Gas separation articles made from amorphous crosslinked fluorocopolymers and methods of making and using same

Abstract

Described herein are articles for separating gases. The articles include a selective layer comprising a crosslinked amorphous fluorinated copolymer containing one or more fluorinated ring monomers, with crosslinks between the fluorinated copolymer chains. This crosslinking improves the mechanical properties of the fluoroplastic, allowing the use of polymers that were previously too brittle. The resulting crosslinked polymer membranes have superior selectivity and reliability performance compared to previous compositions known in the art. Methods for making and using the described articles are also provided.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Application No. 63 / 009,112, filed April 13, 2020, and U.S. Provisional Application No. 63 / 009,114, filed April 13, 2020, both of which are incorporated by reference in their entireties. [Background technology]

[0002] The separation of CO2 and chemically similar gases (including H2S and other water-soluble acid gases) from nonpolar gases, including N2, O2, methane, and other hydrocarbons, is an important industrial problem. A large-scale application of this type of separation is the decarbonization of exhaust gases ("flue gas") from combustion systems, such as power plants, which is crucial for reducing global warming CO2 emissions. Another major application of this type of gas separation is the removal of corrosive acid gases, including CO2 and H2S, from natural gas streams, also known as "natural gas sweetening." Separation of nonacidic gases, particularly those with different global warming potentials (GWPs), including fluorinated refrigerants, is an important goal in climate change mitigation efforts, and presents many significant challenges.

[0003] This type of acid gas separation has historically been achieved by a variety of methods, including chemical absorption, cryogenic distillation, and membrane separation. Chemical absorption has been extensively developed in the oil and gas industry through the "amine scrubbing" technique, in which alkylamines (e.g., monoethanolamine) form chemical complexes with acid gases, thus removing them from the gas stream [see, for example, Bahadori, *Natural Gas Processing: Technology and Engineering Design*, Elsevier, Amsterdam, 2014]. Cryogenic distillation utilizes the principle that CO2 has a higher freezing point than other flue gases (primarily nitrogen), allowing it to be frozen as a liquid or solid, allowing other gases to pass through the system [see, for example, Xu, et al., *An Improved CO2 Separation and Purification System Based on Cryogenic Separation and Distillation Theory*, *Energies* 2014, 7, 3484-3502]. Chemical absorption and cryogenic distillation are effective methods for capturing CO2, but generally require large energy inputs and capital investments. Furthermore, in the case of alkylamine absorption methods, the amines are typically corrosive and toxic liquids. Furthermore, these amines have a limited functional lifespan and must be periodically replaced and properly disposed of. This poses a significant burden in remote operating locations such as offshore platforms. Therefore, a simpler, more energy-efficient, and longer-lasting separation method is desirable.

[0004] Fluorinated refrigerant gases are typically separated by distillation, where the differences in the boiling points and vapor pressures of the components are the primary separation mechanism. However, in some cases, significant separation problems arise where the components are azeotropic or near-azeotropic, making distillation separation impractical. For example, the widely used refrigerant R410a consists of an azeotropic mixture of two components: R32, which has a relatively low global warming potential, and R125, which has a relatively high global warming potential. In these cases, it is desirable to separate the low-GWP component for reuse and the high-GWP component for disposal, such as incineration.

[0005] Membrane-based gas separation processes operate on the principle of differential permeability of gases across a selective layer of a membrane, often composed of polymers. The membrane material in such separation processes is selected to provide very high permeability to one or more gases and much lower permeability to other gases. When a mixture of gases is introduced to one side of the membrane, the highly permeable gases will preferentially pass through the membrane, resulting in a "permeate" gas stream on the other side of the membrane. This permeate stream will be enriched in the highly permeable gas relative to the input gas stream. Meanwhile, as the input stream crosses the input surface of the membrane and proceeds to the outlet of the membrane module, it becomes enriched in the less permeable species relative to the input gas stream. This stream is referred to as the "retentate" stream [see, e.g., Baker, Membrane Technology and Applications, Wiley, West Sussex, 2012].

[0006] Because membrane-based separation requires only a pressure difference across the membrane to operate, it can usually be accomplished with relatively simple and reliable equipment consisting primarily of a compressor and a membrane module. For the same reason, it typically uses much less power than the gas separation methods mentioned above. Furthermore, membrane-based methods of gas separation avoid the use of hazardous and corrosive materials, such as alkylamines, often used in chemical absorption processes, and can also have significantly lower capital costs.

[0007] Furthermore, because membrane-based separation methods separate components based on differences in the permeability of polymeric membranes, their separation characteristics typically differ significantly from those of distillation. Thus, azeotropic mixtures in which the component gases have substantially different membrane permeabilities may be separable by membrane processes even if they cannot be separated by distillation. Therefore, membrane separation methods are considered promising for separating azeotropic and near-azeotropic mixtures of refrigerants and other gases.

[0008] The most commonly used membranes for gas separation are hydrocarbon polymers, including cellulose acetate and polyimides for separating acid gases from methane [see, e.g., Xuezhong He in Encyclopedia of Membranes, Springer-Verlag, Berlin Heidelberg 2015]. While these hydrocarbon membranes typically exhibit relatively high selectivity under ideal conditions, in certain applications, absorbed gases can significantly degrade their performance, causing chemical degradation of the polymer and plasticization of the polymer membrane. For natural gas sweetening applications, CO2 is known to plasticize cellulose acetate and polyimide membranes, resulting in reduced CO2 permeability and reduced CO2 / CH4 selectivity [ibid.]. This problem is typically more severe at higher pressures and higher CO2 contents. Summary of the Invention

[0009] Described herein are articles for gas separation. The articles include a selective layer made of a crosslinked amorphous fluorinated copolymer containing one or more fluorinated ring monomers, with crosslinks formed between the fluorinated copolymer chains. This crosslinking improves the mechanical properties of the fluoropolymer, thereby enabling the use of polymer types that would otherwise be too brittle. The resulting crosslinked polymer membranes have superior selectivity and reliability performance compared to previous compositions known in the art. Methods for making and using the described articles are also provided.

[0010] Other methods, features, and advantages of the present disclosure will be or become apparent to one skilled in the art upon examination of the following drawings and detailed description. All such additional systems, methods, features, and advantages are intended to be included within this specification, be within the scope of this disclosure, and be protected by the accompanying claims. In addition, all optional and preferred features and modifications of the described embodiments can be used in all aspects of the disclosure taught herein. Furthermore, the individual features of the dependent claims, and all optional and preferred features and modifications of the described embodiments, are combinable and interchangeable with each other. DETAILED DESCRIPTION OF THE INVENTION

[0011] [Detailed explanation] Many modifications and other embodiments of the present disclosure will come to mind to one skilled in the art to which the disclosed compositions and methods pertain having the benefit of the teachings presented in the foregoing descriptions and the associated drawings, and it is to be understood, therefore, that it is not to be limited to the specific embodiments disclosed, and that modifications and other embodiments are intended to be included within the scope of the appended claims.

[0012] Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

[0013] As will be apparent to those skilled in the art upon reading this disclosure, each of the individual embodiments described and illustrated herein has individual components and features that can be readily separated from or combined with the features of some other embodiments without departing from the scope or spirit of the disclosure.

[0014] Any recited method can be carried out in the order of events recited or in any other order which is logically possible. That is, unless expressly stated, it is in no way intended that any method or aspect described herein be construed as requiring that its steps be performed in a particular order. Accordingly, unless a method claim expressly recites in the claim or description that the steps are limited to a particular order, no order inference is intended to be drawn in any respect. This applies to all possible non-expressive bases of interpretation, such as logical issues regarding the placement of steps or operational flow, the plain meaning derived from grammatical structure and punctuation, and the number and type of aspects described in the specification.

[0015] All publications mentioned herein are incorporated by reference to disclose and describe the methods and / or materials in connection with which the publications are cited. The publications mentioned herein are provided solely for their disclosure prior to the filing date of the present application. Nothing herein should be construed as an admission that the present invention is not entitled to antedate such publication by virtue of prior invention. Further, the dates of publication provided herein may be different from the actual publication dates, which may require independent confirmation.

[0016] Although aspects of the present disclosure may be described and claimed in particular statutory classes, such as systems statutory classes, this is for convenience and those skilled in the art will understand that each aspect of the present disclosure may be described and claimed in any statutory class.

[0017] It should also be understood that the terms used herein are only for describing specific aspects and are not intended to be limiting.Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the disclosed compositions and methods belong.It should be further understood that terms defined in commonly used dictionaries should be interpreted to have a meaning consistent with the meaning in the context of this specification and related art, and should not be interpreted in an idealized or overly formal sense unless expressly defined herein.

[0018] Prior to describing the various aspects of this disclosure, the following definitions are provided and should be used unless otherwise indicated. Additional terms may be defined elsewhere in this disclosure.

[0019] definition As used herein, the terms "comprise," "comprising," "includes," "has," "having," or other variations thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus consisting of a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed and inherent in the process, method, article, or apparatus.

[0020] As used herein, the terms "about," "approximately," "at or about," and "substantially" mean that the quantity or value in question may be an exact value or a value that provides an equivalent result or effect as recited in the claims or taught herein. That is, it is understood that amounts, sizes, formulations, parameters, and other quantities and characteristics are not, and need not be, exact, but may be approximated and / or made larger or smaller, as desired, to reflect tolerances, conversion factors, rounding, measurement errors, etc., and other factors known to those skilled in the art to provide equivalent results or effects. In some circumstances, a value that will provide an equivalent result or effect cannot be reasonably determined. In such cases, as used herein, "about" and "at or about" are generally understood to mean a ±10% variation from the stated nominal value, unless otherwise indicated or inferred. In general, a quantity, size, formulation, parameter, or other quantity or characteristic is "about," "approximately," or "at or about," whether or not expressly stated as such. When "about," "approximately," or "about" is used before a quantitative value, it is understood that the parameter also includes the specific quantitative value itself, unless otherwise specified.

[0021] As used herein, the terms "optional" or "optionally" mean that the subsequently described event or circumstance may or may not occur, and that the description includes instances in which the event or circumstance occurs and instances in which it does not occur.

[0022] As used herein and in the appended claims, the singular forms "a," "an," and "the" include plural references unless the context clearly dictates otherwise. Thus, for example, reference to a "fluorinated ring monomer," a "comonomer," or a "copolymer" includes, but is not limited to, mixtures or combinations of two or more such fluorinated ring monomers, comonomers, or copolymers.

[0023] As used herein, the term "gas" means a gas or vapor.

[0024] As used herein, the term "polymer" generally includes, but is not limited to, homopolymers, copolymers, such as block, graft, random and alternating copolymers, terpolymers, etc., as well as blends and modifications thereof. Furthermore, unless otherwise limited, the term "polymer" is intended to include all possible geometric configurations of the material. These configurations include, but are not limited to, isotactic and atactic symmetries.

[0025] As used herein, the term "highly fluorinated" means that at least 50% of the available hydrogens attached to the carbon are replaced with fluorine.

[0026] As used herein, the terms "fully fluorinated" and "perfluorinated" are used interchangeably and refer to compounds in which all of the available carbon-bonded hydrogens have been replaced with fluorine.

[0027] As used herein, the term "alkyl" refers to a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. An alkyl group can be cyclic or acyclic. An alkyl group can be branched or unbranched. An alkyl group can be substituted or unsubstituted. For example, an alkyl group can be substituted with one or more groups, including, but not limited to, alkyl, cycloalkyl, alkoxy, amino, ether, halide, hydroxy, nitro, silyl, sulfoxo, or thiol, as described herein. A "lower alkyl" group is an alkyl group containing 1 to 6 (e.g., 1 to 4) carbon atoms. The term alkyl group can be C1 alkyl, C1-C2 alkyl, C1-C3 alkyl, C1-C4 alkyl, C1-C5 alkyl, C1-C6 alkyl, C1-C7 alkyl, C1-C8 alkyl, C1-C9 alkyl, C1-C10 alkyl, etc., up to and including C1-C24 alkyl.

[0028] Throughout this specification, the term "alkyl" is used generally to refer to both unsubstituted and substituted alkyl groups; however, substituted alkyl groups are also specifically referred to herein by identifying the particular substituents on the alkyl group. For example, the term "halogenated alkyl" or "haloalkyl" specifically refers to an alkyl group substituted with one or more halides, such as fluorine, chlorine, bromine, or iodine. Alternatively, the term "monohaloalkyl" specifically refers to an alkyl group substituted with a single halide, such as fluorine, chlorine, bromine, or iodine. The term "polyhaloalkyl" specifically refers to an alkyl group independently substituted with two or more halides; i.e., each halide substituent need not be the same halide as another halide substituent, and multiple instances of halide substituents need not be on the same carbon. The term "alkoxyalkyl" specifically refers to an alkyl group substituted with one or more alkoxy groups, as defined below. The term "aminoalkyl" specifically refers to an alkyl group substituted with one or more amino groups. The term "hydroxyalkyl" specifically refers to an alkyl group substituted with one or more hydroxy groups. If "alkyl" is used in one instance and a specific term such as "hydroxyalkyl" is used in another instance, this is not meant to imply that the term "alkyl" does not refer to the specific term such as "hydroxyalkyl."

[0029] As used herein, the term "alkenyl" or "olefin" refers to a fluorocarbon group of 2 to 24 carbon atoms having a structural formula containing at least one carbon-carbon double bond. 1 A 2 )C=C(A 3 A 4Asymmetric structures such as alkene, olefin, and olefinic alkyl groups are intended to include both the E and Z isomers. This can be assumed in structural formulas herein where an asymmetric alkene or olefin is present, or can be explicitly indicated by the bond symbol C=C. In one aspect, an "alkenyl" or "olefinic" compound can contain two carbon-carbon double bonds (e.g., is a diene).

[0030] It should be noted that ratios, concentrations, amounts, and other numerical data can be expressed herein in a range format. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It will also be understood that there are a number of values ​​disclosed herein, and that each value is also herein disclosed as "about" that particular value in addition to the value itself. For example, if the value "10" is disclosed, then "about 10" is also disclosed. Ranges can be expressed herein as from "about" one particular value and / or to "about" another particular value. Similarly, when values ​​are expressed as approximations, the use of the antecedent "about" will be understood to provide an additional context for the particular value. For example, if the value "about 10" is disclosed, then "10" is also disclosed.

[0031] When a range is expressed, a further aspect includes from one particular value and / or to the other particular value. For example, when the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the disclosure; e.g., a phrase "from x to y" includes ranges from "x" to "y," as well as ranges from "x" to "y." Ranges can also be expressed as upper limits, e.g., "about x, y, z, or less," and should be interpreted to include the specific ranges of "about x," "about y," and "about z," as well as ranges of "less than x," "less than y," and "less than z." Similarly, the phrase "about x, y, z, or more" should be interpreted to include the specific ranges of "about x," "about y," and "about z," as well as the ranges "greater than x," "greater than y," and "greater than z." Furthermore, the phrase "about 'x' to 'y,' where "x" and "y" are numerical values, includes "about 'x' to about 'y'."

[0032] It will be understood that such range formats are used for convenience and brevity and should be interpreted flexibly, not only to the numerical values ​​explicitly stated as range limits, but also to all individual numerical values ​​or subranges encompassed within that range, as if each numerical value and subrange were explicitly stated. For example, a numerical range of "about 0.1% to 5%" should be interpreted to include not only the explicit value of about 0.1% to about 5%, but also individual values ​​within the stated range (e.g., about 1%, about 2%, about 3%, about 4%) and subranges (e.g., about 0.5 to about 1.1%, about 5 to about 2.4%, about 0.5 to about 3.2%, about 0.5 to about 4.4%, and other possible subranges).

[0033] All percentages herein are by volume unless otherwise specified. Unless otherwise specified, temperatures referred to herein are based on atmospheric pressure (i.e., 1 atmosphere).

[0034] Described herein are separation articles, e.g., films, membranes, and the like, that separate at least one component from a gaseous mixture containing two or more components. The disclosed articles include a "selective layer" that is selectively permeable to the desired component to be separated from the gas mixture. The selective layer is composed of an amorphous, crosslinked fluorinated copolymer. Optionally, the article may include other layers that serve various purposes, such as a porous support layer, a "gutter layer" that allows permeating gas to pass from the selective layer to the porous layer with minimal flow impedance, and a protective layer that protects the selective layer from fouling. Each component of the separation articles described herein, as well as methods for making and using them, are provided below.

[0035] Amorphous crosslinked fluorinated copolymer The discrete articles described herein include one or more amorphous crosslinked fluorinated copolymers. In one aspect, the amorphous crosslinked fluorinated copolymer includes a plurality of first copolymers and a plurality of crosslinker units covalently bonded to the first copolymers. In one aspect, the amorphous crosslinked fluorinated copolymer is produced by (a) copolymerizing one or more fluorinated ring monomers and a crosslinker in an amount of 0.2 mol% to 40 mol% to form a first copolymer, and (b) crosslinking the first copolymer to form an amorphous crosslinked fluorinated copolymer. The components of the crosslinked copolymer and a method of production are described below.

[0036] Fluorinated Ring Monomers In one aspect, the amorphous crosslinked fluorinated copolymer is made from one or more different fluorinated ring monomers. In one aspect, the fluorinated ring monomer comprises a 5-membered ring. In another aspect, the fluorinated ring monomer comprises a 6-membered ring. In yet another aspect, the fluorinated ring monomer comprises a 5-membered ring and a 6-membered ring, or comprises two 5-membered rings. Furthermore, in this aspect, when the fluorinated ring monomer comprises two rings, the rings can be fused to form a bicyclic structure. In another aspect, the fluorinated ring monomer can be perfluorinated.

[0037] In another aspect, the fluorinated ring monomer can have an olefin structure, where the monomer has one or more carbon-carbon double bonds. In another aspect, the fluorinated ring monomer can be prepared by cyclic polymerization of a linear monomer having an olefin at one end and a vinyl ether at the other end. In one aspect, representative fluorinated ring monomers include, but are not limited to, one or more of the olefinic compounds and combinations thereof shown in Scheme 1 and Scheme 2 below. Scheme 1: Fluorinated ring monomers containing a single ring [ka] During the ceremony: R1 and R2 are independently F, CF3, CF2CF3, CF2H, CF2CF2H, CFHCF3, CFHCF2H; R3 and R4 are independently F, CF3, or CF2CF3, CF2H, CF2CF2H, CFHCF3, CFHCF2H; R5, R6, R7 and R8 are independently F, CF3, or CF2CF3, CF2H, CF2CF2H, CFHCF3, CFHCF2H, and R6 and R7 can be contained in a 5- or 6-membered ring; and R9 is F, CF3, or CF2CF3. Scheme 2: Fluorinated ring monomers containing multiple rings [ka]

[0038] In another aspect, the fluorinated ring monomer can include one or more acyclic monomers that form a fluorinated ring upon polymerization. For example, the fourth structure depicted in Scheme 1 can cyclize upon polymerization to form a five-membered ring.

[0039] In one aspect, the fluorinated ring monomer can be a single compound in Scheme 1 or 2. In another aspect, the fluorinated ring monomer can be two or more different compounds in Scheme 1 or 2.

[0040] In another aspect, disclosed herein are amorphous copolymers prepared by polymerizing (a) one or more fluorinated ring monomers in an amount of about 1 mol% to about 99.5 mol%, where the fluorinated ring monomer is at least a five-membered ring, and (b) a comonomer in an amount of about 0.5 mol% to about 99 mol%. In one aspect, the amount of fluorinated ring monomer used to prepare the copolymers described herein is 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or about 99.5 mol%, or any combination of the foregoing values, or a range encompassing any of the foregoing values. In one aspect, the amount of fluorinated ring monomer used to prepare the copolymers described herein is about 80 mol% to about 99 mol%.

[0041] Crosslinking agent The crosslinking agent provided herein is a compound having functional groups that allow crosslinking between two or more different copolymers. In one aspect, the crosslinking agent is an olefin-based compound that, when copolymerized with a fluorinated ring monomer, produces an amorphous fluorinated copolymer. In one aspect, the amorphous fluorinated copolymer has multiple crosslinkable groups pendant on the copolymer backbone. In one aspect, the crosslinking agent comprises a perfluorinated olefin compound containing at least one crosslinkable group.

[0042] The nature of the crosslinkable group can vary depending on the crosslinking conditions. In one aspect, the crosslinkable group comprises a photoactive or thermally active group. In one aspect, the crosslinkable group comprises an alkyl ester group, a cyano group, or a fluorinated vinyl ether group.

[0043] In one aspect, the crosslinker comprises one or more compounds having structure I: [ka] In the formula, R F is a perfluoroalkyl group having 1 to 6 carbon atoms, optionally having 1 or 2 ether oxygen atoms, R9 is a linear or branched alkyl group having 1 to 6 carbon atoms.

[0044] In one aspect, R in structure I 9 is methyl or ethyl. In another aspect, R in structure I F (CF2) r where r is 1, 2, 3, or 4. In another aspect, R in Structure I F (CF2) s -O-(CF2) t where s and t are 1, 2, 3, or 4.

[0045] In one aspect, the crosslinker has the structure II: [ka] where RF is a perfluoroalkyl group having 1 to 6 carbon atoms, optionally containing 1 or 2 ether oxygen atoms. The compound includes one or more compounds having the formula:

[0046] In one aspect, R in Structure II F is (CF2) r where r is 1, 2, 3, or 4. In another aspect, R in Structure II F is (CF2) s -O-(CF2) t where s and t are 1, 2, 3, or 4.

[0047] In another aspect, the crosslinker has the structure III: [ka] wherein RF is a perfluoroalkyl group having 1 to 6 carbon atoms, optionally containing 1 or 2 ether oxygen atoms. and one or more compounds having:

[0048] In one aspect, R in Structure III F (CF2) r where r is 1, 2, 3, or 4. In another aspect, R in Structure III F is (CF2) s -O-(CF2) t where s and t are 1, 2, 3, or 4.

[0049] In one aspect, the crosslinker is: [ka] TIFF0007761942000007.tif67150 TIFF0007761942000008.tif24156 or any combination thereof.

[0050] The crosslinker can comprise one or more different compounds. In one aspect, the amount of crosslinker used to prepare the amorphous fluorinated copolymers described herein is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or about 20 mol%, or any combination of, or range including, any of the foregoing values. In one aspect, the amount of crosslinker used to prepare the copolymers described herein is from about 1 mol% to about 10 mol%, or from about 1 mol% to about 5 mol%.

[0051] Comonomers In one aspect, the fluorinated ring monomer and the crosslinker are copolymerized with a third monomer, wherein the third comonomer is different from the fluorinated ring monomer and the crosslinker. In one aspect, the third monomer is a fluorinated vinyl compound or a fluorinated vinyl ether compound. In another aspect, the comonomer is a fluorinated compound having two or more ether oxygens. In one aspect, the third comonomer may be perfluorinated. In one aspect, the third comonomer is an olefinic compound having two or more ether oxygens. In another aspect, the third comonomer is an olefinic compound having two or more perfluoroether groups (CF2-O-CF2-).

[0052] In one aspect, the third comonomer has the following structure: [ka] wherein n and m are independently 1, 2, or 3, and x is 1 or 2. The compound includes one or more compounds having the formula:

[0053] In a further aspect, the third comonomer can be a single compound or can be two or more different compounds having the above structure.

[0054] In another aspect, exemplary third comonomers useful herein include, but are not limited to, those shown in Scheme 3 below, and any combination thereof. Scheme 3: Monomers containing multiple ether oxygens [ka]

[0055] In one aspect, the amount of third comonomer used to prepare the copolymers described herein can be about 0.5, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or about 99.5 mol%, or any combination or range encompassing any of the foregoing values. In a further aspect, the amount of comonomer is from about 1 mol% to about 20 mol%.

[0056] Polymerization method In one aspect, the amorphous fluorinated copolymers described herein can be produced by solution polymerization or aqueous emulsion polymerization. In another aspect, when using a solution method, a suitable solvent can be a poly- or perfluorocompound such as perfluorooctane, hexafluoroisopropanol (HFIP), 1,1,1,3,3,3-hexafluoro-2-methoxypropane (HFMOP), Vertrel® XF (CF3CFHCF2CF3), or Fluorinert® FC-43 (perfluorotributylamine). In another aspect, when using an aqueous emulsion method, a suitable surfactant will be used. In one aspect, the disclosed polymers can optionally be polymerized in the absence of any solvent. In a further aspect, the initiator can be selected from those commonly used in fluoropolymers, such as inorganic types such as hydrocarbon peroxides, fluorocarbon peroxides, hydrocarbon peroxides, and persulfates.

[0057] In one aspect, depending on the relative reactivity of the monomers used in the polymerization, they may be added as a single precharge or may need to be co-charged as a mixture in higher ratios to produce the desired copolymer composition.

[0058] In another aspect, once polymerization is determined to be complete, the polymer can be isolated using methods known in the art. In one aspect, for solution processes, the solvent (and any unreacted monomer(s)) can be removed by distillation at atmospheric or reduced pressure. In some aspects, due to the typical high viscosity and amorphous nature of the polymers of the present disclosure, further rigorous drying may be required to remove residual solvent. In a further aspect, this may involve heating to between 200 and 300°C at atmospheric or reduced pressure for 2 to 48 hours. In another aspect, for aqueous emulsion processes, the emulsion can be broken by several methods, including freeze / thaw, addition of a strong mineral acid such as nitric acid, high shear mixing, or a combination of these methods.

[0059] The examples provide non-limiting procedures for making the copolymers described herein.

[0060] Structural features of amorphous fluorinated copolymers The amorphous fluorinated copolymers described herein include a first copolymer comprising a plurality of fluorinated ring units in an amount of 1 mol% to 99.5 mol%, where the fluorinated ring units are at least five-membered rings and comprise a plurality of crosslinker units. In one aspect, the fluorinated ring units can be present in an amount of about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or about 99.5 mol%, or any combination or range including any of the foregoing values. In one aspect, the fluorinated ring units are present in an amount of about 80 mol% to about 99 mol%. In another aspect, the crosslinker units can be present in an amount of about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or about 20 mol%, or any combination of, or range including, any of the foregoing values. In one aspect, the amount of crosslinker used to prepare the copolymers described herein is from about 1 mol% to about 10 mol%, or from about 1 mol% to about 5 mol%.

[0061] In some aspects, the fluorinated ring unit can be perfluorinated. In other aspects, the fluorinated ring unit can include a 5-membered ring or a 6-membered ring. In some aspects, the fluorinated ring unit can include one or more of the following structures: [ka] During the ceremony: R1 and R2 are independently F, CF3, CF2CF3, CF2H, CF2CF2H, CFHCF3, CFHCF2H; R3 and R4 are independently F, CF 3、 CF2CF3, CF2H, CF2CF2H, CFHCF3 or CFHCF2H; R5, R6, R7 and R8 are independently F, CF3, or CF2CF3, CF2H, CF2CF2H, CFHCF3 or CFHCF2H; R6 and R7 can be contained within a 5-membered or 6-membered ring; and R9 is F, CF3 or CF2CF3.

[0062] In another aspect, the fluorinated ring unit can be a single structural unit. In another aspect, the fluorinated ring unit can be two or more different structural units. In one aspect, the fluorinated ring unit is one of the following: [ka] Or it can be any combination thereof.

[0063] In one aspect, the amorphous fluorinated copolymer has a plurality of crosslinker units having crosslinkable groups pendant to the copolymer backbone. In one aspect, the crosslinker comprises a perfluorinated olefin compound containing at least one crosslinkable group. In one aspect, the crosslinker unit has Structure IV, V, or VI, where R F and R9 is as defined above for Structures I, II and III: [ka]

[0064] In another aspect, when a third comonomer is used to prepare the amorphous fluorinated copolymer, a third comonomer unit can be present. In one aspect, the third comonomer unit can be perfluorinated. In one aspect, the third comonomer unit has the following structure: [ka] wherein n and m are independently 1, 2, or 3, and x is 1 or 2. The device includes one or more units having the following structure:

[0065] In one aspect, the third comonomer unit can be a single structural unit. In another aspect, the third comonomer unit can be two or more different structural units. In another aspect, the third comonomer unit can be one of the following: [ka] Or it can be any combination of these.

[0066] Properties and Composition of Amorphous Fluorinated Copolymers In one aspect, the composition of the amorphous fluorinated copolymers used herein is typically: 19 The end group concentration can be determined by F NMR spectroscopy. In a further aspect, the polymer is readily soluble in perfluorobenzene and can provide a locking signal using a deuterated benzene (CD) intercalation probe. In a further aspect, the glass transition temperature (Tg) can be determined using differential scanning calorimetry (DSC). The molecular weight distribution can be determined using gel permeation chromatography (GPC) using a styrene-divinylbenzene column in a perfluorosolvent coupled with a multi-detector analysis module including refractive index, low-angle light scattering, and right-angle light scattering detectors, or other suitable equipment and / or methods known in the art. Optionally, in one aspect, the type and concentration of end groups can also be determined by pressing a film of the polymer and acquiring an infrared (IR) spectrum in transmission mode.

[0067] In one aspect, the amorphous fluorinated copolymer can have a glass transition temperature of from about 0° C. to about 300° C., or about 25° C., 50° C., 75° C., 100° C., 125° C., 150° C., 175° C., 200° C., 225° C., 250° C., 275° C., or 300° C., or any combination of, or ranges including, any of the foregoing values.

[0068] In yet another aspect, the amorphous fluorinated copolymer has a number average molecular weight (Mn) of about 10 kDa to about 2,000 kDa, or a range of 10 kDa, 50 kDa, 100 kDa, 150 kDa, 200 kDa, 250 kDa, 300 kDa, 350 kDa, 400 kDa, 450 kDa, 500 kDa, 550 kDa, 600 kDa, 650 kDa, 700 kDa, 750 kDa, 800 kDa, 850 kDa, 900 kDa, 950 kDa, 1000 kDa, 1050 kDa, 1100 kDa, 1150 kDa, 1200 kDa, 1250 kDa, 13 ...0 kDa, 500 kDa, Da, 1350 kDa, 1400 kDa, 1450 kDa, 1500 kDa, 1550 kDa, 1600 kDa, 1650 kDa, 1700 kDa, 1.550 kDa, 1.0 kDa, 1.5 kDa, 1.5 kDa, 1.6 kDa, 1.6 kDa, 1.5 kDa, 1.5 kDa, 1.0 kDa, 1.2 kDa, 1,750 kDa, 1800 kDa, 1850 kDa, 1900 kDa, 1950 kDa, or 2000 kDa, or any combination of the foregoing values, or a range encompassing any of the foregoing values.

[0069] In yet another aspect, the amorphous fluorinated copolymer has a weight average molecular weight (Mw) of about 10,000 g / mol to about 3,000,000 g / mol, or 10,000 g / mol, 50,000 g / mol, 10,000 g / mol, 50,000 g / mol, 200,000 g / mol, 300,000 g / mol, 400,000 g / mol, or 500,000 g / mol. 00g / mol, 500,000g / mol, 600,000g / mol, 700,000g / mol, 800,000g / mol, 900,000g / mol, 1, 000,000g / mol, 1,100,000g / mol, 1,200,000g / mol, 1,300,000g / mol, 400,000g / mol, 1,400 ,000 g / mol, 1,500,000 g / mol, 1,600,000 g / mol, 1,700,000 g / mol, 1,800,000 g / mol, 1,900,000 g / mol, 2,000,000 g / mol, 2,100,000 g / mol, 2,200,000 g / mol, 2,300,000 g / mol, 2,400,000 g / mol, 2,500,000 g / mol, 2,600,000 g / mol, 2,700,000 g / mol, 2,800,000 g / mol, 2,900,000 g / mol, or 3,000,000 g / mol or any combination of, or ranges encompassing, any of the foregoing values.

[0070] Preparation of amorphous crosslinked fluorinated copolymers The amorphous fluorinated copolymers described herein can be crosslinked to produce amorphous crosslinked fluorinated copolymers. In one aspect, the amorphous fluorinated copolymer can be formed into a shaped component, which can then be exposed to crosslinking conditions to produce a crosslinked copolymer. The component can be formed using any of a number of techniques, including, but not limited to, casting, extrusion, molding, and shaping. In another aspect, the component can be in the form of a sheet, film, or membrane, or other useful shape.

[0071] The appropriate crosslinking technique or conditions may be determined, at least in part, based on the crosslinking monomer selected and the desired results. In one aspect, the amorphous fluorinated copolymer is heated for a sufficient time and temperature to crosslink the copolymer. In one aspect, the amorphous fluorinated copolymer is crosslinked by heating the copolymer at a temperature greater than 300°C. In another aspect, the amorphous fluorinated copolymer is crosslinked by heating the copolymer at a temperature between about 300°C and about 350°C, or at about 300°C, 305°C, 310°C, 315°C, 320°C, 325°C, 330°C, 335°C, 340°C, 345°C, or 350°C, although any value can be the lower or upper end of the range (e.g., 310°C to 330°C). In another aspect, the amorphous fluorinated copolymer is heated for 0.5 minutes to 60 minutes, or from 0.5 minutes, 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes, or 60 minutes, where any value can be the lower or upper end of a range (e.g., 10 minutes to 30 minutes).

[0072] In another aspect, the amorphous fluorinated copolymer is crosslinked by exposing the copolymer to UV radiation. In one aspect, the amorphous fluorinated copolymer is exposed to UV radiation at a wavelength of less than 300 nm to crosslink the amorphous fluorinated copolymer. In another aspect, the amorphous fluorinated copolymer is exposed to UV radiation at a wavelength of about 250 nm to about 300 nm, or about 250 nm, 255 nm, 260 nm, 265 nm, 270 nm, 275 nm, 280 nm, 285 nm, 290 nm, or 300 nm, any value being the lower and upper end of the range (e.g., 260 nm to 290 nm). In another aspect, the amorphous fluorinated copolymer is exposed to UV radiation for 0.5 hours to 48 hours, or 0.5 hours, 1 hour, 3 hours, 6 hours, 12 hours, 18 hours, 24 hours, 30 hours, 36 hours, or 48 hours, any value can be at the low and high ends of a range (e.g., 3 hours to 24 hours).

[0073] In some aspects, the amorphous crosslinked fluorinated copolymer material has different thermal, mechanical, and / or solubility properties than the uncrosslinked copolymer. In some aspects, the crosslinked copolymer has improved crack resistance compared to a similar uncrosslinked copolymer. In some aspects, the crosslinked copolymer material has a notched tensile strength greater than that of the uncrosslinked amorphous copolymer. In some aspects, the crosslinked polymeric material has a notched tensile strength at least two times greater than that of the uncrosslinked amorphous copolymer.

[0074] Separation items and their application Disclosed herein are discrete articles comprising or made from the amorphous crosslinked fluorinated copolymers described herein. In one aspect, the article can be a multilayer structure article, and at least one layer of the structure comprises or is made from the crosslinked copolymers described herein. In another aspect, the article can be a film, membrane, tube, or fiber.

[0075] In yet another aspect, an article can include a layer or coating of an amorphous crosslinked fluorinated copolymer. In one aspect, the layer or coating has a thickness of 1 μm or less, or a thickness of about 950, 900, 850, 800, 750, 700, 650, 600, 550, or about 500 nm or less, or any combination of, or ranges including, any of the foregoing values. In another aspect, the layer or coating has a thickness of about 50 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm, 500 nm, 550 nm, 600 nm, 650 nm, 700 nm, 750 nm, 800 nm, 850 nm, 900 nm, 950 nm, or 1 μm, or any combination of, or ranges including, any of the foregoing values.

[0076] In a further aspect, the amorphous crosslinked fluorinated copolymer may be formed or molded into any shape necessary or desired for use as a separation article. Numerous methods are known for forming the copolymer selected for the selective layer into a single-layer or multilayer film or membrane. In some aspects, the selective layer may comprise an unsupported film, tube, or fiber of the amorphous crosslinked fluorinated copolymer as a single-layer membrane. In some aspects, the unsupported film may be too thick to permit the desired gas flow through the membrane. Thus, in some aspects, the membrane may comprise a very thin selective layer of the amorphous crosslinked fluorinated copolymer disposed on (i.e., adjacent to or in contact with) a much more permeable support structure. For example, in one aspect, the membrane may comprise an integral asymmetric membrane in which a denser selective layer is disposed on a microporous support layer. Such membranes were originally developed by Loeb and Sourirajan, and their preparation in flat plate or hollow fiber form is described, for example, in U.S. Pat. No. 3,133,132 to Loeb and U.S. Pat. No. 3,133,132 to Henis and Tripodi, the disclosures of which are incorporated herein by reference.

[0077] In some aspects, a membrane may include multiple layers, including at least one selective layer, with each layer serving a distinct purpose. Furthermore, in this aspect, a microporous support layer may be present in such a multilayer composite membrane to provide mechanical strength. In another aspect, a multilayer membrane may include, for example, a nonporous but highly permeable "gutter" layer coated on a microporous support layer. Furthermore, in this aspect, this gutter layer may generally not be selective; instead, it may form a smooth surface for depositing an extremely thin selective layer that performs the membrane's primary selective function. In another aspect, the gutter layer may also channel permeating gases to the pores of the support layer. In a further aspect, the selective layer may be covered by a protective layer. In one aspect, the primary purpose of the protective layer is to prevent fouling of the selective layer by, for example, specific components of the gas stream. In some aspects, the disclosed multilayer structures may be formed by solution casting, but this is not required. General preparation techniques for making composite membranes of this type are described, for example, in U.S. Patent No. 4,243,701 to Riley et al., the disclosure of which is incorporated herein by reference. In one aspect, disclosed herein is a gas separation membrane comprising a feed side and a permeate side, the separation membrane having a selective layer comprising or composed of a copolymer described herein.

[0078] In one aspect, the multilayer composite membrane may take the form of a flat sheet, a tube, or a hollow fiber. In the hollow fiber form, in one aspect, the multilayer composite membrane may be prepared by the coating procedures taught in, for example, U.S. Patent Nos. 4,863,761; 5,242,636; and 5,242,636, or by using a double capillary spinneret of the type described in U.S. Patent Nos. 5,141,642 and 5,318,417, the disclosures of which are incorporated herein by reference.

[0079] In another aspect, the thickness of the selective layer of the membrane may be determined based on one or more parameters of the separation process. In some aspects, the thickness of the selective layer of the membrane is less than about 1 μm. In preferred embodiments, the selective layer can be even thinner, for example, the selective layer can be as thin as 0.5 μm or less. In one aspect, the selective layer is such that the membrane has a pore size (GPU) of at least 100 GPU (1 GPU = 1×10) when measured with pure hydrogen gas at 25° C. -6 cm 3 (STP) / cm 2 s cmHg), preferably at least 400 GPU.

[0080] In one aspect, the separation articles described herein are mechanically robust and exhibit high thermal stability and high chemical resistance. In another aspect, the copolymers described herein that form the selective layer are typically soluble only in perfluorinated solvents, and after crosslinking, are typically insoluble even in perfluorinated solvents. In yet another aspect, they are also typically stable for many years when immersed in acids, alkalis, oils, low molecular weight esters, ethers and ketones, aliphatic and aromatic hydrocarbons, and oxidizing agents. In yet another aspect, they are thermally stable for many years at temperatures below their glass transition temperature. Therefore, in both of these aspects, they are suitable for use in natural gas streams and many other harsh environments.

[0081] In one aspect, the separation article may be used in any suitable device. For example, membranes are typically used in the form of modules, including membranes prepared in any known manner and housed in any convenient type of housing and separation unit. Any number of membrane modules may be combined (e.g., in series or parallel) to process a gas stream. The number of membrane modules may be determined based on one or more factors, including, for example, the required or desired flow rate, the composition of the stream, and other operating parameters of the separation process. In a separation process, in one aspect, the membrane is exposed to a flowing gas feed composition comprising a gas mixture. In another aspect, this gas flow is created by a pressure differential established across the membrane, either by pressurizing the feed / return side of the membrane or by applying a vacuum to the permeate side of the membrane. Separation of the components of the gas stream, in one aspect, occurs through the membrane, producing a gas stream on the permeate side of the membrane that is enriched in the more permeable component of the gas mixture. Conversely, in another aspect, the gas stream exiting the module on the feed / rest side of the membrane has a composition that is depleted in the more permeable component of the gas mixture and therefore enriched in the less permeable component(s) of the gas mixture.

[0082] In one aspect, the present disclosure relates to an apparatus and process for separating at least one component from a gas mixture. In another aspect, the disclosed apparatus includes a separation article (e.g., a membrane) described herein that includes a "selective layer" configured to be selectively permeable to the desired component to be separated from the gas mixture. Optionally, in some aspects, the membrane may include one or more other layers that serve various purposes, such as a porous support layer, a "gutter layer" that allows permeating gas to pass from the selective layer to the porous layer with minimal flow impedance, and a protective layer that protects the selective layer from fouling.

[0083] The separation articles described herein are useful in the field of gas separation. In one aspect, disclosed herein is a method for separating a first gas component from a gas mixture, the process comprising passing the gas mixture across a separation article described herein. In one aspect, the separation article is a membrane having a selective layer composed of an amorphous crosslinked fluorinated copolymer described herein. In some aspects, the amorphous crosslinked fluorinated copolymer can be cast onto the membrane from a solution to produce a selective layer. In one aspect, the amorphous crosslinked fluorinated copolymer is soluble in one or more solvents. Conversely, crystalline fluoropolymers, which typically have negligible solubility in solvents, are not preferred. In another aspect, crystalline polymers typically exhibit lower gas permeability compared to amorphous polymers.

[0084] In some aspects, a process for separating a first component comprising a gas mixture includes introducing a feed stream comprising the gas mixture into the disclosed membrane. Further in these aspects, the membrane has a first side, a second side, and a selective layer that is selectively permeable to the first component, i.e., the first component has a higher permeability through the selective layer than other components of the gas mixture. In one aspect, the feed stream is introduced to the first side of the membrane. Further in this aspect, a driving force (e.g., a pressure differential) causes at least a portion of the gas mixture to permeate the membrane from the first side to the second side, providing a permeate stream on the second side of the membrane. In a further aspect, the resulting permeate stream is enriched in the first component. In another aspect, a residue or residual stream depleted in the first component may be removed from the first side of the membrane.

[0085] In one aspect, in the gas separation method disclosed herein, the method includes at least the following steps: (a) passing a gas mixture through a separation article having a feed side and a permeate side, the separation article having a selective layer that is selectively permeable to at least a first gas component, the selective layer comprising an amorphous crosslinked fluorinated copolymer; and (b) providing a driving force sufficient to cause at least a portion of the gas mixture to permeate through the separation membrane from the feed side to the permeate side, thereby producing a gas permeate stream on the permeate side of the separation membrane and a remaining stream of gas on the feed side of the separation membrane, wherein the gas permeate stream comprises the first gas component.

[0086] In another aspect, the permeate stream has a concentration of the first component that is greater than the concentration of the first component in the remainder of the stream.

[0087] In yet another aspect, the method further includes withdrawing a permeate stream from the permeate side of the separation article. In a further aspect, the method also includes withdrawing a remaining stream from the feed side of the separation membrane.

[0088] In one aspect, the first gas component is carbon dioxide, hydrogen sulfide, helium, or any combination thereof. In one aspect, the gas mixture includes methane and carbon dioxide.

[0089] In another aspect, the gas mixture comprises one or more fluorinated refrigerant gases. In another aspect, the gas mixture comprises an azeotropic or near-azeotropic mixture of gases, one or more components of which are fluorinated refrigerants.

[0090] In another aspect, about 50, 55, 60, 65, 70, 76, 80, 86, 90, or about 95% or more of the first gas component in the gas mixture, or any combination of the foregoing values, or a range including any of the foregoing values, permeates the separation membrane.

[0091] In one aspect, the separation articles described herein will be useful in many applications, particularly those related to the separation of CO from other gases. In one aspect, the disclosed amorphous crosslinked fluorinated copolymers containing fluorinated comonomers containing multiple ether oxygens exhibit further enhancement of the solubility of CO in amorphous fluoropolymers, thus improving the selectivity of these materials for the specific separation of CO gas.

[0092] In one aspect, the separation articles described herein are useful for separating acid gases, including carbon dioxide and hydrogen sulfide, from natural gas streams that may be found either at wells or processing plants. In another aspect, because such natural gas streams often contain high molecular weight hydrocarbon vapors that can foul or plasticize hydrocarbon membranes, the perfluorinated nature of the selective layers in the present disclosure is particularly well-suited for such applications because they are highly resistant to such degradation.

[0093] In addition to undesirable acid gases, in one aspect, natural gas streams sometimes contain helium, which is desirable as a separation product. In a further aspect, the disclosed process is useful for separating helium from natural gas streams so that the resulting helium-rich gas can be further purified to purified helium.

[0094] In one aspect, the process of the present disclosure is useful for separating mixtures of fluorinated refrigerant gases, including azeotropic or near-azeotropic mixtures of such gases.

[0095] aspect Aspect 1. A discrete article comprising a first surface and a second surface, and a layer comprising an amorphous crosslinked fluorinated copolymer adjacent to at least one of the first surface or the second surface.

[0096] Aspect 2. The discrete article of Aspect 1, wherein the amorphous crosslinked fluorinated copolymer is produced by (a) copolymerizing one or more fluorinated ring monomers, wherein the fluorinated ring monomers are at least five-membered rings, in an amount of 1 mol % to 99.5 mol % with a crosslinker in an amount of 0.2 mol % to 40 mol % to form a first copolymer; and (b) crosslinking the first copolymer to form the amorphous crosslinked fluoropolymer.

[0097] Aspect 3. The separation article of Aspect 2, wherein the fluorinated ring monomer is perfluorinated.

[0098] Aspect 4. The separation article of Aspect 2, wherein the fluorinated ring monomer is an olefinic compound.

[0099] Aspect 5. The isolated article of aspect 2, wherein the fluorinated ring monomer comprises a five- or six-membered ring.

[0100] Aspect 6. The discrete article of aspect 2, wherein the fluorinated ring monomer is produced by cyclopolymerization of a linear monomer having an olefin at one end of the monomer and a vinyl ether at the other end of the monomer.

[0101] Aspect 7. The isolated article of aspect 2, wherein the fluorinated ring monomer comprises one or more of the following compounds: [ka] During the ceremony, R1 and R2 are independently F, CF3, CF2CF3, CF2H, CF2CF2H, CFHCF3, or CFHCF2H; R3 and R4 are independently F, CF3, or CF2CF3, CF2H, CF2CF2H, CFHCF3 or CFHCF2H; R5, R6, R7, and R8 are independently F, CF3, or CF2CF3, CF2H, CF2CF2H, CFHCF3, or CFHCF2H, and R6 and R7 can be contained in a 5- or 6-membered ring; and R9 is F, CF3 or CF2CF3.

[0102] Aspect 8. The discrete article of any one of Aspects 2-7, wherein the fluorinated ring monomer is a single compound.

[0103] Aspect 9. The discrete article of any one of Aspects 2-7, wherein the fluorinated ring monomers are two or more different compounds.

[0104] Aspect 10. The fluorinated ring monomer is [ka] 3. The discrete article of aspect 2, wherein the discrete article is a sintered article, ... or a combination thereof.

[0105] Aspect 11. The separation article of any one of Aspects 2-10, wherein the fluorinated ring monomer is present in an amount of 80 mol % to 99 mol %.

[0106] Aspect 12. The separation article of any one of aspects 2-11, wherein the cross-linking agent comprises a perfluorinated olefin compound comprising at least one cross-linkable group.

[0107] Aspect 13. The discrete article of aspect 12, wherein the crosslinkable groups comprise photoactive or thermally active groups.

[0108] Aspect 14. The separation article of aspect 12, wherein the crosslinkable groups comprise alkyl ester groups, cyano groups, or fluorinated vinyl ether groups.

[0109] Aspect 15. The crosslinker has the structure I: [ka] In the formula, R F is a perfluoroalkyl group having 1 to 6 carbon atoms, optionally containing 1 or 2 ether oxygen atoms, and R 9 is a linear or branched alkyl group having 1 to 6 carbon atoms 12. The isolated article of any one of aspects 2-11, comprising one or more compounds having the formula:

[0110] Aspect 16. The crosslinker has the structure II: [ka] In the formula, R F is a perfluoroalkyl group having 1 to 6 carbon atoms, which may optionally have 1 or 2 ether oxygen atoms 12. The isolated article of any one of aspects 2-11, comprising one or more compounds having the formula:

[0111] Aspect 17. The crosslinker has the structure III: [ka] In the formula, R F is a perfluoroalkyl group having 1 to 6 carbon atoms, which may optionally have 1 or 2 ether oxygen atoms 12. The isolated article of any one of aspects 2-11, comprising one or more compounds having the formula:

[0112] Aspect 18. The discrete article of any one of Aspects 2-11, wherein the cross-linking agent is a single compound.

[0113] Aspect 19. The discrete article of any one of Aspects 2-11, wherein the cross-linking agent is two or more different compounds.

[0114] Aspect 20. Crosslinking agent [ka] TIFF0007761942000022.tif67150 TIFF0007761942000023.tif24156 12. The discrete article of any one of aspects 2 to 11, wherein the discrete article is a condensed or uncondensed article.

[0115] Aspect 21. The separation article of any one of Aspects 2-20, wherein the cross-linking agent is present in an amount of 0.2 mol % to 20 mol %.

[0116] Aspect 22. The fluorinated ring monomer is one or more of the following compounds: [ka] During the ceremony, R1 and R2 are independently F, CF3, CF2CF3, CF2H, CF2CF2H, CFHCF3, CFHCF2H; R3 and R4 are independently F, CF3, or CF2CF3, CF2H, CF2CF2H, CFHCF3, CFHCF2H; R5, R6, R7 and R8 are independently F, CF3, or CF2CF3, CF2H, CF2CF2H, CFHCF3, CFHCF2H; and R6 and R7 can be contained within a five-membered or six-membered ring; and R9 is F, CF3 or CF2CF3; and The crosslinker has the following structure: [ka] TIFF0007761942000026.tif2563 TIFF0007761942000027.tif3087In formula, R F is a perfluoroalkyl group optionally having one or two ether oxygen atoms, and R 9 is a linear or branched alkyl group having 1 to 6 carbon atoms 22. The isolated article of any one of aspects 2-21, comprising one or more compounds having the formula:

[0117] Aspect 23. The discrete article of any one of aspects 2-22, wherein the fluorinated ring monomer and crosslinker are copolymerized with a third monomer comprising a fluorinated vinyl compound or a fluorinated vinyl ether compound.

[0118] Aspect 24. The third monomer has the structure: [ka] wherein n and m are independently 1, 2, or 3, and x is 1 or 2. 24. The separation article of aspect 23, having

[0119] Aspect 25. The third monomer is [ka] 24. The discrete article of aspect 23, wherein

[0120] Aspect 26. The separation article of any one of Aspects 2-25, wherein the first copolymer is produced by solution polymerization or aqueous emulsion polymerization.

[0121] Aspect 27. The separation article of any one of Aspects 2-26, wherein the copolymerization is carried out in the presence of an initiator.

[0122] Aspect 28. The separation article of aspect 27, wherein the initiator comprises a hydrocarbon peroxide, a fluorocarbon peroxide, a hydrocarbon peroxydicarbonate, an inorganic fluorocarbon initiator, or any combination thereof.

[0123] Aspect 29. The discrete article of any one of Aspects 2-28, wherein the first copolymer is crosslinked by exposure to UV radiation at a wavelength of less than 300 nm.

[0124] Aspect 30. The discrete article of any one of Aspects 2-28, wherein the first copolymer is crosslinked by exposing it to UV radiation at a wavelength of less than 300 nm for about 0.5 hours to about 48 hours.

[0125] Aspect 31. The discrete article of any one of Aspects 2-28, wherein the first copolymer is crosslinked by exposing it to UV radiation at a wavelength of about 250 nm to about 300 nm for about 0.5 hours to about 48 hours.

[0126] Aspect 32. The discrete article of any one of Aspects 2 to 28, wherein the first copolymer is crosslinked by heating at a temperature of about 300° C. to about 350° C. for 0.5 minutes to 60 minutes.

[0127] Aspect 33. The separated article of Aspect 1, wherein the amorphous crosslinked fluorinated copolymer comprises a plurality of first copolymers and a plurality of crosslinker units covalently bonded to the first copolymers, the first copolymers comprising a plurality of fluorinated ring units in an amount of 1 mol % to 99.5 mol %, and the fluorinated ring units are at least five-membered rings.

[0128] Aspect 34. The separation article of Aspect 33, wherein the fluorinated cyclic unit is perfluorinated.

[0129] Aspect 35. The isolated article of aspect 33, wherein the fluorinated ring unit comprises a five-membered or six-membered ring.

[0130] Aspect 36. The fluorinated ring unit has the following structure: [ka] During the ceremony, R1 and R2 are independently F, CF3, CF2CF3, CF2H, CF2CF2H, CFHCF3, or CFHCF2H; R3 and R4 are independently F, CF3, or CF2CF3, CF2H, CF2CF2H, CFHCF3 or CFHCF2H; R5, R6, R7, and R8 are independently F, CF3, or CF2CF3, CF2H, CF2CF2H, CFHCF3, or CFHCF2H, and R6 and R7 can be contained within a 5- or 6-membered ring; and R9 is F, CF3 or CF2CF 3. is 34. The separation article of aspect 33, comprising one or more of:

[0131] Aspect 37. The discrete article of aspect 36, wherein the fluorinated ring unit is a single structural unit.

[0132] Aspect 38. The isolated article of aspect 36, wherein the fluorinated ring units are two or more different structural units.

[0133] Aspect 39. The fluorinated cyclic unit is [ka] or a combination thereof.

[0134] Aspect 40. The separation article of any one of Aspects 33-39, wherein the fluorinated ring units are in an amount of 80 mol % to 99 mol %.

[0135] Aspect 41. The discrete article of any one of Aspects 33-40, wherein the first copolymer further comprises a perfluorinated comonomer unit that is not a fluorinated ring unit or a crosslinker unit.

[0136] Aspect 42. The comonomer unit has the following structure: [ka] wherein n and m are independently 1, 2, or 3, and x is 1 or 2. 42. The discrete article of aspect 41, comprising one or more units having:

[0137] Aspect 43. The discrete article of Aspect 41, wherein the comonomer unit is a single structural unit.

[0138] Aspect 44. The discrete article of aspect 41, wherein the comonomer units are two or more different structural units.

[0139] Aspect 45. The comonomer unit is: [ka] or any combination thereof.

[0140] Aspect 46. The isolated article of Aspect 41, wherein the comonomer units are present in an amount of 1 mol % to 20 mol %.

[0141] Aspect 47. The separation article of any one of Aspects 1-46, wherein the first copolymer has a glass transition temperature of from 0°C to 300°C.

[0142] Aspect 48. The separated article of any one of Aspects 1 to 46, wherein the first copolymer has an Mn between 10 kDa and 2,000 kDa.

[0143] Aspect 49. The separation article of any one of Aspects 1-46, wherein the first copolymer has a Mw of 10,000 g / mol to 3,000,000 g / mol.

[0144] Aspect 50. The discrete article of any one of Aspects 1-46, wherein the discrete article comprises a multilayer structure article, and at least one layer of the structure comprises the copolymer.

[0145] Aspect 51. The separation article of any one of Aspects 1-46, wherein the article comprises a film, membrane, tube, or fiber.

[0146] Aspect 52. The separation article of any one of Aspects 1-46, wherein the separation article comprises a layer of an amorphous crosslinked fluorinated copolymer, the layer having a thickness of 1 μm or less.

[0147] Aspect 53. A method of separating a first gas component from a gas mixture, the process comprising passing the gas mixture through a separation article of any one of Aspects 1-46.

[0148] Aspect 54. The method of Aspect 53, comprising: (a) passing a gaseous mixture across a separation article having a feed side and a permeate side, the separation article having a selective layer that is selectively permeable to at least a first gas component, the selective layer comprising an amorphous crosslinked fluorinated copolymer; (b) providing a driving force sufficient to provide permeation of at least a portion of the gas mixture from the feed side to the permeate side of the separation article, resulting in a gas permeate stream on the permeate side of the separation article and a gas retentate stream on the feed side of the separation article, wherein the gas permeate stream comprises a first gas component.

[0149] Aspect 55. The method of Aspect 54, wherein the permeate stream has a concentration of the first component that is greater than the concentration of the first component in the retentate stream.

[0150] Aspect 56. The method of Aspect 54 or 55, further comprising withdrawing a permeate stream from the permeate side of the separation article.

[0151] Aspect 57. The method of any one of Aspects 54-56, further comprising withdrawing a retentate stream from the supply side of the separated article.

[0152] Aspect 58. The method of any one of Aspects 54-57, wherein the first gas component is carbon dioxide, hydrogen sulfide, helium, or any combination thereof.

[0153] Aspect 59. The method of any one of Aspects 54-57, wherein the gas mixture comprises methane and carbon dioxide.

[0154] Aspect 60. The method of any one of Aspects 54-59, wherein about 50% or more of the first gas component in the gas mixture permeates the separation article.

[0155] Aspect 61. An amorphous crosslinked fluorinated copolymer, prepared by a process comprising: a) copolymerizing one or more fluorinated ring monomers in an amount of 1 mol % to 99.5 mol % and a crosslinker in an amount of 0.2 mol % to 40 mol % to produce a first copolymer; and (b) crosslinking the first copolymer to produce the amorphous crosslinked fluoropolymer.

[0156] Aspect 62. Fluorinated ring monomers [ka] wherein R5, R6, R7, and R8 are independently F, CF3, or CF2CF3, CF2H, CF2CF2H, CFHCF3, or CFHCF2H, and R6 and R7 can be contained in a 5-membered or 6-membered ring. 62. The copolymer of aspect 61, wherein

[0157] Aspect 63. The copolymer of aspect 62, wherein the crosslinking agent comprises a perfluorinated olefin compound comprising at least one crosslinkable group.

[0158] Aspect 64. The copolymer of Aspect 63, wherein the crosslinkable groups comprise photoactive or thermally active groups.

[0159] Aspect 65. The copolymer of aspect 63, wherein the crosslinkable group comprises an alkyl ester group, a cyano group, or a fluorinated vinyl ether group.

[0160] Aspect 66. The crosslinker has the structure I: [ka] During the ceremony, R F is a perfluoroalkyl having 1 to 6 carbon atoms, optionally having 1 or 2 ether oxygen atoms, and R 9 is a linear or branched alkyl group having 1 to 6 carbon atoms 63. The copolymer of aspect 62, comprising one or more compounds having the formula:

[0161] Aspect 67. The crosslinker has the structure II: [ka] In the formula, R F is a perfluoroalkyl having 1 to 6 carbon atoms, optionally having 1 or 2 ether oxygen atoms 62. The copolymer of aspect 61, comprising one or more compounds having the formula:

[0162] Aspect 68. The crosslinker has the structure III: [ka] wherein the formula is a perfluoroalkyl having 1 to 6 carbon atoms, optionally having 1 or 2 ether oxygen atoms. 62. The copolymer of aspect 61, comprising one or more compounds having the formula:

[0163] Aspect 69. Crosslinking agent: [ka] TIFF0007761942000039.tif67150 TIFF0007761942000040.tif24156, or any combination thereof.

[0164] Aspect 70. The copolymer of aspect 61, wherein the fluorinated ring monomer and crosslinker are copolymerized with a third monomer comprising a fluorinated vinyl compound or a fluorinated vinyl ether compound.

[0165] Aspect 71. The third monomer has structure IV: [ka] wherein n and m are independently 1, 2, or 3, and x is 1 or 2. 71. The copolymer of aspect 70, having

[0166] Aspect 72. The third monomer is [ka] 71. The copolymer of aspect 70, wherein

[0167] Aspect 73. The copolymer of Aspect 61, wherein the first copolymer is produced by solution polymerization or aqueous emulsion polymerization.

[0168] Aspect 74. An amorphous crosslinked fluorinated copolymer comprising a plurality of first copolymers and a plurality of crosslinker units covalently bonded to the first copolymers, wherein the first copolymers comprise a plurality of fluorinated ring units in an amount of 1 mol % to 99.5 mol %, and the fluorinated ring units are at least five-membered rings.

[0169] Aspect 75. The fluorinated ring unit has the following structure: [ka] wherein R5, R6, R7, and R8 are independently F, CF3, or CF2CF3, CF2H, CF2CF2H, CFHCF3, or CFHCF2H, and R6 and R7 can be contained in a 5-membered or 6-membered ring. 75. The copolymer of aspect 74, comprising:

[0170] Example The following examples are presented so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compounds, compositions, articles, devices, and / or methods claimed herein are made and evaluated, and are intended to be purely exemplary of the disclosure and are not intended to limit the scope of what the inventors regard as their disclosure. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperatures, etc.), but some errors and deviations should be accounted for. Unless otherwise specified, parts are parts by weight, temperatures are °C or are at ambient temperature, and pressures are at or near atmospheric. Test Method

[0171] The polymeric materials, membranes and selective layers disclosed herein may be characterized using one or more of the following methods.

[0172] Glass transition temperature

[0173] The glass transition temperature of the polymeric materials may be determined using differential scanning calorimetry (DSC), for example, according to ASTM E1356-08(2014), and may be modified as needed or desired for the disclosed materials and devices.

[0174] Notched Tensile Test

[0175] The polymeric materials may be evaluated according to ASTM F1473-18 (as modified as necessary or desired for the disclosed materials and devices) to determine the notch tensile properties of the polymeric materials.

[0176] fracture toughness

[0177] Polymeric materials may be evaluated according to ASTM E1820-20 (as modified as necessary or desired for the disclosed materials and devices) to determine fracture toughness.

[0178] Determining the JR curve

[0179] Polymeric materials can be evaluated according to ASTM D6068-10(2018), as modified as necessary or desired for the disclosed materials and devices, to characterize the crack growth resistance of the polymeric material.

[0180] Bent Beam Method

[0181] Polymeric materials can be evaluated according to ASTM D3929-03(2015), as modified as necessary or desired for the disclosed materials and devices, to characterize the stress crack properties of the polymeric materials.

[0182] Example 1: Synthesis of PBVE-co-EVE-Me copolymer [ka]

[0183] A 1 L stainless steel reactor was equipped with a magnetic stir bar and perfluorooctane (300 mL) solvent. The lid was attached and a valve to an argon source and vacuum (30 Torr) was connected. The solvent was degassed by four cycles of vacuum / argon backfill. Next, PBVE (CF2=CF-O-CF2CF=CF2, 50 mL, 80 g) was added via a 12-inch stainless steel needle syringe along with EVE-Me (CF2=CF-O-CF2-CF(CF3)-O-CF2CF2CO2Me, 3.1 mL, 5.0 g). The reactor was placed in an oil bath set at 60 °C, and hexafluoropropylene oxide dimer peroxide (HFPO-DP, CF3CF2CF2OCF(CF3)COO) solution (0.16 M in Vertrel XF; 0.5 mL precharge, 1.5 mL added over 8 h via syringe pump) was added. After 24 hours, the solution was transferred to a 500 mL round-bottom flask and reduced at 50°C under a vacuum of 30 Torr to obtain 15 g of a colorless, transparent, soft polymer that remained wet with the solvent. The Tg of this dried polymer was measured by DSC, the molecular weight was measured by GPC, and the like. 19 The comonomer ratio was measured by F NMR spectroscopy. result: Tg = 93°C (PBVE homopolymer = 108°C). The material was amorphous since no melting endotherm was observed. Mn=468,000g / mol,Mw=508,000g / mol 19 F NMR %EVE-Me = 2.7 mol% IR (transmission mode): -CH3=2968cm -1 , ester C=O = 1792 cm -1

[0184] Example 2: Synthesis of PBVE-co-PFBVOP copolymer [ka]

[0185] A 30 mL glass vial was charged with a magnetic stir bar, PBVE (10.0 mL, 16.0 g), and PFBVOP (CF₂=CF-O-CF₂CF₂-O-CF₂CF₂, 3.0 mL, 4.9 g), and polymerization was carried out. No added solvent was used for this polymerization. Argon gas was bubbled through the monomer mixture for 3 minutes to remove oxygen. Next, perfluorobenzoyl peroxide initiator (40 mg, Oldham, PH; prepared as described in Williams, GHJ Chem. Soc. (C), 1970, 1260) was added. The cap was then tightened, and the vial was placed in an oil bath and magnetically stirred at 80 °C for 24 hours. The result was a 20 g cylinder of clear, strong, amorphous fluoropolymer glass. The polymer formed by the reaction between the two monomers may then be further crosslinked to form a three-dimensional network.

[0186] Example 3: Synthesis of PDD-co-EVE-Me copolymer [ka]

[0187] Perfluorooctane solvent (250 mL, 445 g) was added to a 500 mL Duran glass bottle with a magnetic stir bar. The lid was attached, and the valve was connected to an argon source and vacuum (30 mTorr). The solvent was degassed by four cycles of vacuum / argon backfill. Freshly distilled PDD (30.0 mL, 51.6 g) was added via syringe, followed by EVE-Me comonomer (3.2 mL, 5.0 g). Polymerization was initiated by adding hexafluoropropylene oxide dimer peroxide (HFPO-DP, [CFCFCFOCF(CF)COO]) solution (2.0 mL, 0.16 M in Vertrel XF). The solution was stirred at 22 °C for 6 h, at which point it had completely gelled. The gel was dried in a vacuum oven (275 °C, 200 mTorr) for 15 h, yielding 40.2 g of white copolymer. Evidence of EVE-Me monomer incorporation is shown by IR (transmission mode): -CH = 2964 cm -1 , ester C=O = 1789 cm-1 It was decided by.

[0188] Example 4: Preparation of composite membranes using PBVE-co-EVE-Me copolymers

[0189] A highly permeable amorphous fluoropolymer gutter layer was spin-coated onto a porous support layer. After drying to remove substantially all of the solvent from the gutter layer polymer, a selective layer consisting of the PBVE-co-EVE-Me copolymer was spin-coated on top of the gutter layer. This layer was then dried to remove substantially all of the solvent from the composite membrane. Finally, the copolymer was cross-linked by UV irradiation and / or elevated temperature.

[0190] Example 5: Carbon dioxide separation from methane using composite membranes

[0191] The composite membrane sample of Example 2 was tested for CO2 / CH4 mixed gas separation at ambient temperature (20-25°C) with a feed pressure of 60 psig, a CO2 feed concentration of 40%, and a permeate pressure of approximately atmospheric pressure.

[0192] It should be emphasized that the above-described embodiments of the present disclosure are merely possible examples presented for a clear understanding of the principles of the present disclosure. Many variations and modifications can be made to the above-described embodiment(s) without substantially departing from the spirit and principles of the present disclosure. All such modifications and variations are intended to be included within the scope of the present disclosure and protected by the following claims.

Claims

1. 1. A discrete article comprising a first surface and a second surface, and a layer comprising an amorphous crosslinked fluorinated copolymer adjacent to at least one of the first surface or the second surface, The amorphous crosslinked fluorinated copolymer is produced by (a) copolymerizing one or more fluorinated ring monomers in an amount of 1 mol % to 99.5 mol % with a crosslinker in an amount of 0.2 mol % to 40 mol % to form a first copolymer, wherein the fluorinated ring monomer is at least a five-membered ring; and (b) crosslinking the first copolymer to form the amorphous crosslinked fluoropolymer; The cross-linking agent or any combination thereof, a separate article.

2. The separation article of claim 1 , wherein the fluorinated ring monomer is perfluorinated.

3. The separation article of claim 1 , wherein the fluorinated ring monomer is an olefinic compound.

4. The separation article of claim 1 , wherein the fluorinated ring monomer comprises a five- or six-membered ring.

5. 10. The separation article of claim 1, wherein the fluorinated ring monomer is produced by cyclopolymerization of a linear monomer having an olefin at one end of the monomer and a vinyl ether at the other end of the monomer.

6. The fluorinated ring monomer is selected from the group consisting of the following compounds: 【Chemistry 1】 or A compound having the following structure that undergoes cyclic polymerization to form a fluorinated ring: 【change】 [In the formula, R １ and R ２ are independently F, CF ３ , C.F. ２ CF ３ , C.F. ２ H, C.F. ２ CF ２ H, CFHCF ３ or CFHCF ２ H; R ３ and R ４ are independently F, CF ３ , or CF ２ CF ３ , C.F. ２ H, C.F. ２ CF ２ H, CFHCF ３ or CFHCF ２ H; R ５ , R ６ , R ７ and R ８ are independently F, CF ３ or CF ２ CF ３ , C.F. ２ H, C.F. ２ CF ２ H, CFHCF ３ or CFHCF ２ H and R ６ and R ７ can be contained within a five- or six-membered ring; and R ９ , F, CF ３ or CF ２ CF ３ is] The separation article of claim 1 comprising one or more of:

7. The discrete article of claim 1 , wherein the fluorinated ring monomer is a single compound.

8. The separation article of claim 1 , wherein the fluorinated ring monomers are two or more different compounds.

9. The fluorinated ring monomer is 【Chemistry 2】 or a combination thereof.

10. 10. The separation article of claim 1, wherein the fluorinated ring monomer is present in an amount of 80 mol % to 99 mol %.

11. The discrete article of claim 1 , wherein the cross-linking agent is a single compound.

12. The discrete article of claim 1 , wherein the cross-linking agent is two or more different compounds.

13. 10. The separation article of claim 1, wherein the cross-linking agent is present in an amount of 0.2 mol % to 20 mol %.

14. 10. The separation article of claim 1, wherein the fluorinated ring monomer and crosslinker are copolymerized with a third monomer comprising a fluorinated vinyl compound or a fluorinated vinyl ether compound.

15. The third monomer has the structure: 【Chemistry 9】 wherein n and m are independently 1, 2, or 3, and x is 1 or 2.

15. The separation article of claim 14, having:

16. the third monomer is 【Chemistry 10】 15. The separation article of claim 14, wherein:

17. 10. The separation article of claim 1, wherein the first copolymer is produced by solution polymerization or aqueous emulsion polymerization.

18. The separation article of claim 1 , wherein the copolymerization is carried out in the presence of an initiator.

19. 20. The separation article of claim 18, wherein the initiator comprises a hydrocarbon peroxide, a fluorocarbon peroxide, a hydrocarbon peroxydicarbonate, an inorganic fluorocarbon initiator, or any combination thereof.

20. 10. The separation article of claim 1, wherein the amorphous crosslinked fluorinated copolymer comprises a plurality of first copolymers and a plurality of crosslinker units covalently bonded to the first copolymers, the first copolymers comprising a plurality of fluorinated ring units in an amount of 1 mol % to 99.5 mol %, and the fluorinated ring units are at least five-membered rings.

21. 21. The separation article of claim 20, wherein the fluorinated cyclic units are perfluorinated.

22. 21. The separation article of claim 20, wherein the fluorinated ring unit comprises a five- or six-membered ring.

23. The fluorinated ring unit has the following structure: 【Chemistry 11】 [In the formula, R １ and R ２ are independently F, CF ３ , C.F. ２ CF ３ , C.F. ２ H, C.F. ２ CF ２ H, CFHCF ３ or CFHCF ２ H; R ３ and R ４ are independently F, CF ３ , or CF ２ CF ３ , C.F. ２ H, C.F. ２ CF ２ H, CFHCF ３ or CFHCF ２ H; R ５ , R ６ , R ７ and R ８ are independently F, CF ３ , or CF ２ CF ３ , C.F. ２ H, C.F. ２ CF ２ H, CFHCF ３ or CFHCF ２ H and R ６ and R ７ can be contained within a 5- or 6-membered ring; and R ９ is F, CF ３ or CF ２ CF ３． is] 21. The separation article of claim 20, comprising one or more of:

24. 24. The discrete article of claim 23, wherein the fluorinated ring unit is a single structural unit.

25. 24. The separation article of claim 23, wherein the fluorinated ring units are two or more different structural units.

26. The fluorinated cyclic unit is 【Chemistry 12】 or a combination thereof.

27. 21. The separation article of claim 20, wherein the fluorinated ring units are in an amount of 80 mol % to 99 mol %.

28. 21. The separation article of claim 20, wherein the first copolymer further comprises a perfluorinated comonomer unit that is not a fluorinated ring unit or a crosslinker unit.

29. The comonomer unit has the following structure: 【Chemistry 13】 wherein n and m are independently 1, 2, or 3, and x is 1 or 2.

30. The discrete article of claim 28, comprising one or more units having:

30. 30. The discrete article of claim 28, wherein the comonomer unit is a single structural unit.

31. 30. The discrete article of claim 28, wherein the comonomer units are two or more different structural units.

32. The comonomer units are: 【Chemistry 14】 or any combination thereof.

33. 29. The discrete article of claim 28, wherein the comonomer unit is present in an amount of 1 mol % to 20 mol %.

34. The separation article of any one of claims 1 to 33, wherein the first copolymer has a glass transition temperature of from 0°C to 300°C.

35. 34. The separation article of any one of claims 1 to 33, wherein the first copolymer has an Mn of 10 kDa to 2,000 kDa.

36. 34. The separation article of any one of claims 1 to 33, wherein the first copolymer has a Mw of 10,000 g / mol to 3,000,000 g / mol.

37. The separation article of any one of claims 1 to 33, wherein the separation article comprises a multi-layer structure article, and at least one layer of the structure comprises the copolymer.

38. The separation article of any one of claims 1 to 33, wherein the article comprises a film, a membrane, a tube, or a fiber.

39. 34. The separation article of any one of claims 1 to 33, wherein the separation article comprises a layer of an amorphous crosslinked fluorinated copolymer, the layer having a thickness of 1 μm or less.

40. A method of separating a first gas component from a gas mixture, the process comprising passing the gas mixture through a separation article according to any one of claims 1 to 33.

41. 41. The method of claim 40, (a) passing a gaseous mixture across a separation article having a feed side and a permeate side, the separation article having a selective layer that is selectively permeable to at least a first gas component, the selective layer comprising an amorphous crosslinked fluorinated copolymer; (b) providing a driving force sufficient to provide permeation of at least a portion of the gas mixture from the feed side to the permeate side of the separation article, resulting in a gas permeate stream on the permeate side of the separation article and a gas retentate stream on the feed side of the separation article, wherein the gas permeate stream comprises a first gas component.

42. 42. The method of claim 41, wherein the permeate stream has a concentration of the first component that is greater than the concentration of the first component in the retentate stream.

43. 42. The method of claim 41, further comprising withdrawing a permeate stream from the permeate side of the separation article.

44. 42. The method of claim 41, further comprising withdrawing a retentate stream from the supply side of the separation article.

45. 42. The method of claim 41, wherein the first gas component is carbon dioxide, hydrogen sulfide, helium, or any combination thereof.

46. 42. The method of claim 41, wherein the gas mixture comprises methane and carbon dioxide.

47. 42. The method of claim 41, wherein 50% or more of the first gas component in the gas mixture permeates the separation article.

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