WO2013112792A1 - Metal silicon framework composition useful for gas separations - Google Patents

Abstract

The present invention relates to a coordination polymer or solvate thereof. The coordination polymer or solvate thereof includes repeat units having the formula M(SiF₆)(pz)_x(L)_y, wherein pz is pyrazine or a substituted pyrazine, M is Cu, Zn, Ni, Fe, or Co, 1 ≤ x, 0 ≤ y ≤ 2, x+y ≤ 3, and L is any organic group that comprises at least one atom selected from N and O, and provided that L is not pyrazine or substituted pyrazine. The present invention also relates to a filled polymer composition including the coordination polymer, to a supported or unsupported membrane that includes the coordination polymer, to a curable silicone composition including the coordination polymer, to a curable silicone composition including the filled polymer composition, and to a supported or unsupported membrane that includes the filled polymer composition. The present invention also relates to methods of making the coordination polymer, methods of making the filled polymer composition, methods of making the membranes, and to methods of separating gas components in a feed gas mixture using the membrane.

Description

METAL SILICON FRAMEWORK COMPOSITION USEFUL FOR GAS

SEPARATIONS

CLAIM OF PRIORITY

[0001] This application claims the benefit of priority of U.S. Patent Application Serial No. 61/590,610, entitled "METAL SILICON FRAMEWORK

COMPOSITION USEFUL FOR GAS SEPARATIONS," filed on January 25, 2012, which application is incorporated by reference herein in its entirety. [0002] Coordination polymers are structures including metal cation centers linked by ligands, extending in an array. Metal silicon framework materials are new type of coordination polymer structure that include metal (cation) base nodes and silicon containing organic linkers. The combination of metal nodes and linkers result in two-dimensional sheet-like structures or three-dimensional porous structures by self-assembling coordination. Due to their fine pore structure and high porosity, three-dimensional coordination polymers can have surface areas that surpass many zeolites and activated carbon materials.

Some coordination polymers exhibit unique magnetic and luminescent properties. Coordination polymers have many applications, with examples including separation technologies for gases or liquids including membrane technology, adsorbent technology, filtration technology, molecular storage technologies including gas or fuel storage and transport, catalyst technology including alternatives to zeolitic supports for heterogeneous catalysts, electrical conduction, biotechnology, and sensor technologies.

[0003] Artificial membranes can be used to perform separations on both a small and large scale, which makes them very useful in many settings. Some common driving forces used in membrane separations are pressure gradients and concentration gradients. Membranes can be made from polymeric structures, for example, and can have a variety of surface chemistries, structures, and production methods. Membranes can be made by hardening or curing a composition.

SUMMARY OF THE INVENTION

[0004] Various embodiments of the present invention provide a coordination polymer or solvate thereof. The coordination polymer or solvate thereof includes repeat units having the formula M(SiFg)(pz)_x(L)_y, wherein pz is pyrazine or a substituted pyrazine, M is Cu, Zn, Ni, Fe, or Co, 1 < x, 0 < y < 2, x+y < 3, and L is any ligand that includes at least one atom selected from N and 0. The coordination polymer or solvate thereof is subject to the proviso that L is not pyrazine or substituted pyrazine. The coordination polymer or solvate thereof is subject to the proviso that if M is Cu, and y is 2, and L is H2O, and x is

1 , then pz is not pyrazine. The coordination polymer or solvate thereof is subject to the proviso that if M is Zn, and y is 0, and x is 2, then pz is not pyrazine. The coordination polymer or solvate thereof is subject to the proviso that if M is Cu, and y is 0, and x is 2 or 3, then pz is not pyrazine. The coordination polymer or solvate thereof is subject to the proviso that if M is Cu, and y is 0, and x is 1 or 4, then pz is not 2,6-dimethylpyrazine.

[0005] Various embodiments of the present invention provide a filled polymer composition. The filled polymer composition includes a composition selected from a curable polymer composition including a thermosetting polymer, and a polymer composition including a thermoplastic polymer in a fluid state. The filled polymer composition also includes a particulate filler including a coordination polymer or solvate thereof. The coordination polymer or solvate thereof includes repeat units having the formula M(SiFg)(pz)_x(L)_y, wherein pz is pyrazine or a substituted pyrazine, M is Cu, Zn, Ni, Fe, or Co, 1 < x, 0 < y < 2, x+y < 3, and L is any organic group that includes at least one atom selected from N and O. The coordination polymer or solvate thereof is subject to the proviso that L is not pyrazine or substituted pyrazine.

[0006] Various embodiments of the present invention provide a filled polymer composition. The filled polymer composition includes a polymer composition selected from a cured product of a thermosetting polymer, and a thermoplastic polymer composition in a solid state. The filled polymer composition also includes a particulate filler including a coordination polymer or solvate thereof. The coordination polymer or solvate thereof includes repeat units having the formula M(SiFg)(pz)_x(L)_y,wherein pz is pyrazine or a substituted pyrazine, M is

Cu, Zn, Ni, Fe, or Co, 1 < x, 0 < y < 2, x+y < 3, and L is any ligand that includes at least one atom selected from N and O. The coordination polymer or solvate thereof is subject to the proviso that L is not pyrazine or substituted pyrazine.

[0007] Various embodiments of the present invention provide advantages over other compositions, membranes, methods, and apparatus. Some embodiments of membranes of the present invention are suitable for use in storage or separation of gases, and some embodiments include pores that are less than or equal to about 5 A. In an example, some embodiments of the membranes of the present invention exhibit both high permeability and selectivity for particular components in a gas mixture. Some embodiments of the present invention can be made with lower cost or with greater cost-effectiveness than other compositions, membranes, methods, or apparatus, such as, for example, zeolite membranes. Various embodiments provide high thermal stability. In some embodiments, unique performance is provided in terms of gas permeability or selectivity. In another example, some embodiments of the membrane of the present invention exhibit high CO2/N2 or CO2/CH4 selectivity compared with other membranes, such as for example, PDMS membranes cured by hydrosilylation, while retaining high permeability.

[0008] Although coordination polymers having a repeating unit of Cu(SiFe)(4,4'- bipyridine)2-8H20 have been reported, it is surprising and unexpected that a polymer can form with pyrazine, including because 4,4'-bipyridine is substantially larger than pyrazine. It would be expected that in such a situation, there is a high risk of, for example, steric crowding of other elements of the repeating unit preventing the crystal structure from forming, such as for example energetically disfavored overcrowding of SiFg anions.

BRIEF DESCRIPTION OF THE FIGURES

[0009] In the drawings, which are not necessarily drawn to scale, like numerals describe substantially similar components throughout the several views. Like numerals having different letter suffixes represent different instances of substantially similar components. The drawings illustrate generally, by way of example, but not by way of limitation, various embodiments discussed in the present document.

[0010] FIG. 1 illustrates a powder X-ray diffraction pattern of a copper coordination polymer and an iron coordination polymer, in accord with various embodiments.

[0011] FIG. 2 illustrates a thermogravimetric analysis of an iron coordination polymer, in accord with various embodiments.

[0012] FIG. 3 illustrates a SEM image of crystals of an iron coordination polymer, in accord with various embodiments.

DETAILED DESCRIPTION OF THE INVENTION

[0013] Reference will now be made in detail to certain embodiments of the disclosed subject matter, examples of which are illustrated in part in the accompanying drawings. While the disclosed subject matter will be described in conjunction with the enumerated claims, it will be understood that the exemplified subject matter is not intended to limit the claims to the disclosed subject matter. [0014] Values expressed in a range format should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a range of "about 0.1 % to about 5%" or "about 0.1 % to 5%" should be interpreted to include not just about 0.1 % to about 5%, but also the individual values (e.g., 1 %, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.1 % to 0.5%, 1 .1 % to 2.2%, 3.3% to 4.4%) within the indicated range. The statement "about X to Y" has the same meaning as "about X to about Y," unless indicated otherwise. Likewise, the statement "about X, Y, or about Z" has the same meaning as "about X, about Y, or about Z," unless indicated otherwise.

[0015] In this document, the terms "a," "an," or "the" are used to include one or more than one unless the context clearly dictates otherwise. The term "or" is used to refer to a nonexclusive "or" unless otherwise indicated. In addition, it is to be understood that the phraseology or terminology employed herein, and not otherwise defined, is for the purpose of description only and not of limitation. Any use of section headings is intended to aid reading of the document and is not to be interpreted as limiting; information that is relevant to a section heading may occur within or outside of that particular section. Furthermore, all publications, patents, and patent documents referred to in this document are incorporated by reference herein in their entirety, as though individually incorporated by reference. In the event of inconsistent usages between this document and those documents so incorporated by reference, the usage in the incorporated reference should be considered supplementary to that of this document; for irreconcilable inconsistencies, the usage in this document controls.

[0016] In the methods of manufacturing described herein, the steps can be carried out in any order without departing from the principles of the invention, except when a temporal or operational sequence is explicitly recited.

Furthermore, specified steps can be carried out concurrently unless explicit claim language recites that they be carried out separately. For example, a claimed step of doing X and a claimed step of doing Y can be conducted simultaneously within a single operation, and the resulting process will fall within the literal scope of the claimed process. [0017] 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.

[0018] The term "organic group" as used herein 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.

[0019] The term "substituted" as used herein refers to an organic group as defined herein or molecule in which one or more bonds to a hydrogen atom contained therein are replaced by one or more bonds to a non-hydrogen atom. The term "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. Examples of 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.

[0020] The term "alkyl" as used herein refers to straight chain and branched alkyl groups and cycloalkyl 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. Examples of 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. Examples of branched alkyl groups include, but are not limited to, isopropyl, isobutyl, sec-butyl, t-butyl, neopentyl, isopentyl, and 2,2-dimethylpropyl groups. As used herein, the term "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.

[0021] The term "alkenyl" as used herein refers to straight and branched chain and cyclic alkyl groups as defined herein, except that at least one double bond exists between two carbon atoms. Thus, alkenyl groups have from 2 to about 20 carbon atoms, and typically from 2 to 12 carbons or, in some embodiments, from 2 to 8 carbon atoms. Examples include, but are not limited to vinyl, - CH=CH(CH₃), -CH=C(CH₃)₂, -C(CH₃)=CH₂, -C(CH₃)=CH(CH₃), - C(CH2CH₃)=CH2, cyclohexenyl, cyclopentenyl, cyclohexadienyl, butadienyl, pentadienyl, and hexadienyl, among others.

[0022] The term "aryl" as used herein refers to cyclic aromatic hydrocarbons that do not contain heteroatoms in the ring.

[0023] 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. In one example, the polysiloxane material includes T or Q groups.

[0024] The term "radiation" as used herein 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.

[0025] The term "cure" as used herein 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.

[0026] The term "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.

[0027] 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. In some embodiments, 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.

[0028] The term "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.

[0029] The term "permeability" as used herein refers to the permeability coefficient (P_x) of substance X through a membrane, where q_mx = P_x ^* A ^* Δρ_χ ^* (1 /δ), where q_mx is the volumetric flow rate of substance X through the membrane, A is the surface area of one major side of the membrane through which substance X flows, Δρ_χ is the difference of the partial pressure of substance X across the membrane, and δ is the thickness of the membrane. P_x can also be expressed as V-5/(A-t-Ap), wherein P_x is the permeability for a gas

X in the membrane, V is the volume of gas X which permeates through the membrane, δ is the thickness of the membrane, A is the area of the membrane, t is time, Δρ is the pressure difference of the gas X at the retente and permeate side. Permeability is measured at room temperature, unless otherwise indicated.

[0030] The term "Barrer" or "Barrers" as used herein refers to a unit of permeability, wherein 1 Barrer = 10^"^ (cm³ gas) cm cm^-2 s^~1 mmHg^"'' , or 10^"

^{1 0} (cm³ gas) cm cm^-2 s^"1 cm Hg^~1 , where "cm³ gas" represents the quantity of the gas that would take up one cubic centimeter at standard temperature and pressure.

[0031] The term "total surface area" as used herein with respect to membranes refers to the total surface area of the side of the membrane exposed to the feed gas mixture.

[0032] The term "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. In one example, 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.

[0033] The term "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.

[0034] The term "mil" as used herein refers to a thousandth of an inch, such that 1 mil = 0.001 inch.

[0035] The term "coordination polymer" as used herein refers to structures including metal cation centers linked by ligands, extending in an array.

[0036] The term "mixed matrix membrane" as used herein refers to a membrane that includes a coordination polymer.

[0037] The term "repeat unit" as used herein refers to a chemical unit of a coordination polymer that repeats at least once within the polymer. [0038] The term "gas" as used herein refers to gases or vapors.

Coordination Polymer

[0039] Various embodiments of the present invention provide a coordination polymer or solvate thereof. The coordination polymer or solvate thereof includes repeat units having the formula M(SiFg)(pz)_x(L)_y, wherein pz is pyrazine or a substituted pyrazine, M is Cu, Zn, Ni, Fe, or Co, 1 < x, 0 < y < 2, x+y < 3, and L is any ligand that includes at least one atom selected from N and O. In various embodiments, the coordination polymer or solvate thereof can be subject to the proviso that L is not pyrazine or substituted pyrazine. In various embodiments, the coordination polymer or solvate thereof is subject to the proviso that if M is Cu, and y is 2, and L is H2O, and x is 1 , then pz is not pyrazine. In various embodiments, the coordination polymer or solvate thereof is subject to the proviso that if M is Zn, and y is 0, and x is 2, then pz is not pyrazine. In various embodiments, the coordination polymer or solvate thereof is subject to the proviso that if M is Cu, and y is 0, and x is 2 or 3, then pz is not pyrazine. In various embodiments, the coordination polymer or solvate thereof is subject to the proviso that if M is Cu, and y is 0, and x is 1 or 4, then pz is not 2,6-dimethylpyrazine.

[0040] Various embodiments encompass the coordination polymer of the present invention in any suitable physical environment, as will be readily understood by one of skill in the art. In some embodiments, the coordination polymer can be in solution. In some examples, the coordination polymer can be a crystalline material suspended or sitting in a solution or liquid. The coordination polymer can be a combination of in solution and solid crystalline material within the solution. The coordination polymer can be a crystalline material not in a solution. The coordination polymer can be integrated into another material, such as a membrane. In other embodiments, the coordination polymer can be not integrated into any material. The coordination polymer can be ground or powdered.

[0041] The substituted pyrazine can include any suitable substituted pyrazine known to one of skill in the art. The substituent of the pyrazine can be any substituent, such as halogen or an organic group. The substituent can be attached to the pyrazine via a single covalent bond. The pyrazine can have one, two, three, or four substituents. Steric hindrance of the lone pair of electrons of the nitrogen atom can make coordination of the pyrazine to a metal difficult, although 2, 6-substituted pyrazines can perform coordination. Non- aromatic versions of pyrazine (e.g. with H substitution) can be difficult to coordinate to metal centers, as they can have H-substitution of one or more nitrogen atoms, which can make coordination of the nitrogen lone pair to a metal difficult. Substituted pyrazines with one substituent can be substituted in any pattern. Cyclic substituents can be fused to the pyrazine, meaning that they can share at least one bond with the pyrazine ring. The pyrazine can have one or two fused substituents. Examples of substituents that can be substituted on pyrazine via fusion include any cyclic organic group, including for example any suitable aromatic, cycloaliphatic, or heterocyclic organic group. The pyrazine can be both fused with one substituent and attached via a single covalent bond to another. Some examples of suitable substituted pyrazines can include compounds such as 2-substituted pyrazines such as 2-chloropyrazine, 2- fluoropyrazine, 2-methylpyrazine, and 2-methoxypyrazine.

[0042] M can be Cu, Zn, Ni, Fe, or Co. For example, M can be Cu ions, Zn ions, Ni ions, or Co ions, respectively, such as for example, Cu^+ ions, Zn^+ ions, Ν|2+ ions, or Co^⁺ ions.

[0043] The ligand that includes at least one atom selected from N and O is an optional component. In some embodiments, the ligand that includes at least one atom selected from N and O is present. In other embodiments, the ligand that includes at least one atom selected from N and O is not present. In some examples, L is water or any suitable O- or N-containing 5- or 6-membered aromatic or non-aromatic heterocycle. In some embodiments, L is H2O, pyridine, tetrahydrofuran, or 3,4-dihydro-2H-pyrrole. In some embodiments, L is any organic group that comprises at least two atoms independently selected from N and O, wherein the at least two atoms are located on approximately opposite ends of L, for example such that the at least two atoms are located on approximately opposite ends of the longest length of the chemical structure of L. The at least two atoms independently selected from N and O on approximately opposite ends of L are located in the structure of L such that one of the at least two atoms can coordinate to one metal ion of the coordination polymer, and such that the other of the at least two atoms can coordinate to another metal ion of the coordination polymer. For example, L can be alkyleneglycol,

polyalkyleneglycol, ethyleneglycol, polyethyleneglycol, propyleneglycol, polypropyleneglycol, 4,4'-bipyridine, pyridine linked at the 4-position to another pyridine at the 4'-position via C-| .5 alkyl or alkylene linker, 3,3'-bipyridine, pyridine linked at the 3-position to another pyridine at the 3'-position via C-| .5 alkyl or alkylene linker, 3,3'-bi(1 ,2,4,5-tetrazine), terephthalic acid, benzene- 1 ,3,5-tricarboxylic acid, benzene-1 ,2,4,5-tetracarboxylic acid, (1 ,1 '-biphenyl)- 4,4'-dicarboxylic acid, benzoic acid linked at the 4-position to another benzoic acid at the 4' -position via C-| .5 alkyl or alkylene linker, (1 ,1 '-biphenyl)-3,3'- dicarboxylic acid, benzoic acid linked at the 3-position to another benzoic acid at the 3'-position via C-| .5 alkyl or alkylene linker,

hexafluoroisopropyldienebis(benzoic acid), bis(imidazole)dimethylsilane, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, and a dicarboxylic acid wherein the carbonyl carbon of each acid is linked together via C-| .5 alkyl or alkylene linker.

[0044] In some embodiments, the coordination polymer is a solvate. In other embodiments, the coordination polymer is not a solvate. Any suitable number of solvent molecules can be present for a repeating unit of a coordination polymer, such as 1 , 2, 3, 3, 4, 5, 6, 7, or 8 or more. The solvent molecule forming the solvate can be any suitable solvent, such as water, or an organic solvent such as an alcohol or any suitable organic solvent.

[0045] Various embodiments of the present invention provide a method of making the coordination polymer or solvate thereof includes repeat units having the formula M(SiF6)(pz)_x(L)_y, wherein pz is pyrazine or a substituted pyrazine,

M is Cu, Zn, Ni, Fe, or Co, 1 < x, 0 < y < 2, x+y < 3, and L is any ligand that includes at least one atom selected from N and O. The method can include providing a copper compound, a zinc compound, a nickel compound, an iron compound, or a cobalt compound. The copper compound, zinc compound, nickel compound, an iron compound, or cobalt compound can be a source of one of more Cu ions, Zn ions, Ni ions, Fe ions, or Co ions, respectively, such as for example, Cu^+ ions, Zn^+ ions, Ni^+ ions, Fe^⁺ ions or Co^⁺ ions. The method can also include providing a silicon hexafluoride compound. The silicon hexafluoride compound can be a source of one or more SiFg^^" ions. The method can include providing a pyrazine or substituted pyrazine. The method can include optionally providing a ligand that includes at least one atom selected from N and O. The method can include combining the copper compound, the silicon hexafluoride compound, the pyrazine or substituted pyrazine compound, and optionally the ligand that includes at least one atom selected from N and O, to give the coordination polymer described herein. The coordination polymer includes repeat units having the formula

wherein pz is the pyrazine or the substituted pyrazine. [0046] In some embodiments, the copper compound, zinc compound, nickel compound, iron compound, or cobalt compound can be a source of one of more Cu ions, Zn ions, Ni ions, Fe ions, or Co ions, respectively, such as for example, Cu^⁺ ions, Zn^+ ions, Ni2⁺ ions, Fe²⁺ ions or Co^⁺ ions, and can provide the one or more ions after or during a chemical reaction. In some examples, the compound can provide the one or more ions after or during dissolution in a solvent medium. In some examples, the source of the ion can be a salt of the ion. The salt of the ion can be a hydrate. In other embodiments, the salt of the ion can be a non-hydrate. The hydrate can have any suitable number of water molecules per molecule of ion.

[0047] In some examples, the copper compound can any suitable copper salt. In some examples, the copper compounds can be CuF2, CuCl2, CuBr2, Cu(OAc)₂, Cu(N0₃)₂, CuC0₃, CuS0₄, Copper(ll) citrate, Cu(CN)₂, Cu(OH)₂, Cu(NC>2)2, CuO, Cu3(PC>4)2, CUSO4, and the like, or any hydrate thereof. In some examples, the copper compound can be Cu(N03)2-3H20. In some examples, the zinc compound can be any suitable zinc salt. In some examples, the zinc compound can be ZnF2, ZnCl2, ZnBr2, Zn(OAc)2, Zn(N03)2, ZnCC^, ZnS0₄, Zinc(ll) citrate, Zn(CN)₂, Zn(OH)₂, Zn(N0₂)2, ZnO, or Zn₃(P0₄)₂, ZnSC^, and the like, or any hydrate thereof. In some examples, the nickel compound can be any suitable nickel salt. In some examples, the nickel compound can be NiF₂, N1CI2, NiBr₂, Ni(OAc)2, Ni(NC>3)2, N1CO3, N1SO4, Nickel(ll) citrate, Ni(CN)₂, Ni(OH)₂, Ni(N0₂)2, NiO, Ni₃(P0₄)₂, N1SO4, and the like, or any hydrate thereof. In some examples, the nickel compound is Ni(N03)2-6H20. In some examples, the nickel compound can be any suitable iron salt. In some examples, the iron compound can be FeF2, FeC^, FeB^, Fe(OAc)₂, Fe(N0₃)₂, FeC0₃, FeS0₄, iron(ll) citrate, Fe(CN)₂, Fe(OH)₂, Fe(N02)2_> FeO, Fe3(P04)2, FeS04, and the like, or any hydrate thereof. In some examples, the cobalt compound can be C0F2, C0CI2, CoBr2, Co(OAc)2, Co(N0₃)₂, C0CO3, C0SO4, Cobalt(ll) citrate, Co(CN)₂, Co(OH)₂, Co(N0₂)2, CoO, or Co3(P04)2, C0SO4, and the like, or any hydrate thereof.

[0048] In some embodiments, the silicon hexafluoride compound that is a source of one or more SiFg^^" ions can provide the one or more SiFg^^" ions after or during a chemical reaction. In some examples, the silicon hexafluoride compound that is a source of one or more SiFg^2" ions can provide the one or more SiFg^^" ions after or during dissolution in a solvent medium. In some embodiments, the silicon hexafluoride compound is a SiFg^^" salt. The SiFg^^" salt can be a hydrate. In other embodiments, the SiFg^2" salt can be a non- hydrate. The hydrate can have any suitable number of water molecules per molecule of SiFg^- salt. In some examples, the silicon hexafluoride compound can be H₂SiFg. In some examples, the silicon hexafluoride compound can be BeSiFg, MgSiFg, CaSiFg, SrSiFg, BaSiFg, RaSiFg, Li₂SiF₆, Na₂SiF₆, K₂SiF₆, RbSiF₆, CsSiF₆, FrSiF₆, (NH₄)₂SiF₆, FeSiF₆, (C₅H₅NH)₂SiF₆, and the like, or any hydrate thereof. In some examples, the silicon hexafluoride compound can be (NH₄)₂SiF₆.

[0049] In some embodiments, all the components used to form the coordination polymer can be combined at once. Any suitable mixing can be used. Any suitable solvent can be used. In some embodiments, any two or more of the ingredients used to form the coordination polymer can be first combined prior to combining the rest of the ingredients. For example, any two or more of the copper compound, zinc compound, nickel compound, iron compound, or cobalt compound, the silicon hexafluoride compound, the optional ligand that includes at least one atom selected from N and O, the pyrazine or substituted pyrazine, and any other suitable component, can be first combined in a solvent medium prior to combining the remaining components. In some embodiments, the two or more ingredients can be first combined in a solvent medium until they dissolve. The two or more ingredients can be mixed. In some examples, the mixing can occur for less than 1 minute, for 1 minute, 2, minutes, 5 minutes, 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 1 hour, or for greater than 1 hour. In some examples, the mixing can occur using any suitable mixing technique known to one of skill in the art. In some examples, the mixing can occur using magnetic stirring or sonication. The solvent medium can be any suitable solvent, aqueous or organic. In some embodiments, the solvent medium can be miscible with water. The solvent medium can be an alcohol, including, for example, a glycol or triol. The solvent medium can be water. The solvent medium can be ethylene glycol.

[0050] In embodiments wherein two or more components are first mixed prior to combining with the remaining components, prior to mixing all components together one or more of the remaining components can be first mixed in a solvent medium, wherein the solvent medium and mixing can be any suitable solvent medium or mixing, for example as described herein. The solvent medium can be the same or different as the solvent medium used to combine the two or more components. For example, the solvent medium can be aqueous or organic, can be water-miscible, can be water, or can be an alcohol such as ethylene glycol.

[0051] The addition of one or more components can be any suitable addition. The addition can be quick, or slow. The addition can take place for less than 1 minute, for 1 minute, 2, minutes, 5 minutes, 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 1 hour, or for greater than 1 hour. The amount of time taken for the addition can depend on the quantity of material being added together. The amount of time taken for the addition can be based on the amount of heat generated by the addition. The time taken for the addition can be optimized to provide the highest or most efficient yield of the coordination polymer.

[0052] In one example, the coordination polymer forms as a crystalline solid. The crystalline solid can form at the bottom of the container, or can form within any part of the solution and drift to the bottom. In some embodiments, a quantity of crystalline coordination polymer can form in any part of the solution and can seed the solution for further crystal growth. When such seeding occurs, further crystal growth can occur around the seed crystal. In some embodiments, the seed crystal can be added to induce crystal growth. The method can include filtering the coordination polymer from the solution. The filtering can occur using any suitable filtration method known to one of skill in the art. For example, suitable filtration methods can include decantation, vacuum filtration, or gravity filtration. The method can include drying the coordination polymer. In some embodiments, the method includes first filtering the coordination polymer and then drying the coordination polymer. Drying can occur via any suitable drying method known to one of skill in the art. In one example, drying is performed at ambient temperature and ambient pressure. In another example, drying is performed at decreased pressure at ambient temperature. Drying can be performed at elevated temperature at ambient pressure, or at elevated pressure at decreased pressure. In some

embodiments, the conditions used for drying can be optimized based on the types of solvents that are desired to be evaporated from the coordination polymer. For example, the removal of water from the coordination polymer may in some embodiments suitably be performed at elevated temperature and decreased pressure. However, the removal of an organic solvent such as chloroform may in some embodiments suitable be performed at ambient temperature and ambient pressure.

Filled Polymer Composition

[0053] Some embodiments of the present invention provide a filled polymer composition. The filled polymer composition can include the coordination polymer described herein. The filled polymer composition can also include a curable polymer composition that includes a thermosetting polymer. The filled polymer combination can include a polymer composition that includes a thermoplastic polymer. The thermoplastic polymer can be in a fluid state. In some embodiments, the thermoplastic polymer can be in a predominantly fluid state, but with at least some portion of the polymer in a solid state. In some embodiments, the filled polymer composition can include both a thermoplastic polymer and a thermosetting polymer. In one embodiment, the filled polymer composition only includes a thermoplastic polymer. In another embodiment, the filled polymer composition only includes a thermosetting polymer.

[0054] The filled polymer composition includes a particulate filler, wherein the particulate filler includes the coordination polymer described herein. In such embodiments, the coordination polymer of the filled polymer composition can be the particulate filler. The particulate filler can includes particles with an average particle size of, for example, about 0.01 to about 50 micron or from about 0.1 to about 20 micron or from about 0.1 to about 5 micron. The particulate filler can include many different particle sizes across a broad range of sizes.

Alternatively, the particulate filler can include a narrow selection of particle sizes. In another embodiment, the particulate filler can include multiple narrow selections of different particle sizes. The particulate filler can be prepared by, for example, grinding, crushing, or otherwise forming particles from crystals of the coordination polymer by any suitable method known to one of skill in the art. In some embodiments, the particulate filler can be unprocessed coordination polymer crystals.

[0055] The thermosetting polymer can be any suitable thermosetting polymer. The curable polymer composition that includes the thermosetting polymer can be any suitable curable polymer composition. For example, the thermosetting polymer can be, but is not limited to, curable silicone compositions, such as hydrosilylation-curable silicone compositions, condensation curable silicone compositions, radiation-curable silicone compositions, and peroxide-curable silicone compositions; curable polyolefin compositions such as polyethylene and polypropylene compositions; curable polyamide compositions; curable epoxy resin compositions; curable amino resin compositions; curable polyurethane compositions; curable polyimide compositions; curable polyester compositions; and curable acrylic resin compositions.

[0056] The thermoplastic polymer can be any suitable thermoplastic polymer known to one of skill in the art. The polymer composition that includes the thermoplastic polymer in a fluid state can be any suitable polymer composition. For example, the thermoplastic polymer can be, but is not limited to, thermoplastic silicone polymers such as poly(diphenylsiloxane-co- phenylmethylsiloxane); and thermoplastic organic polymers such as polyolefins, polysulfones, polyacrylates and polyetherimides.

[0057] Some embodiments of the present invention provide a method of making a cured product of a filled polymer composition. In some examples, a cured filled polymer composition can be made by curing a filled polymer composition, as described herein. In some example, the curing can include exposing to radiation in any form, heating, or allowing to undergo a chemical reaction that results in hardening or an increase in viscosity, or allowing a polymer to cool such that it transitions from a liquid state to a solid state.

[0058] Various embodiments of the present invention provide a method of making a filled polymer composition. The method can include providing the coordination polymer disclosed herein. The method can include providing a thermoplastic polymer in a liquid state or a thermosetting polymer. The method can include combining the coordination polymer and the thermoplastic polymer of the thermosetting polymer, to give a filled composition. In some

embodiments, the method can include providing a particulate filler that includes the coordination polymer described herein. The method can include combining the particulate filler and the thermoplastic polymer in a liquid state or the thermosetting polymer, to give a filled composition.

[0059] Various embodiments of the present invention provide a cured filled polymer composition. Such compositions can include a reaction product or cured product of the filled polymer composition described herein. The thermoplastic polymer of the filled polymer composition can be cured by, for example, allowing the thermoplastic polymer to cool to a temperature in which it becomes solid. The thermosetting polymer of the filled polymer composition can be cured by, for example, allowing the thermosetting polymer to undergo a chemical reaction that results in a cured product.

Curable Silicone Composition [0060] In various embodiments, the curable polymer composition that includes a thermosetting polymer can be a curable silicone composition. For example, the curable silicone composition can be any suitable curable silicone composition known to one of skill in the art.

[0061] The curable silicone composition includes at least one silicone compound. In some examples the silicone material can be a polysiloxane present in any suitable wt% in the curable silicone composition, for example, about 1 %, 5%, 10%, 20%, 40%, 60%, 80%, 90%, 95%, or about 99 wt%. The silicone composition includes suitable ingredients to allow the composition to be curable in any suitable fashion. In addition to the at least one suitable polysiloxane, the silicone composition can include any suitable additional ingredients, including any suitable organic or inorganic component, including components that do not include silicon, including components that do not include a polysiloxane structure. In some examples, the cured product of the silicone composition includes a polysiloxane.

[0062] The curable silicon composition can include molecular components that have properties that allow the composition to be cured. In some embodiments, the properties that allow the silicone composition to be cured are specific functional groups. In some embodiments, an individual compound contains functional groups or has properties that allow the silicone composition to be cured by one or more curing methods. In some embodiments, one compound can contain functional groups or have properties that allow the silicone composition to be cured in one fashion, while another compound can contain functional groups or have properties that allow the silicone composition to be cured in the same or a different fashion. The functional groups that allow for curing can be located at pendant or, if applicable, terminal positions in the compound.

[0063] The silicone composition can include an organic compound. The organic compound can be any suitable organic compound. The silicone composition can include, for example, an organosilicon compound. The organosilicon compound can be any organosilicon compound. The

organosilicon compound can be, for example, a silane, polysilane, siloxane, or a polysiloxane, such as any suitable one of such compound as known in the art. The silicone composition can contain any number of suitable organosilicon compounds, and any number of suitable organic compounds. An organosilicon compound can include any functional group that allows for curing. [0064] In some embodiments, the organosilicon compound can include a silicon-bonded hydrogen atom, such as organohydrogensilane or an organohydrogensiloxane. In some embodiments, the organosilicon compound can include an alkenyl group, such as an organoalkenylsilane or an

organoalkenyl siloxane. In other embodiments, the organosilicon compound can include any functional group that allows for curing. The organosilane can be a monosilane, disilane, trisilane, or polysilane. Similarly, the organosiloxane can be a disiloxane, trisiloxane, or polysiloxane. The structure of the organosilicon compound can be linear, branched, cyclic, or resinous.

Cyclosilanes and cyclosiloxanes can have from 3 to 12 silicon atoms, alternatively from 3 to 10 silicon atoms, alternatively from 3 to 4 silicon atoms.

[0065] In one example, an organohydrogensilane can have the formula

HR¹2Si-R²-SiR¹2H, wherein R¹ is C-| _-| Q hydrocarbyl or C-| _-| Q halogen- substituted hydrocarbyl, both free of aliphatic unsaturation, linear or branched, and R² is a hydrocarbylene group free of aliphatic unsaturation having a formula selected from monoaryl such as 1 ,4-disubstituted phenyl, 1 ,3- disubstituted phenyl; or bisaryl such as 4,4'-disubstituted-1 ,1 '-biphenyl, 3,3'- disubstituted-1 ,1 '-biphenyl, or similar bisaryl with a hydrocarbon chain including 1 to 6 methylene groups bridging one aryl group to another.

[0066] The organosilicon compound can be an organopolysiloxane compound. In some examples, the organopolysiloxane compound has an average of at least one, two, or more than two functional groups that allow for curing. 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.

[0067] In one example, an organopolysiloxane can include a compound of the formula

(a) R¹ ₃SiO(R¹ ₂SiO)_a(R¹ R²SiO)_pSiR¹ ₃, or (b) R⁴R³ ₂SiO(R³2SiO)_%(R³R⁴SiO)₅SiR³2R⁴.

[0068] In formula (a), a has an average value of about 0 to about 2000, and β has an average value of about 2 to about 2000. Each R¹ 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 R² is independently a functional group that allows for curing of the silicone composition, or R¹.

[0069] In formula (b), χ has an average value of 0 to 2000, and δ has an average value of 0 to 2000. Each R³ 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 R⁴ is independently a functional group that allows for curing of the silicone composition, or R³.

[0070] An organopolysiloxane compound can contain an average of about 0.1 mole% to about 100 mole% of functional groups that allow for curing of the silicone composition, and any range of mole% therebetween. The mole percent of functional groups that allow for curing of the silicon composition in the resin is the ratio of the number of moles of siloxane units in the resin having a functional group that allows for curing of the silicone composition to the total number of moles of siloxane units in the organopolysiloxane, multiplied by 100.

[0071] 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.

[0072] Examples of organopolysiloxanes can include compounds having the average unit formula

(R1 R4R5si0_{1 /2})w(R¹ R⁴Si02/2)x(R⁴Si0₃/2)_y(Si04/2)z (I), wherein R¹ 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, R⁴ is a functional group that allows for curing of the silicone composition or R^ or R^ , is R^ or R⁴, 0<w<0.95, 0<x<1 , 0<y<1 , 0<z<0.95, and w+x+y+z∞1 . In some embodiments, R¹ is C-_| _-_| 0 hydrocarbyl or C-_| _-_| Q halogen-substituted hydrocarbyl, both free of aliphatic unsaturation, or C4 to C14 aryl. In some embodiments, 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, and w+x+y+z∞1.

[0073] In descriptions of average unit formula, such as formula I, the subscripts w, x, y, and z are mole fractions. It is appreciated that those of skill in the art understand that for the average unit formula (I), the variables R¹ , R⁴, and R⁵ can independently vary between individual siloxane formula units. Alternatively, the variables , R^, and can independently be the same between individual siloxane formula units. For example, average unit formula (I) above can include the following average unit formula:

(Rl R4R5si0₁ /2)w(R^{1 a}R⁴Si02/2)xl (R^{1 b}R⁴Si02/2)x2(R⁴Si0₃/2)_y(Si04/2)z wherein subscripts x1 +x2 = x, and where R^ ^a is not equal to R^""³. Alternatively, R^{1 a} can be equal to R¹ b.

Curing

[0074] Embodiments of the membrane include a cured product of a silicone composition. Various methods of curing can be used, including any suitable method of curing, including for example hydrosilylation curing, condensation curing, free-radical curing, amine-epoxy curing, radiation curing, cooling, or any combination thereof. A composition that is cured via one curing method can be cured by other curing methods in addition to the one curing method. The silicone composition can include molecules with properties that allow one curing method, as well as molecules that allow different curing methods. In some embodiments, the silicone composition can include multiple features on the same molecule that allow the composition to be cured via one curing method and cured via other curing methods, and in some embodiments, the silicone composition can include features that allow it to be cured via one curing method on one molecule and features that allow it to be curing via other curing methods on a different molecule.

[0075] A silicone composition that is curable via a particular method can include other compounds curable via the particular method in addition to silicone compounds. In some embodiments, the other compounds curable via the particular curing method can participate with the silicone compounds curable via the particular curing method during the application of the particular curing method. In other embodiments, the other compounds curable via the particular curing method do not participate with the silicone compounds curable via the particular curing method during application of the particular curing method.

[0076] In hydrosilylation curing, for example, an organosilicon compound that includes a silicon atom with a silicon-bonded hydrogen atom reacts with an unsaturated group such as an alkenyl group, adding across the unsaturated group and causing the unsaturated group to lose at least one degree of unsaturation (e.g. a double bond is converted to a single bond), such that the silicon atom is bound to one carbon atom of the originally unsaturated group, and the hydrogen atom is bound to the other carbon atom of the originally unsaturated group. Having an average of at least two unsaturated groups on one or more molecules and an average of at least or greater than two silicon- bonded hydrogen atoms on one or more molecules can help cross-linking to occur. In one example, a curable silicone composition that is hydrosilylation curable can include a compound having an average of at least two unsaturated groups per molecule; an organosilicon compound having an average of at least two silicon-bonded hydrogen atoms per molecule; and an optional

hydrosilylation catalyst. In some embodiments, the hydrosilylation catalyst is present. In other embodiments, the hydrosilylation catalyst is not present. In some embodiments, the unsaturated groups are alkenyl groups.

[0077] In some embodiments, the hydrosilylation catalyst can be any hydrosilylation catalyst including a platinum group metal or a compound containing a platinum group metal. Platinum group metals can include platinum, rhodium, ruthenium, palladium, osmium and iridium. An example of a suitable hydrosilylation catalyst can include a platinum(IV) complex of 1 ,3-diethenyl- 1 ,1 ,3,3-tetramethyldisiloxane. In another embodiment, the hydrosilylation catalyst can be at least one photoactivated hydrosilylation catalyst.

[0078] In condensation curing, for example, an organosilicon compound that includes a silicon atom substituted with a hydrolysable group reacts with water to form a hydroxyl-substituted silicon atom. The reactive hydroxyl group can then attack other silicon atoms, including other silicon atoms with hydrolysable groups or with hydroxyl groups, forming a polysiloxane. In some embodiments, the silicon atom that is attacked by the reactive hydroxyl group can have a protonated hydroxyl group or a hydrolysable group, wherein the protonated hydroxyl group or the hydrolysable group is a good leaving group. In some embodiments, water is not required to hydrolyze a hydrolysable group, but rather a reactive hydroxyl-substituted organosilicon is already present in the curable silicone composition, which can attack other silicon atoms, including silicon atoms with hydroxyl groups or silicon atoms with hydrolysable groups. An acid or base catalyst is an optional component in condensation curable silicone compositions, such as any suitable organic or mineral acid, or any suitable base. In some embodiments, an acid or base catalyst is present. In other embodiments, an acid or base catalyst is not present.

[0079] A condensation curable silicone composition can include an

organosilicon with at least one silicon-substituted hydrolysable group, or with at least one silicon-substituted hydroxyl group. The organosilicon can be a silane, a polysilane, a siloxane, or a polysiloxane. The organosilicon can include an average of one silicon-substituted hydrolysable group per molecule, an average of two silicon-substituted hydrolysable groups per molecule, or more.

[0080] Optionally, a condensation curable composition can include a condensation catalyst. In some embodiments, a condensation catalyst is present. In other embodiments, a condensation catalyst is not present.

Examples of condensation catalysts include, for example, amines, and complexes of lead, tin, zinc, titanium, zirconium, aluminum and iron with carboxylic acids. In one example, the condensation catalyst can be selected from tin(ll) and tin(IV) compounds such as tin dilaurate, tin dioctoate, and tetrabutyl tin; and titanium compounds such as titanium tetrabutoxide.

[0081] In free-radical curing, for example, 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.

[0082] A free-radical curable silicone composition can include an organosilicon with at least one free-radical polymerizable group. The organosilicon can be a silane, a polysilane, a siloxane, or a polysiloxane. The organosilicon can include an average of one free-radical polymerizable group per molecule, an average of two free-radical polymerizable groups per molecule, or more. In some embodiments, a free-radical curable silicone composition can include an organic compound that does not include silicon that has at least one free-radical polymerizable group. The organic compound that does not include silicon can include an average of one free-radical polymerizable groups per molecule, an average of two free-radical polymerizable groups per molecule, 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.

[0083] 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 or an organic peroxide. In another example, the free-radical initiator is a organoborane free-radical intiator. In one example, the free-radical initiator can be an organic peroxide.

[0084] In amine-epoxy curing, for example, a primary- or secondary-amine reacts with an epoxy compound to produce, for example, aminoalcohols. The epoxy-containing compound can be an organosilicon compound, or an organic compound that does not include silicon. The primary- or secondary-amine- containing compound can be an organosilicon, or an organic compound that does not include silicon. An amine-functional compound can be an amine- functionalized organopolysiloxane.

[0085] In an example, an amine-epoxy curable composition includes an epoxy- functional organosilicon compound and an amino-functional curing agent. In one example, the epoxy-functional organosilicon compound is a polysiloxane compound. The epoxy-functional organosilicon compound can have an average or at least two silicon-bonded epoxy-substituted functional groups per molecule and the curing agent can have an average of at least two nitrogen- bonded hydrogen atoms per molecule.

[0086] Radiation that can be used for radiation curing includes any suitable form of radiation. Any of the curing methods disclosed herein can include radiation curing; for example, any of the curing methods disclosed herein can include the application of heat or light.

[0087] In one example of cooling giving a cured product of a silicone composition, an organosilicone composition that essentially has a liquid flowable state is cooled at least as low as room temperature to give a silicone composition that essentially has a solid nonflowable state. Silicone

compositions that include compounds that can behave as thermoplastics are an example of silicon composition that can be cooled to give a cured product of the silicon composition. The compound that behaves as a thermoplastic can be a polymer.

Membrane

[0088] In various embodiments, the present invention provides a membrane that includes the coordination polymer as described herein, or that includes a reaction product or cured product of the curable silicon composition that includes the coordination polymer as described herein. In another embodiment, 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. For any membrane to be considered "on" 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.

[0089] Forming a membrane can at least include two steps. In the first step, the composition that forms the membrane can be applied to at least one surface of the substrate. In the second step, the applied composition that forms the membrane can be cured to form the membrane. In some embodiments, 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. The membrane can be in a solid state.

[0090] The composition that forms the membrane can be applied using conventional coating techniques, for example, immersion coating, die coating, blade coating, extrusion, curtain coating, drawing down, solvent casting, spin coating, dipping, spraying, brushing, roll coating, extrusion, screen-printing, pad printing, or inkjet printing.

[0091] The membrane of the present invention can have any suitable thickness. In some examples, the membrane has a thickness of from about 1 μιτι to about 20 μιτι, about 0.1 μιτι to about 200 μιτι, or about 0.01 μιτι to about 2000 μιτι. Before, during, or after the curing process, the thickness or shape of the 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. In one example, a doctor blade or drawdown bar is used to adjust the thickness of the applied composition. In another example, a conical die is used to adjust the thickness of the applied composition on a fiber that is later removed.

[0092] The membrane of the present invention can be selectively permeable to one substance over another. In some examples, the membrane has an ideal CO2/N2 selectivity of at least about 9, at least about 1 1 , at least about 13, at least about 15, or at least about 20. In some examples, the membrane has a CO2/CH4 selectivity of at least about 3, at least about 5, at least about 7, or at least about 9. In another example, the membrane has a CO2/N2 selectivity of at least about 12, 13, 15, or at least about 16. In some embodiments, with a CO2/N2 mixture for example, the membrane has a CO2 permeation coefficient of at least 300 Barrers, 1300 Barrers, 1400 Barrers, 1800 Barrers, 1900 Barrers, 2100 Barrers, 2400 Barrers, 2500 Barrers, 2700 Barrers, 2800 Barrers, 3000 Barrers, 3200 Barrers, or at least about 4000 Barrers.

[0093] The membrane of the present invention can have any suitable shape. In some examples, the membrane of the present invention is a plate-and-frame 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.

Supported Membrane

[0094] In some embodiments of the present invention, the membrane is supported on a porous or highly permeable non-porous substrate. The substrate can be any suitable 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.

Unsupported Membrane

[0095] In some embodiments of the present invention, 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. In some embodiments, 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. A free-standing membrane can have any suitable shape, regardless of the percent of the free-standing membrane that is supported. Examples of 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. [0096] 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 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.

Method of Separating Gas Components

[0097] 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.

[0098] The membrane can be free-standing or supported by a porous or permeable substrate. In some embodiments, the pressure on either side of the membrane can be about the same. In other embodiments, there can be a pressure differential between one side of the membrane and the other side of the membrane. For example, the pressure on the retentate side of the membrane can be higher than the pressure on the permeate side of the membrane. In other examples, the pressure on the permeate side of the membrane can be higher than the pressure on the retentate side of the membrane.

[0099] The feed gas mixture can include any mixture of gases. For example, 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.

[00100] Any number of membranes can be used to accomplish the separation. For example, 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.

Product-bv-process

[00101 ] One embodiment provides a coordination polymer or solvate thereof, made by a method including: providing a compound selected from a Cu-, Zn-, Ni-, Fe-, and Co-containing compound, wherein the compound is a source of one or more Cu, Zn, Ni, Fe, or Co ions, respectively; providing a silicon hexafluoride compound, wherein the silicon hexafluoride compound is a source of one or more SiFg^2- ions; providing a pyrazine or substituted pyrazine;

optionally providing a compound selected from any ligand that includes at least one atom selected from N and O, wherein the compound does not include pyrazine or a substituted pyrazine; and combining the Cu, Zn, Ni, Fe, or Co compound, the silicon hexafluoride compound, the pyrazine or substituted pyrazine compound, and optionally the N- or O-containing compound, to give a coordination polymer or solvate thereof with repeat units including one of the metal ions selected from Cu, Zn, Ni, Fe, and Co ions; one or more molecules of the pyrazine or substituted pyrazine; one or more SiFg^2" ions; and if provided, one or more molecules of the N- or O-containing ligand; provided that: if the N- or O-containing ligand is provided, and in the repeating unit of the coordination polymer if the metal ion is a Cu ion, and there are two molecules of the N- or O- containing compound, and the N- or O-containing compound is H2O, and there is one molecule of the pyrazine or pyrazine substituted compound, then the pyrazine or pyrazine substituted compound is a substituted pyrazine; if the N- or O-containing ligand is not provided, and in the repeating unit of the coordination polymer the metal ion is a Zn ion, and there are two molecules of the pyrazine or pyrazine substituted compound, then the pyrazine or pyrazine substituted compound is a substituted pyrazine; if the N- or O-containing ligand is not provided, and in the repeating unit of the coordination polymer the metal ion is a Cu ion, and there are two or three molecules of the pyrazine or pyrazine substituted compound, then the pyrazine or pyrazine substituted compound is a substituted pyrazine; and if the N- or O-containing ligand is not provided, and in the repeating unit of the coordination polymer the metal ion is a Cu ion, and there are one or four molecules of the pyrazine or pyrazine substituted compound, then the pyrazine or substituted pyrazine is not 2,6- dimethylpyrazine.

[00102] One embodiment provides a filled polymer composition including: a composition selected from a curable polymer composition including a thermosetting polymer, and a polymer composition including a thermoplastic polymer in a fluid state; and a particulate filler including a coordination polymer or solvate thereof, the coordination polymer or solvate made by a method including providing a compound selected from a Cu-, Zn-, Ni-, Fe-, and Co- containing compound, wherein the compound is a source of one or more Cu, Zn, Ni, Fe, or Co ions, respectively; providing a silicon hexafluoride compound, wherein the silicon hexafluoride compound is a source of one or more SiFg^- ions; providing a pyrazine or substituted pyrazine; optionally providing a compound selected from any ligand that includes at least one atom selected from N and O, wherein the compound does not include pyrazine or a substituted pyrazine; and combining the Cu, Zn, Ni, Fe, or Co compound, the silicon hexafluoride compound, the pyrazine or substituted pyrazine compound, and optionally the N- or O-containing compound, to give a coordination polymer or solvate thereof with repeat units including one of the metal ions selected from Cu, Zn, Ni, Fe, and Co ions; one or more molecules of the pyrazine or substituted pyrazine; one or more SiFg^2" ions; and if provided, one or more molecules of the N- or O-containing ligand.

[00103] 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.

[00104] Cu(N0₃)₂-3H₂0 (98%, Aldrich), Fe(C0₂CH₃)₂ (95%, Aldrich), Pyrazine (99+%, Aldrich), (NH₄)₂SiF₆ (98+%, Gelest Inc.) and ethylene glycol

(99+%, Aldrich), DMF (N,N-Dimethylformamide, 99%), BDC = 1 ,4- benzenedicarboxylic acid (98%, Aldrich), BPDC= 4,4'- biphenyldicarboxylic acid (97%, Aldrich),, HFIPBB = 4,4'-Hexafluoroisopropyldienebis(benzoic acid) (98%, Aldrich), BPY = 4,4'-Dipyridyl (98%, Aldrich), IM-DMS =

bis(imidazole)dimethylsilane (95%, Gelest Inc.), were used as received without further purification. Example 1 . Synthesis and Characterization of Copper Coordination Polymer.

[00105] Cu(N0₃)₂-3H₂0 (2.416 g, 10.0 mmol) and (NH₄)₂SiF₆ (1 .781 g, 10.0 mmol) were dissolved in 30.0 g of de-ionized water using sonication for 1 0 minutes. Pyrazine (1 .601 g, 20 mmol) was dissolved in ethylene glycol (30.1 1 g) with 10 minutes of sonication. The water solution was then slowly layered on top of the ethylene glycol solution at room temperature. After 10 minutes, blue crystals of the copper coordination polymer were formed in the bottom of the jar. After 24 hours, the blue crystals were filtered off and dried at 50°C for 30 minutes under vacuum.

Example 2. Synthesis of Iron Coordination Polymer.

[00106] Fe(C0₂CH₃)₂ (0.348 g, 2.0 mmol) and (NH₄)₂SiF₆ (0.355 g, 2.0 mmol) were dissolved in 6.0 ml_ of de-ionized water using sonication for 2 minutes. Pyrazine (0.32 g, 4.0 mmol) was dissolved in 6 ml_ of ethylene glycol with 2 minutes of sonication. The water solution was then slowly layered on top of the ethylene glycol solution in 20 ml_ glass vial at room temperature. After 5 days, orange crystals of the iron coordination polymer were formed in the bottom of the vial. The blue crystals were filtered off and washed with copious water followed by IPA, and then dried at 50°C for 30 minutes under vacuum. Example 3. Synthesis of CuipzHSiFg BDC), Coordination Polymer.

[00107] 1 .0 mmol (0.322 g) of the synthesized copper coordination polymer crystals of Example 1 mixed with 1 .0 mmol (0.171 g) of an organic ligand, BDC = 1 ,4-benzenedicarboxylic acid, were dispersed in 10.0 ml_ of DMF in 20 ml_ vials. The mixture was then heated at 75°C for 4 days, so that the self-assembly reaction could take place. After the designated reaction time, the synthesized crystals were collected by vacuum filtration, rinsed with the reaction solvent, and dried in a vacuum oven at 60°C for 60 minutes.

Example 4. Synthesis of Cu(pz)(SiFg)(BPDC), Coordination Polymer.

[00108] 1 .0 mmol (0.322 g) of the synthesized copper coordination polymer crystals of Example 1 were mixed with 1 .0 mmol (0.244 g) of an organic ligand, BPDC= 4,4'- biphenyldicarboxylic acid, were dispersed in 10.0 ml_ of DMF in 20 ml_ vials. The mixture was then heated at 80°C for 3 days, so that the self- assembly reaction could take place. After the designated reaction time, the synthesized crystals were collected by vacuum filtration, rinsed with the reaction solvent, and dried in a vacuum oven at 60°C for 60 minutes.

Example 5. Synthesis of Cu(pz)(SiFg)(Hfipbb), Coordination Polymer. [00109] 1 .0 mmol (0.322 g) of the synthesized copper coordination polymer crystals of Example 1 were mixed with 1 .0 mmol (0.393g) of an organic ligand, HFIPBB = 4,4'-Hexafluoroisopropyldienebis(benzoic acid), were dispersed in 1 0.0 ml_ of DMF in 20 ml_ vials. The mixture was then heated at 75°C for 4 days, so that the self-assembly reaction could take place. After the designated reaction time, the synthesized crystals were collected by vacuum filtration, rinsed with the reaction solvent, and dried in a vacuum oven at 60°C for 60 minutes.

Example 6. Synthesis of CuipzHSiFgHlm-DMS), Coordination Polymer.

[00110] 1 .0 mmol (0.322 g) of the synthesized copper coordination polymer crystals of Example 1 were mixed with 1 .0 mmol (0.192 g) of an organic ligand, Im-DMS = bis(imidazole) dimethylsilane, were dispersed in 10.0 ml_ of DMF in 20 ml_ vials. The mixture was then heated at 80°C for 3 days, so that the self- assembly reaction could take place. After the designated reaction time, the synthesized crystals were collected by vacuum filtration, rinsed with the reaction solvent, and dried in a vacuum oven at 60°C for 60 minutes.

Example 7. Synthesis of Cu(pz)(SiFg)(BPY), Coordination Polymer.

[00111 ] 1 .0 mmol (0.322 g) of the synthesized copper coordination polymer crystals of Example 1 were mixed with 1 .0 mmol (0.155 g) of an organic ligand, BPY = 4,4'-Dipyridine, were dispersed in 10.0 ml_ of DMF in 20 ml_ vials. The mixture was then heated at 60°C for 2 days, so that the self-assembly reaction could take place. After the designated reaction time, the synthesized crystals were collected by vacuum filtration, rinsed with the reaction solvent, and dried in a vacuum oven at 60°C for 60 minutes.

Single Crystal X-Ray Study of the Coordination Polymer of Example 1 .

[00112] A blue needle crystal having the formula C4H8CuFgN202Si having approximate dimensions of 0.17 χ 0.03 χ 0.02 mm was mounted using oil (Infineum V8512) on a glass fiber. All measurements were made on a Bruker APEX-II CCD Diffractometer with a CuKa \\iS source. Cell constants and an orientation matrix for data collection corresponded to a Monoclinic cell (see Table 1 ): For Z = 2 and F.W. = 321 .75, the calculated density is 2.425 g/cm³. Based on a statistical analysis of intensity distribution, and the successful solution and refinement of the structure, the space group was determined to be C2/m. The data were collected at a temperature of 100(2)K with a theta range for data collection of 7.31 to 66.97². Data were collected in 0.5² oscillations with 1 0 second exposures. The crystal-to-detector distance was 40.00 mm. Of the 1 678 reflections which were collected, 423 were unique (Rint = 0.0263). Data were collected using Bruker APEX2 detector and processed using SAINTPLUS from Bruker. The linear absorption coefficient, mu, for CuKa radiation is 5.786 mm^"1 . The data were corrected for Lorentz and polarization effects.

[00113] The single-crystal X-ray diffraction study revealed that the Cu coordination polymer of Example 1 is crystallized in the C2/m space group. The crystal is formed in monoclinic symmetry with a 2-dimensional (2-D) layered structure of formula [Cu(PZ)(SiFg)(H20)2], where PZ= Pyrazine.

Elemental Analysis of the Coordination Polymer of Example 1 .

[00114] The elemental analyses (EA) data were obtained from Robertson Microlit Lab, Ledgewood, NJ. EA for [Cu(PZ)(SiF₆)(H₂0)₂], C₄ H₈ Cu F₆ N₂ 0₂ Si: Calculated(%) C, 14.9 %; H, 2.5 %; N, 8.8 %; F, 35.4 %; Cu, 19.8%; Si,

8.7 %. Found(%) C, 15.0 %; H, 2.5 %; N, 8.8 %; F, 32.1 %; Cu, 19.6%; Si, 8.0 %.

[00115] Powder X-ray diffraction (PXRD) patterns confirmed the M-PZ-SiF₆ crystals were highly crystalline as depicted in FIG. 1 , which shows the powder X-ray diffraction pattern of as-synthesized copper coordination polymer of Example 1 and the iron coordination polymer of Example 2. FIG. 2 shows a thermogravimetric analysis result of the as-synthesized iron coordination polymer of Example 2 after drying at 70°C under vacuum. FIG. 3 shows an SEM image of the as-synthesized iron coordination polymer of Example 2. General Procedures Used for the Comparative Example and for Examples 8-14.

[00116] Prior to preparing membranes, the crystals dispersed in CHCI3 and stirred at 900 rpm for overnight to get fine particles. Then, the compositions described in the Examples and Comparative Examples were placed in a vacuum chamber under a pressure of less than 50 mm Hg for about 5 minutes at ambient laboratory temperature (21 ± 2 °C) to remove any entrained air.

[00117] To prepare Part A, 0.57 g of Karstedt's catalyst and 49.43 g of dimethylvinylsiloxy-terminated polydimethylsiloxane (PDMS 1 ) having a viscosity of about 55 Pa-s at 25° C were combined, and mixed in a Hauschild rotary mixer for two 30-second mixing cycles.

[00118] To prepare Part B, 49.25 g of PDMS1 , 0.75 g of a

polydimethylsiloxane-polyhydridomethylsiloxane copolymer having an average viscosity of about 0.005 Pa-s at 25 °C and 0.10 g of 2-Methyl-3-butyn-2-ol, were mixed in a Hauschild rotary mixer for two 30 second mixing cycles. Membranes were then prepared by drawing the composition described in the Examples into a uniform thin film with a doctor blade on a fluorosilicone-coated polyethylene terephthalate release film. The samples were then immediately placed into a forced air convection oven at a time and temperature sufficient to cure the films. After curing, the membranes were then recovered by carefully peeling the cured compositions from the release film and transferred onto a fritted glass support for testing of permeation properties as described in the section of Permeation Measurements. The thickness of the samples was measured with a profilometer (Tencor P1 1 Surface Profiler).

[00119] To prepare the copper coordination polymer/PDMS mixed matrix membranes, vacuum dried 2-D copper coordination polymer of Example 1 was ground in mortar for 5 minutes and vacuum dried 3D copper coordination polymers of Examples 3-7 were dispersed in CHCI3 and stirred for overnight and added into a premixed elastomer mixture (Part A and Part B) in various compositions including 2, 4, 6, 10, 30, 50 and 70 wt%. Then the mixture was mixed again in the Hauschild rotary mixer for 30 seconds. The mixed matrix membranes then prepared using drawing bar like in aforementioned procedure of reference membrane preparation. For each composition, the curing schedule was determined by using differential scanning calorimetry to observe the temperatures at which the curing exotherms were observed.

Comparative Example. PDMS Membrane.

[00120] Part A (1 .5 g) and Part B (1 .5 g) were combined in a polypropylene cup and mixed in a Hauschild rotary mixer for two 20 s cycles with a manual spatula mixing step in between cycles. The mixture was drawn into a membrane, cured for 1 hour at 100 °C and tested as described in Example 18. Example 8. Copper Coordination Polymer (2 wt%)/PDMS Mixed Matrix Membrane.

[00121 ] Part A (1 .0 g) and Part B (1 .0 g) were combined in a polypropylene cup and mixed in a Hauschild rotary mixer for 20 s. Then 0.041 g of ground (powder) copper coordination polymer (Example 1 ) was added into premixed (Part A and B) mixture and mixed in a Hauschild rotary mixer for two 20 s cycles with a manual spatula mixing step in between cycles. The mixture was drawn into a membrane, cured for 0.5 hour at 100 °C and tested as described in Example 18.

Example 9. Copper Coordination Polymer (4 wt%)/PDMS Mixed Matrix Membrane.

[00122] Part A (1 .0 g) and Part B (1 .0 g) were combined in a polypropylene cup and mixed in a Hauschild rotary mixer for 20 s. Then 0.083 g of ground (powder) copper coordination polymer (Example 1 ) was added into premixed (Part A and B) mixture and mixed in a Hauschild rotary mixer for two 20 s cycles with a manual spatula mixing step in between cycles. The mixture was drawn into a membrane, cured for 0.5 hour at 100 °C and tested as described in Example 18.

Example 10. Copper Coordination Polymer (6 wt%)/PDMS Mixed Matrix Membrane.

[00123] Part A (1 .0 g) and Part B (1 .0 g) were combined in a polypropylene cup and mixed in a Hauschild rotary mixer for 20 s. Then 0.128 g of ground (powder) copper coordination polymer (Example 1 ) was added into premixed (Part A and B) mixture and mixed in a Hauschild rotary mixer for two 20 s cycles with a manual spatula mixing step in between cycles. The mixture was drawn into a membrane, cured for 0.5 hour at 100 °C and tested as described in Example 18.

Example 1 1 . Copper Coordination Polymerd 0 wt%)/PDMS Mixed Matrix Membrane.

[00124] Part A (1 .35 g) and Part B (1.35 g) were combined in a polypropylene cup and mixed in a Hauschild rotary mixer for 20 s. Then 0.30 g of ground (powder) copper coordination polymer (Example 1 ) was added into premixed (Part A and B) mixture and mixed in a Hauschild rotary mixer for two 20 s cycles with a manual spatula mixing step in between cycles. The mixture was drawn into a membrane, cured for 2.0 hour at 100 °C and tested as described in Example 18.

Example 12. Copper Coordination Polymer (30 wt%)/PDMS Mixed Matrix Membrane.

[00125] Part A (1 .23 g) and Part B (1.23 g) were combined in a polypropylene cup and mixed in a Hauschild rotary mixer for 20 s. Then 1 .05 g of ground (powder) copper coordination polymer (Example 1 ) was added into premixed (Part A and B) mixture and mixed in a Hauschild rotary mixer for two 20 s cycles with a manual spatula mixing step in between cycles. The mixture was drawn into a membrane, cured for 2.0 hour at 100 °C and tested as described in Example 18.

Example 13. Copper Coordination Polymer (50 wt%)/PDMS Mixed Matrix Membrane.

[00126] Part A (0.75 g) and Part B (0.75 g) were combined in a polypropylene cup and mixed in a Hauschild rotary mixer for 20 s. Then 1 .50 g of ground (powder) copper coordination polymer (Example 1 ) was added into premixed (Part A and B) mixture and mixed in a Hauschild rotary mixer for two 20 s cycles with a manual spatula mixing step in between cycles. The mixture was drawn into a membrane, cured for 2.0 hour at 100 °C and tested as described in Example 18.

Example 14. Copper Coordination Polymer (70 wt%)/PDMS Mixed Matrix Membrane.

[00127] Part A (0.45 g) and Part B (0.45 g) were combined in a polypropylene cup and mixed in a Hauschild rotary mixer for 20 s. Then 2.10 g of ground (powder) copper coordination polymer (Example 1 ) was added into premixed (Part A and B) mixture and mixed in a Hauschild rotary mixer for two 20 s cycles with a manual spatula mixing step in between cycles. The mixture was drawn into a membrane, cured for 1 .0 hour at 100 °C and tested as described in Example 18.

Example 15. Copper Coordination Polymer (10 wt%)/PDMS Mixed Matrix Membrane.

[00128] Part A (0.45 g) and Part B (0.45 g) were combined in a polypropylene cup and mixed in a Hauschild rotary mixer for 20 s. Then 0.1 g of ground (powder) copper coordination polymer (Example 3) was added into premixed (Part A and B) mixture and mixed in a Hauschild rotary mixer for two 20 s cycles with a manual spatula mixing step in between cycles. The mixture was drawn into a membrane, cured for 1 .0 hour at 100 °C and tested as described in Example 18.

Example 16. Copper Coordination Polymer (30 wt%)/PDMS Mixed Matrix Membrane.

[00129] Part A (0.35 g) and Part B (0.35 g) were combined in a polypropylene cup and mixed in a Hauschild rotary mixer for 20 s. Then 0.30 g of ground (powder) copper coordination polymer (Example 5) was added into premixed (Part A and B) mixture and mixed in a Hauschild rotary mixer for two 20 s cycles with a manual spatula mixing step in between cycles. The mixture was drawn into a membrane, cured for 1 .0 hour at 100 °C and tested as described in Example 18.

Example 17. Copper Coordination Polymer (10 wt%)/PDMS Mixed Matrix Membrane.

[00130] Part A (0.45 g) and Part B (0.45 g) were combined in a polypropylene cup and mixed in a Hauschild rotary mixer for 20 s. Then 0.10 g of ground (powder) copper coordination polymer (Example 7) was added into premixed (Part A and B) mixture and mixed in a Hauschild rotary mixer for two 20 s cycles with a manual spatula mixing step in between cycles. The mixture was drawn

into a membrane, cured for 1 .0 hour at 100 °C and tested as described in

Example 18.

Permeation Measurements of Membranes of Comparative Example and

Examples 8-17.

[00131 ] Gas permeability coefficients and ideal selectivities in a binary gas

mixture were measured by a permeation cell including an upstream (feed) and downstream (permeate) chambers that are separated by the membrane. Each chamber had one gas inlet and one gas outlet. The upstream chamber was

maintained at 35 psi pressure and was constantly supplied with a 50/50 (mass) mixture of CO2 and N2 at a flow rate of 200 seem. The membrane was

supported on a glass fiber filter disk with a diameter of 83mm and a maximum

pore diameter range of 10-20 μιτι (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 psi pressure and is constantly supplied with a pure He stream at a flow rate of 20 seem. To analyze the permeability and separation factor of the membrane, the outlet of the downstream chamber 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). The amount of gas permeated through the

membrane was calculated by calibrating the response of the TCD detector to

the gases of interest. The reported values of gas permeability and selectivity

were obtained from measurements taken after the system had reached a steady state in which the permeate side gas composition becomes invariant with time.

All experiments were run at ambient laboratory temperature (21 ± 2 °C).

[00132] Table 1 . Permeability of CO2 and selectivity of CO2 over N2

data

Contents of CO2 N2 CO2

Copper Curing Curing Thickness

Example

Coordination Temp(°C) Time(hr) Selectivity, Permeability (pm) Polymer (wt%) a (Barrers)

Comparative 0 100 1 .0 8.1 2539 107

8 2 100 0.5 10.0 3515 145

9 4 100 0.5 9.8 3318 125

10 6 100 0.5 10.5 3034 143

1 1 10 100 2.0 10.3 3129 135

12 30 100 2.0 1 1 .5 241 1 149

13 50 100 2.0 16.0 1253 164

14 70 100 1 .0 25.1 1 028 197 15 10 100 1 .0 9.3 2595 73

16 30 100 1 .0 10.6 1426 58

17 10 100 1 .0 10.3 1984 76

[00133] The CO2 permeability of pure PDMS polymer membrane is 2539

Barrers. By adding 2 wt % ~ 10 wt% of the copper coordination polymer of

Example 1 into membranes, both selectivity(a) and permeability increased at the same time. The CO2 permeability of mixed membranes increased to about 3034 to about 3515(Barrers) and improved by about 19.5% to about 38.4 % compared with pure polymer membranes and their selectivity also increased from about 8.1 to about 9.8 to approximatelyl 0.5 ( about 21 .0 % to about

29.6%). This behavior is advantageous since there is no tradeoff between

permeability and selectivity between about 2 to about 10 wt% of copper

coordination polymer based mixed matrix membranes. The selectivity

increased with above about 10 wt% addition of copper coordination polymer materials and highest selectivity observed with about 70 wt% of copper

coordination polymer/PDMS mixed matrix membrane where its selectivity is increased by about 210% to a = 25.1 . However, there can be a tradeoff

between selectivity and permeability above about 10 wt% of copper

coordination polymer addition.

[00134] The terms and expressions which have been employed are used as terms of description and not of limitation, and there is no intention that in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various

modifications are possible within the scope of the invention claimed. Thus, it should be understood that although the present invention has been specifically disclosed by preferred embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention as defined by the appended claims.

Claims

CLAIMS We claim:

1 . A coordination polymer or solvate thereof, comprising:

a coordination polymer or a solvate thereof that comprises repeat units having the formula M(SiFg)(pz)_x(L)_y, wherein pz is pyrazine or a substituted pyrazine, M is Cu, Zn, Ni, Fe, or Co, 1 < x, 0 < y < 2, x+y < 3, and L is any ligand that comprises at least one atom selected from N and O; and

provided that

L is not a pyrazine or a substituted pyrazine; if M is Cu, and y is 2, and L is H2O, and x is 1 , then pz is not pyrazine; if M is Zn, and y is 0, and x is

2, then pz is not pyrazine; if M is Cu, and y is 0, and x is 2 or 3, then pz is not pyrazine; and if M is Cu, and y is 0, and x is 1 or 4, then pz is not 2,6- dimethylpyrazine.

2. The coordination polymer or solvate thereof according to claim 1 , provided that when M is Cu or Zn, pz is not pyrazine or 2,6-dimethylpyrazine.

3. The coordination polymer or solvate thereof according to any one of claims 1 -2, wherein x+y is approximately equal to 2 or 3.

4. The coordination polymer or solvate thereof according to any one of claims 1 -3, wherein L is water or an O- or N-containing 5- or 6-membered aromatic or non-aromatic heterocycle.

5. The coordination polymer or solvate thereof according to any one of claims 1 -4, wherein L is selected from H2O, pyridine, tetrahydrofuran, and 3,4- dihydro-2H-pyrrole.

6. The coordination polymer or solvate thereof according to any one of claims 1 -5, wherein L is any organic group that comprises at least two atoms independently selected from N and O, wherein the at least two atoms are located on approximately opposite ends of L.

7. The coordination polymer or solvate thereof according to any one of claims 1 -6, wherein L is substituted or unsubstituted and is selected from alkyleneglycol, polyalkyleneglycol, ethyleneglycol, polyethyleneglycol, propyleneglycol, polypropyleneglycol, 4,4'-bipyridine, pyridine linked at the 4- position to another pyridine at the 4'-position via C-| .5 alkyl or alkylene linker,

3,3'-bipyridine, pyridine linked at the 3-position to another pyridine at the 3'- position via 0-1.5 alkyl or alkylene linker, 3,3'-bi(1 ,2,4,5-tetrazine), terephthalic acid, benzene-1 ,3,5-tricarboxylic acid, benzene-1 ,2,4,5-tetracarboxylic acid, (1 ,1 '-biphenyl)-4,4'-dicarboxylic acid, benzoic acid linked at the 4-position to another benzoic acid at the 4'-position via C-| .5 alkyl or alkylene linker, (1 ,1 '- biphenyl)-3,3'-dicarboxylic acid, benzoic acid linked at the 3-position to another benzoic acid at the 3'-position via C-| .5 alkyl or alkylene linker, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, and a dicarboxylic acid wherein the carbonyl carbon of each acid is linked together via C-| .5 alkyl or alkylene linker.

8. The coordination polymer or solvate thereof according to any one of claims 1 -7, wherein

(a) x+y is approximately equal to 3; or

(b) M is Cu, x+y is approximately equal to 2, and L is any organic group that comprises at least two atoms independently selected from N and O, wherein the at least two atoms are located on approximately opposite ends of L.

9. A filled polymer composition comprising:

a composition selected from a curable polymer composition comprising a thermosetting polymer, and a polymer composition comprising a thermoplastic polymer in a fluid state; and

a particulate filler comprising a coordination polymer or solvate thereof, the coordination polymer or solvate thereof comprising

repeat units having the formula M(SiFg)(pz)_x(L)_y; wherein pz is pyrazine or a substituted pyrazine, M is Cu, Zn, Ni, Fe, or Co, 1 < x, 0 < y < 2, x+y < 3, and L is any organic group that comprises at least one atom selected from N and O; and

provided that L is not pyrazine or substituted pyrazine.

1 0. The filled polymer composition according to claim 9, wherein the curable polymer composition is a curable silicone composition.

1 1 . A cured product of the filled polymer composition according to any one of claims 9-10.

12. A filled polymer composition comprising:

a polymer composition selected from a cured product of a thermosetting polymer, and a thermoplastic polymer composition in a solid state; and

a particulate filler comprising a coordination polymer or solvate thereof, the coordination polymer or solvate thereof comprising

repeat units having the formula M(SiFg)(pz)_x(L)_y; wherein pz is pyrazine or a substituted pyrazine, M is Cu, Zn, Ni, Fe, or Co, 1 < x, 0 < y < 2, x+y < 3, and L is any ligand that comprises at least one atom selected from N and O; and

provided that L is pyrazine or substituted pyrazine.

13. An unsupported membrane comprising the filled polymer composition according to any one of claims 9-10 or 12, wherein the membrane is freestanding and the membrane has a CO2/N2 selectivity of at least 9.

14. A coated substrate, comprising:

a substrate; and

a coating on the substrate, wherein the coating comprises the filled polymer composition according to any one of claims 9-10 or 12.

1 5. The coated substrate according to claim 14, wherein the substrate is porous and the coating is a membrane having a CO2/N2 selectivity of at least 9.

1 6. A method of separating gas components in a feed gas mixture, the method comprising contacting a first side of a membrane 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, the membrane comprises the filled polymer composition according to any one of claims 9-10 or 12, and the membrane has a CO2/N2 selectivity of at least 9.