Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
  • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
  • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
  • B01D71/06—Organic material
  • B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
  • B01D71/702—Polysilsesquioxanes or combination of silica with bridging organosilane groups
• • 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
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
  • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
  • C08J3/212—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase and solid additives
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2256/00—Main component in the product gas stream after treatment
  • B01D2256/24—Hydrocarbons
  • B01D2256/245—Methane
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/50—Carbon oxides
  • B01D2257/504—Carbon dioxide
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2258/00—Sources of waste gases
  • B01D2258/02—Other waste gases
  • B01D2258/0283—Flue gases
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2258/00—Sources of waste gases
  • B01D2258/05—Biogas
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
  • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
  • C08G77/28—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen sulfur-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
  • C08G77/30—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen phosphorus-containing groups
• • 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
  • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
  • Y02C20/00—Capture or disposal of greenhouse gases
  • Y02C20/40—Capture or disposal of greenhouse gases of CO2
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

• Ionic liquids are salts containing poorly coordinated ions, which can render the melting point of the salts equal to or close to room temperature.
• Many ionic liquids have even been developed in recent years for applications such as solvents, lubricants, anti-microbial agents, homogeneous and heterogeneous catalysis, treatment of high-level nuclear waste, and metal ion removal.
• membranes to separate gases is an important technique that can be used in many industrial procedures. Examples can include recovery of hydrogen gas in ammonia synthesis, recovery of hydrogen in petroleum refining, separation of methane from other components in biogas synthesis, enrichment of air with oxygen for medical or other purposes, removal of water vapor from natural gas, removal of carbon dioxide (CO2) from natural gas or biogas, and carbon- capture applications such as the removal of CO2 from flue gas streams generated by combustion processes.
• CO2 carbon dioxide
• the present invention relates to silicone compositions made from mixtures including ionic liquids having hydrolysable silyl groups (ILHSGs).
• the present invention provides methods of making the silicone composition and also provides the silicone compositions made thereby.
• the present invention provides membranes and coated substrates including the silicone composition, including supported and unsupported membranes, methods of making the membranes and coated substrates, and methods of using the membranes and coated substrates.
• the silicone composition is a xerogel or glass.
• the present invention provides a method of preparing a silicone composition.
• the method includes reacting a mixture in a water-miscible solvent in the presence of a condensation catalyst.
• the reacting of the mixture forms a sol.
• the mixture includes (a) an ionic liquid having the formula Z " Q + -R 2 -SiR 1 m x 3-m-
• the mixture optionally includes (b) a silane having the formula R 1 n SiX4 -n .
• At least one of optional elements (b) and (c) is included in the mixture.
• the mixture optionally includes (c) a polysiloxane cross-linking agent having an average of at least 3 silicon-bonded X groups per molecule.
• the mixture optionally includes (d) a polydiorganosiloxane having the formula X3-pR 1 pSiO(R 1 2SiO)qSiR 1 pX3-p.
• the mixture also includes (e) water.
• the method includes concentrating the sol to form a wet gel.
• the method also includes drying the wet gel to form a silicone composition.
• the group Q + is a cationic organic group including at least one of N, S, and P.
• X is independently a hydrolyzable group
• R 1 is independently C-
• R 2 is C-
• Z ⁇ is a counterion
• m is 0, 1 , or 2
• n is 0 or 1
• p is 0, 1 , or 2
• q is about 100 to 2000.
• the sol-gel process of making the silicone composition is advantageous over other methods of making membranes.
• the reaction conditions of the sol-gel process can be moderate, such as room temperature and ambient pressure.
• the sol-gel method can be a solution coating technique, allowing easy control over rheological properties of the sol and facile tailoring of the coating thickness to specific needs via controlling the concentrations of various ingredients of the sol. For example, in some embodiments, adjusting the amount of solvent used in the mixture can control the speed of deposition, which can affect the porosity of the resulting product.
• adjusting the concentration of the cross-linking agent can alter the rheological properties of the sol.
• the sol-gel process can be compatible with many coating configurations and various shapes of substrates, such as for example doctor blade, dip coating, spin coating, slot die coating, and film casting.
• the sols can be well-dispersed colloid suspensions, a high degree of control can be exerted over the chemical homogeneity and microstructure of the membranes.
• the membrane or coated substrate of the present invention can exhibit better permeability and selectivity for particular components in a gas mixture, as compared to other membranes and coated substrates.
• the membrane or coated substrate can exhibit high CO2/N2 and CO2/CH4 selectivity, while retaining high permeability.
• FIG. 1 illustrates CH4/CO2 selectivity and CO2 permeability of a membrane versus loading of an ionic liquid in the mixture used to make the membrane, in accordance with various embodiments.
• FIG. 2 illustrates CH4/CO2 selectivity and CO2 permeability of a membrane versus loading of an ionic liquid in the mixture used to make the membrane, in accordance with various embodiments.
• FIG. 3 illustrates CH4/CO2 selectivity and CO2 permeability versus loading of polydiethoxysiloxane in the mixture used to make the membrane, in accordance with various embodiments.
• references in the specification to "one embodiment,” “an embodiment,” “an example embodiment,” and the like, indicate that the embodiment described can include a particular feature, structure, or characteristic, but every embodiment may not necessarily include the particular feature, structure, or characteristic. Moreover, such phrases are not necessarily referring to the same embodiment. Further, when a particular feature, structure, or characteristic is described in connection with an embodiment, it is submitted that it is within the knowledge of one of ordinary skill in the art to effect such feature, structure, or characteristic in connection with other embodiments whether or not explicitly described.
• substantially refers to a majority of, or mostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more.
• polysiloxane material of any viscosity that includes at least one siloxane monomer that is bonded via a Si-O-Si bond to three or four other siloxane monomers.
• the polysiloxane material includes T or Q groups, as defined herein.
• radiation refers to energetic particles travelling through a medium or space. Examples of radiation are visible light, infrared light, microwaves, radio waves, very low frequency waves, extremely low frequency waves, thermal radiation (heat), and black-body radiation.
• cur refers to exposing to radiation in any form, heating, or allowing to undergo a physical or chemical reaction that results in hardening or an increase in viscosity.
• pore refers to a depression, slit, or hole of any size or shape in a solid object.
• a pore can run all the way through an object or partially through the object.
• a pore can intersect other pores.
• free-standing or “unsupported” refers to a membrane with the majority of the surface area on each of the two major sides of the membrane not contacting a substrate, whether the substrate is porous or not.
• a membrane that is "free-standing” or “unsupported” can be 100% not supported on both major sides.
• a membrane that is "free-standing” or “unsupported” can be supported at the edges or at the minority (e.g. less than about 50%) of the surface area on either or both major sides of the membrane.
• the term "supported” as used herein refers to a membrane with the majority of the surface area on at least one of the two major sides contacting a substrate, whether the substrate is porous or not.
• a membrane that is “supported” can be 100% supported on at least one side.
• a membrane that is “supported” can be supported at any suitable location at the majority (e.g. more than about 50%) of the surface area on either or both major sides of the membrane.
• enriched refers to increasing in quantity or concentration, such as of a liquid, gas, or solute.
• a mixture of gases A and B can be enriched in gas A if the concentration or quantity of gas A is increased, for example by selective permeation of gas A through a membrane to add gas A to the mixture, or for example by selective permeation of gas B through a membrane to take gas B away from the mixture.
• deplete refers to decreasing in quantity or concentration, such as of a liquid, gas, or solute.
• a mixture of gases A and B can be depleted in gas A if the concentration or quantity of gas A is decreased, for example by selective permeation of gas B through a membrane to take gas B away from the mixture, or for example by selective permeation of gas A through a membrane to add gas A to the mixture.
• solvent refers to a liquid that can dissolve a solid, liquid, or gas.
• solvents are silicones, organic compounds, water, alcohols, ionic liquids, and supercritical fluids.
• selectivity or “ideal selectivity” as used herein refers to the ratio of permeability of the faster permeating gas over the slower permeating gas, measured at room temperature.
• total surface area refers to the total surface area of the side of the membrane exposed to the feed gas mixture.
• air refers to a mixture of gases with a composition approximately identical to the native composition of gases taken from the atmosphere, generally at ground level. In some examples, air is taken from the ambient surroundings. Air has a composition that includes approximately 78% nitrogen, 21 % oxygen, 1 % argon, and 0.04% carbon dioxide, as well as small amounts of other gases.
• room temperature refers to ambient
• coating refers to a continuous or discontinuous layer of material on the coated surface, wherein the layer of material can penetrate the surface and can fill areas such as pores, wherein the layer of material can have any three-dimensional shape, including a flat or curved plane.
• a coating can be formed on one or more surfaces, any of which may be porous or nonporous, by immersion in a bath of coating material.
• surface refers to a boundary or side of an object, wherein the boundary or side can have any perimeter shape and can have any three-dimensional shape, including flat, curved, or angular, wherein the boundary or side can be continuous or discontinuous. While the term surface generally refers to the outermost boundary of an object with no implied depth, when the term 'pores' is used in reference to a surface, it refers to both the surface opening and the depth to which the pores extend beneath the surface into the substrate.
• the present invention provides a method of preparing a silicone composition.
• the method includes reacting a mixture in a water-miscible solvent in the presence of a condensation catalyst to form a sol.
• the mixture includes an ionic liquid having hydrolyzable groups, and silicon- containing compounds having hydrolyzable groups, such that upon reacting the mixture generates a cross-linked three-dimensional polymeric chemical structure.
• the method also includes concentrating the sol to form a wet gel.
• the method also includes drying the wet gel to form a silicone composition.
• the reaction can occur under any suitable conditions including suitable time, pressure, temperature, and scale.
• the reaction can occur for about 1 m, 5 m, 10 m, 30 m, 1 h, 2 h, 5 h, 10 h, 1 d, 2 d, 5 d, or about 10 d or more.
• the reaction can be performed at less than room temperature, or at about room temperature, 30 2 C, 40 2 C, 50 2 C, 60 2 C, 70 2 C, 80 2 C, 90 2 C, 100 2 C, 1 10 2 C, 120 2 C, 130 2 C, 140 2 C, 150 2 C, 160 2 C, 170 2 C, 180 2 C, 190 2 C, or at about 200 2 C or higher.
• the reaction can be performed at less than ambient pressure, at about ambient pressure, 2 atm, 4 atm, 6 atm, 10 atm, 20 atm, 50 atm, 1 00 atm, or at about 200 atm or more. In some examples, the reaction can be performed on less than a 1 mg scale, or about 2 mg, 4 mg, 1 0 mg, 20 mg, 50 mg, 100 mg, 500 mg, 1 g, 2 g, 5 g, 10 g, 20 g, 50 g, 100 g, 500 g, 1 Kg, 2 Kg, 5 Kg, 10 Kg, 20 Kg, 50 Kg, 100 Kg, 500 Kg, or about 1000 Kg or greater scale. The reaction can be conducted with or without stirring or agitation.
• the water-miscible solvent can be any water miscible solvent.
• the water miscible solvent is any C1 -C10 alcohol, such as methanol, ethanol, or isopropanol.
• water-miscible solvents can include aldehydes such as acetaldehyde; organic acids such as acetic acid, butyric acid, formic acid, and propanoic acid; ketones such as acetone; sulfoxides such as dimethyl sulfoxide; nitriles and isocyanides such as acetonitrile and methyl isocyanide; diols and polyols such as 1 ,2-butanediol, 1 ,3-butanediol, 1 ,4-butanediol, ethylene glycol, 1 ,3-propanediol, 1 ,5-pentanediol, propylene glycol, and triethylene glycol, gly
• dimethylformamide dimethylformamide
• ethers such as dimethoxyethane and 1 ,4-dioxane
• heterocycles such as pyridine and tetrahydrofuran.
• any suitable amount of the water-miscible solvent can be used.
• the water-miscible solvent can be present in about 0.01 wt% to about 99.99 wt%, about 1 wt % to about 99 wt%, or about 5 wt% to about 95 wt%, wherein wt% in this paragraph refers to the percent by weight based on the total weight of the water miscible solvent, the condensation catalyst, and the mixture.
• the condensation catalyst can be any suitable condensation catalyst that promotes hydrolysis of elements of the mixture and subsequent condensation of the products of hydrolysis.
• the condensation catalyst can be any acid or base. Examples can include organic acids such as formic acid or acetic acid; mineral acids such as hydrochloric acid or sulfuric acid; amines such as ammonia or triethylamine; and other bases such as metal hydroxides like sodium hydroxide or potassium hydroxide; or ammonium hydroxides like ammonium hydroxide or tetraalkyl ammonium hydroxides.
• the condensation catalyst can be an organometalic condensation catalyst such as tin compounds, for example dibutyltin dilaurate (DBDLT), stannous octoate, dibutyltin diacetate, dibutyltin diethylhexanoate, dibutyltin dioctanoate, 4- benzyloxyphenyl)tributylstannane, (dimethylamino)trimethyltin(IV),1 -Methyl-4- (tributylstannyl)-l H-pyrazole, 1 -methyl-5-(tributylstannyl)imidazole, 1 -methyl-2- (tributylstannyl)pyrrole, 1 ,3-diacetoxy-1 ,1 ,3,3-tetrabutyldistannoxane,1 ,3- bis(tributylstannyl)benzene, 1 ,4-bis(tributyl
• ethynyltributylstannane hexamethylditin, hexaphenylditin(IV), methyltin trichloride, N-methyl-2-(tributylstannyl)indole, N-methyl-4-(tributylstannyl)imidazole, phenyltin trichloride, tetraallyltin, tetrabutyltin, tetraethyltin, tetramethyltin, tetraphenyltin, tetravinyltin, tributyl(1 -ethoxyvinyl)tin, tributyl(1 -propynyl)tin, tributyl(3-methyl-2- butenyl)tin, tributyl(4,5-dihydrofuran-2-yl)stannane, tributyl(4- chloro)phenylstannan
• tributyltin bromide tributyltin chloride, tributyltin cyanide, tributyltin ethoxide, tributyltin hydride, tributyltin iodide, tributyltin isocyanate, tributyltin methoxide, tricyclohexyltin chloride, tricyclohexyltin hydride, triethyltin bromide, tri methyl (phenyl)tin , trimethyl(phenylethynyl)tin,
• the condensation catalyst can be present in about 0.000,001 wt% to about 50 wt%, about 0.000,1 wt % to about 30 wt%, or about 0.01 wt% to about 15 wt%, wherein wt% in this paragraph refers to the percent by weight based on the total weight of the water miscible solvent, the condensation catalyst, and the mixture.
• any suitable amount of the mixture can be used.
• the mixture can be present in about 0.000,1 wt% to about 99.999 wt%, about 1 wt % to about 9 wt%, or about 5 wt% to about 95 wt%, wherein wt% in this paragraph refers to the percent by weight based on the total weight of the water miscible solvent, the condensation catalyst, and the mixture.
• a sol refers to a solution.
• the sol can be a colloidal solution, including liquids and products of hydrolysis and condensation reactions of the elements of the mixture. At least some of the hydrolyzable groups on elements of the mixture are hydrolyzed during the reaction to form functionalities such as -OH groups which can then condense together to link molecules together via oxygen linkages, also referred to as curing the mixture.
• the products of hydrolysis and condensation reactions can be polymers in any suitable physical form, ranging from particles of any suitable size to continuous chain-like polymer networks, or any combination thereof.
• the sol is a precursor for the wet gel, wherein the gel is formed at least in part by removing liquids from the sol by concentrating it.
• wet gel refers to an integrated network of polymers, wherein the polymers can have any suitable physical form, ranging from particles of any suitable size to continuous chain-like polymer networks, or any combination thereof.
• the materials in the sol can continue to react as they form the gel, e.g. the materials in the sol can at least partially cure as they form the gel. In other embodiments, little or no reactions such as continued hydrolysis or condensation reactions occur during the concentrating of the sol. Concentrating the sol can be performed in any suitable fashion, including for example by evaporating at least some of the solvents in the sol.
• Evaporation can be performed by use of a suitable amount of heat, vacuum, or a combination thereof, for any suitable time.
• Concentration can be performed at below room temperature, at about room temperature, 30 2 C, 40 2 C, 50 2 C, 60 2 C, 70 2 C, 80 2 C, 90 2 C, 100 2 C, 1 10 2 C, 120 2 C, 130 2 C, 140 2 C, 150 2 C, 160 2 C, 170 2 C, 180 2 C, 190 2 C, or at about 200 2 C or higher.
• the concentration can be performed at above atmospheric pressure, or at about 1 atm, 0.1 atm, 0.01 atm, 0.001 atm, 0.000,1 atm, or at or below about 0.000,01 atm.
• the concentrating can occur for about 1 m, 5 m, 10 m, 30 m, 1 h, 2 h, 5 h, 1 0 h, 1 d, 2 d, 5 d, or about 10 d or more.
• concentrating can be facilitated by allowing a stream of air to pass over the sol for a suitable time.
• the wet gel can be dried to form a silicone composition.
• the silicone composition includes the hydrolysis and subsequent condensation products formed from the mixture.
• the materials in the gel can continue to react as they form the silicone composition, e.g. the materials in the gel can at least partially cure as they form the silicone composition. In other embodiments, little or no reactions such as continued hydrolysis or condensation reactions occur during the drying of the gel to form the silicone composition. Drying the gel can be performed in any suitable fashion, including for example by evaporating at least some of the solvents in the gel. Evaporation can be performed by use of a suitable amount of heat, vacuum, or a combination thereof, for any suitable time.
• Drying can be performed at below room temperature, at about room temperature, 30 2 C, 40 2 C, 50 2 C, 60 2 C, 70 2 C, 80 2 C, 90 2 C, 100 2 C, 1 10 2 C, 120 2 C, 130 2 C, 140 2 C, 150 2 C, 160 2 C, 170 2 C, 180 2 C, 190 2 C, or at about 200 2 C or higher.
• the drying can be performed at above atmospheric pressure, or at about 1 atm, 0.1 atm, 0.01 atm, 0.001 atm, 0.000,1 atm, or at or below about 0.000,01 atm.
• drying can occur for about 1 m, 5 m, 10 m, 30 m, 1 h, 2 h, 5 h, 10 h, 1 d, 2 d, 5 d, or about 10 d or more.
• drying can be facilitated by allowing a stream of air to pass over the gel for a suitable time.
• concentrating and drying can be discrete steps. In some examples, concentrating and drying can be performed with the same conditions, or with different conditions. In some examples, concentrating and drying can be a single step. Embodiments can encompass methods wherein a wet gel is or is not isolated between steps of concentrating and drying. Likewise, a reaction mixture can fulfill different aspects of the gel to silicone progression in different areas of the gel. For example, as a sol is concentrated some areas can proceed more quickly to the silicone composition while other areas remain as wet gels or sols for different lengths of time. In other examples, the entire reaction mixture proceeds to discrete stages of a gel followed by a silicone composition.
• the silicone composition can have any suitable form.
• the silicone composition can be a flexible or malleable solid, such as a white, opaque, tough, paper-like film.
• the silicone composition can be a xerogel or a glass.
• a "xerogel” refers to solid formed from a gel by drying.
• a xerogel can be formed from a gel dried with unhindered shrinkage.
• Xerogels can have high porosity (e.g. about 10% to 80% by volume), high surface area (e.g. about 150-1200 m 2 /g), and small pore size (e.g. about 0.1 -15 nm). Heat treatment of a xerogel can yield a glass.
• a "glass” refers to an amorphous, non-crystalline solid material. Glasses can be optically transparent. In some examples, glasses can be brittle.
• the mixture includes (a) an ionic liquid; optionally, (b) a silane; optionally, (c) a polysiloxane cross-linking agent; optionally, (d) a polydiorganosiloxane; and (e) water; wherein at least one of optional elements (b) and (c) is included in the mixture. In some embodiments, both of optional elements (b) and (c) are included in the mixture. In other embodiments, only optional element (b) is included and optional element (c) is not included. In other embodiments, only optional element (c) is included and optional element (b) is not included.
• the mixture can optionally include any suitable additional material.
• the mixture can include more than one type of any designated material, for example the mixture can include two different types of ionic liquid, or three different types of polydiorganosiloxane.
• the element ionic liquid can be present in the mixture from about 0.01 wt% to about 99 wt%, about 1 wt % to about 50 wt%, or about 5 wt% to about 40 wt% of the mixture, wherein wt% in this paragraph refers to the percent by weight based on the total weight of mixture elements (a), (b), (c), and (d).
• any suitable amount of the silane (b) can be used.
• the silane can be present in the mixture from about 0 wt% to about 99 wr%, about 5 wt % to about 60 wt%, or about 10 wt% to about 35 wt% of the mixture, wherein wt% in this paragraph refers to the percent by weight based on the total weight of mixture elements (a), (b), (c), and (d).
• any suitable amount of the polysiloxane cross-linking agent (c) can be used.
• the polysiloxane cross-linking agent can be present in the mixture from about 0 wt% to about 99 wt%, about 1 wt % to about 30 wt%, or about 5 wt% to about 1 5 wt% of the mixture, wherein wt% in this paragraph refers to the percent by weight based on the total weight of mixture elements (a), (b), (c), and (d).
• any suitable amount of the polydiorganosiloxane (d) can be used.
• the polydiorganosiloxane can be present in the mixture from about 0 wt% to about 99 wt%, about 30 wt % to about 90 wt%, or about 50 wt% to about 80 wt% of the mixture, wherein wt% in this paragraph refers to the percent by weight based on the total weight of mixture elements (a), (b), (c), and (d).
• any suitable amount of water (e) can be used.
• the water can be present in the mixture from about 0.000,1 wt% to about 99 wt%, about 1 wt % to about 90 wt%, or about 5 wt% to about 80 wt% of the mixture, wherein wt% in this paragraph refers to the percent by weight based on the total weight of mixture elements (a), (b), (c), (d), and (e).
• the mixture can include (a) an ionic liquid.
• the ionic liquid has
• the ionic liquid can have the formula Z " Q+-R 2 -SiRl m X3_ m .
• the group Q + can be a cationic organic group including at least one of N, S, and P.
• X can be independently a hydrolyzable group.
• R1 can be independently
• Ci Ci to CiQ hydrocarbyl.
• the substituent R 2 can be to C20 hydrocarbylene.
• the variable m can be 0, 1 , or 2.
• hydrolyzable group refers to any substituent X that can undergo a hydrolysis reaction with water to give a hydroxyl group.
• a compound R-X can undergo hydrolysis to give R-OH and H-X.
• X can be any alkoxy group, such as a C1 -C10 alkoxy group, branched or linear, such as methoxy, ethoxy, propoxy, i-propoxy, t-butoxy, n-butoxy, s-butoxy, and the like; a halogen, such as bromide, chloride, fluoride, or an iodide; a carboxylate such as acetate; or a heteroester such as an organophosphorus ester or an organosulfur ester.
• alkoxy group such as a C1 -C10 alkoxy group, branched or linear, such as methoxy, ethoxy, propoxy, i-propoxy, t-butoxy, n-butoxy, s-butoxy, and the like
• a halogen such as bromide, chloride, fluoride, or an iodide
• a carboxylate such as acetate
• a heteroester such as an organ
• R1 can be independently C ⁇ to C ⁇ Q hydrocarbyl, can be branched, linear or cyclic, can be aliphatic, unsaturated, conjugated, or aromatic, and can include alkyl such as methyl, ethyl, propyl, n-butyl, t-butyl, s-butyl; alkenyl such as ethenyl or propenyl; alkynyl; cycloalkyl such as hexanyl; or aromatic such as phenyl.
• the variable m can be 0, 1 , or 2.
• -SiR 1 m X3_ m can be -S1X3, -SiR ! X2, or -SiR ⁇ X.
• the substituent R 2 can be C ⁇ to C20 hydrocarbylene, can be branched, linear or cyclic, can be aliphatic, unsaturated, conjugated, or aromatic, and can include alkyl such as methylene, ethylene, propylene, butylene; alkenylene such as ethenylene or propenylene; alkynylene; cycloalkylene such as hexanylene; or aromatic such as phenylene.
• R 2 can be -R ⁇ -Ar-R ⁇ -, wherein at each occurrence R ⁇ can be independently a single bond or CI_IQ alkylene and Ar can be a C4.10 divalent cycloalkyl, aryl, heterocyclyl, or heteroaryl group.
• R 2 can be a divalent methylphenyl, methylphenylmethyl, phenyl methyl, methylcyclohexyl, and the like.
• the group Z " can be any suitable counterion for Q+, such as any suitable anion.
• the group Z " can serve as a counterion for a single Q + , or for two or more Q+.
• Z- can be a halide, such as fluoride, chloride, bromide, or iodide.
• Z " can be nitrate, hydrogen sulfate, dihydrogen phosphate, bicarbonate, nitrite, perchlorate, iodate, chlorate, bromate, chlorite, hypochlorite, hypobromite, cyanide, amide, cyanate, hydroxide, permanganate, an acid anion such as acetate or formate, or anions with negative charges greater than -1 such as oxide, sulfide, nitride, arsenate, phosphate, arsenite, hydrogen phosphate, sulfate, thiosulfate, sulfite, carbonate, chromate, dichromate, peroxide, or oxalate.
• the group Q + can be any suitable cationic organic group including at least one of N, S, and P.
• Q+ can be an ammonium group, a phosphonium group, or a sulfonium group.
• Q + - can be R ⁇ P "1" - or R ⁇ N "1" -.
• Q + - can be R ⁇ S "1" -.
• Q+- can be ⁇ a + -, wherein Y+ is a heterocyclic ring bearing a positive charge, the heterocyclic ring including at least one N, S, or P, and a is 1 , 2, or 3.
• Y + can be any suitable heterocyclic ring, and can be substituted by any suitable number of organic substituents.
• Y + can be a heteroaromatic ring.
• Heterocyclic rings can be saturated or unsaturated, aromatic or nonaromatic, can include rings having 5 to 20 ring members, including fused rings.
• Heterocycles including N, S, or P can include any suitable number of N, S, or P atoms such as 1 , 2, 3, or 4 N, S, or P atoms or any combination thereof.
• heterocycles can include any other heteroatom, such as O or B.
• Y + can be pyrrolidinium, pyridinium, pyrimidinium, pyrazolium, benzimidizolium, imidazolium, triazolium, tetrazolium, azepanium, azepinium, benzazepanium, thiazolium, isothiolium, thiolium, benzthiazolium, phospholium, phosphorinolium, oxazolium, oxathiazolium, and the like.
• the heterocyclic ring is bound to the -R 2 -SiRl m X3_ m at a heteroatom in the heterocyclic ring.
• a is 1 and R1Y+- is an imidazolium illustrated as
• the ionic liquid is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N
• the mixture optionally includes (b) a silane having the formula R ⁇ nSiX ⁇ n-
• the mixture includes the silane. In other embodiments, the mixture does not includes the silane.
• the mixture includes at least one of optional elements (b) and (c).
• the silane can be any suitable silane. At each occurrence
• R1 can be independently C ⁇ to C ⁇ Q hydrocarbyl, as defined herein.
• X can be independently a hydrolyzable group, as defined herein.
• the variable n can be 0 or 1 .
• the silane can be RIS1X3 or S1X4. In some examples, the silane is tetraethyl orthosilicate, tetramethyl orthosilicate,
• the mixture optionally includes (c) a polysiloxane cross-linking agent having an average of at least 3 silicon-bonded X groups per molecule. In some embodiments, the mixture does include element (c). In other embodiments, the mixture does not include element (c).
• the mixture includes at least one optional elements (b) and (c).
• the cross-linking agent can be any suitable cross-linking agent. Each siloxane group can be M, D, T, or Q.
• the cross-linking agent can be linear or resinous.
• each silicon atom of the polysiloxane can be substituted by any suitable substituent, such as a halide or an organic group, such as R1 , a to C ⁇ Q hydrocarbyl, as defined herein.
• X can be independently a hydrolyzable group, as defined herein.
• Each individual silicon atom of the cross-linking agent can have 2, 1 , or 0 silicon-bonded X groups.
• the polysiloxane crosslinking agent can have an average of about 3 to 50,000 silicon-bonded X groups per molecule, about 3 to 10,000, about 3 to 1000, about 3 to 100, about 3 to 10, or an average of about 3 to 5 silicon-bonded X groups per molecule.
• element (c) can be a
• element (c) can be a polydiethoxysiloxane.
• the mixture optionally includes (d) a polydiorganosiloxane having the formula X3-pRlpSiO(Rl2SiO)qSiRlpX3_p. In some embodiments, the mixture does include element (d). In other embodiments, the mixture does not include element (d). Element (d) can be any suitable polydiorganosiloxane having the formula X3_pRlpSiO(Rl2SiO)qSiRlpX3_p. At each occurrence X can be independently a hydrolyzable group, as defined herein. At each occurrence can be independently Ci to ( 0 hydrocarbyl, as defined herein. The variable p can be 0, 1 , or 2; thus element (d) can have the formula X3SiO(R 1 2SiO) q SiX3,
• Tne variable q can be about about 50 to 4000, about 1 00 to 2000, about 300 to 1500, or about 600 to 900. In some examples, q is about 800. In some examples, element (d) is a trimethylsiloxy-terminated polydimethylsiloxane.
• the mixture includes (e) water.
• the water can be of any suitable purity.
• the present invention provides a membrane that includes the silicone composition.
• the present invention provides a method of forming a membrane.
• the membrane can be formed directly of the silicone composition, for example the sol can be gelled and dried on a substrate wherein the silicone composition can remain and be used as a membrane.
• the silicone composition can be processed in some fashion, such as ground or crushed.
• the processed silicone composition can be directly formed into a membrane by processing steps such as pressing or heating or a combination thereof.
• the processed silicone composition can be laminated to supports such as polymer supports, such as nylon or polypropylene membrane filters, by use of suitable laminating techniques such as hot press.
• the processed silicone composition can be subsequently integrated into a composition that formed the membrane via a drying or curing process.
• the present invention can include the step of forming a membrane.
• the membrane can be formed on at least one surface of a substrate.
• the membrane can be attached (e.g. adhered) to the substrate, or be otherwise in contact with the substrate without being adhered.
• the substrate can have any surface texture, and can be porous or non-porous.
• the substrate can include surfaces that are not coated with a membrane by the step of forming a membrane. All surfaces of the substrate can be coated by the step of forming a membrane, one surface can be coated, or any number of surfaces can be coated.
• the step of forming a membrane can include two steps.
• the composition that forms the membrane such as the mixture or a curable composition that includes the processed silicone composition
• the applied composition that forms the membrane can be cured to form the membrane.
• the curing process of the composition can begin before, during, or after application of the composition to the surface.
• the curing process transforms the composition that forms the membrane into the membrane.
• the composition that forms the membrane can be in a liquid state, for example a sol.
• the membrane can be in a solid state, for example a dried gel or a cured composition formed from a mixture including a processed dried gel.
• composition that forms the membrane can be applied using conventional coating techniques, for example, immersion coating, spin coating, dipping, spraying, brushing, roll coating, extrusion, screen-printing, pad printing, or inkjet printing.
• Curing the composition can be the reacting, concentrating, and drying steps described herein.
• curing the composition that forms the membrane can include the addition of a curing agent or initiator such as, for example, a hydrosilylation catalyst.
• the curing process can begin immediately upon addition of the curing agent or initiator.
• the addition of the curing agent or initiator may not begin the curing process immediately, and can require additional curing steps.
• the addition of the curing agent or initiator can begin the curing process immediately, and can also require additional curing steps.
• the addition of the curing agent or initiator can begin the curing process, but not bring it to a point where there composition is cured to the point of being fully cured, or of being unworkable.
• the curing agent or initiator can be added before or during the coating process, and further processing steps can complete the cure to form the membrane.
• Curing the composition that forms the membrane can include a variety of methods, including exposing the composition to ambient temperature, elevated temperature, moisture, or radiation. In some embodiments, curing the composition can include combination of methods.
• the membrane of the present invention can have any suitable thickness. In some examples, the membrane has a thickness of from about 1 ⁇ to about 20 ⁇ . In some examples, the membrane has a thickness of from about 0.1 ⁇ to about 200 ⁇ . In other examples, the membrane has a thickness of from about 0.01 ⁇ to about 2000 ⁇ . [0074]
• the membrane of the present invention can be selectively permeable to one substance over another. In one example, the membrane is selectively permeable to one gas over other gases or liquids. In another example, the membrane is selectively permeable to more than one gas over other gases or liquids. In one embodiment, the membrane is selectively permeable to one liquid over other liquids or gases.
• the membrane is selectively permeable to more than one liquid over other liquids.
• the membrane has an ideal CO2/N2 selectivity of at least about 15-55, for example at least about 20, at least about 30, at least about 40, or at least about 50.
• the membrane has a CO2/CH4 selectivity of at least about 1 -30, such as at least about 5, at least about 10, at least about 15, or at least about 20.
• the membrane has a CO2 permeability coefficient of at least about 50-4000 Barrers, such as about 50 Barrers, 100, 150, 200, 500, 1000, 1500, 2000, 2500, 3000, 3500, or about 4000 Barrers.
• the membrane has a CO2/CH4 mixture for example, the membrane has a
• Barrers 100, 150, 200, 500, 1000, 1500, 2000, 2500, 3000, 3500, or about 4000 Barrers.
• the membrane of the present invention can have any suitable shape.
• the membrane of the present invention is a plate-and-f rame membrane, a spiral wound membrane, a tubular membrane, a capillary fiber membrane or a hollow fiber membrane.
• the membrane can be a continuous or discontinuous layer of material.
• the membrane may be used in conjunction with a liquid that enhances gas transport, such as in a membrane contactor (e.g. a device that permits mass transfer between a gaseous phase and a liquid phase across a membrane without dispersing the phases in one another).
• the membrane is unsupported, also referred to as free-standing.
• the majority of the surface area on each of the two major sides of a membrane that is free-standing is not contacting a substrate, whether the substrate is porous or not.
• a membrane that is free-standing can be 100% unsupported.
• a membrane that is free-standing can be supported at the edges or at the minority (e.g. less than 50%) of the surface area on either or both major sides of the membrane.
• the support for a free-standing membrane can be a porous substrate or a nonporous substrate. Examples of suitable supports for a free-standing membrane can include any examples of supports given herein.
• a free-standing membrane can have any suitable shape, regardless of the percent of the free-standing membrane that is supported.
• suitable shapes for free-standing membranes include, for example, squares, rectangles, circles, tubes, cubes, spheres, cones, and planar sections thereof, with any thickness, including variable thicknesses.
• a support for a free-standing membrane can be attached to the membrane in any suitable manner, for example, by clamping, with use of adhesive, by melting the membrane to the edges of the substrate, or by chemically bonding the membrane to the substrate by any suitable means.
• the support for the freestanding membrane can be not attached to the membrane but in contact with the membrane and held in place by friction or gravity.
• the support can include, for example, a frame around the edges of the membrane, which can optionally include one or more cross-beam supports within the frame.
• the frame can be any suitable shape, including a square or circle, and the cross-beam supports, if any, can form any suitable shape within the frame.
• the frame can be any suitable thickness.
• the support can be, for example, a cross-hatch pattern of supports for the membrane, where the cross-hatch pattern has any suitable dimensions.
• a free-standing membrane is made by the steps of coating or applying a composition onto a substrate, curing the composition, and partially or fully removing the membrane from the substrate. After application of the composition to the substrate, the assembly can be referred to as a laminated film or fiber. During or after the curing process the membrane can be at least partially removed from at least one substrate. In some examples, after the unsupported membrane is removed from a substrate, and the unsupported membrane is attached to a support, as described above.
• an unsupported membrane is made by the steps of coating a composition onto one or more substrates, curing the composition, and removing the membrane from at least one of the one or more substrates, while leaving at least one of the one of more substrates in contact with the membrane.
• the membrane is entirely removed from the substrate.
• the membrane can be peeled away from the substrate.
• the substrate can be removed from the membrane by melting, subliming, chemical etching, or dissolving in a solvent.
• the substrate is a water soluble polymer that is dissolved by purging with water.
• the substrate is a fiber or hollow fiber, as described in US 6,797,212 B2.
• the substrate can be porous or nonporous.
• the substrate can be any suitable material, and can be any suitable shape, including planar, curved, solid, hollow, or any combination thereof.
• Suitable materials for porous or nonporous substrates include any materials described above as suitable for use as porous substrates in supported membranes, as well as any suitable less-porous materials.
• the membrane can be heated, cooled, washed, etched or otherwise treated to facilitate removal from the substrate. In other examples, air pressure can be used to facilitate removal of the membrane from the substrate.
• the membrane is supported on a porous or highly permeable non-porous substrate.
• a supported membrane has the majority of the surface area of at least one of the two major sides of the membrane contacting a porous or highly permeable non-porous substrate.
• a supported membrane on a porous substrate can be referred to as a composite membrane, where the membrane is a composite of the membrane and the porous substrate.
• the porous substrate on which the supported membrane is located can allow gases to pass through the pores and to reach the membrane.
• the supported membrane can be attached (e.g. adhered) to the porous substrate.
• the supported membrane can be in contact with the substrate without being adhered.
• the porous substrate can be partially integrated, fully integrated, or not integrated into the membrane.
• a coating can be formed on the at least one porous surface of the substrate or on the at least one surface of the highly permeable non-porous substrate, e.g. by coating the at least one porous surface with the mixture or a curable composition that includes the processed silicone composition.
• a porous or highly permeable non-porous substrate can be placed in contact with the formed coating before, during, or after curing of the coating.
• a porous substrate can have its pores filled at the surface to provide a smooth surface for formation of a membrane; after formation of the membrane, the composition filling the pores can be dried or otherwise removed or shrunk to restore the porosity of the substrate.
• the supported membrane is made in a manner identical to that disclosed herein pertaining to a free-standing membrane, but with the additional step of placing or adhering the free-standing membrane on a porous substrate to make a supported membrane.
• the porous substrate can be any suitable porous material known to one of skill in the art, in any shape.
• the substrate can be a filter.
• the porous substrate can be woven or non-woven.
• the porous substrate can be a frit, a porous sheet, or a porous hollow fiber.
• the at least one surface can be flat, curved, or any combination thereof.
• the surface can have any perimeter shape.
• the porous substrate can have any number of surfaces, and can be any three-dimensional shape. Examples of three-dimensional shapes include cubes, spheres, cones, and planar sections thereof with any thickness, including variable thicknesses.
• the porous substrate or highly permeable non-porous substrate can be smooth, be corrugated or patterned, or have any amount of surface roughness.
• the porous substrate can have any number of pores, and the pores can be of any size, depth, shape, and distribution.
• the porous substrate has a pore size of from about 0.2 nm to about 500 ⁇ .
• the at least one surface can have any number of pores.
• the pore size distribution may be asymmetric across the thickness of the porous sheet, film or fiber.
• porous substrates include porous polymeric films, fibers or hollow fibers, or porous polymers or any suitable shape or form.
• polymers that can form porous polymers suitable for use as a porous substrate in embodiments of the present invention include those disclosed in U.S. Patent No. 7,858,197.
• suitable polymers include polyethylene, polypropylene, polysulfones, polyamides, polyether ether ketone (PEEK), polyarylates, polyaramides, polyethers, polyarylethers, polyimides, polyetherimides, polyphthalamides, polyesters, polyacrylates, polymethacrylates, cellulose acetate, polycarbonates, polyacrylonitrile, polytetrafluoroethylene and other fluorinated polymers, polyvinylalcohol, polyvinylacetate, syndiotactic or amorphous polystyrene, KevlarTM and other liquid crystalline polymers, epoxy resins, phenolic resins, polydimethylsiloxane elastomers, silicone resins, fluorosilicone elastomers, fluorosilicone resins, polyurethanes, and copolymers, blends or derivatives thereof.
• Suitable porous substrates can include, for example, porous glass, various forms and crystal forms of
• the present invention also provides a method of separating gas components or water vapor in a feed gas mixture by use of the membrane described herein.
• the method includes contacting a first side of a membrane with a feed gas mixture to produce a permeate gas mixture on a second side of the membrane and a retentate gas mixture on the first side of the membrane.
• the permeate gas mixture is enriched in the first gas component.
• the retentate gas mixture is depleted in the first gas component.
• the membrane can include any suitable membrane as described herein.
• the membrane can be free-standing or supported by a porous or permeable substrate.
• the pressure on either side of the membrane can be about the same.
• the pressure on the retentate side of the membrane can be higher than the pressure on the permeate side of the membrane.
• the pressure on the permeate side of the membrane can be higher than the pressure on the retentate side of the membrane.
• the feed gas mixture can include any mixture of gases.
• the feed gas mixture can include hydrogen, carbon dioxide, nitrogen, ammonia, methane, water vapor, hydrogen sulfide, or any combination thereof.
• the feed gas can include any gas known to one of skill in the art.
• the membrane can be selectively permeable to any one gas in the feed gas, or to any of several gases in the feed gas. The membrane can be selectively permeable to all but any one gas in the feed gas.
• membranes can be used to accomplish the separation.
• one membrane can be used.
• the membranes can be manufactured as flat sheets or as fibers and can be packaged into any suitable variety of modules including hollow fibers, sheets or arrays of hollow fibers or sheets.
• Common module forms include hollow fiber modules, spiral wound modules, plate-and-frame modules, tubular modules and capillary fiber modules.
• the membrane can be used to separate liquids. In some embodiments, the membrane can be used to separate a gas from a liquid. In another embodiment, the membrane can be used to separate a liquid from a gas. In another example, the membrane can be used to separate a gas from a gas that contains a suspended solid or liquid. In another example, the membrane can be used to separate a liquid from a liquid that contains a suspended or dissolved solid or gas. [0089]
• the present invention can be better understood by reference to the following examples which are offered by way of illustration. The present invention is not limited to the examples given herein.
• Gas permeation test Gas permeability coefficients and ideal selectivities in a binary gas mixture were measured using a permeation cell including upstream (feed/retentate) and downstream (permeate) chambers that were separated by the membrane.
• the upstream chamber had one gas inlet and one gas outlet.
• the downstream chamber had one gas outlet.
• the membrane was supported on a stainless-steel filter disk with a diameter of 55 mm.
• the membrane area was defined by a placing a silicone rubber gasket with a diameter of 50 mm (Exotic Automation & Supply) on top of the membrane.
• the downstream chamber was maintained at ambient pressure and was connected to a 6-port injector equipped with a 1 -mL injection loop. On command, the 6-port injector injected a 1 -mL sample into a gas chromatograph (GC) equipped with a thermal conductivity detector (TCD).
• GC gas chromatograph
• TCD thermal conductivity detector
• Example 1 Synthesis of 1 -(3-triethoxysilylpropyl)-3-butylimidazolium chloride (IL1 ).
• Example 3 Fabrication of sol-gel membranes by co-hvdrolvzinq IL1 with TEOS.
• TEOS:water:ammonia:ethanol 10:960:96:80.
• the solution was stirred vigorously for 30 minutes and was left standing still at room temperature for 5 days.
• the clear sol was heated to 90 °C and volatiles were removed by an air stream.
• the viscous liquid was then heated to 120 °C to further remove volatiles.
• Finally the sol was gelled at 180 °C to afford a transparent glass. Yield: 6.58 g (102.2%, potentially evidencing remaining ethoxy groups).
• Tg 1 .5 °C.
• TGA onset temperature 273 °C.
• Ash content (calcined at 800 °C): 36.8 %. Theoretical ash content: 42%.
• the gel was crushed and grounded into a fine powder.
• the powder was pressed into free standing and continuous membranes by a Carver hot press.
• the gel can also be laminated to polymer supports by the hot press, such as nylon and polypropylene membrane filters.
• Example 6 Analysis of IL1 loading.
• the dependence of the gas separation performance on IL1 content as measured in Examples 4 and 5 is graphically depicted in FIG. 1 .
• FIG. 1 illustrates CH4/CO2 selectivity and CO2 permeability of a membrane versus loading of IL1 in the mixture used to make the membrane.
• the CO2 selectivity of the membranes increased when the IL1 loading increased, while the permeability of CO2 and CH4 decreased and leveled off at about 10-20%.
• Example 7 Sol-gel membrane made using IL2 and variation of IL2 loading.
• FIG. 2 illustrates CH4/CO2 selectivity and CO2 permeability of a membrane versus loading of IL2 in the mixture used to make the membrane.
• FIG. 2 illustrates CH4/CO2 selectivity and CO2 permeability of a membrane versus loading of an ionic liquid in the mixture used to make the membrane.
• the CO2 selectivity of the membranes generally increased when the
• IL2 loading increased, with the highest selectivity measured at about 20.1 % IL2, while the permeability of CO2 and CH4 decreased and leveled off at about 10-20%.
• Membranes containing IL2 generally showed lower selectivity than membranes with IL1 at comparable IL loading level.
• FIG. 3 illustrates CH4/CO2 selectivity and CO2 permeability versus loading of polydiethoxysiloxane in the mixture used to make the membrane.
• the loading of the crosslinker, PDEOS was found have an impact on selectivity. Increase of PDEOS led to decline of the selectivity, while the impact of PDEOS on CO2 permeability was less clear.
• the present invention provides for the following exemplary embodiments, the numbering of which is not to be construed as designating levels of importance:
• Embodiment 1 provides a method of preparing a silicone composition, the method comprising: reacting a mixture in a water-miscible solvent in the presence of a condensation catalyst to form a sol, the mixture comprising (a) an ionic liquid having the formula Z " Q+-R 2 -SiRl m X3_ m ; (b) optionally, a silane having the formula
• Rl n SiX4_ n optionally, a polysiloxane cross-linking agent having an average of at least 3 silicon-bonded X groups per molecule; (d) optionally, a
• polydiorganosiloxane having the formula X3_pRlpSiO(Rl2SiO)qSiRlpX3_p; and (e) water; concentrating the sol to form a wet gel ; and drying the wet gel to form a silicone composition; wherein Q+ is a cationic organic group comprising at least one of N, S, and P, at each occurrence X is independently a hydrolyzable group, at each occurrence R1 is independently Ci to ( 0 hydrocarbyl, R 2 is Ci to C20 hydrocarbylene, Z ⁇ is a counterion, m is 0, 1 , or 2, n is 0 or 1 , p is 0, 1 , or 2, q is about 100 to 2000, and at least one of optional elements (b) and (c) is included in the mixture.
• Embodiment 2 provides the method of Embodiment 1 , wherein the silicone composition is a xerogel or glass.
• Embodiment 3 provides the method of any one of Embodiments 1 -2, wherein the cross-linking agent (c) is a poly(dialkoxysiloxane) comprising from 20 to 90% (w/w) Si0 2 .
• the cross-linking agent (c) is a poly(dialkoxysiloxane) comprising from 20 to 90% (w/w) Si0 2 .
• Embodiment 5 provides the method of any one of Embodiments 1 -3, wherein Q + - comprises Rl a Y + ⁇ > wherein Y + is a heterocyclic ring bearing a positive charge, the heterocyclic ring comprising at least one N, S, or P, and a is 1 , 2, or 3.
• Embodiment 6 provides the method of Embodiment 5, wherein the heterocyclic ring is bound to the -R 2 -SiR 1 m X3_ m at a heteroatom in the heterocyclic ring.
• Embodiment 7 provides the method of any one of Embodiments 5-6, wherein a is 1 and R1Y + - is [00112]
• Embodiment 8 provides the method of any one of Embodiments 1 -7, wherein at each occurrence R1 is independently C ⁇ to C ⁇ Q alkyl.
• Embodiment 9 provides the method of any one of Embodiments 1 -8, wherein R ⁇ is -R ⁇ -Ar-R ⁇ -, wherein at each occurrence R ⁇ is independently a single bond or C ⁇ . ⁇ Q alkylene and Ar is a C4.10 divalent cycloalkyl, aryl, heterocyclyl, or heteroaryl group.
• Embodiment 1 1 provides the method of any one of Embodiments 1 -10, wherein at each occurrence X is independently -OR ⁇ , wherein is C to C Q hydrocarbyl.
• Embodiment 12 provides a silicone composition prepared according the method of any of Embodiments 1 -1 1.
• Embodiment 13 provides an unsupported membrane comprising the silicone composition prepared according to the method of any one of Embodiments 1 -12, wherein the membrane is free-standing.
• Embodiment 14 provides the unsupported membrane of Embodiment 13, wherein the membrane has a thickness of from 0.1 to 200 ⁇ .
• Embodiment 15 provides the unsupported membrane of any one of Embodiments 13-14, wherein the membrane is selected from a plate membrane, a spiral membrane, tubular membrane, and hollow fiber membrane.
• Embodiment 16 provides a coated substrate, comprising: a substrate; and a coating on the substrate, wherein the coating comprises the silicone composition prepared according to the method of any one of Embodiments 1 -1 1 .
• Embodiment 17 provides the coated substrate of Embodiment 16, wherein the substrate is porous and the coating is a membrane.
• Embodiment 18 provides the coated substrate of any one of Embodiments 16-17, wherein the porous substrate is a frit comprising a material selected from glass, ceramic, alumina, and a porous polymer.
• Embodiment 19 provides a method of separating gas components in a feed gas mixture, the method comprising contacting a first side of a membrane comprising the silicone composition prepared according to the method of any one of Embodiments 1 -1 1 with a feed gas mixture comprising at least a first gas component and a second gas component to produce a permeate gas mixture on a second side of the membrane and a retentate gas mixture on the first side of the membrane, wherein the permeate gas mixture is enriched in the first gas component.
• Embodiment 20 provides the method of Embodiment 19, wherein the permeate gas mixture comprises carbon dioxide and the feed gas mixture comprises at least one of nitrogen and methane.
• Embodiment 21 provides the apparatus or method of any one or any combination of Embodiments 1 -20 optionally configured such that all elements or options recited are available to use or select from.

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• 2013
  • 2013-07-30 WO PCT/US2013/052701 patent/WO2014022377A1/fr not_active Ceased

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