WO2013112823A1

WO2013112823A1 - Heterophase synthesis of metal-coordinated framework materials for particle size control

Info

Publication number: WO2013112823A1
Application number: PCT/US2013/023129
Authority: WO
Inventors: Dongchan Ahn; Jeong Yong Lee
Original assignee: Dow Corning Corporation
Priority date: 2012-01-25
Filing date: 2013-01-25
Publication date: 2013-08-01

Abstract

Various embodiments of the present invention relate to a method of preparing coordination polymer crystals, and to the crystals produced thereby. The method includes providing a composition. The composition includes Component (i), a metal-containing compound that is a source of one or more metal ions; Component (ii), a bridging ligand-containing compound that is a source of one or more bridging ligands; Component (iii), a first liquid in which (i) and (ii) are soluble; and Component (iv), a second liquid immiscible with the first liquid. The method includes mixing the composition to form an emulsion. The method also includes maintaining the emulsion for a time sufficient to produce a crystalline coordination polymer. Various embodiments also provide methods of making membranes and membranes made thereby wherein the membrane-forming composition includes the coordination polymer crystals, including methods of making membranes wherein coordination polymer crystals form in the membrane or in the membrane-forming composition before, during, or after curing of the membrane-forming composition. Various embodiments also provide methods of gas separation using the membranes.

Description

HETEROPHASE SYNTHESIS OF METAL-COORDINATED FRAMEWORK MATERIALS FOR PARTICLE SIZE CONTROL

CLAIM OF PRIORITY

[0001] This application claims the benefit of priority of U.S. Patent Application Serial No. 61/590,622, entitled "HETEROPHASE SYNTHESIS OF METAL- COORDINATED FRAMEWORK MATERIALS FOR PARTICLE SIZE CONTROL," filed on January 25, 2012, which application is incorporated by reference herein in its entirety.

[0002] Coordination polymers, also known as metal organic frameworks (MOFs), are structures including metal ions coordinated to ligands that can link one metal to another, extending in a two- or three-dimensional array. The combination of metal nodes and linkers can result in three-dimensional porous frameworks 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.

SUMMARY OF THE INVENTION

[0003] Methods of preparing coordination polymers are known in the art. For example coordination polymers can be prepared by heating a metal salt and ligands in an aqueous solution. However, the crystals formed under these conditions are often relatively large (e.g. > 1 mm). For many applications requiring high surface area or dispersibility, the crystals can be inconveniently milled to reduce particle size.

[0004] In various embodiments, the present invention provides a method of preparing a coordination polymer. The method includes providing a composition. The composition includes (i) a metal-containing compound that is a source of one or more metal ions. The composition includes (ii) a bridging ligand-containing compound that is a source of one or more bridging ligands. The composition includes (iii) a first liquid in which (i) and (ii) are soluble. The composition includes (iv) a second liquid immiscible with the first liquid. The method includes mixing the composition to form an emulsion. The method includes maintaining the emulsion for a time sufficient to produce a crystalline coordination polymer.

[0005] Various embodiments of the present invention provide certain advantages over other methods of making coordination polymers. For example, the emulsion can permit fine-tuned control over the size of the coordination polymer crystals formed. In some examples, the control over size can allow formation of coordination polymer crystals with a more highly uniform size than other methods. In some examples, the control over size can allow formation of coordination polymer crystals with smaller sizes than other methods. In some examples, the methods of the present invention can be easier to carry out, less costly, less energy intensive, less wasteful or otherwise more efficient than other methods. In some embodiments, the method can be more easily and efficiently scaled up than other methods. In some embodiments, the present invention can allow formation of membranes or membrane-forming

compositions that include coordination polymer crystals more easily, more cost effectively, or more scalably than other methods of making membranes. In some examples, the membranes provided by the present invention can have unique properties over other membranes, or properties normally accessible through greater cost or effort than the methods of the present invention. For example, the membrane of the present invention can have higher selectivity or permeability toward certain compounds than other membranes. In some examples, the method of gas separation provided by the present invention can be more efficient or more effective than other methods of gas separation.

[0006] To integrate a coordination polymer into a cured material, such as a membrane, a dispersion of the coordination polymer in the curable material is generally formed. By conventional techniques, where a crystalline coordination polymer is first harvested from its synthetic liquor, dried and milled or ground to the desired particle size, the coordination polymer must then be mixed into a curable composition, which often results in a high viscosity composition that is difficult to mix and consequently requires high energy or heat to attain uniform, fine dispersion of crystals. The act of introducing or mixing the coordination polymer crystals into a curable composition may further result in aggregation of the crystals. However, some embodiments of the present invention

advantageously provide a one-pot method of forming a dispersion of a coordination polymer in a curable compound that avoids the need for a mixing and dispersing step. In some embodiments, the emulsion can be formed in a polymeric continuous phase that can subsequently be crosslinked or gelled to form a cured composition or article containing the coordination polymer, thus reducing the number of wasteful processing and vessel transfer operations. By providing a one-pot method, some embodiments can reduce or eliminate agglomeration of crystals, or can provide better dispersion of crystals than conventional techniques.

BRIEF DESCRIPTION OF THE FIGURES

[0007] 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.

[0008] FIG. 1 is a PXRD spectrum of Cu/BTC coordination polymer crystals, according to various embodiments.

[0009] FIGS. 2A and 2B show SEM images of Cu/BTC coordination polymer crystals, according to various embodiments.

[0010] FIGS. 2C and 2D show SEM images of Cu/BTC coordination polymer crystals.

[0011] FIGS. 3A and 3B show SEM images of Cu/SiFg/pyrazine coordination polymer crystals.

[0012] FIG. 4 shows SEM images of Cu/SiFg/pyrazine coordination polymer crystals, according to various embodiments.

[0013] FIGS. 5A and 5B show SEM images of Cu/SiFg/pyrazine coordination polymer crystals, according to various embodiments.

DETAILED DESCRIPTION OF THE INVENTION

[0014] 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.

[0015] 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.

[0016] 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.

[0017] 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.

[0018] 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.

[0019] 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.

[0020] 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.

[0021] 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.

[0022] 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.

[0023] The term "aryl" as used herein refers to cyclic aromatic hydrocarbons that do not contain heteroatoms in the ring. [0024] 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.

[0025] 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.

[0026] The term "cure" as used herein refers to exposing to radiation in any form, heating, or allowing to undergo a physical change or a chemical reaction that results in hardening or an increase in viscosity.

[0027] 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.

[0028] 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.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] The term "coordination polymer" as used herein refers to structures including metal cation centers linked by ligands, extending in an array, and includes the class of compounds known as metal organic frameworks.

[0034] The term "mixed matrix membrane" as used herein refers to a membrane that includes a coordination polymer.

[0035] 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 cured or hardened coating material.

[0036] 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.

[0037] The term "mil" as used herein refers to a thousandth of an inch, such that 1 mil = 0.001 inch.

[0038] The term "bridging ligand" as used herein refers to a compound that can coordinate to more than one metal ion. A bridging ligand can presently coordinate to more than one metal ion, or a bridging ligand can have the ability to coordinate to more than one metal ion but not presently be coordinated to more than one metal ion. [0039] The term "emulsion" as used herein refers to a mixture of two or more immiscible liquids. In some embodiments, one liquid is dispersed in the other, forming droplets.

[0040] The term "crystalline" as used herein refers to a solid material whose constituent atoms, molecules, or ions are arranged in a regular repeating pattern extending in three dimensions.

[0041] The term "polycarboxylic acid" as used herein refers to an organic compound that has more than one carboxylic acid functional group.

[0042] The term "polyamine" as used herein refers to an organic compound that has more than one amine functional group.

[0043] The term "silicone fluid" as used herein refers to a fluid that includes a silicone compound.

[0044] The term "gas" as used herein refers to gases or vapors.

Method of Preparing a Coordination Polymer

[0045] Various embodiments of the present invention relate to a method of preparing coordination polymer crystals, and to the crystals produced thereby. The method can include providing a composition. The method can include mixing the composition to form an emulsion. The method can also include maintaining the emulsion for a time sufficient to produce a crystalline coordination polymer.

[0046] The method of preparing coordination polymer crystals can include providing a composition. The composition can be any suitable composition that can form a coordination polymer. In one example, the composition can include Component (i), a metal-containing compound that is a source of one or more metal ions. The composition can also include Component (ii), a bridging ligand- containing compound that is a source of one or more bridging ligands.

Additionally, the composition can include Component (iii), a first liquid in which (i) and (ii) are soluble. Also, the composition can include Component (iv), a second liquid immiscible with the first liquid. In various embodiments, the composition can be provided in any form. The composition can be provided neat, including only Components (i)-(iv). In other embodiments, the composition can be provided in combination with other ingredients, for example, any other ingredients. In one example, the composition is provided with an optional ingredient, such as any optional ingredient described herein. In one example, the composition is provided with an optional surfactant. In some embodiments, a surfactant is present. In other embodiments, a surfactant is not present. The Components of the composition can be added in any suitable order. [0047] The coordination polymer can be any suitable coordination polymer. The coordination polymer includes metal centers linked by ligands, extending in an array. One of skill in will readily understand that in some areas, for example as at or near the edges of the array, or for example in areas in which a barrier or particle blocks or otherwise influences the formation of the array, the number of atoms, ions, or groups coordinating to one another may differ from the generally consistent three-dimensional pattern followed by other areas of the array.

Correspondingly, in some embodiments the array may correspondingly form a less consistent or more random three-dimensional structure at these and other locations.

[0048] Various embodiments of the present invention provide a coordination polymer or solvate thereof. The coordination polymer or solvate thereof can be any suitable coordination polymer or solvate thereof that can be made using the method described herein. In some examples, 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. 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.

[0049] 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, N|2+ ions, or Co^⁺ ions.

[0050] 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 0-1.5 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, 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.

[0051] 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.

[0052] In one example, the coordination polymer can include repeat units including the formula

or Cu(pz)SiFe(H20)2, wherein pz is pyrazine or a substituted pyrazine.

[0053] In one example, the coordination polymer can include repeat units having the formula, Cu_x(BTC)_y(L)_z , where y= (2x/3), and 0 < z < 2y. The repeat unit can include a {Cu-| 5BTC}_n moiety and two BTC ligands can share three Cu cations to form the framework structure. In some examples, L can be a monodentate ligand, and for example can include H2O, MeOH, EtOH, iPA, pyridine, CH2CI2, CHCI3, tetrahydrofuran, or 3,4-dihydro-2H-pyrrole.

[0054] The method of preparing coordination polymer crystals can include mixing the composition to form an emulsion. The mixing can be any suitable form of mixing, wherein the mixing forms an emulsion. The composition can be shaken to mix it and to produce the emulsion. Any suitable type of mixing and shearing equipment, including batch, continuous, semi-batch mixers, such as homogenizers, sonicators, sonolators, and extruders, may be used to apply shear force to the composition to form an emulsion. Sonication can be used to mix the composition. In one example, the mixing is performed using a magnetic stir bar. In some examples, the mixing is performed using a rotary mixer, such as with a paddle, screw shape, or other suitable shape that generates turbulence or other mixing effect as it is rotated through the composition. In some examples, the mixing is performed using an ultrasonic mixing wand that generates turbulence or other mixing effect. In some examples, the mixing is performed using a rotor/stator homogenizer. In some examples, the mixing is performed using a Hauschild rotary mixer.

[0055] The components of the emulsion can be combined and mixed in any order. The order of mixing can affect the droplet size and stability of the emulsion. In some examples, the order of mixing can be dependent on the nature of the components used. In some embodiments, the Components (i), (ii) and (iii) can be partitioned into two separate solutions that are pre-mixed before introducing Component (iv) and the optionally surfactants. In some

embodiments, the Components (i), (ii) and (iii) can be partitioned into two separate solutions that are then not combined until after they have each been mixed in Component (iv) and optionally the surfactants. In some embodiments, the Components (i), (ii), and (iii) are not pre-partitioned and can be loaded together with Component (iv) and optionally surfactants and mixed together.

[0056] Any suitable amount of emulsion can be formed. For example, in one example about 50% by mass of Component (iii) can be an emulsion with about 50% by mass of Component (iv), while for example the other about 50% by mass of Component (iii) and the other 50% by mass of Component (iv) form two phases that are not an emulsion. In some examples, about 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, or about 100% by mass of both Component (iii) and Component (iv) form an emulsion, while for example the remainder of Component (iii) and (iv) form two phases that are not an emulsion. In some examples, the percent by mass of one Component that forms an emulsion is not equal to the percent by mass of the other Component that forms an emulsion with the first component. For example, an average of about 5% by mass of Component (iii) can be suspended as emulsion droplets in about 50% by mass of Component (iv), while the other 95% by mass of Component (iii) and the other about 50% by mass of Component (iv) can form two phases that are not an emulsion, e.g. the ratio of Component (iii) to Component (iv) in the emulsion is about 1 :19. In various embodiments, the ratio of Component (iii) to Component (iv) in the emulsion is less than about 100:1 , or is about 100:1 , 75:1 , 50:1 , 25:1 , 20:1 , 15:1 , 10:1 , 5:1 , 4:1 , 3:1 , 2:1 , 1 :1 , 1 :2, 1 :3, 1 :4, 1 :5, 1 :1 0, 1 :1 5, 1 :20, 1 :25, 1 :50, 1 :75, about 1 :100, or greater than about 1 :100. In some embodiments, the proportion of one Component forming an emulsion with another Component can vary based on the location of the mixture analyzed.

[0057] The size of the emulsion droplets of one Component in another can be any suitable size. In some embodiments, variation between the size of droplets can occur. In other embodiments, the size of the droplets can be uniform. The shape of the droplets can be any suitable shape. For example, in some embodiments the average droplet diameter can be greater than 10 microns, between 1 and 10 microns, less than 1 micron, or less than 0.1 micron. In some embodiments, the size of the droplets can influence the size of the resulting coordination polymer crystals. For example, the size of a droplet of Component (iii) can serve to limit the amount of Component (i) and Component (ii) or other additional ingredients available for participation in crystal formation within the local area of the emulsion droplet. In other examples, the size of the droplets makes little difference in the size of the resulting coordination polymer crystals. In some embodiments, the droplets are so close together that the amount of

Component (i) and Component (ii) or other additional ingredients within the local area of a droplet is so proximate to Components or ingredients present in other droplets that the droplet size makes little difference in the size of the resulting crystals. Some embodiments include a combination of droplets that are adequately spaced to limit crystal formation, and droplets that are proximate enough that droplet size has little effect on crystal formation, such that while some crystals may form without droplet size-influenced limitation, the majority of or a significant number of crystals form such that their size is limited by the size of the emulsion droplets. In some embodiments, clusters of emulsion droplets are present, such that even though within a cluster of droplets each droplet is not far enough from other droplets to allow the droplet size to limit the size of the resulting crystals, the number of droplets present in the cluster does limit the size of the crystals formed. The degree or type of mixing, the amount and properties of Components (iii) and (iv) and the corresponding miscibility thereof, the amount and properties of Components (i) or (ii), and the amount and properties of any optional ingredients that are included in the composition, are all examples of factors that can influence the size of the droplets in the emulsion; therefore, these are also examples of factors that in some embodiments can be varied to change the size of the respective crystals.

[0058] The type or degree of mixing that can produce an emulsion can be influenced by various factors. For example, the degree of immiscibility of Component (iii) and Component (iv), the proportion of Component (iii) to Component (iv), or the presence or lack of certain optional components can influence what type of mixing or what degree of mixing can create a suitable emulsion. For example, the presence of a surfactant can allow more facile formation of an emulsion, or can stabilize an emulsion once formed. In some examples, the amount of surfactant can also affect the droplet size, shape and distributions thereof of the emulsion.

[0059] The method of preparing coordination polymer crystals can include maintaining the emulsion for a time and temperature sufficient to provide a crystalline coordination polymer. The maintaining can be any suitable maintaining of the emulsion, such that a crystalline coordination polymer is formed. The maintaining can be a passive maintaining, such that no action is taken to maintain the emulsion, but wherein no action is taken or minimal action is taken that would destroy the emulsion. The maintaining can include a lack of movement of the emulsion, which can help to allow the crystals of the coordination polymer to form. The maintaining can include any amount of movement or agitation of the emulsion, which can help maintain the

characteristics of the emulsion during formation of the coordination polymer. The maintaining can include ambient temperature, cooling or heating or combinations thereof to promote growth of the desired coordination polymer crystals. In some examples, the emulsion is maintained at room temperature with no deliberate external movement or agitation.

[0060] In some embodiments, the method can include a step of harvesting the crystals. The harvesting step can include removing the crystals from the solvent medium (e.g. Component (iii), Component (iv), or both) and allowing them to dry. In some examples, harvesting includes vacuum filtration, gravity filtration, or any other suitable filtration method to separate the solid crystals from the liquid medium. The harvesting step can include a step of washing the crystals with a solvent, for example and aqueous or organic solvent. In some embodiments, Component (iv) comprises groups that can be polymerized or crosslinked into a final cured article, such as a silicone rubber, such that the need to harvest the crystals from Component (iv) is eliminated; in such embodiments, Component (iii) may be removed from the composition before, during or after the curing process, for example by drying, or alternately, not removed at all.

[0061] The crystals of the coordination polymer can be any size. The size of the coordination polymer crystals can vary and be governed by the synthetic conditions such as reaction temperature and time. In some examples, the average maximum dimension can be about 0.01 micron to about 2 mm, or about 0.1 micron to about 1 mm. In one example, the coordination polymer crystals can have an average maximum dimension of about 100 microns. In another example, the coordination polymer can have an average maximum dimension of about 20 microns. In another example, the coordination polymer can have an average maximum dimension of about 5 microns. In another example, the coordination polymer can have an average maximum dimension of about 1 micron. In another example, the coordination polymer can have an average maximum dimension of less than 1 micron. An average maximum dimension, for example, can be the longest aspect of a particle, such as the length or diameter or a particle. For example, the maximum dimension of a rectangular crystal would be the longest of greatest length of a side in the x, y, or z dimension, and the maximum dimension of a cylinder is the larger of diameter and length.

[0062] In some examples, the crystals can be essentially monodisperse in size or have a broad distribution of sizes. The crystals may take on any suitable shape including for example cubes, rods, needles, and flakes. The crystals can be formed as single crystals (primary particles) or they can form agglomerates (secondary particles) of single crystals. In this case, the resulting agglomerates of smaller primary crystals can range from about 1 micron to about 100 mm, or about 10 microns to 10 millimeters.

[0063] In some examples, Component (i), the metal-containing compound that is a source of one or more metal ions, can be present in the coordination polymer-forming composition from about 0.001 wt% to about 99.999 wt%, about 0.5 wt % to about 75 wt%, or about 1 wt% to about 50 wt% of the total weight of the coordination polymer-forming composition. In some embodiments, Component (i) can be present in from about 0.1 wt% to about 15 wt%, about 2 wt% to about 8 wt%, or about 3 wt% to about 5 wt%, or about 4 % of the total weight of the coordination polymer forming composition. In some embodiments, component (i) can be present in from about 0.1 wt% to about 15 wt%, about 0.5 wt% to about 8 wt%, or about 1 wt% to about 3 wt% or about 2 % of the total weight of the coordination polymer-forming composition. Wt% in this paragraph refers to the percent by weight based on the total weight of the coordination polymer-forming composition (e.g. Components (i), (ii), (iii), (vi) and optional surfactants), prior to formation of the coordination polymer crystals.

[0064] In some examples, Component (ii), the bridging ligand-containing compound that is a source of one or more bridging ligands, can be present in the coordination polymer-forming composition from about 0.001 wt% to about 99.999 wt%, 0.01 wt% to about 90 wt%, about 0.1 wt% to about 70 wt%, or about 0.5 wt% to about 50 wt% of the total weight of the coordination polymer- forming composition. In some embodiments, Component (ii) can be present in from about 0.1 wt% to about 20 wt%, about 0.2 wt% to about 10 wt%, or about 0.3 wt% to about 3 wt% or about 1 wt % of the total weight of the coordination polymer-forming composition. In some embodiments, Component (ii) can be present in from about 0.1 wt% to about 40 wt%, about 0.5 wt% to about 10 wt%, or about 1 wt% to about 5 wt% or about 2.5 wt% of the total weight of total weight of the coordination polymer-forming composition. Wt% in this paragraph refers to the percent by weight based on the total weight of the coordination polymer-forming composition (e.g. Components (i), (ii), (iii), (vi) and optional surfactants), prior to formation of the coordination polymer crystals.

[0065] In some examples, Component (iii), the first liquid in which (i) and (ii) are soluble, can be present in the coordination polymer-forming composition from about 0.001 wt% to about 99.999 wt%, 0.1 wt% to about 99 wt%, about 1 wt % to about 90 wt%, about 5 wt % to about 70 wt%, or about 10 wt% to about 60 wt% of the total weight of the coordination polymer-forming composition. In some embodiments, Component (iii) can be present in from about 10 wt% to about 70 wt%, about 30 wt% to about 60 wt%, or about 40 wt% to about 50 wt% or about 45 wt % of the total weight of Components (i), (ii), (iii), and (vi). In some embodiments, Component (iii) can be present in from about 5 wt% to about 60 wt%, about 10 wt% to about 50 wt%, or about 20 wt% to about 50 wt% of the total weight of the coordination polymer-forming composition. Wt% in this paragraph refers to the percent by weight based on the total weight of the coordination polymer-forming composition (e.g. Components (i), (ii), (iii), (vi) and optional surfactants), prior to formation of the coordination polymer crystals. [0066] In some examples, Component (iv), the second liquid immiscible with the first liquid, can be present in the coordination polymer-forming composition from about 0.001 wt% to about 99.999 wt%, 5 wt% to about 99 wt%, about 10 wt% to about 95 wt%, or about 15 wt% to about 80 wt% of the total weight of the coordination polymer-forming composition. In some embodiments,

Component (iv) can be present in from about 10 wt% to about 70 wt%, about 30 wt% to about 60 wt%, or about 40 wt% to about 50 wt%, or about 45 wt % of the total weight of the coordination polymer-forming composition. In some embodiments, Component (iv) can be present in from about 10 wt% to about 80 wt%, about 20 wt% to about 70 wt%, or about 30 wt% to about 60 wt% of the total weight of total weight of the coordination polymer-forming composition. Wt% in this paragraph refers to the percent by weight based on the total weight of the coordination polymer-forming composition (e.g. Components (i), (ii), (iii), (vi) and optional surfactants), prior to formation of the coordination polymer crystals.

[0067] In some examples, an optional surfactant (or surfactants) can be present in the coordination polymer-forming composition from about 0.001 wt% to about 99.999 wt%, 0.001 wt% to about 70 wt%, or about 0.1 wt % to about 50 wt% of the total weight of the coordination polymer-forming composition. In some embodiments, a surfactant can be present in from about 0.1 wt% to about 30 wt%, about 0.5 wt% to about 20 wt%, or about 2 wt% to about 1 0 wt%, or about 6 wt %f the total weight of the coordination polymer-forming composition. In some embodiments, a surfactant can be present in from about 0.5 wt% to about 40 wt%, about 1 wt% to about 20 wt%, or about 2 wt% to about 15 wt% of the total weight of total weight of the coordination polymer-forming composition. Wt% in this paragraph refers to the percent by weight based on the total weight of the coordination polymer-forming composition (e.g. Components (i), (ii), (iii), (vi) and optional surfactants), prior to formation of the coordination polymer crystals.

(i), Metal-Containing Compound that is a Source of One or More Metal Ions

[0068] The composition can include Component (i), metal-containing compound that is a source of one or more metal ions. The metal-containing compound can be any suitable metal-containing compound that is a source of one or more metal ions. The one or more metal ions can be any one or more metal ions that can form a coordination polymer. In some embodiments, the metal-containing compound is a salt that includes one or more metal ions. [0069] In some embodiments, the metal-containing compound that is a source of one or more metal ions can provide the one or more metal ions after or during a chemical reaction. In some examples, the metal-containing compound that is a source of one or more metal ions can provide the one or more metal ions after or during dissolution in a solvent medium, for example after or during dissolution in Component (iii). 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. In some embodiments, the metal containing compound can be a copper compound, a zinc compound, a nickel compound, an iron compound, or a cobalt compound, which can be a source of one of more Cu ions, Zn ions, Ni ions, Fe ions, or Co ions, respectively, such as for example, Cu2+ ions, Zn2+ ions, Ν|2+ ions, Fe^+ ions, or Co^⁺ ions.

[0070] In some examples, the copper compound can any suitable copper salt. In some examples, the copper compounds can be CuF2, CuC^, CuBr₂,

Cu(OAc)₂, Cu(N0₃)₂, CuC0₃, CuS0₄, Copper(ll) citrate, Cu(CN)₂, Cu(OH)₂, Cu(N0₂)₂, CuO, Cu₃(P0₄)₂, CuS0₄, 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, ZnCI₂, ZnBr₂, Zn(OAc)₂, Zn(N03)₂, ZnC03, ZnS0₄, Zinc(ll) citrate, Zn(CN)₂, Zn(OH)₂, Zn(N0₂)₂, ZnO, or Zn₃(P0₄)₂, ZnS0₄, 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, NiCI₂, NiBr₂, Ni(OAc)₂, Ni(N0₃)₂, NiC0₃, NiS0₄, Nickel(ll) citrate, Ni(CN)₂, Ni(OH)₂, Ni(N0₂)₂, NiO, Ni₃(P0₄)₂, NiS0₄, 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, FeCI₂, FeBr₂,

Fe(OAc)₂, Fe(N0₃)₂, FeC0₃, FeS0₄, iron(ll) citrate, Fe(CN)₂, Fe(OH)₂, Fe(N0₂)₂, FeO, Fe₃(P0 )₂, FeS0 , and the like, or any hydrate thereof. In some examples, the cobalt compound can be CoF₂, CoCI₂, CoBr₂, Co(OAc)₂,

Co(N0₃)₂, CoC0₃, CoS0₄, Cobalt(ll) citrate, Co(CN)₂, Co(OH)₂, Co(N0₂)₂,

CoO, or Co₃(P0₄)₂, CoS0₄, and the like, or any hydrate thereof. (ii). Bridging Liaand-Containing Compound that is a Source of One or More Bridging Ligands

[0071] The composition can include Component (ii), a bridging ligand- containing compound that is a source of one or more bridging ligands. The bridging ligand-containing compound can be any suitable compound that is a source of one or more bridging ligands. The bridging ligands can be any suitable ligand that can coordinate to more than one metal ion, such as the metal ions provided by Component (i). In some examples, the bridging ligand- containing compound is the bridging ligand provided by the bridging ligand- containing compound; for example, the bridging ligand-containing compound can be pyrazine, and the bridging ligand provided by the compound can be pyrazine. In another example, the bridging ligand-containing compound is not the same as the bridging ligand provided by the bridging ligand-containing compound; for example, the bridging ligand can be a silicon hexafluoride salt, and the bridging ligand provided by the compound can be a silicon hexafluoride ion.

[0072] In some embodiments, the bridging ligand-containing compound that is a source of one or more bridging ligands can provide the one or more bridging ligands after or during a chemical reaction. In some examples, the bridging ligand-containing compound that is a source of one or more bridging ligands can provide the one or more bridging ligands after or during dissolution in a solvent medium, for example after or during dissolution in Component (iii). The bridging ligand-containing compound can be a hydrate. The bridging ligand- containing compound can be a non-hydrate. The bridging ligand-containing compound can have any suitable number of water molecules per bridging ligand.

[0073] In some examples, the bridging ligand-containing compound is a silicon hexafluoride salt, and the bridging ligand provided by the compound is a silicon hexafluoride ion. In some examples, the silicon hexafluoride compound can be H₂SiFg. In some examples, the silicon hexafluoride compound can be BeSiFg,

MgSiF₆, CaSiF₆, SrSiF₆, BaSiF₆, RaSiF₆, 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. [0074] In some examples, the bridging ligand-containing compound is benzene- 1 ,3,5-tricarboxylic acid, and the bridging ligand provided by the compound is the corresponding -3 ion of the acid, a benzene-1 ,3,5-tricarboxylate.

[0075] In some examples, the bridging ligand-containing compound, and the one or more bridging ligands, can be pyrazine, or a substituted pyrazine. 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.

[0076] In some embodiments, the bridging ligand-containing compound, or the one or more bridging ligands, can be an organic compound that includes at least one atom selected from N and O. For example, the bridging ligand can be 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 the ligand, 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 the ligand are located within the chemical structure of the ligand 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, the bridging ligand-containing compound, or the one or more bridging ligands, can be pyrazine, 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, 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.

(iii) . First Liquid in which (i) and (ii) are Soluble

[0077] The composition can include Component (iii), a first liquid in which Components (i) and (ii) are soluble. The first liquid can be any solvent, aqueous or organic. In some embodiments, the first liquid can be miscible with water. The first liquid can be an alcohol, including, for example, a mono-alcohol, a glycol, triol, or polyol. The first liquid can be aqueous, or can be water. The first liquid can be ethylene glycol. Examples of organic first liquids can include dimethyl formamide (DMF), 1 ,4-dioxane, and dimethylsulfoxide(DMSO), N,N- Diethylformamide (DEF) and Ν,Ν-Dimethylethanamide (DMA). The first liquid can include a combination of solvents, such as a combination of water and ethylene glycol, for example, or a combination of water, ethanol and

dimethylformamide (DMF).

(iv) , Second Liquid Immiscible with the First Liquid

[0078] The composition can include Component (iv), a second liquid immiscible with the first liquid. The second liquid can be any suitable liquid that is immiscible with the first liquid. In one example, the second liquid is water or an organic solvent. In one example, the second liquid is a organosilicon liquid. In one example, the second liquid is comprises polymerizable or crosslinkable functional groups, such as for example ethylenic unsaturated groups, acrylate groups, methacrylate groups, vinyl ether groups, epoxy groups, amine groups, silicon hydride groups, silicon hydroxyl groups, or alkoxysilane groups. In one example, the second liquid is a curable composition, as described herein. In some embodiments, the second liquid and the first liquid are a curable composition. In some embodiments, Components (i), (ii), (iii), (iv), and optional additional ingredients form a curable composition, as described herein.

[0079] In some embodiments, the second liquid is an organopolysiloxane comprising hydrosilylation-reactive groups. In some embodiments, the second liquid is an organopolysiloxane having an average of at least two vinyl or silicon hydride functional groups per molecule. In some embodiments, the second liquid is dimethylvinylsiloxy-terminated polydimethylsiloxane.

[0080] In some embodiments, component (iv) comprises functional groups that can be used for subsequent polymerization or crosslinking of the emulsion to form a cured organosilicon composition that comprises a dispersion of coordination polymer crystals.

Surfactant

[0081] In some embodiments, the composition includes a surfactant. In some embodiments, a surfactant is included. In some embodiments a surfactant is not included. The surfactant can be any suitable surfactant, such as a surfactant commonly used to generate oil/water emulsions or other types of emulsions. The surfactant can be cationic, anionic or non-ionic. The surfactant can be aqueous, non-aqueous, and in diluted or undiluted form.

[0082] In one example, the surfactant is sorbitan monooletate. In one example, the surfactant can be a non-ionic surfactant. Examples of non-ionic surfactants can include polyoxyethylene alkyi ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene lauryl ethers, polyoxyethylene sorbitan monoleates, polyoxyethylene alkyi esters, polyoxyethylene sorbitan alkyi esters, polyethylene glycol, polypropylene glycol, diethylene glycol, ethoxylated trimethylnonanols, polyoxyalkylene glycol modified polysiloxane surfactants, and mixtures, copolymers or reaction products thereof. In one example, the surfactant is polyglycol-modified trimethylsilylated silicate surfactant.

[0083] Examples of suitable cationic surfactants can include, but are not limited to, quaternary ammonium hydroxides such as octyl trimethyl ammonium hydroxide, dodecyl trimethyl ammonium hydroxide, hexadecyl trimethyl ammonium hydroxide, octyl dimethyl benzyl ammonium hydroxide, decyl dimethyl benzyl ammonium hydroxide, didodecyl dimethyl ammonium hydroxide, dioctadecyl dimethyl ammonium hydroxide, tallow trimethyl ammonium hydroxide and coco trimethyl ammonium hydroxide as well as corresponding salts of these materials, fatty amines and fatty acid amides and their derivatives, basic pyridinium compounds, and quaternary ammonium bases of benzimidazolines and poly(ethoxylated/propoxylated) amines.

[0084] Examples of suitable anionic surfactants can include, but are not limited to, alkyl sulphates such as lauryl sulphate, polymers such as acrylates/C-|o-30 alkyl acrylate crosspolymer alkylbenzenesulfonic acids and salts such as hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid and

myristylbenzenesulfonic acid; the sulphate esters of monoalkyi polyoxyethylene ethers; alkylnapthylsulfonic acid; alkali metal sulfoccinates, sulfonated glyceryl esters of fatty acids such as sulfonated monoglycerides of coconut oil acids, salts of sulfonated monovalent alcohol esters, amides of amino sulfonic acids, sulfonated products of fatty acid nitriles, sulfonated aromatic hydrocarbons, condensation products of naphthalene sulfonic acids with formaldehyde, sodium octahydroanthracene sulfonate, alkali metal alkyl sulphates, ester sulphates, and alkarylsulfonates. Anionic surfactants can include alkali metal soaps of higher fatty acids, alkylaryl sulfonates such as sodium dodecyl benzene sulfonate, long chain fatty alcohol sulfates, olefin sulfates and olefin sulfonates, sulfated monoglycerides, sulfated esters, sulfonated ethoxylated alcohols, sulfosuccinates, alkane sulfonates, phosphate esters, alkyl isethionates, alkyl taurates, and alkyl sarcosinates.

[0085] Examples of suitable non-ionic surfactants can include, but are not limited to, condensates of ethylene oxide with long chain fatty alcohols or fatty acids such as a (C-| 2-i 6)^alconol _> condensates of ethylene oxide with an amine or an amide, condensation products of ethylene and propylene oxide, esters of glycerol, sucrose, sorbitol, fatty acid alkylol amides, sucrose esters, fluoro- surfactants, fatty amine oxides, polyoxyalkylene alkyl ethers such as polyethylene glycol long chain alkyl ether, polyoxyalkylene sorbitan ethers, polyoxyalkylene alkoxylate esters, polyoxyalkylene alkylphenol ethers, ethylene glycol propylene glycol copolymers and alkylpolysaccharides, polymeric surfactants such as polyvinyl alcohol (PVA) and polyvinylmethylether. In certain embodiments, the surfactant is a polyoxyethylene fatty alcohol or mixture of polyoxyethylene fatty alcohols. In other embodiments, the surfactant is an aqueous dispersion of a polyoxyethylene fatty alcohol or mixture of polyoxyethylene fatty alcohols.

[0086] In some embodiments, the surfactant can be selected from Tergitol™ 1 5-S-3, Tergitol™ 15-S-40, sorbitan monooleate, polylycol-modified

trimethsilylated silicate, polyglycol-modified siloxanes, polyglycol-modified silicas, ethoxylated quaternary ammonium salt solutions, and

cetyltrimethylammonium chloride solutions.

Compound Capable of Forming a Monodentate Liqand with the Metal Ion

[0087] In some embodiments, the composition includes a compound capable of forming a monodentate ligand with the metal ion, such that the resulting coordination polymer includes metal ions with the monodentate ligand coordinated thereto. In some embodiments, the monodentate ligand is not included. Examples of the monodentate ligand includes water or an organic compound that includes at least one atom selected from N and O. For example, the monodentate ligand can be H2O, pyridine, tetrahydrofuran, DMSO, or 3,4- dihydro-2H-pyrrole.

In-Situ Coordination Polymer Synthesis

[0088] Various embodiments also provide methods of making membranes and membranes made thereby wherein the membrane-forming composition includes the coordination polymer crystals, including methods of making membranes wherein coordination polymer crystals form in a component of a membrane, such as the polymer that comprises the continuous phase of a mixed matrix membrane, or in the membrane-forming composition before, during, or after curing of the membrane-forming composition. In various embodiments, the present invention provides the method of making a coordination polymer, wherein the coordination polymer-forming composition includes a curable composition, or a curable component of a curable composition. In such embodiments, for example, to integrate the coordination polymer crystals or a derivative thereof in a cured composition, a harvesting step for collecting the coordination polymer crystals can be avoided, and the coordination polymer crystals or a derivative thereof can be generated directly in a curable compound or curable composition or the cured product thereof to create a cured product having well dispersed coordination polymer crystals with greater efficiency than conventional methods that require high intensity mixing to disperse separately grown and harvested crystals into the curable composition or components thereof.

[0089] For example, the first liquid, the second liquid, or the first and second liquid together, can include components of a curable composition or be a curable composition. In some examples, a curable composition can be derived from a composition that includes curable components or curable compounds by the removal of solvent or by other suitable transformation. The curable compound or composition can be any suitable curable compound or composition. In some examples, the curable compound or composition is a curable organosilicon compound or composition. The method can include curing the emulsion that includes the curable composition to provide a cured composition. In embodiments in which the curable composition is a curable organosilicon composition, the cured composition includes a cured

organosilicon composition, such as for example a polysiloxane, such as a silicone rubber or fluorosilicone rubber. The curing can be any suitable curing, for example, hydrosilylation curing, condensation curing, free-radical curing, amine-epoxy curing, radiative curing, evaporative curing, or cooling.

[0090] The coordination polymer crystals can form before, during, or after the curing of the curable composition. In some embodiments, the cured composition includes the coordination polymer crystals. In some examples, the coordination crystals are physically or chemically transformed before, during, or after the curing process, such that the resulting cured composition does not include the coordination polymer crystals as they were originally formed. In other examples, no physical or chemical transformation occurs before, during, or after the curing process, such that the resulting cured composition does include the coordination polymer crystals.

[0091] The cured composition can be any suitable form. In one example, the cured composition is a membrane, as further discussed below. In another example, the cured composition is not a membrane. The cured composition can be any suitable three-dimensional shape. The cured composition can be a cured article. The cured composition can be used for any suitable purpose, including, for example, separation technology including membrane 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.

Membrane

[0092] In one embodiment, the present invention provides a membrane that includes a cured product of a curable composition. In some embodiments, the curable composition includes coordination polymer crystals formed by the method of making coordination polymer crystals of the present invention. In some embodiments, the curable composition includes the emulsion generated during the method of making coordination polymer crystals of the present invention (e.g. the coordination polymer-forming composition is the curable composition). 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.

[0093] Forming a membrane can include at least two steps. In the first step, the composition that forms the membrane (e.g. the curable composition) can be applied to at least one surface of the substrate. The curable composition that forms the membrane can include the emulsion. The composition that forms the membrane can be a curable composition that includes the coordination polymer crystals formed by embodiments of the method of forming coordination polymer crystals of the present invention. 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. In some embodiments, the coordination polymer crystals can form 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. In some embodiments, the coordination polymer crystals can form before, during, or after the curable composition is cured. 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.

[0094] The membrane of the present invention can have any suitable thickness. In some examples, the membrane has a thickness of about 1 μιτι to about 20 μιτι, 0.1 μιτι to about 200 μιτι, or about 0.01 μιτι to about 2000 μιτι. The membrane of the present invention can be selectively permeable to one substance over another. In one example, the membrane is selectively permeable to one gas over other gases or liquids. In another example, the membrane is selectively permeable to more than one gas over other gases or liquids. In one embodiment, the membrane is selectively permeable to one liquid over other liquids or gases. [0095] In embodiments wherein the curable composition includes the emulsion, the emulsion can be generated before, during, or after the curable composition is formed. For example, in some embodiments the curable composition includes only Components (i), (ii), (iii), (iv), and any optional components, such that once an emulsion is formed no further additions to the composition is necessary prior to formation of the coating. In another example, the curable composition can include additional components beyond Components (i), (ii), (iii), (iv), or optional components, such that an emulsion could be formed prior to addition of additional ingredients that form the curable composition, or such that additional ingredients that form the curable composition could be added prior to formation of the emulsion.

[0096] Curing the composition that forms the membrane can include a variety of methods, including exposing the polymer to ambient temperature, elevated temperature, moisture, or radiation. In some embodiments, curing the composition can include a combination of methods.

[0097] 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. In some embodiments, the membrane may be used in conjunction with a liquid that enhances gas transport, such as in a membrane contactor (e.g. a device that permits mass transfer between a gaseous phase and a liquid phase across a membrane without dispersing the phases in one another).

Supported Membrane

[0098] 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

[0099] 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.

[00100] 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 in a Feed Gas Mixture

[00101 ] The present invention also provides a method of separating gas components in a feed gas mixture by use of the membrane described herein. The method includes contacting a first side of a membrane with a feed gas mixture to produce a permeate gas mixture on a second side of the membrane and a retentate gas mixture on the first side of the membrane. The permeate gas mixture is enriched in the first gas component. The retentate gas mixture is depleted in the first gas component. The membrane can include any suitable membrane as described herein. [00102] 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.

[00103] 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.

[00104] 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.

Curable Composition

[00105] Various embodiments of the present invention include methods that include the use of curable compositions. For example, the present invention provides the method of forming coordination polymer crystals as described herein that further includes curing a curable composition that includes the emulsion to provide a cured product of the curable composition, such as for example a polysiloxane polymer; in some examples, the present invention further provides forming a coating, wherein the coating includes the emulsion, wherein the cured composition is a membrane. In some examples, the present invention provides a method of forming a cured product of a curable composition, wherein the curable composition includes the coordination polymer crystals as generated by embodiments of the method of forming coordination polymer crystals described herein, wherein the method includes curing the curable composition. In another example, the present invention provides a method of forming a membrane including forming a coating, wherein the coating includes a curable composition and the coordination polymer crystals generated by an embodiment of the present invention. The method further includes curing the coating, to provide a membrane. In some embodiments, a combination of these embodiments is provided, such that coordination polymer crystals are added to a curable composition, wherein the curable composition includes the emulsion.

[00106] In some embodiments, the composition that is made into an emulsion can be a curable composition. The combination of the individual components of the composition can give the composition the quality of being a curable composition. The individual components of the composition that give the composition the curable characteristic can together or individually be curable compositions. For example, the first liquid can be a curable composition. In some embodiments, the second liquid can be a curable composition. In another example, the first liquid and the second liquid together can be a curable composition. In another embodiment, none of Components (i), (ii), (iii), or (iv) form a curable composition together, but one or more components can be added to the composition to form a curable composition; in some embodiments, the combination of one or more of Components (i), (ii), (iii), or (iv) with the additional components gives the composition the curable characteristic; in some embodiments, the additional components have a curable characteristic independent of Components (i), (ii), (iii), or (iv).

[00107] The curable composition in embodiments of the present invention can be any suitable curable composition. In one example, the curable composition is an organosilicon composition. The cured composition of the present invention or the membrane of the present invention that includes a cured composition can include the cured product of an organosilicon composition. The organosilicon composition can be any suitable curable organosilicon composition. The curing of the organosilicon composition gives a cured product of the organosilicon composition. The cured product of the organosilicon composition can be a polysiloxane. The polysiloxane can be any suitable polysiloxane. In one example, the organosilicon composition is any

organosilicon composition that gives a suitable cured product that includes a polysiloxane. The curing of the organosilicon composition can be any suitable curing process.

[00108] 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.

[00109] 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.

[00110] The silicone composition can include an organic compound. The organic compound can be any suitable organic compound. The organic compound can be, 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.

[00111 ] 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. [00112] In some embodiments, the curable composition can include a curing catalyst such as a hydrosilylation catalyst, a condensation catalyst, a free radical initiatior, a photoinitiator, or acid or base. In some embodiments, the curable composition can further include a co-catalyst, decomplexer or catalyst activator.

[00113] 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, exposure to water, water vapor, acid, base, reactive vapors, or any combination thereof.

[00114] 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.

[00115] Cu(N0₃)2-3H₂0 (98%, Aldrich) and trimesic acid (benzene-1 ,3,5- tricarboxylic acid, "BTC") (Aldrich, 95%) were used as received without further purification.

Reference Example 1 : Scanning Electron Microscopy (SEM).

[00116] Sample preparation included sprinkling a small portion of sample on a SEM sample stub and coating them with 30nm of Pt/Pd to make the samples conductive for analysis on the JEOL JSM-6335F field emission scanning electron microscope (FESEM). FESEM conditions for imaging were 5kV, ~8mm working distance, and aperture 4. The particle size varied from sample to sample so images were taken between 150X to X10K magnification.

Reference Example 2: Powder X-Rav Diffraction (PXRD).

[00117] The powder diffraction patterns were collected in Bragg-Brentano geometry from 5 to 80° 2Θ in 0.02° increments at 5°/minute with a Cu anode operating at 40 kV and 44 mA. A 10 mm height limiting slit, 1 /2² divergence slit, open scattering slit, and open receiving slit were used, and intensity data were collected with a high speed detector.

Example 1 . Synthesis and characterization of Cu/BTC coordination polymer crystals.

[00118] A mixture was formed by combining Cu(N03)2-3H20 (7.83 g) dissolved in de-ionized water (50 ml_), BTC (2.00 g) dissolved in ethanol (50 ml_), and DMF (5.0 ml_), to give a blue Cu²⁺/BTC-ligand-containing solution.

[00119] Next, dimethylvinylsiloxy-terminated polydimethylsiloxane (17.60 g) having a viscosity of about 0.45 Pa-s at 25 °C and polyglycol-modified trimethylsilylated silicate surfactant (0.97 g) were combined in a polypropylene cup and mixed using a Hauschild rotary mixer for about 30 s. Then sorbitan monooleate (1 .59 g) was added to the polysiloxane mixture, and the mixture was mixed in a Hauschild mixer for two approximately 30 s cycles. A portion of the blue Cu²⁺/BTC-ligand-containing solution (19.87 g) was added, and the mixture was mixed in a Hauschild mixer for two approximately 30 s cycles. The mixture was then placed in an oven at about 40 °C for about 5 days. Blue coordination polymer crystals were found gathered at the bottom of the cup and were isolated by filtration using a Buchner funnel, followed by washing with 1 0mL of iPA in three times and dried under the air overnight.

[00120] The crystals were characterized by powder X-ray diffraction (PXRD) measurement and scanning electron microscope (SEM) analysis. FIG. 1 shows a PXRD spectrum of the blue coordination polymer crystals (top) and a simulated pattern of Cu-BTC coordination polymer crystals (bottom) provided from its cif file (Chui et al. Science 1999, 283, 1 148). The structure file (cif) was obtained from CCDC(Cambridge Crystallographic Data Centre) and PXRD pattern was simulated via mercury software (ver 2.4 from CCDC). The PXRD peak positions match well with its simulated patterns, providing evidence that the synthesized crystals are Cu-BTC coordination polymer.

[00121 ] The SEM image of the blue coordination polymer crystals are shown in FIGS. 2A and 2B and compared with one synthesized from conventional route and commercial product as shown in FIGS. 2C and 2D. FIGS. 2C and 2D shows Cu-BTC coordination polymers synthesized via typical solution route (top, comparative example 1 ) using same mother liquid and purchased from Sigma-Aldrich (C300 Basolite) as reference (bottom, comparative example 2). The Cu-BTC coordination polymer from a conventional route (Comparative Example 1 ) or from a commercial source (Comparative Example 2) showed irregular shape and wide range of particle size from about 1 μιτι to about 20 μιτι, with the range centered around about 10 μιτι. However, the Cu-BTC coordination polymer crystals synthesized from the emulsion route, shown in FIGS. 2A and 2B, are much smaller, with an approximate average crystal size of about 1 μιτι, with a range of about 0.2 μιτι to about 15 μιτι. FIGS. 2A and 2B show Cu-BTC coordination polymer crystals synthesized via the emulsion route in different scales (top 1 mm scale bar, bottom 10 mm scale bar).

Comparative Example 1 . Conventional Synthesis of Cu/BTC coordination polymer crystals.

[00122] Cu/BTC crystals were obtained from a reaction of

Cu(NO3)2-3H2O(0.435 g, 1 .8 mmol) dissolved in 6ml_ of de-ionized water with

BTC (0.1 10 g, 0.5 mmol) dissolved in 6ml_ of ethanol. The solution was then transferred into a Teflon-lined autoclave and heated in an oven at about 403K for about 12 h. After the reaction, Cu/BTC crystals were isolated by filtration followed by washing with plenty of Dl water and dried in the air overnight. The dried as-made crystals were used for characterization without any further treatment.

Comparative Example 2. Commercially obtained Cu/BTC coordination polymer crystals.

[00123] A sample of Cu/BTC coordination polymer was purchased from Sigma Aldrich (C300 Basolite) and was examined as-received via SEM.

Example 2. Synthesis of Cu/SiFg/pyrazine coordination polymer crystals.

[00124] Part A was formed by combining Cu(N03)2-3H20 (10 mmol),

(NH^SiFg (10 mmol), and de-ionized water (30 ml_). Part B was formed by combining pyrazine (20 mmol) and ethylene glycol (30 ml_).

[00125] Next, dimethylvinylsiloxy-terminated polydimethylsiloxane (0.89 g) having a viscosity of about 0.45 Pa-s at 25° C was combined with polyglycol- modified trimethylsilylated silicate surfactant (0.05 g) in a polypropylene mixing cup and mixed for about 30 s in a Hauschild rotary mixer. A portion of the Part B solution (0.50 g) was then added to the mixture and mixed for about 30 s in the Hauschild mixer. Lastly, 0.08 g of sorbitan monooleate surfactant was added to the mixture and mixed for two approximately 30 s cycles in the Hauschild mixer. To this mixture was added a portion of the Part A solution (0.50 g) and the mixture was mixed for two more approximately 30 s cycles in the Hauschild mixer. The composition formed a light blue paste. Within about 1 0-13 minutes at room temperature, the formation of dark microcrystals was observed using an optical microscope. The primary (non-agglomerated) particles formed in rod shape and agglomerated to form secondary particles. The largest rod particles appeared to be about 0.21 mm in length and 4μιτι to 40μιτι in width respectively. The average particle size was measured ~ 70 μιτι with the majority of particles of much smaller size.

Comparative Example 3. Preparation of Cu/SiFg/pyrazine crystals using non- emulsion technique.

[00126] Part A solution of Example 2 (1 part by volume) was slowly poured to form a layer on top of the part B solution of Example 2 (1 part by volume) in an 8 oz. vial. The layered solution was allowed to sit for 3 days on the lab bench at room temperature, resulting in the formation of blue crystals. The crystals were filtered with a Buchner funnel, and were washed with isopropyl alcohol ("iPA", 1 0 ml_ x 3). The crystals were dried for about 3 hours at about 50 ²C under vacuum. A SEM image of the crystals is shown in FIGS. 3A and 3B. FIGS. 3A and 3B shows different areas of the sample at different zoom levels. The mean particle size was about 70 μιτι, with lengths ranging from about 6 μιτι to about 210 μιτι, and about 4 μιτι to about 40 μιτι in width.

Example 3. Synthesis of Cu/SiFg/pyrazine coordination polymer crystals.

[00127] Dimethylvinylsiloxy-terminated polydimethylsiloxane (1 7.60 g) having a viscosity of about 0.45 Pa-s at 25° C and polyglycol-modified trimethylsilylated silicate surfactant (0.97 g) were combined in a polypropylene cup and mixed in a Hauschild rotary mixer for 30 s. Sorbitan monooleate (1 .60 g) was added, and the mixture was mixed in a Hauschild mixer for 30 s to form a first solution. In a 20 ml glass vial was combined a portion of Part A of Example 2 (9.85 g) and a portion of Part B of Example 2 (9.99 g) Example 2 and mixed by shaking to form a second solution. This second solution was added to the first solution and then, mixed in a Hauschild mixer for two 30 s cycles. The teal colored mixture was then allowed to sit on a lab bench at room temperature for about 4 days. After 4 days and also after 13 days, the mixture was mixed in a Hauschild mixer for 30 s. After about four weeks, the mixture was transferred into a glass beaker, 100 ml_ of heptanes were added, and the mixture was stirred. Then, the blue crystals were filtered off using a Buchner funner, the crystals were washed with iPA, then the crystals were dried at about 70²C under vacuum for about 3 hours. A SEM image of the crystals is shown in FIG. 4. The mean particle size was about 13 μιτι, with lengths of about 1 .5 μιτι to about 25 μιτι, and with widths of about 1 .5 μιτι to about 6 μιτι.

Example 4. Synthesis of Cu/SiFg/pyrazine coordination polymer crystals.

[00128] Dimethylvinylsiloxy-terminated polydimethylsiloxane (1 7.60 g) having a viscosity of about 0.45 Pa-s at 25° C and polyglycol-modified trimethylsilylated silicate (0.98 g) were mixed in a polypropylene cup in a Hauschild rotary mixer for about 30 s. A portion of Part B of Example 2 (9.99 g) was added and the mixture was mixed in a Hauschild rotary mixer for about 30 s. Then, sorbitan monooleate (1 .60 g) was added, and the mixture was mixed in a Hauschild rotary mixer for two approximately 30 s cycles. Then, a portion of Part A of Example 2 (9.85 g) was added and the mixture was mixed in a Hauschild rotary mixer for about 30 s. The teal colored mixture then was allowed to sit on a lab bench at room temperature. After about three weeks, the mixture was diluted with heptanes (100 ml_), and the blue crystals were filtered off using a Buchner funnel, the crystals were washed with iPA, and the crystals were dried at about 70 ²C under vacuum for about 3 hours. A SEM image of the crystals is shown in FIGS. 5A and 5B. FIGS. 5A and 5B show different areas of the sample at similar zoom levels. The mean primary particle size was about 30 μιτι, with length ranges from about 4 μιτι to about 70 μιτι, and with width ranges from about 1 .5 μιτι to about 6 μιτι.

[00129] 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 method of preparing a coordination polymer, the method comprising: providing a composition comprising

(i) a metal-containing compound that is a source of one or more metal ions;

(ii) a bridging ligand-containing compound that is a source of one or more bridging ligands;

(iii) a first liquid in which (i) and (ii) are soluble; and

(iv) a second liquid immiscible with the first liquid; mixing the composition to form an emulsion; and

maintaining the emulsion for a time sufficient to produce a crystalline coordination polymer.

2. The method according to claim 1 , wherein the one or more metal ions comprise a metal cation comprising (a) an alkali metal cation, (b) an alkaline earth metal cation, (c) a transition metal cation, (d) a lanthanide metal cation, (e) or a mixture comprising at least two of (a), (b), (c), and (d).

3. The method of any one of claims 1 -2, wherein the one or more metal ions comprise a copper, zinc, iron, nickel, or cobalt cation.

4. The method of any one of claims 1 -3, wherein the bridging ligand 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 the bridging ligand.

5. The method of any one of claims 1 -4, wherein the one or more bridging ligands are selected from benzene-1 ,3,5-tricarboxylate, pyrazine or substituted pyrazine, SiFg^2", 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 Ci -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 0-1.5 alkyl or alkylene linker.

6. The method of any one of claims 1 -5, wherein the first liquid comprises water or a mixture comprising water and a water-miscible solvent.

7. The method of any one of claims 1 -6, wherein the second liquid comprises a liquid having polymerizable or crosslinkable groups.

8. The method of any one of claims 1 -7, wherein the composition further comprises a compound containing an anion having the formula AFg2-, wherein A is Si or Ge.

9. The method of any one of claims 1 -8, wherein the composition further comprises a surfactant.

1 0. The method of any one of claims 1 -9, wherein the coordination polymer crystals have a mean maximum dimension of not greater than about 100 μιτι.

1 1 . The method of any one of claims 1 -10, further comprising:

curing a curable composition to provide a polysiloxane polymer;

wherein the curable composition comprises the emulsion or a curable composition derived from the emulsion.

12. A method of forming a cured product of a curable composition, comprising

providing a curable composition comprising coordination polymer crystals, the coordination polymer crystals formed by a method comprising providing a composition comprising

(i) a metal-containing compound that is a source of one or more metal ions; (ii) a bridging ligand-containing compound that is a source of one or more bridging ligands;

(iii) a first liquid in which (i) and (ii) are soluble; and

(iv) a second liquid immiscible with the first liquid;

mixing the composition to form an emulsion; and maintaining the emulsion for a time sufficient to produce the coordination polymer crystals; and

curing the curable composition, to provide a cured product of the curable composition.

13. A method of forming a membrane, comprising the method of claim 11 , further comprising:

forming a coating, the coating comprising the emulsion;

wherein the polysiloxane polymer comprises a membrane.

14. A method of forming a membrane, comprising:

forming a coating, the coating comprising

a curable composition; and

coordination polymer crystals formed by a method comprising providing a composition comprising

(i) a metal-containing compound that is a source of one or more metal ions;

(iii) a first liquid in which (i) and (ii) are soluble; and

(iv) a second liquid immiscible with the first liquid; mixing the composition to form an emulsion; and maintaining the emulsion for a time sufficient to produce the coordination polymer crystals; and

curing the coating, to provide a membrane.

1 5. The method of any one of claims 13-14, wherein the membrane is selected from a supported membrane and an unsupported membrane.

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 membrane comprises the membrane of any one of claims

13-14,

wherein the permeate gas mixture is enriched in the first gas component, and the retentate gas mixture is depleted in the first gas component.