WO2013096211A1 - Liquides ioniques à base de silicone et applications associées - Google Patents

Liquides ioniques à base de silicone et applications associées Download PDF

Info

Publication number
WO2013096211A1
WO2013096211A1 PCT/US2012/070122 US2012070122W WO2013096211A1 WO 2013096211 A1 WO2013096211 A1 WO 2013096211A1 US 2012070122 W US2012070122 W US 2012070122W WO 2013096211 A1 WO2013096211 A1 WO 2013096211A1
Authority
WO
WIPO (PCT)
Prior art keywords
membrane
curable composition
per molecule
group
free
Prior art date
Application number
PCT/US2012/070122
Other languages
English (en)
Inventor
Gang Lu
Dongchan Ahn
Christopher Wong
Original Assignee
Dow Corning Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Corning Corporation filed Critical Dow Corning Corporation
Publication of WO2013096211A1 publication Critical patent/WO2013096211A1/fr

Links

Classifications

    • 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
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
    • 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
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0053—Inorganic membrane manufacture by inducing porosity into non porous precursor membranes
    • B01D67/006—Inorganic membrane manufacture by inducing porosity into non porous precursor membranes by elimination of segments of the precursor, e.g. nucleation-track membranes, lithography or laser methods
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/107—Organic support material
    • B01D69/1071—Woven, non-woven or net mesh
    • 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
    • B01D71/701—Polydimethylsiloxane
    • 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
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/395—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing phosphorus
    • 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
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups

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.
  • Embodiments of the present invention provide silicone-based ionic liquids and methods of making the same, curable compositions that include the same, materials such as membranes made therefrom, and methods of using those materials.
  • Various embodiments of the present invention provide a curable composition that includes a polysiloxane having an average of at least about one quaternary phosphonium group or quaternary ammonium group per molecule, a cured product of the curable composition, a supported or unsupported membrane including the cured product, and a method of separating gas components in a feed gas mixture using the membrane.
  • the curable composition includes Component (A), an organic compound having at least one free-radical polymerizable group per molecule.
  • the curable composition also includes Component (B), a mercapto-functional organic compound having an average of at least about three mercapto groups per molecule.
  • the curable composition also includes Component (C), a polysiloxane having an average of at least about one quaternary phosphonium group or quaternary ammonium group per molecule, wherein the polysiloxane has an average of at least about five Si atoms per molecule.
  • the curable composition includes a catalytic amount of a free-radical initiator.
  • Various embodiments of the present invention provide a method of separating gas components in a feed gas mixture.
  • the method includes contacting a first side of a membrane with a feed gas mixture.
  • the membrane includes a cured product of a curable composition.
  • the feed gas mixture includes at least a first gas component and a second gas component.
  • the contacting produces a permeate gas mixture on a second side of the membrane.
  • the contacting also produced 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 curable composition includes Component (A), an organic compound having at least one free-radical polymerizable group per molecule.
  • the curable composition also includes Component (B), a mercapto-functional organic compound having an average of at least about three mercapto groups per molecule.
  • the curable composition also includes Component (C), a polysiloxane having an average of at least about one quaternary phosphonium group or quaternary ammonium group per molecule, wherein the polysiloxane has an average of at least about five Si atoms per molecule.
  • the curable composition includes a catalytic amount of a free-radical initiator.
  • Various embodiments of the present invention have certain advantages over other ionic liquids or products such as membranes made therefrom, at least some of which are unexpected.
  • the ionic liquids of the present invention are neither known nor suggested in the art.
  • the present invention advantageously combines the high gas permeability of silicones with the exceptional selectivity of ionic liquids to form new materials that can have a variety of beneficial properties.
  • Some embodiments of the membrane of the present invention have higher permeability or selectivity for particular components in a gas mixture than other membranes.
  • membranes of the present invention exhibit higher CO2/N2 or CO2/CH4 selectivity, while retaining high permeability, as compared to other membranes.
  • the silicone-based ionic liquids, or materials such as membranes made therefrom can be made more efficiently than materials or membranes made using other methods.
  • the membranes or materials of the present invention made from silicone-based ionic liquids can have properties that are more difficult to achieve in membranes or materials made by other methods.
  • Some procedures of making ionic liquids suffer from problems including pre-made salt-groups being immiscible in any solvent conditions with polysiloxanes. The difficulty and limitations of other procedures can discourage one of skill in the art from pursuing membrane applications of silicon-based ionic liquids.
  • the method of making silicone-based ionic liquids solves these limitations and problems, for example via a different synthetic route. In some examples, the method allows access silicone-based ionic liquids that are neither known nor suggested in the art.
  • the method of making ionic liquids is superior to other methods, including because it has fewer and simpler synthetic steps, uses cheaper starting materials than other methods, allows access to a greater number of ionic liquids such as by giving greater control over the linking group between the salt-group and the polysiloxane, and by giving greater control over the number of silicon-atoms in the polysiloxane that are connected to a salt-group.
  • the method of making ionic liquids, and the ionic liquids produced thereby can advantageously be better suited for membrane applications than other ionic liquids or methods of making the same.
  • the method of the present invention can allow synthesis of polysiloxanes having silicon-pendant salt-groups on a greater number of siloxane units, and with a higher degree of control, than other methods.
  • the term "about” can allow for a degree of variability in a value or range, for example, within 10%, within 5%, or within 1 % of a stated value or of a stated limit of a range.
  • organic group refers to but is not limited to any carbon-containing functional group.
  • examples include acyl, cycloalkyl, aryl, aralkyl, heterocyclyl, heteroaryl, or heteroarylalkyl, linear and/or branched groups such as alkyl groups, fully or partially halogen-substituted haloalkyl groups, alkenyl groups, alkynyl groups, acrylate and methacrylate functional groups; and other organic functional groups such as ether groups, cyanate ester groups, ester groups, carboxylate salt groups, and masked isocyano groups.
  • substituted refers to an organic group as defined herein or molecule in which one or more hydrogen atoms contained therein are replaced by one or more non-hydrogen atoms.
  • functional group or “substituent” as used herein refers to a group that can be or is substituted onto a molecule, or onto an organic group.
  • substituents or functional groups include, but are not limited to, any organic group, a halogen (e.g., F, CI, Br, and I); a sulfur atom in groups such as thiol groups, alkyl and aryl sulfide groups, sulfoxide groups, sulfone groups, sulfonyl groups, and sulfonamide groups; a nitrogen atom in groups such as amines, hydroxylamines, nitriles, nitro groups, N-oxides, hydrazides, azides, and enamines; and other heteroatoms in various other groups.
  • a halogen e.g., F, CI, Br, and I
  • a sulfur atom in groups such as thiol groups, alkyl and aryl sulfide groups, sulfoxide groups, sulfone groups, sulfonyl groups, and sulfonamide groups
  • a nitrogen atom in groups such
  • alkyl refers to straight chain and branched alkyl groups and cycloalkyi groups having from 1 to about 20 carbon atoms, and typically from 1 to 12 carbons or, in some embodiments, from 1 to 8 carbon atoms.
  • straight chain alkyl groups include those with from 1 to 8 carbon atoms such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n- heptyl, and n-octyl groups.
  • branched alkyl groups include, but are not limited to, isopropyl, isobutyl, sec-butyl, t-butyl, neopentyl, isopentyl, and 2,2-dimethylpropyl groups.
  • alkyl encompasses all branched chain forms of alkyl.
  • Representative substituted alkyl groups can be substituted one or more times with any functional group, for example, amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy, and halogen groups.
  • aryl refers to cyclic aromatic hydrocarbons that do not contain heteroatoms in the ring.
  • aryl groups include, but are not limited to, phenyl, azulenyl, heptalenyl, biphenyl, indacenyl, fluorenyl, phenanthrenyl, triphenylenyl, pyrenyl, naphthacenyl, chrysenyl, biphenylenyl, anthracenyl, and naphthyl groups.
  • aryl groups contain about 6 to about 14 carbons in the ring portions of the groups.
  • Aryl groups can be unsubstituted or substituted, as defined herein.
  • Representative substituted aryl groups can be mono-substituted or substituted more than once, such as, but not limited to, 2-, 3-, 4-, 5-, or 6-substituted phenyl or 2-8 substituted naphthyl groups, which can be substituted with carbon or non-carbon groups.
  • the term "resin” as used herein refers to 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” as used herein 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. In some embodiments, 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 B if the concentration or quantity of gas B 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. Unless otherwise designated, “selectivity” as used herein designates ideal selectivity.
  • P x can also be expressed as V-5/(A-t-Ap), wherein P x is the permeability for a gas
  • V is the volume of gas X which permeates through the membrane
  • ⁇ is the thickness of the membrane
  • A is the area of the membrane
  • t is time
  • ⁇ is the pressure difference of the gas X at the retente and permeate side. Permeability is measured at room temperature, unless otherwise indicated.
  • 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.
  • room temperature refers to ambient temperature, which can be, for example, between about 15 °C and about 28 °C.
  • 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.
  • the present invention relates to silicone-based ionic liquids and methods of making the same, curable compositions that include the same, materials such as membranes made therefrom, and methods of using those materials.
  • Various embodiments of the present invention provide a curable composition.
  • the curable composition includes Component (A), an organic compound having at least one free-radical polymerizable group per molecule.
  • the curable composition also includes Component (B), a mercapto-functional organic compound having an average of at least about three mercapto groups per molecule.
  • the curable composition also includes Component (C), a polysiloxane having an average of at least about one phosphonium group or ammonium group per molecule, wherein the polysiloxane has an average of at least about five Si atoms per molecule. Additionally, the curable composition includes a catalytic amount of a free-radical initiator.
  • the curable composition can be cured via any suitable method, for example via thiol-ene chemistry.
  • the present invention provides a method of separating gas components in a feed gas mixture using a membrane that includes a cured product of the curable composition.
  • Component (A) the organic compound having at least one free-radical polymerizable group per molecule, can be present in from about 5 wt% to about 50 wt%, about 10 wt % to about 35 wt%, or about 20 wt% to about 25 wt% of the curable composition.
  • Wt% in this paragraph refers to the percent by weight based on the total weight of Components (A), (B), (C), and (D).
  • Component (B), the mercapto-functional organic compound having an average of at least about three mercapto groups per molecule can be present in from about 1 wt% to about 30 wt%, about 3 wt % to about 15 wt%, or about 5.5 wt% to about 7.5 wt% of the curable composition.
  • Wt% in this paragraph refers to the percent by weight based on the total weight of Components (A), (B), (C), and (D).
  • Component (C), the polysiloxane having an average of at least about one phosphonium group or ammonium group per molecule can be present in from about 10 wt% to about 99 wt%, about 40 wt% to about 90 wt%, or about 55 wt% to about 75 wt% of the curable composition.
  • Wt% in this paragraph refers to the percent by weight based on the total weight of Components (A), (B), (C), and (D).
  • Component (D), the free-radical initiator can be present in from about 0.1 wt% to about 6 wt%, or about 1 wt % to about 3 wt% of the curable composition, based on the weight based on the total weight of Components (A), (B), (C), and (D).
  • Component (A) Organic Compound having at least One Free-Radical Polymerizable Group per Molecule.
  • the curable composition includes Component (A), an organic compound having at least one free-radical polymerizable group per molecule.
  • Component (A) can be any suitable organic compound having any suitable number of independently selected suitable free-radical polymerizable group per molecule, such that the composition is curable.
  • the free-radical curable composition can include an organic compound with at least one free-radical polymerizable group.
  • the free-radical polymerizable group of Component (A) can be any suitable free-radical polymerizable group.
  • the organic compound can have any suitable number of free-radical polymerizable groups, such as about one, two, three, four, about five, or more. Examples of free-radical polymerizable groups include, for example, alkenyl groups and alkynyl groups, as well as groups such as ethers, ketones, aldehydes, carboxylates, ketals, acetals, cyano groups, nitro groups, or halogens.
  • the free-radical polymerizable group of Component (A) can be any suitable free-radical polymerizable group.
  • the free-radical polymerizable group of Component (A) can have the formula
  • the one or more free-radical polymerizable group of Component (A) is an alkene having two hydrogen-groups bound at one terminus, allowing easy steric accessibility of for polymerization.
  • Component (A) can be an allyl triazine, allyl isocyanurate, acrylate, unsaturated ester, maleimide, methacrylate, acrylonitrile, styrene, diene, or an N-vinyl amide.
  • reactivity can be selected based on the electron density of the double bond, where higher density can correspond to higher reactivity.
  • the free-radical polymerizable group of Component (A) can be acrylic acid
  • Component (B) Mercapto-Functional Organic Compound having an Average of at least About Three Mercapto Groups per Molecule
  • the curable composition includes Component (B), a mercapto-functional organic compound having an average of at least about two mercapto (thiol) groups per molecule.
  • the mercapto-functional organic compound can have an average of at least three mercapto groups per molecule.
  • the organic compound can be any suitable organic compound.
  • Component (B) can have any suitable average number of mercapto groups per molecule, such as about one, two, three, four, five, or more than about five.
  • Component (B) can participate in a polymerization reaction with
  • Component (A) via thiol-ene chemistry for example via a free-radical mechanism.
  • a thiol group can add across an alkenyl group to generate a sulfur-substituted alkane, or in another example a thiol group can add across an alkynyl group to generate a sulfur- substituted alkene.
  • free-radical polymerizable groups of Component (A) can participate in multiple propagation steps prior to termination of the polymerization, such that several free-radical polymerizable groups are joined via the polymerization, including in some examples non-alkenyl or non- alkynyl groups.
  • a thiol group can add across a single alkene or alkyne, without multiple propagation steps.
  • the mercapto-functional organic compound can be an alkyl 3-mercaptopriopionate
  • R 1 is any organic group of suitable valence (e.g. can be mono-, di-, tri-, tetra-, or poly-substituted), such as a C-
  • suitable valence e.g. can be mono-, di-, tri-, tetra-, or poly-substituted
  • n can be between 1 and 100.
  • the mercapto-functional organic compound can be trimethylolpropane tris(3-mercaptopropionate), also referred to as 2-ethyl-2-(((3- mercaptopropano ptopropanoate),
  • Component (C) Polysiloxane having an Average of at least About One Phosphonium Group or Ammonium Group per Molecule
  • the curable composition includes Component (C), a polysiloxane having an average of at least about one phosphonium group or ammonium group per molecule.
  • Component (C) can be any suitable polysiloxane having at least one phosphonium group or ammonium group.
  • the polysiloxane has an average of at least about two phosphonium groups or ammonium groups per molecule.
  • the polysiloxane has an average of at least about five silicon atoms per molecule.
  • the Component (C) can be held in place in the cured product of the curable composition via a polymeric matrix formed by polymerization of one or more of the other components of the curable composition.
  • Component (C) is held in place passively, such that other bonding interactions between Component (C) and the polymeric matrix do not occur.
  • reactive moieties on the polysiloxane such as bound to the silicon atoms or bound to the phosphonium or ammonium group, can participate in a curing process of the curable composition such that Component (C) is bound to and part of the polymeric matrix formed by polymerization of one or more of the other components of the curable composition.
  • other suitable interactions can occur between Component (C) and the polymeric matrix formed by
  • Component (C) can undergo an ion-exchange process such that it bonds to the polymeric matrix.
  • acidic moieties in the matrix such as polyacrylic acid (including copolymers thereof) can form compounds between the acidic proton and the counter-ion of the ionic liquid (e.g. halogen such as CI " , to release HCI), which can allow the ammonium or phosphonium ion to electrostatically bond to the anionic conjugate base of the acid (e.g. carboxylate ion).
  • the polysiloxane having an average of at least about one phosphonium group or ammonium group per molecule can be an organopolysiloxane.
  • the organopolysiloxane compound can have a linear, branched, cyclic, or resinous structure.
  • the organopolysiloxane compound can be a homopolymer or a copolymer.
  • the organopolysiloxane compound can be a disiloxane, trisiloxane, or polysiloxane.
  • the organopolysiloxane can have an average of at least 5 silicon atoms per molecule.
  • the organopolysiloxane can have about 2 silicon atoms per molecule, or about 5, 7, 1 0, 12, 15, 17, 20, 22, 25, 27, 30, 35, 40, 45, 50, 75, 100, 125, 150, 175, 200, 220 or greater than about 220 silicon atoms per molecule, such as about 220 to about 2000 silicon atoms per molecule.
  • the organopolysiloxane can have about 2 silicon atoms per molecule, or about 5, 7, 1 0, 12, 15, 17, 20, 22, 25, 27, 30, 35, 40, 45, 50, 75, 100, 125, 150, 175, 200, 220 or greater than about 220 silicon atoms per molecule, such as about 220 to about 2000 silicon atoms per molecule.
  • the organopolysiloxane can have about 2 silicon atoms per molecule, or about 5, 7, 1 0, 12, 15, 17, 20, 22, 25, 27, 30, 35, 40, 45, 50, 75, 100, 125, 150, 175, 200, 220 or greater than about 220 silicon atoms per molecule
  • organopolysiloxane has about 12 to about 220 Si atoms per molecule.
  • an organopolysiloxane can include a compound of the formula
  • a has an average value of about 0 to about 2000, and ⁇ has an average value of about 1 to about 2000.
  • Each R 1 is independently a monovalent functional group. Suitable monovalent functional groups include, but are not limited to, acrylic groups; alkyl; halogenated hydrocarbon groups; alkenyl; alkynyl; aryl ; and cyanoalkyl.
  • Each R 2 is independently a phosphonium group or ammonium group, or R 1 .
  • a siloxy-unit can be di- substituted with a phosphonium group or ammonium group.
  • ⁇ has an average value of 0 to 2000, and ⁇ has an average value of 1 to 2000.
  • Each R 3 is independently a monovalent functional group. Suitable monovalent functional groups include, but are not limited to, acrylic groups; alkyl; halogenated hydrocarbon groups; alkenyl; alkynyl; aryl; and cyanoalkyl.
  • Each R 4 is independently a phosphonium group or ammonium group, or R 3 .
  • a siloxy-unit can be di-substituted with a phosphonium group or ammonium group, or a siloxy-end-unit can be mono-, di-, or tri-substituted with a phosphonium group or ammonium group.
  • the organopolysiloxane compound can be a single organopolysiloxane or a combination including two or more organopolysiloxanes that differ in at least one of the following properties: structure, viscosity, average molecular weight, siloxane units, and sequence.
  • organopolysiloxanes can include compounds having the average unit formula
  • R 1 is a functional group independently selected from any optionally further substituted C-i .- ⁇ functional group, including C-i .- ⁇ monovalent aliphatic hydrocarbon groups, 04.-15 monovalent aromatic hydrocarbon groups, and monovalent epoxy-substituted functional groups
  • R 4 is a phosphonium group or ammonium group or R ⁇ or R ⁇
  • R ⁇ is R ⁇ or R 4 , 0 ⁇ w ⁇ 0.95, 0 ⁇ x ⁇ 1 , 0 ⁇ y ⁇ 1 , 0 ⁇ z ⁇ 0.95, and w+x+y+z ⁇ 1 .
  • R ⁇ is C- ⁇ .- ⁇ Q hydrocarbyl or C-
  • w is from 0.01 to 0.6
  • x is from 0 to 0.5
  • y is from 0 to 0.95
  • z is from 0 to 0.4
  • w+x+y+z ⁇ 1 .
  • a siloxy unit can be mono-, di-, or tri -substituted with a phosphonium group or ammonium group.
  • average unit formula (I) can include the following average unit formula:
  • the phosphonium group or ammonium group can be directly bound to a silicon atom of the polysiloxane.
  • the phosphonium group or ammonium group can be bound to a silicon atom of the polysiloxane via linking group, wherein the linking group can be any suitable linking group.
  • the linking group can be any organic group, such as any C- ⁇ _20 group, including any alkyl, alkenyl, aryl, heteroaryl, acyl, amine, ether, amide, or any combination thereof.
  • a linking group can separate the phosphonium group or ammonium group from the polysiloxane by about 2 atoms, 3, 4, 5, 6, 7, 8, 9, 1 0, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19, 20, or more than about 20 atoms.
  • a shorter linker can be preferable (e.g. about 2-5 atoms, or about 3-7 atoms, or about 4-9 atoms separating the polysiloxane from the phosphonium or ammonium ion), for example because as the proportion of silicon gets lower in the polysiloxane, the gas permeability of a membrane made therefrom can become less.
  • a longer linker e.g. 10-20 atoms separating the polysiloxane from the phosphonium or ammonium ion
  • the phosphonium group can be any suitable phosphonium group.
  • the phosphonium group can be any +1 charged quaternary phosphorus atom, substituted with two to four substituents (with four bonds to the phosphorus atom total, e.g. four single bonds, two single bonds and one double bond, two double bonds), for example the substitutents can be independently selected from H, C-
  • the ammonium group can be any suitable ammonium group.
  • the ammonium group can include any +1 charged quaternary nitrogen atom, substituted with two to four substitutents (with four bonds to the nitrogen atom total, e.g. four single bonds, two single bonds and one double bond, two double bonds), for example the substitutents can be independently selected from H, C-
  • the ammonium group can be an imidazolium group.
  • An imidazolium group can be N- substituted with any suitable organic group, such as any C-j ⁇ o alkyl, alkenyl, or alkynyl group.
  • the phosphonium group or quaternary ammonium group can include any suitable -1 charged counterion, such as any deprotonated C-
  • An organopolysiloxane compound can have any suitable average number of phosphonium or ammonium groups per molecule, the properties of cured product of the curable composition are as desired.
  • the polysiloxane can have an average of at least about one phosphonium group or ammonium group per molecule, or an average of less than about 1 , or an average of about 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 30, 50, 100, 150, 200, 250, 300, 350, or about 400 phosphonium groups or ammonium groups per molecule, or an average of greater than about 400 phosphonium groups or ammonium groups per molecule.
  • the phosphonium or ammonium group can have a substituent that allows further reaction, such as an alkyl group having at least one unsaturated C-C bond, such as an alkenyl or alkynyl group, such as a Q>2-
  • the at least one unsaturated C-C bond can participate in the curing process, for example by participating in a thiol-ene polymerization reaction with the other components of the curable composition.
  • a pendant alkenyl group on a phosphonium or ammonium group can be allowed to react via an olefin metathesis in the presence of an appropriate catalyst, such as for example a Grubbs, Hoveyda, Grubbs-Hoveyda, or other related catalyst, and in the presence of an appropriate reagent, such as a suitably substituted alkene.
  • an appropriate catalyst such as for example a Grubbs, Hoveyda, Grubbs-Hoveyda, or other related catalyst
  • an appropriate reagent such as a suitably substituted alkene.
  • any suitable method can be used to make the organopolysiloxane having an average of at least about one phosphonium group or ammonium group per molecule.
  • the methods of making the organopolysiloxane given herein are merely examples, and the suitable methods of making the organopolysiloxane can encompass methods beyond those given herein.
  • the organopolysiloxane can be made using a suitable organohydrogenpolysiloxane.
  • the organopolysiloxane can be made using a suitable organohydrogenpolysiloxane.
  • organohydrogenpolysiloxane can be a suitable polymethylhydrogensiloxane (PMHS) or polymethylhydrogensiloxane-polydimethylsiloxane copolymer (PMHS-PDMS) copolymer.
  • suitable organohydrogenpolysiloxanes include any organopolysiloxane described in section (a), describing the general structure of the polysiloxane having a phosphonium group or a ammonium group, but wherein all of the phosphonium groups and ammonium groups are replaced by H-groups, such that the polysiloxane is an organohydrogenpolysiloxane described in section (a), describing the general structure of the polysiloxane having a phosphonium group or a ammonium group, but wherein all of the phosphonium groups and ammonium groups are replaced by H-groups, such that the polysiloxane is an
  • organohydogenpolysiloxane in such examples, the
  • organohydrogenpolysiloxane can have the same number of Si-H groups as the number of phosphonium or ammonium groups possessed by the product polysiloxane.
  • suitable organohydrogenpolysiloxanes can include any organopolysiloxane described in section (a), describing the general structure of the polysiloxane having a phosphonium group or a ammonium group, but wherein all of the phosphonium groups and ammonium groups are replaced by H-groups, and additionally wherein any other suitable number of Si- R groups are replaced by Si-H groups.
  • the organohydrogenpolysiloxane can have a greater number of Si-H groups than the number of phosphonium or ammonium groups possessed by the product polysiloxane.
  • the organohydrogenpolysiloxane can be allowed to react with a terminally-halide-substituted alkene- or alkyne-containing compound.
  • the halide atom can be substituted on a terminus of the compound.
  • the alkenyl group in the compound can be at a different terminus of the compound than the halide, or can be at a non-terminus position.
  • the structure of the terminally-halide-substituted compound can be
  • R 1 is any suitable monovalent organic group
  • R 2 is any suitable divalent organic group
  • X is any suitable halide.
  • R 1 and R 2 are independently selected from any C-j ⁇ rj alkyl, aryl, alkyl, alkenyl, aryl, heteroaryl, acyl, amine, ether, amide, or any combination thereof, wherein R1 is monovalent, and R 2 is divalent, and X is any suitable halide, e.g. F, Br, CI, I.
  • the terminally-halide substituted compound can be identical to the structure above but having an alkynyl substituent in place of the alkenyl substituent, and correspondingly having X-R 2 - bound to one end of the alkyne and R ⁇ bound to the other.
  • the terminally-halide- substituted compound can be 2-chloroethylvinyl ether or 4-bromobutene.
  • the terminally-halide substituted compound can be allowed to undergo a hydrosilylation reaction with the organohydrogenpolysiloxane, such that Si-H groups react with the alkenyl or alkynyl group to give an organopolysiloxane compound having a terminally-substituted halogen atom linked via a linker unit to a silicon atom of the polysiloxane.
  • the hydrosilylation reaction can be optionally catalyzed by a suitable amount of hydrosilylation catalyst.
  • the hydrosilylation can be allowed to proceed until a desired amount of Si-H groups have been consumed by the terminally-halide-substituted alkene- or alkyne- containing compound.
  • the alkene- or alkyne-containing compound is too unreactive to consume all of the Si-H groups in a suitable period of time, notably alkene- or alkyne-containing compounds wherein the alkene or alkyne group is not at the terminus of the compound, e.g. when the alkene or alkyne is more highly substituted the compound can tend to be less reactive.
  • Si-H groups can be substantially entirely eliminated from the polysiloxane in order to have favorable results from the next chemical step to form the phosphonium or ammonium ion, otherwise undesirable reactions can occur at the Si-H groups. In some examples, the undesirable reactions can lead to gelation or gas evolution (hydrogen).
  • the Si- H groups can be eliminated by treatment with a reactive alkene or alkyne to allow a hydrosilylation reaction with the Si-H groups.
  • the reactive alkene or alkyne can be any reactive alkene or alkyne, for example the reactive alkene or alkyne can be a terminally-halide-substituted alkenyl- or alkynyl-containing compound, as described herein, but wherein the compound is more reactive than the first terminally-halide-substituted alkenyl- or alkynyl-containing compound allowed to react with the organohydrogenpolysiloxane (e.g.
  • the reactive alkenyl or alkyl compound can have no halogen atoms.
  • the reactive alkenyl- or alkynyl-containing compound used to substantially eliminate residual Si-H groups can be ethylene, or any suitable vinyl or allyl ether such as for example 2-chloroethylvinyl ether, propyl vinyl ether, allyl propionate, vinyl acetate, or allyl acetate.
  • the resulting terminally-substituted halide of the organopolysiloxane can then be allowed to react with a suitable reagent to give a product wherein the halide atom is replaced with a phosphonium or ammonium group, e.g. the silicone-based ionic liquid, an organopolysiloxane having an average of at least about two phosphonium groups or ammonium groups per molecule.
  • suitable reagents for the preparation of a phosphonium group from the terminal-halide include any tri-C-
  • Ci -20 alkyl substituent is independently selected, such as triethylphosphine.
  • suitable reagents for the preparation of an ammonium group from the terminal-halide include any C- ⁇ _20 alkyl substituted imidazole, such as N- butylimidazole.
  • Scheme 1 illustrates an example of synthesis of a silicone-based ionic liquid, in accordance with various embodiments, as described herein.
  • a polymethylhydrogensiloxane-polydimethylsiloxane copolymer (PMHS-PDMS) copolymer is allowed to react with 2-chloroethylvinyl ether to give a chloroethoxyethyl-substituted organosiloxane polymer.
  • the terminally- substituted halide is then allowed to react with an N-R-substituted-imidazole to replace the halogen with an imidazolium-group, giving the silicone-based ionic liquid, an imidazole-substituted organopolysiloxane.
  • Scheme 1 Synthesis of a silicone-based ionic liquid, in accordance with various embodiments.
  • the curable composition includes Component (D), a free-radical initiator.
  • the free-radical initiator can be any suitable free-radical initiator.
  • the free- radical initiator can be present in a catalytic amount, for example a quantity sufficient to efficiently initiate or promote free-radical chemical reactions in the curable composition. Free-radical polymerization can allow the curable composition to cure.
  • the free-radical photoinitiator can be a single free-radical photoinitiator or a mixture including two or more different free-radical photoinitiators.
  • a free-radical is generated.
  • the free- radical then can attack a free-radical polymerizable functional group.
  • the attacking group forms a bond to the free-radical polymerizable group, and transfers a radical thereto.
  • the free-radical polymerizable functional group can then go on to attack other free-radical polymerizable functional groups.
  • Free-radicals can be generated by any suitable method. Free-radicals can be initiated by, for example, thermal decomposition, photolysis, redox reactions, persulfates, ionizing radiation, electrolysis, plasma, sonication, or a combination thereof. In one example, a free-radical is generated using a free- radical initiator. In one example, the free-radical initiator can be a free-radical photoinitiator, an organic peroxide, or a free-radical initiator activated by heat.
  • a free-radical photoinitiator can be any free-radical photoinitiator capable of initiating cure (cross-linking) of the free-radical polymerizable functional groups upon exposure to radiation, for example, having a wavelength of from 200 to 800 nm.
  • the free-radical initiator is a organoborane free-radical intiator.
  • the free-radical initiator can be an organic peroxide.
  • elevated temperatures can allow a peroxide to decompose and form a highly reactive radical, which can initiate free-radical polymerization.
  • decomposed peroxides and their derivatives can be byproducts.
  • Suitable free-radical photoinitiators that can be activated by, for example, ultraviolet light, include a-hydroxyketones such as 1 - hydroxy-cyclohexyl-phenyl-ketone, benzophenone, 2-hydroxy-2-methyl-1 - phenyl-1 -propanone, 2-hydroxy-1 -[4-(2-hydroxyethoxy)phenyl]-2-methyl-1 - propanone; phenylglyoxylates such as methylbenzoylformate, oxy-phenyl-acetic acid 2- ⁇ 2 oxo-2-phenyl-acetoxy-ethoxy]-ethyl ester (CAS 211510-16-6), or oxy- phenyl-acetic 2-[2-hydroxy-ethyoxy]-ethyl ester (CAS 442536-99-4) ;
  • a-hydroxyketones such as 1 - hydroxy-cyclohexyl-phenyl-ketone, benzophenone, 2-hydroxy-2-methyl-1
  • benzyldimethyl-ketals like ⁇ , ⁇ -dimethoxy-a-phenylacetophenone; a- aminoketones such as 2-benzyl-2-(dimethylamino)-1 -[4-(4-morpholinyl)phenyl- 1 -butanone, 2-methyl-1 -[4-(methylthio)phenyl]-2-(4-morpholinyl)-1 -propanone); mono acyl phosphines (MAPOs) such as diphenyl (2,4,6-trimethylbenzoyl)- phosphine oxide; bis acyl phosphines (BAPOs) such as phenyl bis(2,4,6- trimethyl benzoyl) phosphine oxide; metallocenes such as bis(n5-2,4- cyclopentadien-1 -yl) bis [2,6-difluoro-3-(1 H-pyrrol-1 -yl)phenyl]titanium;
  • Darocur 4265 can be used, including components of about 50 wt% diphenyl (2,4 phine oxide
  • the present invention includes a membrane that includes a cured product of the curable composition.
  • the present invention provides a method of forming a membrane.
  • 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 the membrane by the step of forming the membrane. All surfaces of the substrate can be coated by the step of forming the membrane, one surface can be coated, or any number of surfaces can be coated.
  • forming a membrane can include two steps.
  • the curable composition can be applied to at least one surface of the substrate.
  • the applied composition 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 curable composition into the membrane.
  • the composition that forms the membrane can be in a liquid state.
  • the membrane can be in a solid state.
  • the curable composition be applied using conventional coating techniques, for example, immersion coating, die coating, blade coating, curtain coating, drawing down, solvent casting, spin coating, dipping, spraying, brushing, roll coating, extrusion, screen-printing, pad printing, or inkjet printing.
  • conventional coating techniques for example, immersion coating, die coating, blade coating, curtain coating, drawing down, solvent casting, spin coating, dipping, spraying, brushing, roll coating, extrusion, screen-printing, pad printing, or inkjet printing.
  • Curing the curable composition 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.
  • the membrane can have any suitable thickness.
  • the membrane can have a thickness of from about 1 ⁇ to about 20 ⁇ .
  • the membrane can have a thickness of from about 0.1 ⁇ to about 200 ⁇ .
  • the membrane can have a thickness of from about 0.01 ⁇ to about 2000 ⁇ .
  • the membrane can be selectively permeable to one substance over another.
  • the membrane is selectively permeable to one gas over other gases or liquids.
  • the membrane is selectively permeable to more than one gas over other gases or liquids.
  • the membrane has a CO2/CH4 ideal selectivity of at least about 2.8, at least about 3.0, 4, 5, 6, 7, 8, 9, 1 0, 15, 20, 25, 50, 75, 100, 150, 200, 300, 400, 500, 600, 700, 800, 900, 1 000, 2000,3000, 4000, or at least about 5000 at room temperature.
  • the membrane has an CO2 permeability coefficient of at least about 300 Barrer, 500 Barrer, 700 Barrer, 900 Barrer, 1000 Barrer, 1200 Barrer, 1400 Barrer, 1600 Barrer, 1800 Barrer, 2000 Barrer, 2500 Barrer, or at least about 3000 Barrer at room temperature.
  • the membrane of the present invention can be solid, flexible, or any suitable combination thereof.
  • the membrane of the present invention can have any suitable shape.
  • the membrane can be a plate-and- frame membrane, spiral wound membrane, tubular membrane, capillary fiber membrane, or hollow fiber membrane.
  • the membrane can 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).
  • 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 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 supported membrane can be made by providing a substrate, wherein at least one surface of the substrate includes a plurality of pores or is highly permeable to the materials of interest.
  • the substrate can be any suitable shape, including planar, curved, or any combination thereof.
  • porous substrates or highly permeable non-porous substrates includes a sheet, tube or hollow fiber.
  • the porous substrate or highly permeable non-porous substrate can be smooth, be corrugated or patterned, or have any amount of surface roughness.
  • 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.
  • 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.
  • the porous or highly permeable non-porous substrate can be laid upon an uncured, partially cured or fully cured coating, or drawn through an uncured or fully cured coating.
  • Forming the coating can include applying the coating, and curing the coating. The steps of applying and curing can occur in any order and can occur simultaneously.
  • a supported membrane can be made by providing a substrate, wherein at least one surface of the substrate includes a plurality of pores or is highly permeable to the materials of interest.
  • a first coating can be formed on the at least one porous or highly permeable surface of the substrate. Forming the first coating can include applying the coating, and curing the coating. The first coating can be formed sufficiently to at least partially fill the pores. The first coating can be removed, such that a substantially exposed substrate surface is formed, and such that the cured coating remains at least partially in the pores of the substrate.
  • the first coating can be any suitable material, and can include materials that swell and absorb solvent or water.
  • a second coating can be formed on the exposed substrate surface. Forming the second coating can include applying the coating, and curing the coating.
  • the second coating can include a membrane, where the membrane includes a cured product of a curable composition.
  • the method can further include at least partially restoring the porosity of the porous substrate. For example, in embodiments with a first coating that swells and absorbs solvent or water, the porosity of substrate can be at least partially recovered by drying the first coating to remove the majority of the absorbed solvent or water.
  • 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, for example, a filter, or any substrate of any suitable shape that includes a fibrous structure or any structure.
  • 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 porous substrate can be any suitable porous material known to one of skill in the art, in any shape.
  • 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.
  • 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 pores 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.
  • 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.
  • embodiments of the present invention can also include other copolymers or polymeric alloys, which can be two or more miscible or partially miscible polymers, and polymeric blends, which can have discrete non-miscible phases.
  • polymers that can form porous polymers suitable for use as a porous or highly permeable substrate in embodiments of the present invention include thermoplastic or thermoset polymers, including but not limited to those commonly known in the art.
  • the polymers that can form porous polymers suitable for use as a porous substrate in embodiments of the present invention may be modified with supplemental additives including, but not limited to, antioxidants, coloring agents such as pigments and dyes, flame retardants, process aids, antistatic agents, impact modifiers, nucleating agents, flow aids, ignition resistant additives, coupling agents, lubricants, antiblocking agents, mold release additives, plasticizers, ultraviolet ray inhibitors, or thermal stabilizers.
  • supplemental additives including, but not limited to, antioxidants, coloring agents such as pigments and dyes, flame retardants, process aids, antistatic agents, impact modifiers, nucleating agents, flow aids, ignition resistant additives, coupling agents, lubricants, antiblocking agents, mold release additives, plasticizers, ultraviolet ray inhibitors, or thermal stabilizers.
  • Suitable porous substrates can include, for example, porous glass, various forms and crystal forms of porous metals, ceramics and alloys, including porous alumina, zirconia, titania, steel, stainless steel, titanium, aluminum, copper, nickel, zinc, iron, manganese, magnesium, iron, chromium, vanadium, silver, gold, platinum, palladium, rhodium, lead, tin, antimony, silicon, germanium, silicon carbide, tungsten carbide.
  • porous glass various forms and crystal forms of porous metals, ceramics and alloys, including porous alumina, zirconia, titania, steel, stainless steel, titanium, aluminum, copper, nickel, zinc, iron, manganese, magnesium, iron, chromium, vanadium, silver, gold, platinum, palladium, rhodium, lead, tin, antimony, silicon, germanium, silicon carbide, tungsten carbide.
  • 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 free-standing membrane are not contacting a substrate, whether the substrate is porous or not.
  • a free-standing membrane can be 100% unsupported.
  • a free-standing membrane 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 or highly permeable substrate, or a nonporous or non-highly permeable substrate. Examples of suitable supports for a free-standing membrane can include but is not limited to any examples of supports given herein for supported membranes.
  • a free-standing membrane can have any suitable shape, regardless of the percent of the freestanding membrane that is supported.
  • suitable shapes for freestanding membranes include, for example, squares, rectangles, circles, tubes, cubes, spheres, cones, and planar sections thereof, wherein the free-standing membrane can have any suitable 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 free-standing membrane can be unattached to the membrane but nonetheless in contact with the membrane and held in place by friction or gravity or other suitable means.
  • 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 can be made, for example, by the steps of coating or applying a curable composition onto a release substrate, curing the composition, and removing the membrane from the release substrate. After application of the composition to the release 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 release substrate. In some examples, after the unsupported membrane is removed from a release substrate, the membrane is then attached to a support, as described herein.
  • an unsupported membrane is made by the steps of coating a composition onto one or more release substrates, curing the composition, and removing the membrane from at least one of the one or more release substrates, while leaving at least one of the one of more substrates in contact with the membrane.
  • the membrane is entirely removed from the release substrate.
  • the membrane can be peeled away from the release substrate.
  • the release substrate can be any suitable release substrate that allows a membrane formed thereon to be removed, such as for example Teflon or another slippery material.
  • the thickness or shape of the applied composition can be altered via any suitable means, for example leveled or otherwise adjusted, such that the membrane that results after the curing process has the desired thickness and shape.
  • a doctor blade or drawdown bar is used to adjust the thickness of the applied composition.
  • a conical die is used to adjust the thickness of the applied composition on a fiber that is later removed.
  • the substrate can be porous or nonporous.
  • the substrate can be any suitable material, and can be any suitable shape or size, including planar, curved, solid, hollow, or any combination thereof. Suitable materials for porous or nonporous substrates include any polymers described above as suitable for use as porous substrates in supported membranes.
  • the substrate can be a water soluble polymer that is dissolved by purging with water.
  • the substrate can be a fiber or hollow fiber, as described in US 6,797,212 B2.
  • the substrate is coated with a material prior to formation of the membrane that facilitates the removal of the membrane once formed. The material that forms the substrate can be selected to minimize sticking between the membrane and the substrate.
  • 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 present invention also provides a method of separating gas components 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 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 air, 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.
  • two, three, four, five, six, seven, eight, nine, ten, or any suitable number of membranes can be used.
  • the membranes need not all include the same reaction product. In some embodiments, all the membranes include the same reaction product.
  • the membranes can have different properties, and can have different permeability for a particular gas. In other embodiments, the membranes have the same properties. Any combination of free-standing and supported membranes 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.
  • Modules can include hollow fiber modules, spiral wound modules, plate-and-frame modules, tubular modules and capillary fiber modules.
  • the sheets, fibers or leaflets may be of any size or aspect ratio and can assume any packing density in the module.
  • Methods of making hollow fibers modules and spiral wound modules are known in the art, such as described in Baker, R. W. Membrane Technology and Applications, 2nd Edition; 2nd ed. ; John Wiley & Sons Inc. : West Wales, England, 2004, and in U.S. Patents 3,339,341 and 4,871 ,379 (Maxwell et al. , Edwards et al.) and U.S. Patent 5,034, 126 (Reddy et al.).
  • Various methods and configurations for delivering the feed gas mixture and recovering the permeate and retentate mixtures are also
  • membrane separations can identify operating conditions for a given combination of membrane performance properties such as selectivity and flux to achieve a desired level of separation optimized on the basis of capital and operating costs, plant footprint, environmental conditions, and maintenance and reliability.
  • the membrane system can be operated in conjunction with compressors, vacuum systems, pre-filters, heaters, chillers, condensers, or any other type of suitable operation either upstream or downstream of the membrane system.
  • the permeate side of the membrane can be operated under a positive pressure, ambient pressure, or negative pressure (e.g. vacuum) with or without a sweep gas or a sweep liquid such as found in a membrane contactor (e.g.
  • the sweep gas can be any gas, and can originate from outside the process or be recycled from within the process, or include a mixture thereof.
  • hollow fiber modules can be fed from the bore side or from the shell side, at any position of entry.
  • the feed gas inlets and permeate gas outlets can be positioned to permit a counter-current, crosscurrent or co-current flow configuration.
  • the modules can be operated as single membrane modules or organized further into arrays or banks of modules.
  • the individual membrane modules or arrays or banks of modules can further be configured into additional staged superstructures, such as in series, parallel or cascade configurations, to allow enhanced flux or separation. Partial recycling of the permeate or retentate can be used to achieve a more efficient separation. For example, if the residue stream requires further purification, it may be passed to a second bank of membrane modules for further separation. Likewise, if the permeate stream requires further concentration, it may be passed to a second bank of membrane modules for a second-stage separation.
  • any optional ingredient described herein can be present in the membrane or in the composition that forms the membrane; alternatively, any optional ingredient described herein can be absent from the membrane or the composition that forms the membrane.
  • optional additional components include surfactants, emulsifiers, dispersants, polymeric stabilizers, crosslinking agents, combinations of polymers, crosslinking agents, catalysts useful for providing a secondary polymerization or crosslinking of particles, rheology modifiers, density modifiers, aziridine stabilizers, cure modifiers such as hydroquinone and hindered amines, free- radical initiators, polymers, diluents, acid acceptors, antioxidants, heat stabilizers, flame retardants, scavenging agents, silylating agents, foam stabilizers, solvents, diluents, plasticizers, fillers and inorganic particles, pigments, dyes and dessicants.
  • Liquids can optionally be used.
  • An example of a liquid includes water, an organic solvent, any liquid organic compound, a silicone liquid, organic oils, ionic fluids, and supercritical fluids.
  • Other optional ingredients include polyethers having at least one alkenyl group per molecule, thickening agents, fillers and inorganic particles, stabilizing agents, waxes or wax-like materials, silicones, organofunctional siloxanes, alkylmethylsiloxanes, siloxane resins, silicone gums, silicone carbinol fluids can be optional components, water soluble or water dispersible silicone polyether compositions, silicone rubber, hydrosilylation catalyst inhibitors, adhesion promoters, heat stabilizers, UV stabilizers, and flow control additives.
  • a variety of methods can be used to measure the permeability of a membrane to particular gases.
  • gas permeability coefficients and ideal selectivities in a binary gas mixture were measured using a permeation cell including upstream (feed/retentate) and downstream
  • the upstream chamber had one gas inlet and one gas outlet.
  • the downstream chamber had one gas outlet.
  • the upstream chamber was maintained at 35 psig pressure and was continuously supplied with a suitable mixture of CO2 gas and CH4 gas at a flow rate of between 0-200 standard cubic centimeters per minute (seem).
  • the membrane was supported on a glass fiber filter disk with a diameter of 83 mm and a maximum pore diameter range of 10-20 ⁇ (Ace Glass).
  • the membrane area was defined by a placing a butyl rubber gasket with a diameter of 50 mm (Exotic Automatic & Supply) on top of the membrane.
  • the downstream chamber was maintained at 5 psig pressure and was continuously supplied with a pure He stream at a flow rate of 20 seem.
  • the outlet of the downstream chamber was connected to a 6-port injector equipped with a 1 -mL injection loop.
  • 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 silicone-based ionic liquid having imidazolium groups.
  • Scheme. 1 illustrates a reaction scheme showing synthesis of a silicone-based ionic liquid via hydrosilylation of a organohydrogenpolysiloxane compound using 2-chloroethylvinyl ether wherein the synthesized silicone compounds have imidizolium groups.
  • SPIL B (68.2 parts), acrylic acid (17.0 parts), 1 ,3,5-Triallyl-1 ,3,5- triazine-2,4,6(1 H,3H,5H)-trione (6.8 parts), Trimethylolpropane tris(3- mercaptopropionate) (6.8 parts), and Darocur 4265 (about 50 wt% diphenyl
  • Example 5 Membrane fabrication and evaluation.
  • SPIL A (59.2 parts), diallylimidazolium chloride (12.3 parts), acrylic acid (14.9 parts), 1 ,3,5-Triallyl-1 ,3,5-triazine-2,4,6(1 H,3H,5H)-trione (6.3 parts), Trimethylolpropane tris(3-mercaptopropionate) (5.9 parts), and Darocur 4265 (about 50 wt% diphenyl (2,4,6-trimethyl benzoyl)-phosphine oxide and about 50 wt% diphenyl (2,4,6-trimethyl benzoyl)-phosphine oxide) (1 .2 parts) were mixed in SpeedyMixer® thoroughly.
  • 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 curable composition comprising: (A) an organic compound having at least one free-radical polymerizable group per molecule; (B) a mercapto-functional organic compound having an average of at least about three mercapto groups per molecule; (C) a polysiloxane having an average of at least about one quaternary phosphonium group or quaternary ammonium group per molecule, wherein the polysiloxane has an average of at least about five silicon atoms per molecule; and (D) a free-radical initiator.
  • Embodiment 3 provides the curable composition according to any one of Embodiments 1 or 2, wherein the phosphonium group has a cyclic structure.
  • Embodiment 4 provides the curable composition according to any one of Embodiments 1 or 2, wherein the quaternary ammonium group has a cyclic structure.
  • Embodiment 5 provides the curable composition according to any one of Embodiments 1 -4, wherein the quaternary ammonium group comprises an imidazolium ion.
  • Embodiment 6 provides the curable composition according to any one of Embodiments 1 -5, wherein the polysiloxane has an average of from about 5 to about 2000 Si atoms per molecule.
  • Embodiment 7 provides the curable composition according to any one of Embodiments 1 -6, wherein the polysiloxane has an average of from about 12 to about 220 Si atoms per molecule.
  • Embodiment 8 provides the curable composition according to any one of Embodiments 1 -7, wherein the quaternary phosphonium group or quaternary ammonium group comprises a C2-12 group that includes at least one unsaturated carbon-carbon bond.
  • Embodiment 9 provides a cured product of the curable composition according to any one of Embodiments 1 -8.
  • Embodiment 10 provides an unsupported membrane comprising the cured product according to Embodiment 9, wherein the membrane is free- standing.
  • Embodiment 1 1 provides the unsupported membrane according to Embodiment 10, wherein the membrane has a thickness of from 0.1 to 200 ⁇ .
  • Embodiment 12 provides the unsupported membrane according to any one of Embodiments 10 or 1 1 , wherein the membrane is selected from a plate membrane, a spiral membrane, tubular membrane, and hollow fiber membrane.
  • Embodiment 13 provides a coated substrate, comprising: a substrate; and a coating on the substrate, wherein the coating comprises the cured product according to Embodiment 9.
  • Embodiment 14 provides the coated substrate according to
  • Embodiment 13 wherein the substrate is porous and the coating is a membrane.
  • Embodiment 15 provides the coated substrate according to
  • Embodiment 14 wherein the porous substrate is a frit comprising a material selected from glass, ceramic, alumina, a porous polymer, and combinations thereof.
  • Embodiment 16 provides a method of separating gas components in a feed gas mixture, the method comprising: contacting a first side of a membrane comprising a cured product of a curable composition 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, the retentate gas mixture is depleted in the first gas component, and wherein the curable composition comprises (A) an organic compound having at least one free-radical polymerizable group per molecule; (B) a mercapto-functional organic compound having an average of at least about three mercapto groups per molecule; (C) an polysiloxane having an average of at least about one quaternary phosphonium group or quaternary ammonium group per molecule, wherein the polysiloxane has an average
  • Embodiment 18 provides the method according to any one of Embodiments 16-17, wherein the free-radical polymerizable group of
  • Embodiment 19 provides the method according to any one of Embodiments 16-18, wherein the polysiloxane has an average of from about 5 to about 2000 Si atoms per molecule.
  • Embodiment 20 provides the method according to any one of Embodiments 16-19, wherein the quaternary ammonium group comprises an imidazolium ion.
  • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Optics & Photonics (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Silicon Polymers (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

La présente invention concerne des liquides ioniques à base de silicone et leurs procédés de fabrication, des compositions durcissables comprenant ces liquides ioniques, des matériaux tels que des membranes fabriquées à partir de celles-ci et des procédés d'utilisation de ces matériaux. Plusieurs modes de réalisation de la présente invention concernent une composition durcissable. La composition durcissable selon l'invention comprend un constituant (A), un composé organique comprenant au moins un groupe polymérisable par voie radicalaire par molécule. La composition durcissable selon l'invention comprend également un constituant (B), un composé organique à groupes fonctionnels mercapto comprenant une moyenne d'au moins environ trois groupes mercapto par molécule. La composition durcissable selon l'invention comprend également un constituant (C), un polysiloxane comprenant une moyenne d'au moins environ un groupe phosphonium ou un groupe ammonium par molécule, dans laquelle le polysiloxane contient une moyenne d'au moins environ cinq atomes de Si par molécule. En outre, la composition durcissable selon l'invention comprend une quantité catalytique d'un initiateur de radicaux libres. Dans certains modes de réalisation, la présente invention concerne un produit durci de la composition durcissable, une membrane supportée ou non comprenant le produit durci, et un procédé de séparation de constituants gazeux dans un mélange gazeux d'alimentation utilisant cette membrane.
PCT/US2012/070122 2011-12-22 2012-12-17 Liquides ioniques à base de silicone et applications associées WO2013096211A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201161579146P 2011-12-22 2011-12-22
US61/579,146 2011-12-22

Publications (1)

Publication Number Publication Date
WO2013096211A1 true WO2013096211A1 (fr) 2013-06-27

Family

ID=47520283

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2012/070122 WO2013096211A1 (fr) 2011-12-22 2012-12-17 Liquides ioniques à base de silicone et applications associées

Country Status (1)

Country Link
WO (1) WO2013096211A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103506156A (zh) * 2013-09-18 2014-01-15 南京工业大学 一种非均相酸性催化剂及其制备方法与应用
US20150073069A1 (en) * 2013-09-11 2015-03-12 Evonik Industries Ag Coating composition comprising polysiloxane quats
US10044062B2 (en) 2013-12-13 2018-08-07 Tufts University Silicone-containing ionic materials
WO2023007201A1 (fr) * 2021-07-29 2023-02-02 The Regents Of The University Of Colorado, A Body Corporate Membranes à matrice mixte réticulée, composition et procédé

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080213598A1 (en) * 2007-01-19 2008-09-04 Airbus Deutschland Gmbh Materials and processes for coating substrates having heterogeneous surface properties
JP2010285519A (ja) * 2009-06-10 2010-12-24 Kaneka Corp 光硬化性組成物およびそれを用いた絶縁性薄膜および薄膜トランジスタ

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080213598A1 (en) * 2007-01-19 2008-09-04 Airbus Deutschland Gmbh Materials and processes for coating substrates having heterogeneous surface properties
JP2010285519A (ja) * 2009-06-10 2010-12-24 Kaneka Corp 光硬化性組成物およびそれを用いた絶縁性薄膜および薄膜トランジスタ

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150073069A1 (en) * 2013-09-11 2015-03-12 Evonik Industries Ag Coating composition comprising polysiloxane quats
CN104419241A (zh) * 2013-09-11 2015-03-18 赢创工业集团股份有限公司 包含聚硅氧烷季铵盐的涂层组合物
US9353289B2 (en) * 2013-09-11 2016-05-31 Evonik Degussa Gmbh Coating composition comprising polysiloxane quats
CN103506156A (zh) * 2013-09-18 2014-01-15 南京工业大学 一种非均相酸性催化剂及其制备方法与应用
US10044062B2 (en) 2013-12-13 2018-08-07 Tufts University Silicone-containing ionic materials
WO2023007201A1 (fr) * 2021-07-29 2023-02-02 The Regents Of The University Of Colorado, A Body Corporate Membranes à matrice mixte réticulée, composition et procédé

Similar Documents

Publication Publication Date Title
US20150000522A1 (en) High free volume siloxane compositions useful as membranes
CA2782798C (fr) Membranes composites a base de silicone, presentant un effet de separation eleve
US20140060324A1 (en) Method of preparing gas selective membrane using epoxy-functional siloxanes
EP2718000A1 (fr) Membrane dérivée d'une composition de silicone à teneur en polyéther en charge siliceuse
WO2013096211A1 (fr) Liquides ioniques à base de silicone et applications associées
TWI593725B (zh) 經親水性改質之氟化膜（ｖ）
EP3155036B1 (fr) Procédé de formation d'un produit d'organosilicium à l'aide d'un contacteur à membrane pour réagir à un gaz et un liquide
WO2014059132A2 (fr) Membranes comprenant des copolymères de polysiloxane-poly(oxyde d'alkylène) et leurs procédés d'utilisation
JP5969169B2 (ja) 複合分離膜
US9957364B2 (en) Modified elastomer surface
US20150231556A1 (en) Method Of Manufacturing A Silicone Membrane
WO2013070912A1 (fr) Synthèse de membranes ionomères de silicone et leur utilisation
Wang et al. Synthesis, in-situ membrane preparation, and good gas permselectivity of insoluble poly (substituted acetylene) s loosely cross-linked with short and soft siloxane and silanol linkages
US9962657B2 (en) Method of and system for separating volatile siloxane from feed mixture
JP2019218493A (ja) 変性膜の製造方法
UA66694A (en) Method for production of a composite matrix membrane

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12812470

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12812470

Country of ref document: EP

Kind code of ref document: A1