WO2020173911A1 - Matériau d'aérogel composite - Google Patents

Matériau d'aérogel composite Download PDF

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Publication number
WO2020173911A1
WO2020173911A1 PCT/EP2020/054851 EP2020054851W WO2020173911A1 WO 2020173911 A1 WO2020173911 A1 WO 2020173911A1 EP 2020054851 W EP2020054851 W EP 2020054851W WO 2020173911 A1 WO2020173911 A1 WO 2020173911A1
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Prior art keywords
aerogel
particulate
group
solvent
matrix
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PCT/EP2020/054851
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English (en)
Inventor
Elisabet TORRES CANO
Ilaria DE SANTO
Asta SAKALYTE
Belen Del Saz-Orozco
Fouad Salhi
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Henkel Ag & Co. Kgaa
Henkel IP & Holding GmbH
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Publication of WO2020173911A1 publication Critical patent/WO2020173911A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C08J9/286—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum the liquid phase being a solvent for the monomers but not for the resulting macromolecular composition, i.e. macroporous or macroreticular polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/026—Crosslinking before of after foaming
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
    • C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/054—Precipitating the polymer by adding a non-solvent or a different solvent
    • C08J2201/0542—Precipitating the polymer by adding a non-solvent or a different solvent from an organic solvent-based polymer composition
    • C08J2201/0543—Precipitating the polymer by adding a non-solvent or a different solvent from an organic solvent-based polymer composition the non-solvent being organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
    • C08J2205/026—Aerogel, i.e. a supercritically dried gel
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • the present invention is directed to a composite aerogel material comprising a particulate aerogel component dispersed within a polymeric aerogel matrix. More particularly, the present invention is directed to a composite aerogel material comprising: a dispersed, particulate aerogel component selected from inorganic aerogels; and, a polymeric aerogel matrix.
  • insulating panel For many such applications, it is possible to use a thick insulating panel to reduce heat transfer.
  • other applications can impose size and weight limitations on their component parts and, as such, may require thinner insulating panels or layers.
  • the thin insulating panels or layers must often possess mechanical properties which are not deleterious to the strength and integrity of the apparatus, device or appliance including them but importantly must possess an extremely low thermal conductivity in order to achieve the same insulating properties as thicker insulating panels or layers. Aerogels constitute a class of lightweight materials of very low thermal conductivity which have found utility in this context.
  • an aerogel is defined as a gel comprised of a microporous solid in which the dispersed phase is a gas.
  • aerogels are thus typically low density solids (0.003-0.5 g/cm 3 ), which are further characterized by a low thermal conductivity, poor sound transmission and high specific surface area (500-1200 m 2 /g). Aerogels are deemed environmentally friendly because they are gas (air) filled, and furthermore, are not subject to ageing.
  • Aerogels may have a thermal conductivity lower than that of the gas they contain: this is caused by the Knudsen effect which is a reduction of thermal conductivity in gases when the size of the cavity encompassing the gas becomes comparable to the mean free path. Effectively, the cavity restricts the movement of the gas particles, decreasing the thermal conductivity in addition to eliminating convection.
  • aerogels are inorganic aerogels, mainly based on silica.
  • thermal conductivities commonly being in the range from 0.005-0.01 W/mK - the commercial adoption of silica aerogels has been stymied by their fragility and poor mechanical properties.
  • the fragility of silica aerogels derives from their structure: ball-like secondary particles accumulate through neck regions, creating a“pearl necklace-like” structure with large voids; when an external load is applied, fracture occurs at the interface of secondary particles while primary particles remain intact.
  • This fragility may be overcome by different methods including: cross-linking silica aerogels with organic polymers; and, post-gelation casting of a thin, conformal polymer coating over the entire internal porous surface of the pre-formed wet-gel, silica nanostructure.
  • TMOS tetramethyl orthosilicate
  • APTES 3-aminopropyl triethoxy silane
  • the amine sites are anchors for the cross-linking of the nanoparticles of the skeletal backbone of the aerogel by attachment of di-, tri-, and tetra-functional epoxies.
  • the resulting conformal coatings increase the density of the native aerogels by a factor of 2-3 but the strength of the resulting materials may increase by more than 2 orders of magnitude.
  • organic aerogels have also been described in the literature as an alternative to inorganic, in particular silica aerogels. These materials are generally based on polymeric networks, formed by cross-linking of monomers in a solution to yield a gel that is subsequently dried to obtain a porous material.
  • the organic aerogels are generally not fragile materials but their thermal insulative properties are generally inferior to silica aerogels: the thermal conductivities of organic aerogels are rarely lower than 0.016 W/mK.
  • WO2017/016755 (Henkel AG & Co. KGaA et al.) describes an organic aerogel having thermal insulation properties and which is obtained by reacting an isocyanate compound having a functionality of at least 2 and a cyclic ether compound having a functionality of at least 2 in the presence of a solvent.
  • WO2017/178548 (Henkel AG & Co. KGaA et al.) describes a benzoxazine-based copolymer aerogel obtained by reacting in the presence of a solvent and electively a catalyst: a benzoxazine monomer or oligomer; and, a comonomer selected from the group consisting of an isocyanate compound, a cyclic ether compound and an acid anhydride compound. Said catalyst is an optional ingredient when said comonomer is an acid anhydride compound or an isocyanate compound.
  • US2017/096548 (Korea Institute of Science & Technology) describes an aerogel-containing heat insulation composite obtained by: introducing a volatile material into the pores of the aerogel; blending the aerogel with a polymer resin, preferably a flexible polymer resin, to form a composite; and, removing the volatile material.
  • This method is intended to prevent a decline in the the porosity of the aerogel caused by infiltration and impregnation of the pores of the aerogel with the resin.
  • WO2017/198658 (Henkel AG & Co. KGaA et al.) describes a hybrid aerogel having thermal insulation properties and which is obtained by reacting an aromatic or aliphatic isocyanate compound and silanol moieties on the surface of a clay and in the presence of a solvent.
  • WO2017/216034 (Henkel AG & Co. KGaA et al.) relates to polysiloxane-based aerogels obtained by reacting a functionalized poly(dimethylsiloxane) oligomer and an aliphatic or aromatic isocyanate compound in a presence of a catalyst and a solvent.
  • WO2018/077862 (Henkel AG & Co. KGaA et al.) describes an aerogel which is obtained by reacting, in the presence of at least one solvent: silanol moieties on a surface of a clay; a first isocyanate compound A; a second isocyanate compound B; and, a cyclic ether compound.
  • WO2018/188932 (Henkel AG & Co. KGaA et al.) discloses an organic aerogel obtained by reacting an amine compound having at least two amine functionalities and a cyclic ether compound in the presence of a solvent.
  • PCT/EP2018/084569 (Henkel AG & Co. KGaA et al.) describes an organic aerogel obtained by reacting a thiol compound and an epoxide compound in a presence of a solvent.
  • PCT/EP2018/084948 (Henkel AG & Co. KGaA et al.) discloses a thiourethane based aerogels obtained by reacting an isocyanate compound having a functionality equal to or greater than 2 and a thiol compound having a functionality equal to or greater than 2 in the presence of a solvent.
  • a composite aerogel material comprising:
  • a polymeric aerogel matrix i) a polymeric aerogel matrix; and, ii) a particulate aerogel component dispersed in said matrix, said particulate aerogel component being selected from inorganic aerogels.
  • the composite aerogel material is preferably characterized by a ratio by volume of the particulate aerogel component to the polymeric aerogel matrix of from 1 : 100 to 1 : 1 , for example from 1 : 10 to 1 :1 .
  • the polymeric aerogel matrix is based on at least one polymer selected from the group consisting of: polyurethanes; poly(thiourethanes); polyurea; polyimide; polyacrylates; polymethylmethacrylate; polysiloxanes; polyoxyalkylenes; polybutadiene; melamine- formaldehyde resins; phenol-furfural resins; epoxy resins; and, benzoxazine resins.
  • the polymeric aerogel matrix is based on at least one polymer selected from the group consisting of: polyurethanes; poly(thiourethanes); polysiloxanes; and, benzoxazine resins.
  • polyurethanes poly(thiourethanes); polysiloxanes; and, benzoxazine resins.
  • These polymers show fast gelation - for instance, in less than 20 hours and even less than 5 hours - which presents the benefit that the gas-filled pores of inorganic particulate aerogel component - which is dispersed in the polymer matrix - are substantially preserved.
  • the particulate inorganic aerogel is preferably selected from the group consisting of alumina, titania, zirconia, silica and mixtures thereof. Alternatively or additionally to this embodiment, it is preferred that the constituent particles of the particulate inorganic aerogel are characterized by at least one of the following parameters:
  • porosities of from 50 to 99.0% percent, preferably from 60 to 98%;
  • pore diameters of from 2 nm to 500 nm, preferably from 10 to 400 nm or from 20 to 100 nm;
  • an average volume particle size as measured by laser diffraction / scattering methods, of from 1 to 1000 pm, preferably from 2 to 500 pm or from 5 to 200 pm;
  • the particulate inorganic aerogel component comprises, consists essentially of or consists of a particulate silica silicate aerogel having: an average particle size of 5-20 microns; a porosity of at least 90%; a bulk density of 40-100 kg/m 3 ; and, a surface area of 600-900 m 2 /g.
  • step iii) adding a catalyst to the mixture of step ii) to initiate the reaction of said monomers and thereby form a gel;
  • the word“may” is used in a permissive sense - that is meaning to have the potential to - rather than in the mandatory sense.
  • ambient conditions refers to a set of parameters that include temperature, pressure and relative humidity of the immediate surroundings of the element in question.
  • ambient conditions are: a relative humidity of from 30 to 100% percent; a temperature in the range from 20 to 40°C; and, a pressure of 0.9 to 1 .1 bar.
  • room temperature is 23°C ⁇ 2°C.
  • critical refers to a fluid medium that is at a temperature that is sufficiently high that it cannot be liquefied by pressure.
  • critical temperature of C0 2 is about 31 °C.
  • gelation indicates that colloidal particles have formed a three- dimensional network with some interstitial liquid, such that the dispersion becomes essentially non-flowing and exhibits solid-like behavior at the stated temperature.
  • dispersion refers to a composition that contains discrete particles that are distributed throughout a continuous liquid medium.
  • the terms "monomer” and " comonomer” refer to a molecule that is capable of conversion to polymers, synthetic resins or elastomers by combination with itself or other similar molecules or compounds.
  • the terms are not limited to small molecules but include oligomers, polymers and other large molecules capable of combining with themselves or other similar molecules or compounds.
  • polymerization conditions are those conditions that cause the at least one monomer to form a polymer, such as temperature, pressure, atmosphere, ratio of starting components used in the polymerization mixture, reaction time, or external stimuli of the polymerization mixture.
  • the polymerization process herein is conventionally carried out in solution. The process is operated at any of the reaction conditions appropriate to the polymerization mechanism.
  • epoxide compound denotes monoepoxide compounds and polyepoxide compounds: it is intended to encompass epoxide functional prepolymers.
  • polyepoxide compound is thus intended to denote epoxide compounds having at least two epoxy groups.
  • diepoxide compound is thus intended to denote epoxide compounds having two epoxy groups.
  • Suitable polyisocyanates - for use in deriving the polymeric aerogel matrix in accordance with several embodiments of the present invention described herein below - include aliphatic, cycloaliphatic, aromatic and heterocyclic isocyanates, dimers and trimers thereof, and mixtures thereof.
  • Aliphatic and cycloaliphatic polyisocyanates can comprise from 6 to 100 carbon atoms linked in a straight chain or cyclized and have at least two isocyanate reactive groups.
  • suitable aliphatic isocyanates include but are not limited to straight chain isocyanates such as ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, 1 ,6-hexamethylene diisocyanate (HDI), octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, 1 ,6,1 1 -undecanetriisocyanate, 1 ,3,6-hexamethylene triisocyanate, bis(isocyanatoethyl)-carbonate, and bis (isocyanatoethyl) ether.
  • straight chain isocyanates such as ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, 1
  • cycloaliphatic polyisocyanates include, but are not limited to, dicyclohexylmethane 4,4'-diisocyanate (H12MDI), 1-isocyanatomethyl-3-isocyanato-1 ,5,5-trimethyl-cyclohexane (isophorone diisocyanate, IPDI), cyclohexane 1 ,4-diisocyanate, hydrogenated xylylene diisocyanate (H 6 XDI), 1 -methyl-2,4- diisocyanato-cyclohexane, m- or p-tetramethylxylene diisocyanate (m-TMXDI, p-TMXDI) and dimer fatty acid diisocyanate.
  • H12MDI dicyclohexylmethane 4,4'-diisocyanate
  • IPDI isophorone diisocyanate
  • IPDI isophorone diisocyanate
  • aromatic polyisocyanate is used herein to describe organic isocyanates in which the isocyanate groups are directly attached to the ring(s) of a mono- or polynuclear aromatic hydrocarbon group.
  • the mono- or polynuclear aromatic hydrocarbon group means an essentially planar cyclic hydrocarbon moiety of conjugated double bonds, which may be a single ring or may include multiple condensed (fused) or covalently linked rings.
  • aromatic also includes alkylaryl. Typically, the hydrocarbon (main) chain includes 5, 6, 7 or 8 main chain atoms in one cycle.
  • planar cyclic hydrocarbon moieties include, but are not limited to, cyclopentadienyl, phenyl, napthalenyl-, [10]annulenyl-(1 ,3,5,7, 9-cyclodecapentaenyl-), [12]annulenyl-, [8]annulenyl-, phenalene (perinaphthene), 1 ,9-dihydropyrene, chrysene (1 ,2- benzophenanthrene).
  • alkylaryl moieties are benzyl, phenethyl, 1 -phenylpropyl, 2- phenylpropyl, 3-phenylpropyl, 1 -naphthylpropyl, 2-naphthylpropyl, 3-naphthylpropyl and 3- naphthylbutyl.
  • aromatic polyisocyanates include, but are not limited to: all isomers of toluene diisocyanate (TDI), either in the isomerically pure form or as a mixture of several isomers; naphthalene 1 ,5-diisocyanate; diphenylmethane 4,4'-diisocyanate (MDI); diphenylmethane 2,4'- diisocyanate and mixtures of diphenylmethane 4,4'-diisocyanate with the 2,4' isomer or mixtures thereof with oligomers of higher functionality (so-called crude MDI); xylylene diisocyanate (XDI); diphenyl-dimethylmethane 4,4'-diisocyanate; di- and tetraalkyl-diphenylmethane diisocyanates; dibenzyl 4,4'-diisocyanate; phenylene 1 ,3-diisocyanate; and,
  • olyisocyanate is intended to encompass pre-polymers formed by the partial reaction of the aforementioned aliphatic, cycloaliphatic, aromatic and heterocyclic isocyanates with polyols to give isocyanate functional oligomers, which oligomers may be used alone or in combination with free isocyanate(s).
  • Ci-C 3 o alkyr group refers to a monovalent group that contains 1 to 30 carbons atoms, that is a radical of an alkane and includes straight-chain and branched organic groups.
  • alkyl groups include, but are not limited to: methyl; ethyl; propyl; isopropyl; n-butyl; isobutyl; sec-butyl; tert-butyl; n-pentyl; n-hexyl; n-heptyl; and, 2-ethylhexyl.
  • alkyl groups may be unsubstituted or may be substituted with one or more substituents such as halo, nitro, cyano, amido, amino, sulfonyl, sulfinyl, sulfanyl, sulfoxy, urea, thiourea, sulfamoyl, sulfamide and hydroxy.
  • substituents such as halo, nitro, cyano, amido, amino, sulfonyl, sulfinyl, sulfanyl, sulfoxy, urea, thiourea, sulfamoyl, sulfamide and hydroxy.
  • C 3 -C 3 o cycloalkyt is understood to mean a saturated, mono-, bi- or tricyclic hydrocarbon group having from 3 to 30 carbon atoms.
  • cycloalkyl groups include: cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; cycloheptyl; cyclooctyl; adamantane; and, norbornane.
  • an“C 6 -C 18 aryl” group used alone or as part of a larger moiety - as in“aralkyl group” - refers to optionally substituted, monocyclic, bicyclic and tricyclic ring systems in which the monocyclic ring system is aromatic or at least one of the rings in a bicyclic or tricyclic ring system is aromatic.
  • the bicyclic and tricyclic ring systems include benzofused 2-3 membered carbocyclic rings.
  • aryl groups include: phenyl; indenyl; naphthalenyl, tetrahydronaphthyl, tetrahydroindenyl; tetrahydroanthracenyl; and, anthracenyl. And a preference for phenyl groups may be noted.
  • alkylaryf refers to alkyl-substituted aryl groups and "substituted alkylaryt' refers to alkylaryl groups further bearing one or more substituents as set forth above.
  • hetero refers to groups or moieties containing one or more heteroatoms, such as N, O, Si and S.
  • heterocyclic refers to cyclic groups having, for example, N, O, Si or S as part of the ring structure.
  • heteroalkyi' and “heterocycloalkyr moieties are alkyl and cycloalkyl groups as defined hereinabove, respectively, containing N, O, Si or S as part of their structure.
  • a“ rimary thiol group” is constituted by a thiol group (-SH) attached to a methylene group and a“secondary thiol group” is constituted by a thiol group (-SH) attached to a saturated carbon atom which has two other carbon atoms attached to it.
  • a“tertiary thiol group” is constituted by a thiol group (-SH) attached to a saturated carbon atom which has three other carbon atoms attached to it.
  • catalytic amount means a sub-stoichiometric amount of catalyst relative to a reactant.
  • the particulate aerogels of the present invention may most broadly be selected from the group consisting of inorganic aerogels, in particular silica aerogels.
  • the first component of the composite of the present invention may contain more than one type of particulate inorganic aerogel.
  • Particulate inorganic aerogels may conventionally be comprised of one or more of alumina, titania, zirconia or silica. They generally formed by sol-gel polycondensation of (metal) oxides to form highly cross-linked, transparent hydrogels: these hydrogels are then subjected to supercritical drying.
  • the present invention does not preclude the aerogel particles of this component from being modified by chemical substitution upon or within the molecular structure of the aerogel.
  • the aerogel particles may be surface treated with a material which contains a functionality reactive to that aerogel and which modifies the surface interactions - such as the hydrophobicity, hydrophilicity or surface energy - of the aerogel.
  • the aerogel particles may, for instance, be modified to have a surface functionality selected from the group consisting of: alkylsilane; alkylchlorosilane; alkylsiloxane; polydimethylsiloxane; aminosilane; and, methacrylsilane.
  • surface hydroxyl groups of inorganic aerogel particles may be replaced with at least partially fluorinated organic groups.
  • the component i) of the present invention is necessarily particulate.
  • the shape of the particles employed particles that are acicular, spherical, ellipsoidal, cylindrical, bead-like, cubic or platelet-like may be used alone or in combination.
  • agglomerates of more than one particle type may be used.
  • the particle type, porosity, pore size, and amount of the particulate aerogel component which is used for a particular embodiment may be chosen based upon the desired properties of the resultant composition and upon the properties of the polymers and solutions thereof into which the particulate aerogel is to be combined.
  • the aerogel particles of the present invention should be characterized by at least one of the following parameters:
  • porosities of from 50 to 99.0% percent, preferably from 60 to 98%;
  • pore diameters of from 2 nm to 500 nm, preferably from 10 to 400 nm or from 20 to 100 nm;
  • an average volume particle size as measured by laser diffraction / scattering methods, of from 1 to 1000 pm, preferably from 2 to 500 pm or from 5 to 200 pm;
  • x) surface areas of from 400 to 1200 m 2 /g, preferably from 500 to 1200 m 2 /g and 600 to 900 m 2 /g;
  • An exemplary particulate aerogel may meet one, two, three, four, five or six of the defined parameters.
  • the particulate aerogel component comprises, consists essentially of or consists of a particulate silica aerogel.
  • that component comprises, consists essentially of or consists of a particulate silica silicate aerogel having: an average particle size of 5-20 microns; a porosity of 90% or more; a bulk density of 40-100 kg/m 3 ; and, a surface area of 600- 900 m 2 /g.
  • the particulate aerogel component can be either formed initially at the desired particle size particles or can be formed as larger particles and then comminuted to the desired size for inclusion in the composite material.
  • comminution of the aerogel particles may be performed by one or more of: grinding; milling; homogenization; and, sonication.
  • Grinding can, for instance, be effected using a planetary ball mill having a grinding chamber that includes a rotor shaft that is used to rotate grinding media.
  • a planetary ball mill having a grinding chamber that includes a rotor shaft that is used to rotate grinding media.
  • Milling may be performed in any high-energy mill, of which examples include: centrifugal mills; planetary ball mills; jet mills, such as spinning air flow jet mill; and, fluid energy mills.
  • the high-energy mill should be able to impart an impact force of at least 0.5G, for example from 0.5 to 25G, to the milling media.
  • Non-limiting examples of mills which may find utility in the present invention are disclosed in: US Patent No. 5,522,558; US Patent No. 5,232, 169; US Patent No. 6, 126,097; and, US Patent No. 6,145,765.
  • the present invention does not preclude milling being conducted under heat - such as described in WO 00/56486 - and / or in the presence of additives, such as lubricants, surfactants, dispersants and solvents.
  • a typical sonication would first comprise adding said particles to at least one solvent and optionally at least one reactant.
  • the employed solvent(s) should comprise or consist of a non-polar solvent selected from the group consisting of: alkanes (R— H); cyclic alkanes; branched alkanes; aromatics (Ar— H); alkyl halides (R— X); and, mixtures thereof.
  • exemplary but non-limiting non polar solvents include n-pentane, n-hexane, cyclohexane, n-heptane, isooctane, trimethylpentane, toluene, xylene and benzene.
  • reactants - such as silylating agents and organofunctional silanes - serve to pacify the newly generated aerogel particle surfaces created during sonication and the fragmentation of the starting aerogel particles and to thereby yield unreactive aerogel particles.
  • Sonic energy is then applied to the formed medium.
  • the frequency of sonication, the time of sonication and the power used are key determinants for the end particle size distribution.
  • MisoNix Sonicator® 3000 available from Cole-Parmer Instrument Company may be mentioned as an exemplary sonic probe for performing sonication.
  • any fluid present in the comminution step(s) may be separated from the particles.
  • One or more separation process such as air-drying, heating, filtration and evaporation, can be employed in this regard but it is preferred that the fluid is removed under heating to a sufficient temperature to prevent agglomeration of the particle during the drying thereof.
  • the Polymeric Aerogel Matrix is based on at least one polymer selected from the group consisting of: polyurethanes; poly(thiourethanes); polyurea; polyimides; polyacrylates; polymethylmethacrylate; polysiloxanes; polyoxyalkylenes; polybutadiene; melamine- formaldehyde resins; phenol-furfural resins; resorcinol-formaldehyde resins; epoxy resins; and, benzoxazine resins.
  • the disclosures of the following citations may be instructive in forming such matrices: US Patent No. 5,476,878; US Patent No. 5,081 ,163; US Patent No. 4,997,804; US Patent No. 4,873,218; US Patent No. 9,434,832; US 2014/0171526; and, US 2015/0141544.
  • the polymeric aerogel matrix is based on at least one polymer selected from the group consisting of: polyurethanes; poly(thiourethanes); polysiloxanes; and, benzoxazine resins. These polymers generally show fast gelation which presents the benefit that the gas-filled pores of inorganic particulate aerogel component - dispersed in the polymer matrix - are substantially preserved.
  • a polymeric matrix aerogel component obtained by reacting in the presence of a catalyst and a solvent:
  • the polythiol is not precluded from having at least one tertiary thiol group.
  • the polythiol is preferably characterized by having at least 2 and in particular at least 3 primary thiol groups per molecule.
  • the polythiols may be synthesized according to procedures known to the skilled artisan.
  • the polythiols used in the invention are polyfunctional thiols and the skilled artisan will appreciate that monofunctional secondary thiols can be used to produce polyfunctional secondary thiols.
  • hydroxy functional secondary thiol materials - such as 1 -mercaptoethanol, 2-mercapto- 1 -propanol, 3-mercapto-1 -butanol or 4-mercapto-1 -pentanol - and carboxylic acid functional secondary thiols, such as 2-mercaptopropanoic acid, 3-mercaptobutanoic acid or 4- mercaptopentanoic acid may be converted into higher polyfunctional secondary thiol materials via esterification procedures.
  • Polyfunctional tertiary thiol materials may be prepared using procedures known from the literature, including the Markovnikov addition of hydrogen sulphide to a substituted olefin.
  • Instructive disclosures for the preparation of polyfunctional tertiary thiol materials include: Fokin et al. , Organic Letters 2006 Vol. 8 No. 9 pages 1767-1770; Tetrahedron Vol. 62 (35) pages 8410-8418 (2006); Mukaiyama et al. , Chemistry Letters Vol. 30 (2001) No. 7 page 638; and, US Patent No. 5,453,544.
  • Exemplary polythiols which have shown positive utility in this embodiment of the present invention include: pentaerythritol tetrakis (3-mercaptobutyrate); 1 ,3,5-tris(3-mercaptobutyloxy ethyl)-1 ,3,5- triazine-2,4,6(1 H,3H,5H)-trione; and, 1 ,4-bis(3-Mercaptobutyloxy) butane.
  • Exemplary polythiols are also commercially available from Showa Denko under the tradename Karenz® MT and from Bruno Bock under the tradenames Thiocure PETMP, Thiocure TMPMP, Thiocure Tempic, Thiocure ETTMP 700 and Thiocure GDMP.
  • a polymeric matrix aerogel component obtained by reacting in the presence of a catalyst and a solvent: a) a polyisocyanate as defined hereinabove; and,
  • a cyclic ether compound selected from the group consisting of epoxide compounds and oxetane compounds.
  • the cyclic ether reacts with the polyisocyanate compound to form a urethane, which forms the matrix polymer of the aerogel according to the present invention.
  • This reaction should desirably be performed at an equivalent ratio of epoxy or oxetane groups to isocyanate groups of from 15:1 to 1 : 15, preferably 10: 1 - 1 :10, more preferably 5:1 - 1 :5. It should of course be noted that an equivalent ratio of 1 : 1 falls within these stated ranges.
  • cyclic ether compound is an epoxide compound, it is preferably selected from the group consisting of:
  • R 5 is selected from the group consisting of a C1-C30 alkyl group, a C3-C30 cycloalkyl group, a C 6 -Ci 8 aryl group, a C7-C30 alkylaryl group, a C3-C30 heterocycloalkyl group and a C1 -C30 heteroalkyl group;
  • n is an integer from 1 to 30;
  • R 6 is selected independently from the group consisting of hydrogen, halogen, alkyl and alkenyl
  • n is an integer from 1 to 10;
  • R 7 is selected independently from the group consisting of hydrogen, hydroxyl, halogen, alkyl and alkenyl;
  • n is an integer from 0 to 16.
  • said epoxide compound is selected from the group consisting of: N, N-diglycidyl- 4-glycidyloxyaniline; sorbitol glycidyl ether-aliphatic polyfunctional epoxy resin; 4,4'- methylenebis(/V,/V-diglycidylaniline); 2-[[4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2- yl]phenoxy]methyl]oxirane; and, poly[(o-cresyl glycidyl ether)-co-formaldehyde].
  • Suitable commercially available epoxide compounds for use in this embodiment of the present invention include, but are not limited to: 1 ,4-butanediol diglycidyl ether (ErisysTM GE21 ); cyclohexandimethanol diglycidyl ether (Erisys TM GE22); ethylene glycol diglycidyl ether (Erisys TM EDGE); dipropylene glycol diglycidyl ether (Erisys TM GE23); 1 ,6-hexanediol diglycidyl ether (Erisys TM GE25); trimethylolpropane triglycidyl ether (Erisys TM GE30); polyglycerol-3- polyglycidyl ether (Erisys TM GE38); sorbitol glycidyl ether-aliphatic polyfunctional epoxy resin (Erisys TM GE60); phenol novolac epoxy resins
  • epoxide compounds suitable epoxide compound for use in the present invention are selected from the group consisting of
  • e 1 , e 2 , e 3 are same or different and independently selected from 1 to 12; f , f 2 , f 3 are same or different and independently selected from 1 to 12; g 1 , g 2 , g 3 are same or different and independently selected from 1 to 26; h 1 , h 2 , h 3 are same or different and independently selected from 0 to 6, provided that h 1 +h 2 +h 3 is at least 2; i 1 , i 2 , i 3 are same or different and independently selected from 0 to 25; j 1 , j 2 , j 3 are same or different and independently selected from 1 to 26; k 1 , k 2 , k 3 are same or different and independently selected from 0 to 6, provided that k 1 +k 2 +k 3 is at least 2; and I 1 , 1 2 , I 3 are same or different and independently selected from 0 to 25;
  • R 3 represents a substituent or different substituent and is selected independently from the group consisting of hydrogen, halogen and linear or branched C1-C15 alkyl or alkenyl groups, attached to their respective phenyl ring at the 3-, 4- or 5-position and their respective isomers and m is an integer from 1 to 5; wherein n and 0 are same or different and independently selected from 1 to 10;
  • p is an integer from 1 to 5;
  • said epoxide compound is selected from the group consisting of 2-[(3- ⁇ [2-hydroxy-3- ( ⁇ 2-[(2-oxiranyl)methoxy]-4-pentadecylphenyl ⁇ methyl)-4-pentadecylphenyl]methyl ⁇ -2-[(2- oxiranyl)methoxy]-4-pentadecylphenyl)methyl]-6-( ⁇ 2-[(2-oxiranyl)methoxy]-6- pentadecylphenyl ⁇ methyl)-3-pentadecylphenol, 2,3-bis ⁇ (E)-1 1 -[(2-oxiranyl)methoxy]-8- heptadecenylcarbonyloxy ⁇ propyl (E)-12-[(2-oxiranyl)methoxy]-9-octadecenoate, 2- ⁇ [m-(8- ⁇ p-[(2- oxiranyl)methoxy]phenyl ⁇ pentadecyl
  • epoxide compounds are preferred because they provide hydrophobic aerogels.
  • Examples of commercially available epoxide compound for use in the present invention are but not limited to Cardolite NC-547, Cardolite NC-514S and Cardolite NC-514 from Cardolite, Erisys GE35 from CVC thermosets, CER 4221 from DKSH, Vikoflex 7170 and Vikoflex 7190 from Arkema, Epiclon HP-5000, Epiclon HP-7200H and Epiclon HP-9500 from DIC Corporation, and Jagroxy-505 from Jayant Agro-Organics Ltd. KR-470, X-12-981 S, KR-517, KR-516, X-41 -1059A and X-24-9590 from Shin Etsu.
  • cyclic ether compound is an oxetane compound, it is preferably selected from the group consisting of:
  • R 8 is selected from the group consisting of a C1-C30 alkyl group, a C3-C30 cycloalkyl group, a C 6 -Ci 8 aryl group, a C7-C30 alkylaryl group, a C3-C30 heterocycloalkyl group and a C1-C30 heteroalkyl group;
  • n is an integer from 1 to 30.
  • said oxetane compound is selected from the group consisting of 1 ,4-bis[(3-ethyl- 3-oxetanylmethoxy)methyl]benzene and bis[1 -ethyl(3-oxetanyl)]methyl ether.
  • Suitable commercially available oxetane compound for use in this embodiment of the present invention include, but are not limited to: 1 ,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene (Eternacoll OXBP); bis[(3-ethyl-3-oxetanyl)methyl]terephthalate (Eternacoll OXTP); bis[1 -ethyl(3- oxetanyl)]methyl ether (Aron OXT 221); and, 1 ,4-bis[(3-ethyl-3-oxetanylmethoxy) methyl]benzene (Aron OXT 121 ), available from Toagosei America Inc. Benzoxazine Resins
  • a benzoxazine matrix aerogel component obtained by reacting in the presence of a catalyst and a solvent: a) a benzoxazine monomer or oligomer; and,
  • a co-monomer selected from the group consisting of a polyisocyanate compound, a cyclic ether compound and an acid anhydride.
  • the reactants meet at least one of the following polymerization conditions: the reactant benzoxazine monomer or oligomer has a functionality from 1 to 4, preferably of 1 or 2; the polyisocyanate compound has a functionality from 2 to 6, preferably of 2 or 3; said cyclic ether compound is an epoxide compound or an oxetane compound having a functionality from 2 to 5, preferably from 3 to 5; and, said acid anhydride compound has a functionality 1 or 2 and is derived from aliphatic or aromatic carboxylic acids.
  • Suitable benzoxazine monomers and oligomers are disclosed in WO2017/178548A1 (Henkel AG & Co. KGaA), the disclosure of which is incorporated by reference.
  • said benzoxazine monomer is preferably selected from the group consisting of: 4'-bis(3,4-dihydro-2H-1 ,3-benzoxazin-3-yl)phenyl methane; 6,6'-propane-2,2-diylbis(3-phenyl- 3,4-dihydro-2H-1 ,3-benzoxazine); 6,6'-methylenebis(3-phenyl-3,4-dihydro-2H-1 ,3-benzoxazine; 3-phenyl-3,4-dihydro-2H-1 ,3-benzoxazine; and, mixtures thereof.
  • exemplary anhydride compounds which are suitable for use in this embodiment of present invention include, but are not limited to: benzophenonetetracarboxylic dianhydride (4,4-BTDA); trimellitic anhydride; phthalic anhydride; biphenyltetracarboxylic dianhydride (S-BDPA); 4,4'-oxydiphthalicanhydride (ODPA); 4,4'-
  • hexafluoroisopropylidenediphthalic anhydride (6FDA); 4,4'-bisphenol A dianhydride (BPADA); pyromellitic dianhydride (PMDA); trimellitic anhydride (TMA); phthalic anhydride; 3, 4,5,6- tetrahydrophthalic anhydride; 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride; and, mixtures thereof.
  • the acid anhydride compound is selected from the group consisting of: benzophenonetetracarboxylic dianhydride (4,4-BTDA); trimellitic anhydride; phthalic anhydride; biphenyltetracarboxylic dianhydride (S-BDPA); and, mixtures thereof
  • the benzoxazine based copolymer matrix according to the present invention should have a ratio by weight of benzoxazine monomer or oligomer to co-monomer of from 20:1 to 1 :1 , based on the total monomers in the solution: preferred weights ratios are from 10:1 to 2: 1 and from 10: 1 to 3:1 .
  • a polysiloxane matrix aerogel component obtained by reacting in the presence of a catalyst and a solvent: a) a functionalised poly(dimethylsiloxane) oligomer; and,
  • the reaction takes place between the terminal groups of the poly(dimethylsiloxane) (PDMS) oligomers and the isocyanate moieties.
  • the final chemical structure of the matrix aerogel component obtained depends on the nature of the functional group of the PDMS oligomer.
  • a suitable poly (dimethylsiloxane) oligomer for use in the present invention is a compound having a functionality of at least 2, for example from 2 to 6.
  • Suitable poly(dimethylsiloxane) oligomers can be functionalized with a variety of chemical compounds, such as amino, hydroxyl or epoxy groups. In the cases of either a hydroxyl-PDMS or an epoxy-PDMS being used in the reaction, a polyurethane-polysiloxane material is obtained. Where the PDMS-NH 2 oligomer is used, this yields a polyurea-polysiloxane material.
  • Scheme 1 illustrates the chemical reactions involved in each case with a di-functional isocyanate.
  • Functionalised poly(dimethylsiloxane) oligomers with different molecular weights can be used in order to obtain aerogels with different properties. It is submitted that said PDMS-OH, PDMS- NH 2 or PDMS-epoxy oligomers should have a weight average molecular weight (Mw) of at least 300 g/mol. On the other hand, the weight molecular weight (Mw) of said PDMS-OH, PDMS-NH 2 and PDMS-epoxy oligomers should generally be ⁇ 12000 g/mol, preferably ⁇ 6000 g/mol and more preferably ⁇ 3000 g/mol, for example ⁇ 2000 g/mol.
  • Suitable functionalised poly(dimethylsiloxane) oligomers for use in the present invention are selected from the group consisting of:
  • R 1 is selected from the group consisting of C1-C20 alkyl or C 6 -Ci 8 aryl group;
  • n is an integer from 0 to 200, in particular from 0 to 100;
  • p is an integer from 1 to 20, in particular from 1 to 10.
  • said functionalised poly(dimethylsiloxane) oligomer is selected from the group consisting of: silanol terminated polydimethylsiloxanes; aminopropyl terminated polydimethylsiloxanes; N-ethylaminoisobutyl terminated polydimethylsiloxane; epoxypropoxypropyl terminated polydimethylsiloxanes; (epoxypropoxypropyl)dimethoxysilyl terminated polydimethylsiloxanes; epoxycyclohexylethyl terminated polydimethylsiloxanes; carbinol (hydroxyl) terminated polydimethylsiloxanes; and, mixtures thereof.
  • Examples of commercially available functionalised poly(dimethylsiloxane) oligomer for use in his embodiment of the present invention include but are not limited to: FLUID NH 15 D, FLUID NH 40 D, FLUID NH 130 D, FLUID NH 200 D and IM 1 1 available from Wacke; poly(dimethylsiloxane) diglycidyl ether terminated, poly(dimethylsiloxane) hydroxy terminated, poly(dimethylsiloxane) bis(hydroxyalkyl) terminated and poly(dimethylsiloxane) bis(3-aminopropyl) terminated, available from Sigma-Aldrich; and, silanol terminated polydimethylsiloxanes, aminopropyl terminated polydimethylsiloxanes, N-ethylaminoisobutyl terminated polydimethylsiloxane, epoxypropoxypropyl terminated polydimethylsiloxanes, (epoxypropoxy
  • a polysiloxane based aerogel according to the present invention should have a functionalized poly(dimethylsiloxane) oligomer content from 5 to 80 wt.%, for example from 10 to 70 wt.%, based on the total weight of the reactant compounds.
  • the composite aerogel material of the present invention is produced by a process comprising the steps of:
  • step ii) adding a catalyst to the mixture of step ii) to initiate the reaction of said monomers and thereby form a gel
  • reaction mixture of step ii) is conventionally either prepared in or formed and transferred to a closed container or mould. That mould determines the geometry of the final composite aerogel material, for which no particular limit is intended: composite materials of both simple and complex geometries may be formed.
  • the first solvent - in which the polymeric aerogel matrix component is prepared - is suitably a polar solvent and preferably a polar aprotic solvent.
  • Polar aprotic solvents do not have hydrogen atoms that can be donated into an H-bond: therefore, anions participating in a nucleophilic addition reaction are not solvate, and they are not inhibited from reaction.
  • said compounds for use as said first solvent include: dimethylacetamide (DMAc); dimethylformamide (DMF); tetrahydrofuran (THF); 1-methyl- 2-pyrrolidinone (NMP); dimethyl sulfoxide (DMSO); acetonitrile; ethyl acetate; acetone; methyl ethyl ketone (MEK); methyl isobutyl ketone (MIBK); and, mixtures thereof.
  • DMAc dimethylacetamide
  • DMF dimethylformamide
  • THF tetrahydrofuran
  • NMP 1-methyl- 2-pyrrolidinone
  • DMSO dimethyl sulfoxide
  • MEK methyl ethyl ketone
  • MIBK methyl isobutyl ketone
  • the admixture of the particulate aerogel component with the first solution may be performed by under agitation using commonplace methods in the art: the agitation or stirring should be sufficient to ensure a homogenous dispersion of the particles in the first solution.
  • the particulate aerogel component can be mixed directly with the first solution, it is also possible to independently disperse at least a portion of the particles in a polar aprotic solvent - which may be the same or different from said first solvent - and then mix that dispersion with the first solution.
  • the particulate aerogel component is conventionally admixed in an amount such that the ratio by weight of the particulate aerogel component to the total monomers is from 1 :100 to 1 : 1 , for example from 1 :10 to 1 :1 , from 1 :5 to 1 :1 or from 1 :2 to 1 :1 .
  • This characterization is not intended to be mutually exclusive of the above mentioned characterization of the composite aerogel material by ratio by volume.
  • Suitable catalysts may, in particular, be selected from the group consisting of: alkyl amines; aromatic amines; imidazole derivatives; aza compounds; guanidine derivatives; and, amidines.
  • the catalysts may comprise one or more of the following compounds: triethylamine; trimethylamine; benzyldimethylamine (DMBA); /V,/V-dimethyl-1-phenylmethanamine; 1 ,4- diazabicyclo[2.2.2]octane; 2-ethyl-4-methylimidazole; 2-phenylimidazole; 2-methylimidazole; 1 - methylimidazole; 4,4'-methylene-bis(2-ethyl-5-methylimidazole); 3,4,6,7,8,9-hexahydro-2H- pyrimido[1 ,2-a]pyrimidine; 2, 3, 4, 6, 7, 8, 9, 10-octahydropyrimido-[1 ,2-a]azepine; 1 ,8- diazabicyclo[5.4.0]undec-7-ene (DBU); 1 ,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD); 1 ,
  • DMBA benzyldimethylamine
  • TBD 1,5,7-triazabicyclo[4.4.0]dec- 5-ene
  • DBU 1 ,8-diazabicyclo[5.4.0]undec-7-ene
  • DBTDL dibutyltin dilaurate
  • triethylamine benzyldimethylamine
  • TBD 1,5,7-triazabicyclo[4.4.0]dec- 5-ene
  • DBU 1 ,8-diazabicyclo[5.4.0]undec-7-ene
  • DBTDL dibutyltin dilaurate
  • triethylamine benzyldimethylamine
  • the catalyst will conventionally be employed in an amount up to 10 wt.%, for example from 0.5 to 5 wt.%, based on the weight of the reactant monomers.
  • reaction or gelation step iii) should not be performed at temperatures higher than 160°C as this would necessitate the use of high boiling point solvents.
  • reaction or gelation temperatures of step iii) should typically be from 20 to 160°C, preferably from 25 to 120°C, for example from 25 to 100°C.
  • the container or vessel in which the mixture of step ii) is disposed may be transferred to an oven for the determined gelation time.
  • Said gelation time is typically from 0.1 to 20 hours although gelation times of from 0.5 to 15 hours, for example from 0.5 to 12 hours would be expedient.
  • the gel is washed at least once and commonly several times over a period of up to 96 hours using a second solvent: the intention of the washing step is to displace the first solvent present during the gelation step with the preferred solvent for the subsequent supercritical drying process.
  • That second solvent may, in particular, be ethanol, acetone, hexane, dimethyl sulfoxide (DMSO) or mixtures thereof and further that second solvent may be independently selected for each washing step.
  • the washing step iv) may be performed step-wise using the following sequence of solvents: 1 ) DMSO; 2) DMSO/acetone and a given ratio by weight; and, 3) acetone.
  • the washing step iv) may be performed step-wise using the following sequence of solvents: 1) DMSO; 2) DMSO/acetone at a pre-determined weight ratio; 3) acetone; 4) acetone/hexane at an excess of acetone; 5) acetone/hexane at a weight ratio of 1 : 1 ; 6) acetone/hexane at an excess of hexane; and, 7) hexane.
  • the stage of gel drying in a supercritical fluid is then performed.
  • This supercritical drying broadly includes the following steps: a) displacement of the solvent in the wet gel by a supercritical fluid when placed in an appropriate reactor; and, b) pressure release, the transfer of the supercritical fluid in a gas and the removal of the gas phase of the sample to preserve the highly porous structure.
  • the conditions employed throughout the supercritical drying stage must allow the gel structure of the polymeric matrix to be preserved without damage.
  • the supercritical drying stage of the present invention should commonly comprise: placing the gel in the reactor and charging the reactor with additional ethanol or acetone to prevent air-drying of the gel; pressuring the reactor with C0 2 to at least 5-15 MPa under cooling to 0-10°C; flushing liquid C0 2 through the reactor to commence the extraction of said second solvent; gently heating and pressurizing the reactor over the critical temperature and pressure; flushing the reactor with C0 2 in the supercritical state at a pressure of 5-15 MPa and a temperature of from 20-60°C; permitting diffusion; and, slowly releasing the applied pressure in the reactor until ambient pressure is attained.
  • the high pressure reactor is desirably under computer control and should: (a) provide no stagnant zones; (b) be constructed of materials which permit isothermal conditions to be maintained without appreciable heating; (c) ideally include a transparent area to permit observation of the drying process; and, (d) possess means, such as terminal flanges, which facilitate cleaning and the loading and unloading of material.
  • the composite aerogel may be aged at room temperature and pressure, it may be beneficial in certain circumstances to post-cure the aerogel at an elevated temperature. Temperatures up to 250°C may be appropriate, with temperatures of from 100°C to 200 °C being preferred. iv) Adjunct Materials
  • the composite material of the present invention may contain reinforcement materials to improve the structural integrity and / or the handling of the composite.
  • Suitable reinforcement materials include but are not limited to: glass fibers; glass mats; felt; glass wool; carbon fibers; boron fibers; ceramic fibers; rayon fibers; nylon fibers; olefin fibers; alumina fibers; asbestos fibers; clay; mica; calcium carbonate; talc; zinc oxide; barium sulfates; wood; and, polystyrene.
  • Further suitable reinforcement materials are described in inter alia WO 95/03358, WO 96/36654 and WO 96/37539.
  • the reinforcement material may be included in the composite material in an amount up to 100 wt.%, preferably up to 50 wt.%, for example from 10 to 50 wt.%, based on the weight of the particulate aerogel component.
  • the composite may further comprise at least one opacifier.
  • Suitable opacifiers are particulate materials and include but are not limited to: carbon black; graphite; carbon nanotubes; rutile zirconium dioxide; chromium dioxide; titanium dioxide, including ilmenite; ferrosoferric oxide; iron oxide; manganese oxide; zinc oxide; magnesium oxide; antimony oxide; ilmenite; silicon carbide; and, metal silicates.
  • the opacifier may be included in the composite material in an amount up to 100 wt.%, preferably up to 50 wt.%, for example from 10 to 50 wt.%, based on the weight of the particulate aerogel component.
  • the aforementioned reinforcement materials and opacifiers may be dispersed in one or more of the monomer solution of step i) above (1 st solution), a dispersion of the aerogel particles and / or the catalyst component, prior to the polymerization and gelation step iii).
  • the skilled artisan would however be aware that woven fibers and mats may also be included in the composite material - as reinforcement materials - through being disposed at the bottom and / or the top of the mould in which an aerogel monolith is cast.
  • the composite material is prepared in the presence of at least one wetting agent: that wetting agent would thereby remain in - and contribute to the overall thermal conductivity of - the composite material.
  • wetting agent might be added during the polymerization and gelation step iii), this is not preferred where the agent is operative to permit the wetting of the aerogel particles. Consequently, it is preferred that the wetting agent is present in the monomer solution (1 st solution) and / or the dispersion of the aerogel particles.
  • the wetting agent may be added in an amount such that the composite material contains up to 100 wt.%, preferably up to 50 wt.%, for example from 10 to 50 wt.% of said wetting agent, based on the weight of the particulate aerogel component.
  • the wetting agent must, most broadly, be compatible with the particulate aerogel component and will conventionally be selected from the group consisting of: anionic surfactants; cationic surfactants; amphoteric surfactants; non-ionic surfactants; and, high molecular weight dispersants.
  • anionic surfactants include alkyl sulfates and higher alkyl ether sulfates of which groups ammonium lauryl sulfate and sodium polyoxyethylene lauryl ether sulfate may be mentioned as specific examples.
  • Exemplary cationic surfactants include aliphatic ammonium salts and amine salts, of which groups alkyl trimethylammonium and polyoxyethylene alkyl amine may be mentioned as specific examples.
  • Amphoteric surfactants may, for instance, be of the betaine type - such as alkyl dimethyl betaine - or of the oxido type, such as alkyl dimethyl amine oxido.
  • non-ionic surfactants include: glycerol fatty acid esters; propylene glycol fatty acid esters; sorbitan fatty acid esters; polyoxyethylene sorbitan fatty acid esters; tetraoleic acid polyoxyethylene sorbitol; polyoxyethylene alkyl ether; polyoxyethylene alkyl phenyl ether; polyoxyethylene polyoxypropylene glycol; polyoxyethylene polyoxypropylene alkyl ether; polyethylene glycol fatty acid esters; higher fatty acid alcohol esters; and, polyhydric alcohol fatty acid esters.
  • AEROSOL® OT sodium di-2-ethylhexylsulfosuccinite available from Sigma Aldrich
  • BARLOX® 12i a branched alkyldimethylamine oxide available from Lonza
  • TRITON® 100 octylphenoxypolyethoxy(9-10)ethanol available from Dow Chemical
  • TWEEN® surfactants such as Tween 100, available from Sigma Aldrich
  • Renex® surfactants such as Renex 20, available from Croda
  • Hypermen polymer surfactants and, Pluronic® surfactants, available from BASF.
  • the composite aerogel materials of the present invention may be utilized per se or as one element of more complex thermal and acoustic insulation constructs.
  • the composite materials may be attached to blankets of fibrous materials or utilized as one or more layers within a laminar thermal and / or acoustic insulating material.
  • the fine structure of the composite aerogel materials may be modified after formation to meet a particular purpose.
  • the structure of composite aerogel material may be locally disrupted by needling or punching in which processes the following are illustrative result effective variables: needle puncture density; needle penetration depth; and, needle characteristics, such as crank, shank, blade, barb and points thereof.
  • DBTDL Dibutyltin dilaurate available from Merck.
  • Desmodur N3300 Aliphatic polyisocyanate (HDI trimer) available from Covestro.
  • EnovaTM Aerogel IC 31 10 Particulate silica aerogel available from Worlee-Chemie GmbH
  • EnovaTM Aerogel MT 1 100 Particulate silica aerogel available from Worlee-Chemie GmbH
  • a thiourethane organic aerogel was prepared as follows. A first solution was prepared by dissolving 1 .13g of Karenz MT NR1 in 10g of acetone, followed by the addition of 0.79 g of MDI thereto. A second solution was prepared by dissolving 0.193 g of DMBA in 12.20 g of acetone.
  • the first and second solutions were then mixed at room temperature and a gel was obtained after approximately 1 minute. That resulting gel was washed three times with acetone at 24 hour intervals using a solvent volume three times that of the gel at each washing step. Subsequently the gel was dried via carbon dioxide (C0 2 ) supercritical drying (SCD).
  • C0 2 carbon dioxide
  • SCD supercritical drying
  • a first solution was prepared by dissolving 1.13g of Karenz MT NR1 in 10g of acetone, followed by the addition of 0.79 g of MDI thereto. The solution was then added to a container in which 0.97g of silica aerogel particles (EnovaTM Aerogel IC 31 10) had previously been disposed.
  • a second solution was prepared by dissolving 0.193 g of DMBA in 12.20 g of acetone.
  • the first and second solutions were then mixed at room temperature and a gel was obtained after approximately 1 minute. That resulting gel was washed three times with acetone at 24 hour intervals using a solvent volume three times that of the gel at each washing step. Subsequently the gel was dried via carbon dioxide (C0 2 ) supercritical drying (SCD).
  • C0 2 carbon dioxide
  • SCD supercritical drying
  • a first solution was prepared by dissolving 0.57g of PDMS-OH in 10g acetone, followed by the addition of 1 .61 g of Desmodur N3300. The solution was then added to a container in which 1 .09 g of silica aerogel particles (EnovaTM Aerogel MT1 100) had previously been disposed.
  • a second solution was prepared by dissolving 0.13g of DBTDL in 12.04g of acetone.
  • the first and second solutions were then mixed at room temperature and a gel was obtained after approximately 10 hours. That resulting gel was washed three times with acetone at 24 hour intervals using a solvent volume three times that of the gel at each washing step. Subsequently the gel was dried via carbon dioxide (C0 2 ) supercritical drying (SCD).
  • C0 2 carbon dioxide
  • SCD supercritical drying

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Abstract

La présente invention concerne un matériau d'aérogel composite comprenant : i) une matrice d'aérogel polymère ; et ii) un composant d'aérogel particulaire dispersé dans ladite matrice, ledit composant d'aérogel particulaire étant choisi parmi des aérogels inorganiques. La présente invention concerne également un procédé d'obtention du matériau d'aérogel composite défini, ledit procédé comprenant les étapes consistant à : a) dissoudre les monomères réactifs de la matrice d'aérogel polymère dans un premier solvant afin de former une première solution ; b) mélanger la première solution avec le composant d'aérogel particulaire afin de former une dispersion desdites particules ; c) ajouter un catalyseur au mélange de l'étape ii) afin d'initier la réaction desdits monomères et ainsi former un gel ; d) laver ledit gel avec un second solvant ; e) sécher ledit gel par séchage supercritique ; et éventuellement f) post-durcir l'aérogel obtenu par traitement thermique.
PCT/EP2020/054851 2019-02-25 2020-02-25 Matériau d'aérogel composite WO2020173911A1 (fr)

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CN112194180A (zh) * 2020-10-14 2021-01-08 北京化工大学 一种增强气凝胶力学性能的改性方法
CN113150365A (zh) * 2021-05-27 2021-07-23 淮阴工学院 常压干燥法制备密胺气凝胶和纤维型黏土增强密胺复合气凝胶
CN115246745A (zh) * 2022-07-14 2022-10-28 航天特种材料及工艺技术研究所 一种耐高温复合组分气凝胶材料及其制备方法
WO2022216703A3 (fr) * 2021-04-05 2022-12-29 The Curators Of The University Of Missouri Aérogels de carbone amorphe et graphitique issus de poudres de xérogel comprimées
CN115725110A (zh) * 2022-11-16 2023-03-03 航天特种材料及工艺技术研究所 一种硅树脂改性聚苯并噁嗪气凝胶及其制备方法
CN116535732A (zh) * 2023-05-23 2023-08-04 西南石油大学 一种阻燃型双网络苯并噁嗪气凝胶及其制备方法
CN117903491A (zh) * 2024-03-13 2024-04-19 西南石油大学 一种苯并噁嗪改性超疏水型三聚氰胺泡沫及制备方法

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112194180A (zh) * 2020-10-14 2021-01-08 北京化工大学 一种增强气凝胶力学性能的改性方法
WO2022216703A3 (fr) * 2021-04-05 2022-12-29 The Curators Of The University Of Missouri Aérogels de carbone amorphe et graphitique issus de poudres de xérogel comprimées
CN113150365A (zh) * 2021-05-27 2021-07-23 淮阴工学院 常压干燥法制备密胺气凝胶和纤维型黏土增强密胺复合气凝胶
CN115246745A (zh) * 2022-07-14 2022-10-28 航天特种材料及工艺技术研究所 一种耐高温复合组分气凝胶材料及其制备方法
CN115725110A (zh) * 2022-11-16 2023-03-03 航天特种材料及工艺技术研究所 一种硅树脂改性聚苯并噁嗪气凝胶及其制备方法
CN115725110B (zh) * 2022-11-16 2024-03-26 航天特种材料及工艺技术研究所 一种硅树脂改性聚苯并噁嗪气凝胶及其制备方法
CN116535732A (zh) * 2023-05-23 2023-08-04 西南石油大学 一种阻燃型双网络苯并噁嗪气凝胶及其制备方法
CN116535732B (zh) * 2023-05-23 2024-04-05 西南石油大学 一种阻燃型双网络苯并噁嗪气凝胶及其制备方法
CN117903491A (zh) * 2024-03-13 2024-04-19 西南石油大学 一种苯并噁嗪改性超疏水型三聚氰胺泡沫及制备方法

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