein step (b) comprises a temperature of 15 °C to 120 °C, or 65 °C to 95 °C form the gel. Embodiment 36 is the method of any one of clams 33 to 35, wherein step (b) comprises subjecting the gel to a drying step to remove a portion of the solvent. Embodiment 37 is the method of embodiment 36, further comprising heating the dried gel under vacuum at a temperature of 15 to 90 °C. Embodiment 38 is the method of any one of embodiments 33 to 37, wherein the drying step is supercritical drying, subcritical drying, thermal drying, evaporative drying, ambient drying, or any combination thereof. Embodiment 39 is the method of embodiment 38, wherein the drying step is evaporative drying. Embodiment 40 is the method of embodiment 40, wherein the drying step is ambient drying without the use of a gaseous stream. Embodiment 41 is the method of embodiment 41, wherein the drying step comprises heating the gel to a temperature of 15 °C to 50 °C, preferably 20 °C to 30 °C. Embodiment 42 is the method of embodiment 33, wherein step (b) 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 43 is the method of embodiment 33, further comprising subjecting the gel formed in step (a) to at least one solvent exchange to replace the solvent with a second solvent prior to performing step (b). Embodiment 44 is the method of embodiment 43, wherein at least one solvent exchange is performed with acetone, tetrahydrofuran, toluene, xylene, hexane, heptane, methanol, ethanol, isopropanol, a methyl siloxane containing material, a hexamethyldisiloxane containing material, a mixture of fluorocarbon and trans-l,2-dichloroethylene, or combinations thereof. Embodiment 45 is the method of embodiment 33, wherein no solvent exchange is performed. Embodiment 46 is the method of any one of embodiments 33 to 45, wherein the POSS material is methacyrloPOSS, or an acryloPOSS. Embodiment 47 is the method of any one of embodiments 33 to 46 wherein the core precursor material of (a)(i) or the flexible hydrocarbon spacer precursor material of (a)(ii) has the structure:

10, R2 is methyl, ethyl, or propyl, and X is O or N. Embodiment 48 is the method of embodiment 46 wherein the core precursor material of (a)(i) or the flexible hydrocarbon spacer material of (a)(ii) has the structure:

Embodiment 49 is the method of any one of embodiments 33 to 48 wherein the core precursor material of (a)(i) or an additional flexible hydrocarbon spacer material of (a)(ii) has the structure of:

Embodiment 50 is the method of any one of embodiments 33 to 49 wherein the flexible hydrocarbon precursor material of (a)(i) comprises alpha-olefins, preferably, ethylene propylene, or alpha-olefins have 2 to 20 carbons, dienes, vinyl aromatic monomers, preferably styrene, vinyl toluene, t-butyl styrene, di-vinyl benzene, vinyl acetates, and all isomers or derivatives of these compounds, acrylates preferably, methacrylate, methylmethacrylate, hexane diol diacrylate, unsaturated polyesters, epoxides, preferably glycidyl compounds, divinyldimethyl silane, and any combination thereof. Embodiment 51 is the method of embodiment 33, wherein the core precursor material and the spoke precursor material are the same material, preferably, l,3,5-trivinyl-l,3,5-trimethylcyclotrisiloxane, or dimethoxymethylvinylsilane.

[0020] Embodiment 52 is an article of manufacture comprising the hyperbranched organic polymer aerogel of any one of embodiment 1 to 33. Embodiment 53 is the article of manufacture of embodiment 52, 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.

[0021] The following includes definitions of various terms and phrases used throughout this specification.

[0022] 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 polymer aerogels of the present invention can include a degree of branching (DB) of at least 2 or more branches per core.

[0023] 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 D1993-03(2008) Standard Test Method for Precipitated Silica - Surface Area by Multipoint BET Nitrogen).

[0024] The term“rigid” means a polymer with few degrees of freedom (rotation or bending), across 3 or more covalent bonds along more than 50% of the polymer backbone. An example of this is poly-para-phenylene where there is no bending in the benzene rings and only limited rotation between rings due to steric constraints. Additional examples include polyaramids including Nomex where the aromatic rings are rigid segments with limited rotation at the amide bond. In polyimides including Kapton where the benzene ring and fused cyclic imide ring are rigid and there is limited rotation between the fused cyclic imide and the adjacent benzene ring.

[0025] The term “flexible” means a polymer with many degrees of freedom (rotation or bending). In the flexible polymer system the covalent bonds have lower energy barrier to rotation due to steric constraints. An example of this is polyethylene where in solution and melt the -Cth- Ctb- bond can rotate. An additional example is polyethylene terephthalate. In this polymer there is a rigid segment (the benzene ring) but there is rotation freedom at the ester bond and in the ethylene group.

[0026] 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. [0027] 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.

[0028] The term“radio frequency (RF)” refers to the region of the electromagnetic spectrum having wavelengths ranging from 10⁴ to 10⁷ m.

[0029] 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.

[0030] 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. Non-limiting examples of aliphatic group substituents include halogen, hydroxyl, alkyloxy, ethers, haloalkyl, haloalkoxy, carboxylic acid, ester, amine, amide, nitrile, acyl, thiol, silanes, siloxanes, and thioether. A branched aliphatic group includes at least one tertiary and/or quaternary carbon. Non-limiting Branched aliphatic group substituents can include halogen, hydroxyl, alkyloxy, ethers, haloalkyl, haloalkoxy, carboxylic acid, ester, amine, amide, nitrile, acyl, thiol, silanes, siloxanes, 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 halogen, hydroxyl, alkyloxy, ethers, haloalkyl, haloalkoxy, carboxylic acid, ester, amine, amide, nitrile, acyl, thiol, silanes, siloxanes, and thioether.

[0031] An “alkyl group” is linear or branched, substituted or unsubstituted, saturated hydrocarbon. Non-limiting examples of alkyl group substituents can include halogen, hydroxyl, alkyloxy, ethers, haloalkyl, haloalkoxy, carboxylic acid, ester, amine, amide, nitrile, acyl, thiol, silanes, siloxanes, and thioether.

[0032] An“aryl” or“aromatic” group is a substituted or unsubstituted, mono- or polycyclic hydrocarbon with alternating single and double bonds within each ring structure. Non-limiting examples of aryl group substituents can include halogen, hydroxyl, alkyloxy, ethers, haloalkyl, haloalkoxy, carboxylic acid, ester, amine, amide, nitrile, acyl, thiol, silanes, siloxanes, and thioether. [0033] The term“acrylate” includes substituted and unsubstituted vinyl carboxylic acids. A

Non-limiting examples of acrylate include acrylate and methacrylate.

[0034] 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%.

[0035] 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.

[0036] The term“substantially” and its variations are defined to include ranges within 10%, within 5%, within 1%, or within 0.5%.

[0037] 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.

[0038] The term“effective,” as that term is used in the specification and/or claims, means adequate to accomplish a desired, expected, or intended result.

[0039] 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.”

[0040] 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.

[0041] The hyperbranched 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 polymer aerogels of the present invention is their non-caged structure that includes a core and 3 to 8 flexible hydrocarbon-containing spacers that can be tuned to provide desired optical and physical properties.

[0042] 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.

DETAILED DESCRIPTION OF THE INVENTION

[0043] A discovery has been made that provides at least one solution to at least some of the problems relating to optical properties of silica aerogels or polymer aerogels. The discovery is focused on a hyperbranched polymer aerogel that contains an open-cell structured core/spoke polymer matrix of an organically modified polymer. The hyperbranched polymer aerogel of the present invention can have good optical properties ( e.g ., low haze and high percentage of light transmission). The hyperbranched 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

[0044] The materials, solvents, compounds, reagents and the like used to produce the hyperbranched polymer aerogels of the present invention can be made using known synthetic methods or obtained from commercial sources.

1. Cores

[0045] Materials having connecting groups (e.g. 2 to 8) can be used as cores. Non-limiting examples of core materials can include trifunctional siloxane (e.g., l,3,5-trivinyl-l,3,5- trimethylcyclotrisiloxane (TVMS)) and penta-functional acrylates (e.g., dipentaerythritol pentaacrylate). When the flexible spacers (described below in Section 1.2) are attached to the core, a structure similar to a wheel with spokes is produced, but in 3 dimensions. Without wishing to be bound by theory, it is believed that the core can expand in all directions, thus allowing it to chemically bond to the other regions nearby. Unlike some aerogels, which are a collection of nanometer sized balls that are only held together by surface energy, the cores of the present invention are chemically bound over longer distances.

[0046] In one embodiment, the core can have a formula of: [(Ri)(R₂)(R₃)-[A-X-A]_n] where Ri, R₂, and R₃ are each independently, an aliphatic group, a substituted aliphatic group, an aromatic group, a substituted aromatic group, and at least one of Ri, R₂, and R₃ is bound to the flexible spacer; A is Si, P, or S; X is O or N; and n is 1 to 8. In one embodiment, Ri and R₂, Ri and R₃, or

R₂ and R₃, are aliphatic groups. In one embodiment, Ri and R₂, Ri and R₃, or R₂ and R₃, are aliphatic groups, A is Si, and X is O or N. In some embodiments, Ri and R₂, Ri and R₃, or R₂ and R₃, are aliphatic groups, A is Si and X is O and n is 3. A non-limiting example of a core structure can be:

represents the bond to the flexible hydrocarbon- containing spacer. In a specific, preferred aspect, the core can have the structure:

represents the bond to the flexible hydrocarbon-containing spacer.

[0047] In some embodiments, the core can have a formula of [R₁-A-X-A-R₂], where: R¹ and R² can each be independently, an aliphatic group, a substituted aliphatic group, an aromatic group, a substituted aromatic group, or a carbon based polymer; A is silicon (Si), phosphorous (P), or sulfur (S); and X is oxygen (O) or nitrogen (N).

[0048] In some embodiments, core has a structure of:

where R₂, R₅, R₆, and R₇ are an aliphatic group, preferably methyl or ethyl, and

represents the bond to the flexible hydrocarbon-containing spacer.

[0049] In another embodiment, the core can be a substituted ether having the following structure:

bond to the spacer. [0050] Precursors to the cores include groups that are capable of reacting with a flexible spacer having a reactive group. Non-limiting examples of reactive groups include vinyl groups, acrylates, esters, polyesters, epoxides and the like. A non-limiting example of a precursor for the above- described core cyclic silicon containing compound can include

10, R2 is methyl, ethyl, or propyl, and X is

O or N. In a preferred embodiment, the precursor material is

[0051] Another example of a precursor material can include dipentaerythritol pentaacrylate shown below. Dipentaerythritol pentaacrylate is available from commercial vendors such as Sartomer under the tradename SR399 LV:

2. Flexible Hydrocarbon- Containing Spacers

[0052] Without wishing to be bound by theory, it is believed that the flexible spacers attached to core can act as a molecular-level rubber hardening agent. In rubber hardening, the soft region can elastically absorb and distribute stress and strain that would fracture or break hard regions. In the aerogel polymeric matrix of the present invention the rigid nanometer size cores make up the hard regions and the short chain alkanes make up the flexible regions. The hard regions are required to maintain the pore structure. In a polymeric aerogel with only hard regions, the shrinkage during drying causes internal strain that leads to pore collapse and cracking. By way of example, an aerogel that is made up of 100% divinylbenzene cracks severely during drying. In contrast, using the flexible spacers of the present invention, and as illustrated in a non-limiting manner in the Examples, 10 cm x 10 cm x 4 mm aerogel composites were made without cracks. By controlling the volume ratio of soft regions and hard regions, we can maximize porosity while producing crack free aerogels.

[0053] Flexible f hydrocarbon-containing spacer can have the structure of

where Y can be C¾, Si, O, S, N, or combinations thereof and tv is 1 to 20, preferably 4 to 7, or 6, and

represents the bond to the core. In another embodiment, the flexible hydrocarbon- containing spacer can have the structure of

represents the bond to the core.

[0054] The flexible hydrocarbon-containing spacer precursor material can include alpha-olefins, preferably, ethylene propylene, or alpha-olefins have 2 to 20 carbons, dienes, vinyl aromatic monomers, preferably styrene, vinyl toluene, t-butyl styrene, di-vinyl benzene, vinyl acetates, and all isomers or derivatives of these compounds, acrylates preferably, methacrylate, methylmethacrylate, hexane diol diacrylate, unsaturated polyesters, epoxides, preferably glycidyl compounds, silanes, preferable dimethyldivinylsilane, siloxanes, preferably structure VII, and any combination thereof. The additional reactants can react with the reactive groups of the core to form covalent bonds. The reactants can be polymerized prior to or after reacting with the R groups.

[0055] In certain embodiments, the flexible hydrocarbon-containing spacers are derived from the core precursor materials described in Section A.l. For example, silicon precursor materials can be used as flexible hydrocarbon-containing spacers as well as functionalized acrylates (e.g., penta- functional acrylate). Non-limiting examples of silicon precursor materials can include divinyldimethylsilane, vinyltrimethyl silane (VTMS), l,3,5-trivinyl-l,3,5-trimethylcyclotrisiloxane (TVMS)) and the like.

3. Other Cores and Flexible Hydrocarbon Spacers

[0056] In some embodiments, the cores can be inorganic materials or a combination of organic/inorganic materials (e.g., SiO_x, or POSS). A SiO_x core can be made in situ to produce a SiO_x bound to flexible hydrocarbon spacers having an A-X (Si-O) functionality. By way of example, in non-limiting manner, poly(dimethoxymethylvinylsilane) (PDMMVS) can be converted to SiO_x core via a reaction with tetramethylammonium hydroxide and water, which then reacts with PDMMVS to form a SiO_x core with flexible hydrocarbon spacer having an A-X (Si-O) functionalities.

[0057] POSS -containing materials can be used as cores bound to a flexible hydrocarbon spacer that includes an ester functional group and a silicon containing group. The ester functionality can obtained from functionalized POSS containing materials. For example, methylacrylate-POSS and acrylate-POSS, which are shown below.

[0058] The silicon functionality of the flexible hydrocarbon spacers is bound to at least one vinyl functionality of the ester bound to the POSS cage. In a non-limiting manner, a first flexible hydrocarbon spacer can represented as X— Si-CH2CH2CH20C=0CH2CH2(Ri)CH2CH2Si(R2R3R4) where X-Si is the POSS core. Ri and R2 are each independently a hydrocarbon group, preferably a methyl or an ethyl group. R₃ and R4 are each independently a methyl group, an ethyl group, or R₃ and R4 can form a ring, or R4 can be bound to another POSS material and/or a functionalized material (e.g., a second ester functional group), or a combination thereof. Silicon precursor materials can include divinyldimethylsilane, vinyltrimethyl silane (VTMS), l,3,5-trivinyl-l,3,5- trimethylcyclotrisiloxane (TVMS)) and the like. In some embodiments, R4 is bound to another acrylate. For example, a penta-functional acrylate (e.g., dipentaerythritol pentaacrylate) to form a second ester functionality in the first flexible hydrocarbon spacer or a second flexible hydrocarbon spacer on the same POSS cage.

4. Gel Forming Agents, Photocuring Agents, Promoters, and Chain Transfer Agents

[0059] Gel forming agents, photocuring agents, promoters, and/or chain transfer agents can be used to assist in polymerization of the core/flexible spacer materials with each other or other monomers. Gel forming agents can produce a radical species from R of the multi-functionalized core or flexible spacer material to start the polymerization process. Non-limiting examples of gel forming agents 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. Non-limiting examples of photocuring agents include 1,4- butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth) acrylate, 1,2-ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, neopentyl glycol adipate di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentanyl di(meth)acrylate, ethylene oxide-modified di(meth)acrylate, di(meth)acryloxy ethyl isocyanurate, allylated cyclohexyl di(meth)acrylate, tricyclodecanedimethanol (meth)acrylate, dimethylol dicyclopentane di(meth)acrylate, ethylene oxide-modified hexahydrophthalic acid di(meth)acrylate, tricyclodecanedimethanol (meth)acrylate, neopentyl glycol-modified trimethylpropane di(meth)acrylate, adamantane di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid-modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, tris(meth)acryloxyethyl isocyanurate, diglycerin tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, propionic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and urethane (meth) acrylate which is a reaction product of an isocyanate monomer and trimethylolpropane tri(meth)acrylate. 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 MilliporeSigma (U.S.A.), Wako Chemical (Japan), and Shepherd (U.S.A.). 5. Solvents

[0060] 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 core and flexible spacer precursor materials. Non limiting examples of solvents for the polymerization reaction include acetone, tetrahydrofuran, formamide, N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, N,N- dimethylacetamide, N,N-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, dimethoxyethane, 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- 1 -butanol, 2-methyl- 1-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, benzotrichloride, 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, dichloromethane, diiodomethane, FC-75, haloalkane, halomethane, hexachlorobutadiene, hexafluoro-2-propanol, parachlorobenzotrifluoride, perfluoro- 1 ,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 phenylacetate, methyl propionate, propyl acetate, propylene carbonate, dimethyl carbonate, and triacetin; water, or mixtures thereof.

[0061] 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, diethylene 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

[0062] Aerogels of the present invention can be made using a multi-step process that includes 1) preparation of the hyperbranched organic polymer matrix gel that has a core/flexible spacer structure, 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 Organic Polymer Gels

[0063] Processes and methods to produce an organic polymeric material having a core/spoke type structure can include combining a gel forming agent, a core precursor material or a POSS- containing core material, and a spoke precursor material with a solvent to form a reaction mixture. In some embodiments, the core precursor material and the spoke precursor material are the same. The reaction mixture can be subject to conditions suitable to form a hyperbranched organic polymeric 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, 110 °C, 115 °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 core precursor material can range from 5 wt.% to 95 wt.%, 5 wt. % to 95 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.%. An amount of flexible spacer precursor 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. Gel forming agents, 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, core precursor material, flexible spacer precursor material, AIBN, optional cobalt naphthenate and optional decane thiol can be solubilized in tetrahydrofuran. The optical properties of the aerogel can be tuned by varying the amount of core precursor material used, flexible spacer precursor material used, type of solvent used, polymerization speed, and/or pore size of the resulting aerogel.

[0064] In some embodiments, the organic 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 hyperbranched 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

[0065] After the organically modified hyperbranched 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 desired to conduct a plurality of rounds of solvent exchange.

[0066] The time for conducting 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, 110, 115, 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, methanol, ethanol, isopropanol, a methyl siloxane containing material, a hexamethyldisiloxane containing material, a mixture of fluorocarbon and trans-l,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.

[0067] 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

[0068] 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.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] In some embodiments, the dried gel can be heated under vacuum at 20 to 90 °C, or at least any one of, equal to any one of, or between any two of 20, 30, 40, 50, 60, 70, 80, and 90 °C for a desired amount of time (e.g., 1 to 80 hours, or 10 to 70 hours, 20, to 50 hours, etc.).

C. Hyperbranched Organic Polymer Aerogels

[0073] In some embodiments, the hyperbranched polymer aerogel of the present invention can have a specific surface area of 0.15 m²/g to 1500 m²/g and higher, 0.4 m²/g to 800 m²/g. The hyperbranched polymer aerogel can have a haze value of 0.5 to 25, or greater than any one of, equal to any one of, 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, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, 15.5, 16, 16.5, 17, 17.5, 18, 18.5, 19, 19.5, 20, 20.5, 21, 21.5, 22, 22.5, 23, 23.5, 24, 24.5, and 25, and/or a total percent light transmission of 10 to 99 greater than any one of, equal to any one of, 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 polymer aerogel is transparent, translucent or opaque. In a preferred embodiment, the hyperbranched 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.

[0074] In some embodiments, the hyperbranched polymer aerogel of the present invention can have a POSS core. For example, a POSS core bound to a flexible spacer can be derived from methacryloPOSS and dimethyldivinylsilane. Such a hyperbranched polymer aerogel can be transparent aerogel and have a specific surface area of 0.15 to 1500 m²/g, 10 to 1000 m²/g, 300 to 500 m²/g, or any range or value there between.

[0075] In another embodiment, the hyperbranched polymer aerogel with a POSS can be derived from methacryloPOSS, dipentaerythritol penataacrylate and divinyldimethylsilane. Such an aerogel can be transparent and have a specific surface area of 0.15 to 1500 m²/g, 10 to 1000 m²/g, 300 to 500 m²/g, 100 to 150 m²/g, or any range or value there between. [0076] In another instance, the hyperbranched polymer aerogel with a POSS can be derived from methacryloPOSS, and l,3,5-trivinyl-l,3,5-trimethylcyclotrisiloxane. Such an aerogel can be transparent and have a specific surface area of 0.15 to 1500 m²/g, 10 to 1000 m²/g, 300 to 500 m²/g, or any range or value there between.

[0077] In another instance, the hyperbranched polymer aerogel with a POSS can be derived from methacryloPOSS, and vinyltrimethylsilane. Such an aerogel can be transparent and have a specific surface area of 0.15 to 1500 m²/g, 10 to 1000 m²/g, 300 to 500 m²/g, or any range or value there between.

[0078] In another embodiments, the hyperbranched polymer aerogel can have a core and flexible hydrocarbon-containing spacers derived from l,3,5-trivinyl-l,3,5-trimethylcyclotrisiloxane. Such a hyperbranched polymer aerogel can be transparent and have a specific surface are of 0.15 to 1500 m²/g, 10 to 1000 m²/g, 300 to 500 m²/g, or any range or value there between.

[0079] In another embodiments, the hyperbranched polymer aerogel can have a core and flexible hydrocarbon-containing spacers derived from dimethoxymethylvinylsilane monomer or. Such a hyperbranched polymer aerogel can be transparent and have a specific surface are of 0.15 to 1500 m²/g, 500 to 900 m²/g, 550 to 850 m²/g, 600 to 800 m²/g, 650 to 750 m²/g, or any range or value there between.

[0080] In some embodiments, the hyperbranched polymer aerogel of the present invention has a core derived from dipentaerythritol penataacrylate attached to flexible hydrocarbon-containing spacers derived from dimethyldivinylsilane. Such a hyperbranched polymer aerogel can be transparent and have a specific surface are of 0.15 to 1500 m²/g or any range or value there between.

[0081] In one embodiment, the hyperbranched polymer aerogel can have a core derived from dipentaerythritol penataacrylate attached (bonded) to flexible hydrocarbon-containing spacers derived from l,3,5-trivinyl-l,3,5-trimethylcyclotrisiloxane and 1,6-hexandiol diacrylate. Such a hyperbranched polymer aerogel can be transparent and have a specific surface are of 0.15 to 1500 m²/g, or any range or value there between.

[0082] In one embodiment, the hyperbranched polymer aerogel can have a core derived from dipentaerythritol penataacrylate attached (bonded) to flexible hydrocarbon-containing spacers derived from vinyltrimethylsilane and 1,6-hexandiol diacrylate. Such a hyperbranched polymer aerogel can be transparent and have a specific surface are of 0.15 to 1500 m²/g, or any range or value there between.

[0083] In yet another embodiment, the hyperbranched polymer aerogel can have a core derived from pentaerythritol tetrakis(3-mercaptopropionate) and flexible hydrocarbon-containing spacers derived from l,3,5-trivinyl-l,3,5-trimethylcyclotrisiloxane. Such a hyperbranched polymer aerogel can be transparent and have a specific surface are of 0.15 to 1500 m²/g, or any range or value there between.

D. Articles of Manufacture

[0084] 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 organic aerogel of the present invention. 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

[0085] In some embodiments, the open-cell aerogel with a hyperbranched organic aerogel of the present invention can be used in fluid filtration systems and apparatus. A feed fluid can be contacted with the hyperbranched organic polymer of the present invention 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 organic aerogel of the present invention can be further processed to release the impurities and/or desired substances from the aerogel.

[0086] The hyperbranched organic aerogel of the present invention 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.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] The hyperbranched organic aerogel of the present invention 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 organic aerogels of the present invention or one or more hyperbranched organic aerogel of the present invention 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 organic aerogel of the present invention 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 organic polymer aerogels of the present invention 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.

[0091] 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.

[0092] The compatibility of the hyperbranched organic aerogel of the present invention with a fluid and/or filtration application can be determined by methods known in the art. Non-limiting properties of the hyperbranched organic aerogels of the present invention 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

[0093] Due to their low density, mechanical robustness, lightweight, and low dielectric properties, the hyperbranched organic aerogels of the present invention can be used in radiofrequency (RF) applications. The use of hyperbranched organic aerogels of the present invention 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 organic aerogel of the present invention and/or a combination of the hyperbranched organic aerogels of the present invention 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 organic aerogels of the present invention in antennas enables the design substrates with higher throughput. In addition, the hyperbranched organic aerogels of the present invention 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 organic aerogels of the present invention can minimize signal loss due to their low dielectric constant, and can provide structural integrity due to their stiffness.

EXAMPLES

[0094] 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 DVDMS I MAPOSS Aerogel

(Preparation of Hyperbranched Polymer Aerogel)

[0095] A solution of 2,2'-azobis(2-methylpropionitrile) (AIBN, 0.7 mass %) initiator was prepared in 14 g N-methyl-2-pyrrolidone (NMP) solvent. 0.81 g dimethydivinylsilane (DVDMS, MilliporeSigma, USA, 0.0072 moles) and 5.19 g methacryloPOSS (MAPOSS, Hybrid Plastics, USA, 0.0036 moles) were dissolved in the AIBN/NMP solution. To the above solution, 73.8 mg 1- decanethiol (Millipore Sigma, USA) was added. The above solution was purged with argon gas for 30 minutes, and sealed. The solution was heated at 90 °C and hard transparent gel was formed without any visible cracks or defects after 4 min. The polymer gel was further cured for 30 min at 90 °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. After the final exchange, the gelled sample was removed and allowed to air dry in a 0.0508 mm thick sealable plastic bag ( e.g ., Ziploc®, S.C. Johnson and Sons, USA) for 21 days. After ambient drying, the samples were vacuum dried for 72 h at 60 °C to produce a transparent aerogel having a specific surface area of 600 m²/g ± 3 m²/g as determined by Bmnauer- Emmett-Teller (BET) surface area analysis.

Example 2 - MAPOSS I SR399 LV I DVDMS Aerogel

(Preparation of Hyperbranched Polymer Aerogel)

[0096] A solution of AIBN (0.7 mass %) initiator was prepared in 14 g NMP solvent. MAPOSS (4.15 g, 0.0028 mole), dipentaerythritol penataacrylate (SR399 LV, Sartomer Americas, USA, 1.52 g, 0.0028 mole), and DVDMS (0.32 g, 0.0028 mole) were dissolved in the AIBN/NMP solution. To the above solution, 60.6 mg 1-decanethiol was added. The above solution was purged with argon gas for 30 minutes, and sealed. The solution was heated at 90 °C and hard transparent gel was formed without any visible cracks or defects after 4 min. The polymer gel was further cured for 30 min at 90 °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. After the final exchange, the gelled sample was removed and allowed to air dry in a 0.0508 mm thick sealable plastic bag (e.g., Ziploc®, S.C. Johnson and Sons, USA) for 21 days. After ambient drying, the samples were vacuum dried for 72 h at 60 °C to produce a transparent aerogel having a specific surface area of 120 m²/g ± 3 m²/g as determined by Bmnauer- Emmett-Teller (BET) surface area analysis.

Example 3 - MAPOSS I TVMS Aerogel

(Preparation of Hyperbranched Polymer Aerogel)

[0097] A solution of AIBN (0.7 mass %) initiator was prepared in 14 g NMP solvent. 5.08 g MAPOSS, 0.92 g l,3,5-trivinyl-l,3,5-trimethylcyclotrisiloxane (TVMS, Gelest, USA) were dissolved in the AIBN/NMP solution. To the above solution, 49.4 mg 1-decanethiol was added. The above solution was purged with argon gas for 30 minutes, and sealed. The solution was heated at 90 °C and hard transparent gel was formed without any visible cracks or defects after 4 min. The polymer gel was further cured for 30 min at 90 °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. After the final exchange, the gelled sample was removed and allowed to air dry in a 0.0508 mm thick sealable plastic bag ( e.g Ziploc®, S.C. Johnson and Sons, USA) for 21 days. After ambient drying, the samples were vacuum dried for 72 h at 60 °C to produce a transparent aerogel having a specific surface area of 401 m²/g ± 3 m²/g as determined by Brunauer-Emmett-Teller (BET) surface area analysis.

Example 4 - TVMS Aerogel

(Preparation of Hyperbranched Polymer Aerogel)

[0098] A solution of DTBPO, (Millipore, 0.5 mass %) initiator was prepared in NMP solvent. TVMS was dissolved in the DTBPO/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 purged with argon gas for 30 minutes, and sealed. The solution was heated at 120 °C and hard transparent gel was formed without any visible cracks or defects after 20 h. 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 0.0508 mm thick sealable plastic bag followed by vacuum drying of aerogels for 72 h at 90 °C to produce a transparent aerogel having a specific surface area of 455 m²/g ± 3 m²/g as determined by Brunauer-Emmett-Teller (BET) surface area analysis and an average pore diameter of 3.5 nm as determined by Barrett- Joyner-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 5 - MAPOSS I VTMS Aerogel

(Preparation of Hyperbranched Polymer Aerogel)

[0099] A solution of AIBN (0.7 mass %) initiator was prepared in 14 g NMP solvent. MAPOSS (5.26 g), vinyltrimethylsilane (VTMS, 0.74 g, MilliporeSigma) were dissolved in the AIBN/NMP solution. To the above solution, 76.8 mg 1-decanethiol was added. The above solution was purged with argon gas for 30 minutes, and sealed. The solution was heated at 90 °C and hard transparent gel was formed without any visible cracks or defects after 4 min. The polymer gel was further cured for 30 min at 90 °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. After the final exchange, the gelled sample was removed and allowed to air dry in a 0.0508 mm thick sealable plastic bag ( e.g Ziploc®, S.C. Johnson and Sons, USA) for 21 days. After ambient drying, the samples were vacuum dried for 72 h at 60 °C to produce a transparent aerogel having a specific surface area of 330 m²/g ± 3 m²/g as determined by Brunauer-Emmett-Teller (BET) surface area analysis.

Example 6 - DMMVS Aerogel

(Preparation of Hyperbranched Polymer Aerogel)

[00100] DTBPO and dimethoxymethylvinylsilane monomer (DMMVS, MilliporeSigma, USA) were mixed at 1:20.8 molar ratio and heated at 120 °C for 72 h to produce a viscous solution of poly(dimethoxymethylvinylsilane) (PDMMVS) in unconverted DMMVS monomer solution (collectively “PDMMVS solution”). A specified molar amount (0.5 moles) with respect to DMMVS monomer/monomer unit of the PDMMVS solution was dissolved in benzyl alcohol (BzOH, 2.3 mole MilliporeSigma, USA) solvent to produce a monomer/solvent solution having a total monomer: solvent ratio of 20:80 with respect to mass. To the above solution was added tetramethylammonium hydroxide (TMAOH, 5.4 g of 25% solution in water MilliporeSigma, USA, which contains 0.015 mole of pure TMAOH and 0.22 mole of water). Water (0.8 mole) was added to the solution and, after shaking, the solution was poured into a mold at 80 °C for 96 hours. A hard clear transparent gel was formed without any visible cracks or defects after 90 min. The gelled sample was collected and placed into bath heated to 65 °C containing isopropanol. After immersion for 24 hours, the isopropanol bath was exchanged. The soak and exchange process was repeated a total of four times. After the final exchange, the gelled sample was removed and allowed to air dry on the benchtop for 5 days. After ambient drying the samples were vacuum dried 72 h at 60 °C to produce a transparent aerogel having a specific surface area of 735 m²/g ± 3 m²/g as determined by Brunauer-Emmett-Teller (BET) surface area analysis. By MIP the samples had a bulk density of 0.57 g/cc and a porosity of 48%.

Example 7

(Preparation of Hyperbranched Polymer Aerogel)

[00101] A solution of 2,2'-azobis(2-methylpropionitrile) (AIBN, 0.14 mass %) initiator was prepared in N-methyl-2-pyrrolidone (NMP) solvent. Dipentaerythritol penataacrylate (SR399 LV, Sartomer Americas, USA) and dimethydivinylsilane (DVDMS, MilliporeSigma, USA) were mixed at 1:0.5 molar ratio and dissolved in the AIBN/NMP solution to produce a monomer/solvent solution having a total monomer: solvent ratio of 28:72 with respect to mass. To the above solution, 1-decanethiol (46.00 mg, 0.26 mM, MilliporeSigma, USA) was added. The above solution was purged with argon gas for 30 minutes, and sealed. The solution was heated at 90 °C and hard transparent gel was formed without any visible cracks or defects after 4 min. The polymer gel was further cured for 30 min more at 90 °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. After the final exchange, the gelled sample was removed and allowed to air dry in a 2 MIL (0.0508 mm) thick sealable plastic bag ( e.g Ziploc®, S.C. Johnson and Sons, USA) for 21 days. After ambient drying the samples were vacuum dried for 72 h at 60 °C to produce a transparent aerogel having a specific surface area of 0.44 m²/g ± 3 m²/g as determined by Brunauer-Emmett-Teller (BET) surface area analyst

Example 8

(Preparation of Hyperbranched Polymer Aerogel)

[00102] A solution of AIBN (0.085 mass %) initiator was prepared in NMP solvent. SR399 LV, 1,6-hexanediol diacrylate (HDDA, SigmaMillipore, USA) and l,3,5-trivinyl-l,3,5- trimethylcyclotrisiloxane (TVMS, Gelest, USA) were mixed at 1:1:1 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 (33.00 mg, 0.19 mM, SigmaMillipore, USA) was added, and the above solution was purged with argon gas for 30 minutes, and sealed. The solution was heated at 90 °C and hard transparent gel was formed without any visible cracks or defects after 5 min. The polymer gel was further cured for 30 min more at 90 °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. After the final exchange, the gelled sample was removed and allowed to air dry in a 2 MIL (0.0508 mm) thick sealable plastic bag for 1-21 days. After ambient drying the samples were vacuum dried 72 h at 60 °C to produce a transparent aerogel having a specific surface area of 0.63 m²/g ± 3 m²/g as determined by Brunauer-Emmett-Teller (BET) surface area analysis.

Example 9

(Preparation of Hyperbranched Polymer Aerogel)

[00103] TVMS and pentaerythritol tetrakis(3-mercaptopropionate) (4 CTA, Millipore Sigma, USA) were mixed at 1:0.75 molar ratio and dissolved in NMP solvent to produce a monomer/solvent solution having a total monomer: solvent ratio of 30:70 with respect to mass. The above solution was purged with argon gas and sealed. The solution was heated at 80 °C and hard clear transparent gel was formed without any visible cracks or defects after 90 min. 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 2 MIL (0.0508 mm) thick sealable plastic bag for 1-21 days. After ambient drying the samples were vacuum dried 72 h at 60 °C to produce a transparent aerogel having a specific surface area of 0.40 m²/g ± 3 m²/g as determined by Brunauer-Emmett-Teller (BET) surface area analysis. Such a hyperbranched polymer aerogel can be transparent and have a specific surface are of 0.1 to 1 m²/g, 0.2 to 0.8 m²/g, 0.3 to 0.7 m²/g, 0.4 to 0.6 m²/g, or any range or value there betweem

Example 10

(Preparation of Hyperbranched Polymer Aerogel)

[00104] A solution of AIBN (3.1 mass %) initiator was prepared in NMP solvent. SR399 LV, HDDA and vinyltrimethylsilane (VTMS, Gelest, USA) were mixed at 1:0.45:5.2 molar ratio and dissolved in the AIBN/NMP solution to produce a monomer/solvent solution having a total monomer: solvent ratio of 29:71 with respect to mass. To the above solution, 1-decanethiol (259.00 mg, 1.5 mM, Millipore Sigma, USA) was added, and the above solution was purged with argon gas for 30 minutes, and sealed. The solution was heated at 90 °C and a hard transparent gel was formed without any visible cracks or defects after 4 min. The polymer gel was further cured for 30 min more at 90 °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. After the final exchange, the gelled sample was removed and allowed to air dry in a 2 MIL (0.0508 mm) thick sealable plastic bag for 21 days. After ambient drying the samples were vacuum dried 72 h at 60 °C to produce a transparent aerogel having a specific surface area of 0.34 m²/g ± 3 m²/g as determined by Brunauer-Emmett-Teller (BET) surface area analysis.

[00105] 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

1. A hyperbranched polymer aerogel comprising a core bound to 3 to 8 flexible hydrocarbon-containing spacers, wherein the core, flexible hydrocarbon-containing spacers, or both, comprise 1 to 3 A-X functional groups, where A is silicon (Si), phosphorous (P), or sulfur (S) and X is oxygen (O) or nitrogen (N).

2. The hyperbranched polymer aerogel of claim 1, wherein the core does not include a caged or cage-like structure.

3. The hyperbranched polymer aerogel of claim 2, wherein the core does not include a polyoctahedral silsesquioxane like structure, an adamantane like structure, a dicyclopentadiene like structure, or a norbomene like structure.

4. The hyperbranched polymer aerogel of any one of claims 1 to 3, wherein in the flexible spacer is an aliphatic group, a substituted aliphatic group having 2 to 20 carbon atoms, or an aromatic group having 2 to 20 carbon atoms.

5. The hyperbranched polymer aerogel of any one of claims 1 to 4, wherein the aerogel has a compression strength of at least 1 or at least 5 MPa.

6. The hyperbranched polymer aerogel of any one of claims 1 to 5, having mesopores and optional micropores, and/or optional macropores.

7. The hyperbranched polymer aerogel of claim 6, wherein the mesopores have an average pore size of less than 50 nm, preferably 2 to 50 nm.

8. The hyperbranched polymer aerogel of claim 1, having a haze value of 0.5 to 25 as measured by ASTM D1003.

9. The hyperbranched polymer aerogel of any one of claims 1 to 8, having a total percent light transmission of 10 to 99 at 550 wavelength as measured by ASTM D1003.

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

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

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

13. The hyperbranched polymer aerogel of claim 1, wherein the core has a formula of [R1-A-X-A-R2],

where:

R¹ and R² are each independently, an aliphatic group, a substituted aliphatic group, an aromatic group, a substituted aromatic group, or a carbon based polymer;

A is silicon (Si), phosphorous (P), or sulfur (S); and

X is oxygen (O) or nitrogen (N), wherein Ri and R2 are bound to the flexible hydrocarbon-containing spacer.

14. The hyperbranched polymer aerogel of claim 1, wherein the core has a formula of:

[(R_I)(R₂)(R₃)-[A-X-A]„]

where:

Ri, R2, and R3 are each independently, an aliphatic group, a substituted aliphatic group, an aromatic group, a substituted aromatic group, and at least one of Ri, R2, and R3 is bound to the flexible spacer;

A is silicon (Si), phosphorous (P), or sulfur (S);

X is oxygen (O) or nitrogen (N); and

n is 1 to 8.

15. The aerogel of claim 14, wherein Ri and R2, Ri and R3, or R2 and R3, are aliphatic groups.

16. The aerogel of any one of claims 14 to 15, wherein A is Si.

17. The aerogel of any claim 16, wherein X is O or N.

18. The aerogel of any one of claims 14 to 17, wherein n is 3.

19. The aerogel of claim 18, wherein the core has the structure:

represents the bond to the flexible hydrocarbon-containing spacer.

20. The aerogel of claim 19, wherein the core has the structure:

represents the bond to the flexible hydrocarbon-containing spacer.

21. The aerogel of claim 1, wherein the core has a structure of:

where R2, R5, R₆, and R7 are an aliphatic group, preferably methyl or ethyl, and

represents the bond to the flexible hydrocarbon-containing spacer, preferably having at least three extended chains.

22. The aerogel of claim 1, wherein the core has the structure of:

represents the bond to the flexible hydrocarbon-containing spacer.

23. The aerogel of any one of claims 1 to 22, wherein the flexible hydrocarbon-containing spacer comprises a substituted aromatic group, an aliphatic hydrocarbon chain, an ester, a substituted ester, an ether, a polyether, a polyester, a silane, a polysilane, a siloxane, a polysiloxane, a thiol, or any combination thereof.

24. The aerogel of claim 23, wherein the flexible hydrocarbon-containing spacer has the structure of

where Y comprises Cth, Si, O, S, N, or combinations thereof and tv is 1 to 20, preferably

4 to 7, or 6, and

represents the bond to the core.

25. The aerogel of claim 23, wherein the flexible hydrocarbon-containing spacer has the structure of

where Rs, R9, Rio, and Rn are each independently an aliphatic group or an aromatic group, preferably methyl, ethyl, or phenyl, and

represents the bond to the core.

26. The aerogel of any one of claims 1 to 25, wherein the core is rigid.

27. A method to produce a hyperbranched organic polymer aerogel of any one of claims 1 to 26, the method comprising:

(a) subjecting a solution comprising a solvent, a gel forming agent, a core precursor material, and a flexible hydrocarbon precursor material to conditions suitable to form a hyperbranched organic polymer matrix gel, wherein: the core precursor material, the flexible hydrocarbon precursor material, or both comprise at least 1 A-X functional group, where A is silicon (Si), phosphorous (P), or sulfur (S) and X is X is oxygen (O) or nitrogen (N); and

(b) subjecting the organically modified organic polymer matrix gel to conditions suitable to form the hyperbranched organic polymer aerogel of claim 1 or 26.

28. The method of claim 27, 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.

29. The method of any one of claims 27 to 28, wherein step (b) comprises a temperature of 15 °C to 120 °C, or 65 °C to 95 °C form the gel.

30. The method of any one of clams 27 to 28, wherein step (b) comprises subjecting the gel to a drying step to remove a portion of the solvent.

31. The method of claim 30, further comprising heating the dried gel under vacuum at a temperature of 15 to 90 °C.

32. The method of any one of claims 28 to 31, wherein the drying step is supercritical drying, subcritical drying, thermal drying, evaporative drying, ambient drying, or any combination thereof.

33. The method of claim 32, wherein the drying step is evaporative drying.

34. The method of claim 33, wherein the drying step is ambient drying without the use of a gaseous stream.

35. The method of claim 34, wherein the drying step comprises heating the gel to a temperature of 15 °C to 50 °C, preferably 20 °C to 30 °C.

36. The method of claim 27, wherein step (b) 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.

37. The method of claim 27, further comprising subjecting the gel formed in step (a) to at least one solvent exchange to replace the solvent with a second solvent prior to performing step (b).

38. The method of claim 38, wherein at least one solvent exchange is performed with acetone, tetrahydrofuran, toluene, xylene, hexane, heptane, methanol, ethanol, isopropanol, a methyl siloxane containing material, a hexamethyldisiloxane containing material, a mixture of fluorocarbon and trans-l,2-dichloroethylene, or combinations thereof.

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

40. The method of any one of claims 27 to 29, wherein the core precursor material or the flexible hydrocarbon spacer precursor material has the structure:

where a is 0 to 10, R2 is methyl, ethyl, or propyl, and X is O or N.

41. The method of claim 40 wherein the core precursor material or the flexible hydrocarbon spacer material has the structure:

42. The method of any one of claims 27 to 41 wherein the core precursor material or the flexible hydrocarbon spacer material has the structure of:

43. The method of any one of claims 27 to 42 wherein the flexible hydrocarbon precursor material comprises alpha-olefins, preferably, ethylene propylene, or alpha-olefins have 2 to 20 carbons, dienes, vinyl aromatic monomers, preferably styrene, vinyl toluene, t-butyl styrene, di- vinyl benzene, vinyl acetates, and all isomers or derivatives of these compounds, acrylates preferably, methacrylate, methylmethacrylate, hexane diol diacrylate, unsaturated polyesters, epoxides, preferably glycidyl compounds, , a siloxane, a silane, divinyldimethyl silane, and any combination thereof.

44. The method of claim 27, wherein the core precursor material and the flexible hydrocarbon precursor material are the same material, preferably, l,3,5-trivinyl-l,3,5- trimethylcyclotrisiloxane, or dimethoxymethylvinyl silane.

45. An article of manufacture comprising the hyperbranched organic polymer aerogel of any one of claim 1 to 26.