Liquid purification films containing carbonaceous materials and methods for forming them

Abstract

A porous polymeric filter membrane is provided that includes a polymer having at least one carbonaceous material mixed therein. The membrane is capable of removing trace amounts of a variety of impurities from liquid compositions, including metal ions, acids, bases, and organic contaminants.

Description

[Technical Field]

[0001] This disclosure generally relates to the field of liquid purification using membrane technology. [Background technology]

[0002] Filter products are essential tools in modern industry, used to remove unwanted materials from the flow of useful fluids. Useful fluids processed using filters include water, liquid industrial solvents and processing fluids, industrial gases used in manufacturing or processing (e.g., in semiconductor manufacturing), and liquids with medical or pharmaceutical applications. Unwanted substances removed from fluids include impurities and contaminants such as particles, microorganisms, and dissolved chemical species. Specific examples of filter applications include their use with liquid materials in the manufacture of semiconductors and microelectronic devices.

[0003] The field of microelectronic device processing requires steady improvements in processing materials and methods to sustain the parallel and steady improvement of the performance (e.g., speed and reliability) of microelectronic devices. Opportunities to improve microelectronic device fabrication exist in all aspects of the manufacturing process, including methods and systems for filtering liquid materials.

[0004] A wide variety of liquid materials are used as process solvents, cleaning agents, and other processing solutions in the processing of microelectronic devices. Many of these materials require very high levels of purity, if not very high. For example, liquid materials (e.g., solvents) used in the photolithography of microelectronic devices must be of very high purity. Specific examples of liquids used in microelectronic device processing include spin-on-glass (SOG) technology, back-surface anti-reflective coating (BARC) methods, and process solutions for photolithography. [Overview of the Initiative]

[0005] In summary, this disclosure relates to a membrane capable of removing impurities from liquid compositions such as alcohols and ammonium hydroxide (i.e., aqueous ammonia). The membrane is prepared by dispersing a carbonaceous material, such as activated carbon, within a polymer and preparing a filter membrane therefrom. The filter membranes of this disclosure can remove trace amounts of certain amines and metal cations from such solutions. In one specific embodiment, this disclosure provides a membrane comprising a polymer, the polymer containing more than 0 and less than about 80% (by weight) of carbonaceous material. The membrane can provide liquid solutions of C1-C4 alkanols and alcohols such as very high-purity ammonium hydroxide. [Brief explanation of the drawing]

[0006] [Figure 1] This is an example of a filter component of this disclosure. [Figure 2] This is a graph showing particle retention rate (%) versus particle loading (single layer %). [Modes for carrying out the invention]

[0007] As used herein and in the appended claims, the singular forms "a," "an," and "the" refer to multiple subjects unless the context clearly indicates otherwise. As used herein and in the appended claims, the term "or" is generally used to mean "and / or" unless the context clearly indicates otherwise.

[0008] The term "approximately" generally refers to a range of numbers that are considered equivalent to the listed values ​​(e.g., having the same function or result). Often, the term "approximately" may include numbers rounded to the nearest significant figure.

[0009] A numerical range expressed using endpoints includes all digits contained within that range (for example, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

[0010] To perform a filtration function, the filter may include a filter membrane that serves to remove unwanted materials from the fluid passing through the filter membrane. The filter membrane may be in the form of a flat sheet, rolled (e.g., spiral), flat, pleated, or disc-shaped, as needed. Alternatively, the filter membrane may be in the form of hollow fibers. The filter membrane may be housed in a housing or otherwise supported so that the fluid being filtered enters through the filter inlet and must pass through the filter membrane before passing through the filter outlet.

[0011] Filter membranes can consist of porous structures with average pore sizes that can be selected based on the use of the filter, i.e., the type of filtration performed by the filter. Typical pore sizes range from microns to submicrons, e.g., about 0.001 microns to about 10 μm. Membranes with an average pore size of about 0.001 to about 0.05 microns are sometimes classified as ultrafiltration membranes. Membranes with a pore size of about 0.05 to 10 μm are sometimes called microporous membranes.

[0012] Filter membranes having pore sizes in the micron or submicron range, or simply referred to herein as “membrane,” may be effective in removing undesirable material (i.e., impurities) from a fluid flow by either a sieving mechanism or a non-sieving mechanism, or both. A sieving mechanism is a mode of filtration that removes particles from a liquid flow by mechanically holding them on the surface of the filter membrane, which works to mechanically interfere with particle movement, holding particles within the filter and mechanically preventing the flow of particles through the filter. Typically, the particles can be larger than the pores of the filter. A “non-sieving” filtration mechanism is a mode of filtration in which the filter membrane holds suspended particles or dissolved material contained in the fluid flow through the filter membrane by a non-mechanical means, for example, including an electrostatic mechanism in which particulate matter or dissolved impurities are electrostatically attracted to and held on the filter surface and removed from the fluid flow; the particles may be dissolved or solids having a particle size smaller than the pores of the filter material.

[0013] Accordingly, in a first aspect, the present disclosure provides a film comprising a polymer mixed with carbonaceous material greater than 0 and less than about 80% (by weight), which exhibits (a) a bubble point of about 2 psi to about 200 psi when measured using ethoxy-nonafluorobutane HFE7200 at a temperature of about 22°C, (b) an isopropanol flow time of about 20 seconds / 500 ml to about 10,000 seconds / 500 ml when measured at 14.2 psi, and (c) a G25 particle retention rate of about 25% to about 100%.

[0014] A filter including a membrane can be any desired form suitable for filtration applications. The material forming the filter can be a structural component of the filter itself and provide the filter with a desired structure. The filter membrane can be porous and can be any desired shape or configuration. The filter membrane itself can be a single article or can be represented by a number of individual articles such as particles (e.g., resin beads). The membrane is formed from a polymer material, a mixture of different polymer materials, or a polymer material and a non-polymer material. Polymer materials that can be used to form the membranes of this disclosure include hydrophobic polymers or hydrophilic polymers. Suitable polymers include polyamides, polyimides, polyolefins, polyethersulfones, polyacrylates, polyesters, cellulose, cellulose esters, polycarbonates, poly(phenylene oxide), poly(styrene), or combinations thereof. For example, the polymer material of the membrane may be a hydrophobic polymer selected from ultra-high molecular weight polyethylene; polyethylene; polypropylene; polymethylpentene; polybutene; polyisobutylene; copolymers of two or more ethylene, propylene, and butylene; halogenated polymers; or combinations thereof.

[0015] In certain embodiments, the filter film material includes ultra-high molecular weight polyethylene (UPE). UPE filter materials, such as UPE films, are typically about 1 × 10⁻⁶ 6 ~9×10 6 Da, or 1.5 × 10 6 ~9×10 6 The range of Da is approximately 1 × 10 6 It is formed from a resin having a molecular weight (weight-average molecular weight) exceeding Dalton (Da). Crosslinking between polyolefin polymers such as polyethylene can be promoted by heat or the use of crosslinking chemicals, such as peroxides (e.g., dicumyl peroxide or di-tert-butyl peroxide), silanes (e.g., trimethoxyvinylsilane), or azoester compounds (e.g., 2,2'-azo-bis(2-acetoxy-propane)).

[0016] Exemplary halogenated polymers include polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), fluorinated ethylene polymer (FEP), polyhexafluoropropylene, and polyvinylidene fluoride (PVDF).

[0017] In one embodiment, the porous filter membrane is asymmetrical. In one example of an asymmetric membrane, the pore size of one face and region of the membrane is larger than that of the opposite face and region. In another example, there may be an asymmetrical structure in which the pore size is larger on opposing faces (and regions) of the membrane, and the pore size of the central region of the membrane is smaller than that of either face (e.g., an hourglass pore profile). In other embodiments, a microporous membrane may have a pore structure that is essentially symmetrical across its thickness (substantially the same pore size across the thickness of the membrane).

[0018] In some embodiments, the filter membrane may be a composite membrane comprising two or more porous polymer membranes that may be made from the same material but different materials and / or have the same or different structures. At least one of the porous polymer membranes of the composite membrane comprises the carbonaceous material described herein. For example, the filter membrane may comprise a first porous polymer membrane comprising the membrane(s) of the disclosure having a carbonaceous material, and a second filter material which does not contain the membrane(s) of the disclosure or which is in some way different from the membrane(s) of the disclosure, such as having a different polymer, a different type or amount of carbonaceous material, or a different pore structure. Additional filter material layers may also be possible, which are various combinations of polymers with or without carbonaceous material mixed in, and at least one layer is the membrane of the disclosure. Thus, the composite membrane can be considered as a multilayer membrane having a first filter layer in contact with a second filter layer. Specifically, the composite membrane may be a co-cast or co-pleated membrane of the first polymer and the second polymer, where one or both of these polymer layers comprise the carbonaceous material.

[0019] Therefore, in certain embodiments, this disclosure is, Provided is a composite filter including a first filter material and a second filter material, wherein an outer surface of the first filter material is in contact with an outer surface of the second filter material. The first filter material includes a porous polymer membrane including a polymer in which a carbonaceous material greater than 0 and less than about 80% (by weight) is mixed therein. The second filter material is different from the first filter material. The outer surface of the first filter material can be an output-facing surface (in the direction of flow through the composite membrane), the outer surface of the second filter material can be an input-facing surface, or vice versa.

[0020] As used herein, a "porous polymer membrane" is a polymeric solid (e.g., microporous) that includes pores that are interconnected passages extending from one surface of the membrane to the opposite surface of the membrane. The passages generally provide a tortuous tunnel or path through which the liquid to be filtered must pass. Of the particles contained in this liquid, particles larger than the pores are prevented from entering the microporous membrane or are trapped within the pores of the microporous membrane (i.e., removed by a sieving-type filtration mechanism) when the fluid containing the particles passes through the microporous membrane. Particles smaller than the pores can also be trapped or absorbed upon interaction with the pore structure and can be removed, for example, by a non-sieving filtration mechanism.

[0021] The membranes of the present disclosure include a carbonaceous material distributed throughout the membrane structure. The carbonaceous material can include, for example, activated carbon, carbon black, graphene, and carbon nanotubes. For example, activated carbon is an adsorbent derived from any carbonaceous precursor that can be converted to activated carbon. Examples of such carbonaceous precursors include wood, corn cobs, kelp, coffee beans, rice husks, fruit pits, peat, lignite, coconut shells, petroleum and / or coal pitch, coke, carbon black, phenolic resins, polyvinyl chloride, and the like. The form of the carbonaceous material mixed with the polymer of the porous polymer membrane is not particularly important and can be selected from powders, microparticles, fibers, sheets, and the like. In one embodiment, the carbonaceous material is in powder, microparticle, or extruded form.

[0022] For example, the carbonaceous material is in the form of a solid microporous material having a high surface area mainly composed of elemental carbon, and in the case of a carbonaceous material derived from lignin, it can be activated carbon further containing a small amount of other trace elements initially found in the carbonaceous precursor material in which the activated carbon was formed. Further, the activated carbon can be obtained from a completely synthetic (i.e., petrochemical) source, such as polystyrene, poly(vinylidene chloride), or poly(vinylidene chloride)-methyl acrylate copolymer, provided that in any case, the final activated carbon surface has the porosity necessary to be effective in the methods of the present disclosure taught herein. In this regard, activated carbon is carbon in a non-graphitic form of microcrystals that is treated to increase its porosity. The surface area of activated carbon depends on its pore volume. Since the surface area per unit volume decreases as the individual pore diameters increase, the surface area is maximized by increasing the number of pores of very small dimensions and / or limiting the number of pores of large dimensions. Pore diameters are defined by the International Union of Pure and Applied Chemistry as micropores (pore width < 2 nm), mesopores (pore width 2 - 50 nm), and macropores (pore width > 50 nm). Further, in such activated carbon, micropores and mesopores contribute to the adsorption capacity of the activated carbon, while macropores actually reduce the density and can be harmful to the adsorbent effectiveness of the activated carbon on a carbon volume basis.

[0023] In the present disclosure, in one embodiment, the carbonaceous material is in the form of powder or particles. Such a carbonaceous material can be purchased in this desired form or can be milled or jet milled to achieve the desired particle size before being added to the polymeric material used to make the membrane. In certain embodiments, the porous polymeric membrane containing the polymers disclosed herein has from greater than 0 to about 80%, such as from about 1 to about 60% (by weight), from 2 wt% to about 40 wt%, or from 5 wt% to about 20 wt% of the carbonaceous material mixed therein. A low level of carbonaceous material, such as activated carbon, may be preferred to maintain the structural integrity or physical form of the membrane.

[0024] Furthermore, the carbonaceous material and / or polymer of the porous polymer membrane preferably contains less than about 65 μg of extractable organic compounds and / or metal ions. This level of purity of the components can be achieved by washing with a suitable solvent before forming the membrane using techniques known to those skilled in the art. Lower levels of impurities, such as less than 50 μg, are even more preferable.

[0025] In certain embodiments, the porous polymer membrane is in the form of a sheet or hollow fibers. In some embodiments, the sheet or hollow fibers can have any useful thickness, for example, in the range of about 35 μm to about 400 μm, about 80 μm to about 350 μm, or about 120 μm to about 310 μm, or about 160 μm to 270 μm, or any range and partial ranges in between. The porous polymer membrane sheet can be used as a flat sheet membrane or can be corrugated to form a pleated membrane.

[0026] In specific embodiments, the carbonaceous material is an activated carbon material. Activation of the carbonaceous material can be carried out by known methods. For example, the carbonaceous material may be activated by an oxidizable chemical substance such as zinc chloride, phosphoric acid, sulfuric acid, calcium chloride, sodium hydroxide, potassium dichromate, or potassium permanganate (chemical activation); or by gas activation, such as steam, propane gas, exhaust gas produced from combustion gases which are a mixture of CO2 and H2O, or carbon dioxide gas. See, for example, U.S. Patent No. 6,589,904, which is incorporated herein by reference in its entirety. Alternatively, a commercially available activated carbon product from Calgon Carbon, for example, available as powder or granules, may be used. In one embodiment, after grinding, the median mean particle size of the activated carbon is about 30 μm to about 60 μm, or about 45 μm. In another embodiment, the activated carbon is about 800 μm 2 It has a surface area of ​​1 / g or more.

[0027] The porous polymer films of this disclosure can be prepared by combining a polymer material and a carbonaceous material, dispersing a desired amount of carbonaceous material within the polymer components. The dissolving or dispersing solvent can also be used with the polymer, with or without heating, as required by the given polymer. For example, a polymer such as polysulfone can be dissolved in a suitable solvent such as N-methylpyrrolidone (NMP), and a non-solvent such as isopropanol can be added to form a dope or lacquer. Activated carbon can be added to this mixture, and the resulting mixture can be homogenized by vigorously stirring. The mixture can then be applied to a glass plate and subsequently immersed in a non-solvent. In other words, a porous polymer film containing a mixed carbonaceous material can be formed using the immersion casting method. Furthermore, in the case of polymers with different solubility characteristics, such as high molecular weight polyethylene, the carbonaceous material can be dispersed together with, for example, dioctyl phthalate (DOP) and mineral oil to form a slurry. The slurry can then be extruded into a sheet, treated with various liquids to remove the mineral oil and dioctyl phthalate, and dried to form a porous polymer film in sheet form. In other words, once the carbonaceous material is dispersed within a polymer matrix, the films of this disclosure can be prepared using known temperature-induced (TIPS) or solvent-induced phase separation (SIPS) processes used to form polymer sheets containing thermoplastic polymers.

[0028] Therefore, in a further embodiment, the present disclosure is a method for preparing a porous polymer membrane in the form of a sheet for filtering a liquid containing organic and metal ion impurities, wherein the porous polymer membrane comprises a polymer in which a carbonaceous material such as activated carbon is dispersed. Combining a carbonaceous material with a flowable form of a polymer, wherein the polymer is (i) mixed with at least one solvent and / or dispersant in an effective amount to provide a flowable form; and / or (ii) heated to a temperature sufficient to provide a flowable form; To provide a polymer composition in which a carbonaceous material is dispersed by physically dispersing the carbonaceous material within the polymer; and This includes removing the solvent or dispersant from the polymer composition if present, and / or cooling the polymer composition while casting or extruding it into a sheet; The present invention provides a method for removing up to approximately 60% to 100% of amine contaminants and approximately 75% to 95% of metal ion contaminants from a liquid using a porous polymer membrane.

[0029] In one embodiment of this method, the polymer is selected from polyamides, polyimides, polyolefins, polyethersulfones, polyacrylates, polyesters, celluloses, cellulose esters, polycarbonates, poly(phenylene oxide), poly(styrene), or combinations thereof. In another embodiment, the polymer is selected from ultra-high molecular weight polyethylene; polyethylene; polypropylene; polymethylpentene; polybutene; polyisobutylene; copolymers of two or more ethylenes, propylenes, and butylenes; polytetrafluoroethylene; polychlorotrifluoroethylene; fluorinated ethylene polymers; polyhexafluoropropylene; polyvinylidene fluoride; polyamides; polyimides; polysulfones; polyethersulfones; polyarylsulfones; polyacrylates; polyesters; nylons; celluloses; cellulose esters; polycarbonates; polysulfones; poly(phenylene oxide); poly(styrene); or combinations thereof.

[0030] Referring to the porous polymer filter membranes described herein, such membranes can be characterized by physical features including pore size, bubble points, and porosity. In this regard, porous polymer filter membranes can have any pore size that makes them effective for implementation as filter membranes, including pores (average pore size) of a size that may be considered, for example, a microporous membrane or an ultrafiltration membrane, as described herein. Examples of useful porous polymer membranes have an average pore size in the range of about 0.001 μm to about 1 or 2 μm, for example, 0.01 to 0.8 μm, and the pore size is selected based on one or more factors including the particle size or type of impurities to be removed, the pressure and pressure drop requirements, and the viscosity requirements of the liquid being processed by the filter. Ultrafiltration membranes can have an average pore size in the range of 0.001 μm to about 0.05 μm. Pore ​​size is often reported as the average pore size of porous materials, and this can be measured by known techniques such as mercury porosimetry (MP), scanning electron microscopy (SEM), liquid displacement spectroscopy (LLDP), or atomic force microscopy (AFM).

[0031] The bubble point is also a known characteristic of porous membranes. The bubble point test method involves wetting a sample of a porous polymer filter membrane by immersion in a liquid with known surface tension, and applying gas pressure to one side of the sample. The gas pressure is gradually increased. The minimum pressure at which the gas flows through the sample is called the bubble point. A specific method for determining the bubble point of a porous polymer material involves wetting a sample of the porous material by immersion in ethoxy-nonafluorobutane HFE7200 (available from 3M) at a temperature of 20-25°C (e.g., 22°C). Gas pressure is applied to one side of the sample using compressed air, and the gas pressure is gradually increased. The minimum pressure at which the gas flows through the sample is called the bubble point. All bubble point values ​​provided herein are measured using this procedure. Examples of useful or preferred bubble point values ​​for porous polymer filter membranes measured using the procedure described herein may be in the range of about 2 to about 200 psi, about 2 to about 150 psi, about 2 to about 100 psi, about 10 to about 200 psi, about 10 to about 150 psi, about 10 to about 100 psi, about 10 to about 40 psi, about 20 to about 200 psi, about 20 to about 150 psi, about 20 to about 100 psi, about 40 to about 200 psi, about 40 to about 150 psi, about 40 to about 100 psi, about 60 to about 200 psi, about 60 to about 150 psi, about 60 to about 100 psi, about 80 to about 200 psi, about 80 to about 150 psi, about 100 to about 200 psi, about 100 to about 150 psi, about 150 to about 200 psi, or any range in between. The porous polymer filter membranes described herein may have any degree of porosity that enables the porous polymer filter membrane to be effective as described herein. Exemplary porous polymer membranes may have relatively high porosity, for example, at least 60, 70, or 80%. As used herein, and in the art of porous materials, the “porosity” (sometimes called void ratio) of a porous material is a measure of the void (i.e., “empty”) space within the body as a percentage of the total volume of the body, and is calculated as the ratio of the volume of voids in the body to the total volume of the body. A body with 0% porosity is perfectly solid.

[0032] The porous polymer filter membranes of this disclosure may be useful in any type of industrial or life science process that requires a high-purity liquid material as input. Non-limiting examples of such processes include processes for preparing microelectronic or semiconductor devices, a specific example of which is a method for filtering liquid process materials (e.g., solvents or solvent-containing liquids) used in semiconductor photolithography. Examples of impurities present in process liquids or solvents used for preparing microelectronic or semiconductor devices may include metal ions dissolved in the liquid, solid particles suspended in the liquid, and gelled or solidified materials present in the liquid (e.g., generated during photolithography).

[0033] As described above, the porous polymer membrane may be a single layer or a multilayer, and may be combined with another filter material to form a composite filter membrane. In either case, the filter membrane may be useful for removing dissolved or suspended contaminants or impurities from a liquid flowing through the filter membrane by either a sieving mechanism or a non-sieving mechanism, preferably a combination of both non-sieving and sieving mechanisms.

[0034] Such porous polymer membranes have been found useful in removing metal ion impurities along with organic impurities such as amines to provide very high-purity liquid compositions. Exemplary liquid compositions include organic solvents, such as alcohols and ketones, and materials such as dissolved ammonia water, i.e., NH4OH. In this regard, references to ammonia water or simply "ammonia" are understood to refer to aqueous NH4OH solutions containing ammonia at any concentration. Thus, in further embodiments, the disclosure provides purified liquid compositions comprising one or more ketones or alcohols, wherein the purified compositions contain organic amine impurities of about 2000 ppb or less. In one embodiment, the organic amine impurity is selected from triethylamine, N,N-diisopropylamine, heptylamine, and 3,3,5,5-tetramethylbenzylidene. In another embodiment, the alcohol is a C1-C4 alcohol such as isopropanol.

[0035] Furthermore, various metal impurities can be removed by the porous polymer membrane described herein. In certain embodiments, the resulting purified liquid composition contains metal ions totaling about 12 ppb or less, such as cations of magnesium, aluminum, titanium, vanadium, manganese, nickel, copper, zinc, molybdenum, silver, cadmium, tin, and lead.

[0036] In one particular embodiment, the purified liquid composition contains 99.99% by weight or more of isopropanol, and the composition contains amines totaling about 2000 ppb or less and metal ions totaling about 12 ppb or less. In another embodiment, the purified liquid composition contains NH4OH, and the composition contains impurities selected from triethylamine, isopropylamine, heptylamine, N,N-diisopropylethylamine, and tetramethylbenzylidine at a concentration of about 2000 ppb or less.

[0037] Accordingly, the porous polymer membranes of the present disclosure enable processes or methods for filtering or purifying various liquids and organic compositions. Accordingly, in another embodiment, the present disclosure provides a method for preparing a purified liquid composition comprising (a) one or more ketones or alcohols, or (b) aqueous ammonia. In one embodiment, the composition contains impurities of 2000 ppb or less, selected from one or more of triethylamine, N,N-diisopropylamine, heptylamine, N,N-diisopropylethylamine, and 3,3,5,5-tetramethylbenzylidene. This purified composition can be obtained by a method comprising exposing a liquid composition requiring purification, comprising (i) one or more ketones or alcohols, or (ii) NH4OH and at least one organic amine impurity selected from one or more of triethylamine, N,N-diisopropylamine, heptylamine, and N,N-diisopropylethylamine, and 3,3,5,5-tetramethylbenzylidene, to one or more of the porous polymer membranes of the present disclosure. In one embodiment, the purified composition contains about 99.99% by weight or more of ketones or alcohols (such as isopropanol) or aqueous ammonia. Exposure to a porous polymer membrane can be achieved by actively passing the liquid composition through the membrane or simply by immersing the membrane in the liquid composition to be purified. In another embodiment, the purified composition contains a total of 12 ppb or less of metal ions.

[0038] Accordingly, the porous polymer filter membranes described herein can be used for purifying various types of liquid compositions, such as those used in semiconductor or microelectronic fabrication applications or useful chemicals (including solvents). For example, the liquid composition may contain a chemical or a combination of chemicals together with one or more impurities, and optionally further contain various additional components, such as polymer materials used in photoresists. The porous polymer filter membranes of this disclosure can effectively remove all or a substantial portion of impurities (i.e., undesirable species) from the liquid composition. Examples of suitable chemicals include, but are not limited to, methyl amyl ketone, ethyl-3-ethoxypropionate, propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), a mixed solution of propylene glycol monomethyl ether (PGME) and PGMEA (e.g., 7:3), methanol, ethyl acetate, ethyl lactate, and combinations thereof. Additional examples include organic amines such as hydroxylamine, monoethanolamine (MEA), triethanolamine (TEA), morpholine, N-methyldiethanolamine (MDEA), N-monomethylethanolamine (MMEA), N-ethylaminoethoxyethanol (2-(2-aminoethoxy)ethanol), tetraethylammonium hydroxide (TEAH), tetrabutylammonium hydroxide (TBAH), and combinations thereof. Further examples of chemical solutions from which impurities can be removed by the porous polymer filter membranes of this disclosure include n-butyl acetate (nBA), isopropyl alcohol (IPA), 2-ethoxyethyl acetate (2EEA), xylene, cyclohexanone, methyl isobutylcarbinol (MIBC), methyl isobutyl ketone (MIBK), isoamyl acetate, and undecane. Other process liquids such as deionized water, hydrogen peroxide, hydrochloric acid, sulfuric acid, and mixtures thereof can also be purified using the porous polymer membranes described herein. Therefore, the disclosed film can be used to remove impurities such as metal ions and / or organic impurities such as fluorinated organic compounds from liquid compositions such as acids, bases, peroxides, chemical solutions (including those containing polymers), and mixtures thereof.

[0039] Therefore, the membranes of the present disclosure can purify certain liquid compositions described herein to provide, after filtration, an extremely pure composition having amounts of impurities such as amine / organic and metal ion contaminants close to the detection limit. Thus, in further embodiments, the present disclosure provides a purified liquid composition, the composition is a) One or more ketones or alcohols, b) Contains ammonia water, The composition contains impurities of 2000 ppb or less, selected from one or more of triethylamine, isopropylamine, heptylamine, N,N-diisopropylethylamine, and tetramethylbenzylidine. composition, i) One or more ketones or alcohols, ii) A liquid composition requiring purification containing aqueous ammonia and at least one amine impurity selected from one or more of triethylamine, isopropylamine, N,N-diisopropylamine, heptylamine, and 3,3,5,5-tetramethylbenzylidene, This is obtained by exposure to one or more porous polymer films of the disclosure described herein.

[0040] Retention test

[0041] "Particle retention rate" or "coverage rate" refers to the percentage of particles that can be removed from a fluid flow by a membrane placed in the fluid path of the fluid flow. The particle retention rate obtained by the following procedure is called the "G25 particle retention rate". The particle retention rate of a 47 mm membrane disk can be measured by passing a sufficient amount of feed aqueous solution of 0.1% Triton X-100 with a pH of approximately 5, containing 8 ppm of polystyrene particles with a nominal diameter of 0.03 μm (available from Duke Scientific G25B), through the membrane at a constant flow rate of 7 mL / min to achieve a 1% single-layer coverage rate, and collecting the permeate. Unless otherwise specified, the G25 particle retention rate shall be measured at a 1% single layer. The concentration of polystyrene particles in the permeate can be calculated from the absorbance of the permeate. The particle retention rate is then calculated using the following formula. Particle retention = [Supply]-[Filtrate] ×100% [supply]

[0042] The number of particles (#) required to achieve a 1% single-layer coverage can be calculated using the following formula. TIFF0007853325000001.tif18170In formula, a = Effective film surface area d p = particle diameter n = single layer %

[0043] As used herein, “nominal diameter” refers to the diameter of a particle determined by photon correlation spectroscopy (PCS), laser diffraction, or optical microscopy. Typically, the calculated diameter, i.e., the nominal diameter, is expressed as the diameter of a sphere having the same projected area as the projection image of the particle. PCS, laser diffraction, and optical microscopy techniques are well known in the art. See, for example, Jillavenkatesa, A., et al.; “Particle Size Characterization”; NIST Recommended Practice Guide; National Institute of Standards and Technology Special Publication 960-1; January 2001.

[0044] In some embodiments, the G25 particle retention rate is approximately 25% to 100%, 25% to 99%, 25% to 97%, 25% to 95%, 25% to 90%, 25% to 85%, 50% to 100%, 50% to 99%, 50% to 97%, 50% to 95%, 50% to 90%, 50% to 85%, 70% to 100%, 70% to 99%, 70% to 97%, 70% to 95%, 70% to 90%, and 70% to 90%. The ranges are 85%, 75% to approximately 100%, approximately 75% to approximately 99%, approximately 75% to approximately 97%, approximately 75% to approximately 95%, approximately 75% to approximately 90%, approximately 75% to approximately 85%, 80% to approximately 100%, approximately 80% to approximately 99%, approximately 80% to approximately 97%, approximately 80% to approximately 95%, approximately 80% to approximately 90%, approximately 80% to approximately 85%, 85% to approximately 100%, approximately 85% to approximately 99%, approximately 85% to approximately 97%, approximately 85% to approximately 95%, approximately 85% to approximately 90%, or all and partial ranges between these.

[0045] In some embodiments, the films disclosed herein have one G25 particle retention rate (i.e., in a 1% monolayer) within the range disclosed above, and also have G25 particle retention rates in a 5% monolayer in the ranges of about 60% to about 80%, about 60% to about 75%, about 60% to about 70%, about 65% to about 80%, about 65% to about 75%, about 70% to about 80%, or all and partial ranges in between.

[0046] The filter membranes described herein, preferably in combination with a relatively high bubble point, can have relatively low flow times and good filtration performance (e.g., measured by particle retention, dye binding ability, or both). Examples of useful or preferred isopropanol flow times may be less than about 20,000 seconds / 500 mL, for example, less than about 4,000 or 2,000 seconds / 500 mL.

[0047] The membrane isopropanol (IPA) flow times reported herein are 13.8 cm with 500 ml of isopropyl alcohol (IPA) fluid. 2The flow time can be determined by measuring the time it takes for the fluid to pass through a membrane equipped with a 47 mm membrane disk having an effective surface area at a temperature of 14.2 psi and 21°C. In some embodiments, the flow time is approximately 20 seconds / 500 ml to approximately 10,000 seconds / 500 ml, approximately 20 seconds / 500 ml to approximately 5,000 seconds / 500 ml, approximately 20 seconds / 500 ml to approximately 1,000 seconds / 500 ml, approximately 20 seconds / 500 ml to approximately 800 seconds / 500 ml, approximately 20 seconds / 500 ml to approximately 500 seconds / 500 ml, and approximately 100 seconds. / 500ml ~ approx. 10,000 seconds / 500ml, approx. 100 seconds / 500ml ~ approx. 5,000 seconds / 500ml, approx. 100 seconds / 500ml ~ approx. 1,000 seconds / 500ml , about 100 seconds / 500ml~about 800 seconds / 500ml, about 100 seconds / 500ml~about 500 seconds / 500ml, about 500 seconds / 500ml~about 10,000 seconds / 500 ml, approx. 500 seconds / 500ml ~ approx. 5,000 seconds / 500ml, approx. 500 seconds / 500ml ~ approx. 1,000 seconds / 500ml, approx. 500 seconds / 500ml ~ approx. 800 seconds / 500ml, approx. 845 seconds / 500ml ~ approx. 10,000 seconds / 500ml, approx. 845 seconds / 500ml ~ approx. 5,000 seconds / 500ml, approx. 845 seconds / 500ml ~ approx. 1 The ranges are 665 seconds / 500ml, approximately 845 seconds / 500ml to approximately 1000 seconds / 500ml, approximately 1000 seconds / 500ml to approximately 10,000 seconds / 500ml, approximately 1000 seconds / 500ml to approximately 5000 seconds / 500ml, approximately 20 seconds / 500ml to approximately 2500 seconds / 500ml, or all and partial ranges in between.

[0048] In certain embodiments, the membranes described herein may have flow times approximately equal to or longer than those of the same filter membranes without carbonaceous material. In other words, the mixing of carbonaceous material does not substantially adversely affect the flow characteristics of the filter membrane, but further improves the filtration function of the filter membrane, particularly the non-sieving filtration function of the membrane, which is measured, for example, by dye binding capacity, particle retention, or both, depending on the pore size.

[0049] The porous polymer filter membranes described herein can be housed within larger filter structures, such as multilayer filter assemblies or filter cartridges used in filtration systems. The filtration system places the filter membrane within a filter housing, for example as part of a multilayer filter assembly or as part of a filter cartridge, exposing the filter membrane to the flow path of the liquid composition, so that at least a portion of the flow of the liquid composition passes through the porous polymer filter membrane containing carbonaceous material, so that the filter membrane removes a certain amount of impurities or contaminants from the liquid composition. The structure of the multilayer filter assembly or filter cartridge may include one or more additional materials and structures that support the filter membrane within the filter assembly or filter cartridge, allowing the fluid to flow from the filter inlet through the membrane (including the filter layer) and through the filter outlet, thereby passing through the filter membrane. The filter membrane supported by the filter assembly or filter cartridge may be of any useful shape, in particular, for example, a pleated cylinder, a cylindrical pad, one or more non-pleated (flat) cylindrical sheets, pleated sheets, etc.

[0050] A particular example of a filter structure including a porous polymer filter membrane in the form of a pleated cylinder can be prepared to include the following components, any of which may be included in the filter structure but may not be essential: a rigid or semi-rigid core supporting the interior of the pleated cylindrical porous polymer filter membrane; a rigid or semi-rigid cage supporting or surrounding the outside of the pleated cylindrical coated filter membrane on the outside of the filter membrane; optional end pieces or "packs" located at each of the two opposing ends of the pleated cylindrical coated filter membrane; and a filter housing including an inlet and outlet. The filter housing can be of any useful and desired size, shape, and material, and can preferably be made from a suitable polymer material.

[0051] As an example, Figure 1 shows a filter component 30 which is a product of a pleated cylindrical component 10 and an end piece 22 and other optional components. The cylindrical component 10 includes a filter membrane 12 and is pleated, as described herein. The end piece 22 is attached to one end of the cylindrical filter component 10 (e.g., “potted”). The end piece 22 can preferably be made from a melt-workable polymer material. A core (not shown) can be placed in the internal opening 24 of the pleated cylindrical component 10, and a cage (not shown) can be placed around the outside of the pleated cylindrical component 10. A second end piece (not shown) can be attached to the second end of the pleated cylindrical component 10 (“potted”). The resulting filter component 30 having two opposing potted ends and optional cores and cages can then be placed in a filter housing which includes an inlet and an outlet, and which is configured such that the entire amount of fluid entering the inlet must pass through the filter membrane 12 before exiting the filter at the outlet. [Examples]

[0052] Example 1: Preparation of a porous polymer membrane containing ultra-high molecular weight polyethylene (UPE) and activated carbon

[0053] A 15% (w / w) dispersion of UPE (ultra-high molecular weight polyethylene) in a mixture of DOP (dioctyl phthalate) and mineral oil was prepared at room temperature, and 5% (w / w) powdered activated carbon was added to this mixture. The UPE polymer had an average particle size of approximately 120 μm. The mineral oil had a viscosity of 68 CP at 40°C and a specific gravity of 0.86 at 25°C. The three-component mixture, having the consistency of a viscous slurry, was fed into a Brabender twin-screw mixer / extruder equipped with a pair of 42 mm slotted counter-rotating screws L / D-(7:1). A zenith gear pump and a 5-inch wide die were also attached to the extruder to extrude the molten blend into a sheet. The temperatures of the various extrusion zones were set to 180°C to 260°C. The volume output of the molten blend from the extruder was 46 cc / min. The extruded film was quenched on a rotating chrome-plated cooling roll, with the temperature controlled to 90°C by circulating a fluid at a constant temperature. The rapidly cooled film was wound up at a speed of approximately 6 feet / minute using an electric winder and interleaved with a highly porous, lightweight polypropylene spunbond nonwoven fabric. To extract mineral oil from the rapidly cooled gel film, the interleaved roll was placed in a metal frame, secured with clips, and the frame was placed in a Baron-Blakslee degreasing machine containing hydrofluoroethane (HFE) for reflux extraction. The extraction time was 12–24 hours. This was then dried at room temperature to remove the extractant and further heat-cured at 100°C for 5 minutes. During drying and heat-curing, the film was constrained by the material wrapped around it. This helps prevent the film from experiencing excessive shrinkage.

[0054] This general procedure can also be used to prepare other activated carbon loading levels, e.g., 20% or 50% (w / w). Isolated porous polymer UPE membranes containing 5, 20% and 50% (w / w) activated carbon were found to have the IPA (isopropanol) flow time and bubble point values ​​shown in Table 1 using the method described above. TIFF0007853325000002.tif51170

[0055] Example 2: Preparation of a porous polymer film containing polysulfone and activated carbon

[0056] M w A 12% (w / w) polyphenylsulfone (PPSU) resin with M = 50,700 Da was dissolved in N-methyl-2-pyrrolidone (NMP) at room temperature. Isopropyl alcohol (IPA) was slowly added to this solution to form a dope (lacquer) solution. 5% - 10% (w / w) powdered activated carbon was added to the resulting mixture and dispersed in the mixture for 5 - 10 minutes using a handheld homogenizer. Subsequently, the obtained dope mixture was coated onto a glass plate using a 7-mil knife, and a porous polysulfone membrane containing mixed activated carbon was isolated by immersion casting into a non-solvent.

[0057] Example 3: Determination of the filter retention of G25 beads for a porous UPE membrane containing activated carbon

[0058] The G25 particle retention was determined using the above method (pH 5) for the UPE membrane. Using the method described in Example 1, a ultra-high molecular weight polyethylene membrane containing mixed activated carbon was prepared. The G25 particle retention was calculated for 0.5, 1, 1.5, 2, 3, 4, and 5% monolayers. The porous UPE membrane containing mixed activated carbon showed improved G25 bead retention when compared to a porous UPE membrane不含 activated carbon. With 5% and 20% activated carbon loadings, the bead retention rate increased compared to a porous UPE membrane不含 activated carbon. The results are shown in Table 2 and plotted in Figure 2. TIFF0007853325000003.tif49170

[0059] Example 4: Determination of organic removal in IPA using a porous UPE membrane containing activated carbon

[0060] The following examples demonstrate the removal of organic impurities from isopropyl alcohol (IPA) using an activated carbon-containing UPE membrane. A porous UPE membrane containing activated carbon was prepared using the same method as in Example 1, and then cut into 47 mm membrane coupons. To determine the efficiency of organic removal by filtration, the membrane coupons were immersed in an IPA solution and spiked with organic impurities (2 ppm each). The removal efficiency was determined using GC-MS. The results are shown in Table 3 for organic removal (%): TIFF0007853325000004.tif182170

[0061] As shown, porous UPE membranes containing activated carbon exhibit efficient organic removal compared to UPE controls. Using a 50% carbon-modified membrane, amine-based impurities such as tetramethylbenzylidine (TMB) and heptylamine are removed 100%. The same impurities are not removed by non-activated carbon-containing UPE membranes. Similarly, large-chain hydrocarbons are also removed efficiently (>95%) compared to UPE alone.

[0062] Example 5: Determination of organic removal in 29% ammonia using a porous UPE membrane containing activated carbon.

[0063] The following examples demonstrate the removal of organic impurities from a 29% ammonia solution. A UPE membrane containing mixed activated carbon was prepared using the same method as in Example 1 and cut into 47 mm membrane coupons. To determine the filtration organic removal efficiency, the membrane coupons were immersed in a 29% ammonia solution, spiked with organic impurities, and a static immersion test was performed for 24 hours. Removal efficiency was determined using LC-QToF and is shown in Table 4: TIFF0007853325000005.tif57170

[0064] As shown, porous UPE membranes containing activated carbon removed all target impurities from ammonia compared to porous UPE membranes without activated carbon. Removal efficiency increased as the amount of activated carbon in the membrane increased.

[0065] Example 6: Determination of metal removal from IPA using a porous UPE membrane containing activated carbon.

[0066] The following examples are typical examples demonstrating metal removal by UPE films from organic solvents such as isopropyl alcohol (IPA), propylene glycol methyl ether (PGME), (2-methoxy-l-methylethyl acetate), propylene glycol monomethyl ether acetate (PGMEA), OK73™ (a 70 / 30 blend of propylene glycol methyl ether acetate / propylene glycol methyl ether (PGMEA / PGME)), and cyclohexanone.

[0067] A porous UPE membrane containing activated carbon was prepared using the same method as in Example 1, and then the membrane was cut into 47 mm diameter discs (coupons). The membrane was first washed several times with 10% HCl, then rinsed with DI water, and finally immersed overnight in 10% HCl and equilibrated with deionized water. For each solvent, a 47 mm coupon was immersed in a solution spiked with aqueous metal standards (SCP Science) containing 21–28 metals to achieve a target concentration of 5 ppb for each total metal. The feed samples and filtrate samples were then analyzed by Agilent Model 8800 ICP-MS (Inductively Coupled Plasma Mass Spectrometry) to determine the membrane's ability to remove metal ions from these solvents. The results are shown in Tables 5–9. TIFF0007853325000006.tif179170TIFF0007853325000007.tif132170TIFF00078533250 00008.tif174170TIFF0007853325000009.tif185170TIFF0007853325000010.tif138170

[0068] Porous polymer membranes containing activated carbon were tested for metal removal efficiency using S21 and S28 metal standards from Inorganic Ventures. As shown, better metal removal was observed from organic solvents by carbon-containing membranes compared to aqueous solutions. Metal removal using 20% ​​(w / w) activated carbon-containing UPE membranes showed higher removal efficiency (>80%) compared to aqueous solutions in most organic solvents, particularly for metals such as copper (Cu), zinc (Zn), molybdenum (Mo), silver (Ag), cadmium (Cd), and lead (Pb).

[0069] Example 7: Determination of metal removal from diluted peroxide and DIW

[0070] This example demonstrates the ability of a porous polymer membrane containing activated carbon to reduce metals in solvents such as diluted hydrogen peroxide and deionized water (DIW) under static immersion conditions.

[0071] The porous UPE membrane containing activated carbon (0.2 μm) prepared as described above was cut into 47 mm disks. These membrane disks were then washed several times with 10% HCl and 70% IPA, followed by immersion in 10% HCl overnight, equilibration with deionized water, and drying at room temperature for conditioning. Inorganic Venturi (IV-62491) standard metals were spiked into the solvent at a target concentration of 5 ppb for each metal. To determine the metal removal efficiency by static immersion, 20 mL of the metal spike solvent solution was placed in a PFA bottle containing the dried 47 mm membrane disks and rotated for 18 hours. After 18 hours, the membrane disks were removed, and the metal concentrations in the metal spike-containing solvent and the supernatant samples of each solvent membrane were determined using ICP-MS. The results are shown in Table 10. TIFF0007853325000011.tif183170

[0072] As shown, efficient removal of metals was observed. For metals that were not removed, it is thought that the activated carbon mixed into the PE film also caused the metals to detach.

[0073] Example 8: Metal removal from SC1(DIW:NH4OH:H2O2(5:1:1) application)

[0074] This example demonstrates the ability of a porous UPE membrane containing activated carbon to remove target metals from aggressive applications such as SC1 under static immersion conditions. Nine target metals (Al, Ca, Cr, Cu, Fe, Mn, Ni, Ti, Zn) from Inorganic Ventures (IV-62491) were spiked into a freshly prepared SC1 solution at a concentration of 5 ppb each. A 47 mm membrane disk was cut, washed overnight in 10% HCl / 70% IPA, and then equilibrated with deionized water. The membrane disk was further purified with a freshly prepared SC1 solution and then immersed in the spiked metal solution for 16 hours. After 16 hours, the membrane disk was removed, and the metal removal efficiency was measured by ICP-MS. The results are reported in Table 11 as removal percentages. TIFF0007853325000012.tif71170

[0075] Example 9: Removal of organic contaminants from DIW

[0076] The following examples demonstrate the removal of organic impurities from DIW. A porous UPE membrane containing activated carbon was prepared using the same method as in Example 1, and then cut into 47 mm membrane disks. The percentage of organic impurities removed was determined by immersing the membrane disk in 20 ml of DIW solution containing the target impurity, and the removal efficiency was measured by LC-QToF. The results are summarized in Table 12. TIFF0007853325000013.tif35170

[0077] manner

[0078] In the first embodiment, the porous polymer film comprises a polymer mixed with carbonaceous material that is greater than 0 and less than approximately 80% (by weight), (a) When measured using ethoxy-nonafluorobutane HFE7200 at a temperature of approximately 22°C, the bubble point ranges from approximately 2 psi to approximately 200 psi. (b) Isopropanol flow time of approximately 20 seconds / 500ml to approximately 10,000 seconds / 500ml when measured at 14.2 psi, and (c) Shows a G25 particle retention rate of approximately 25% to 100%.

[0079] In the second embodiment according to the first embodiment, the carbonaceous material is selected from the group consisting of activated carbon, carbon black, carbon nanotubes, and graphene.

[0080] A third embodiment according to the first or second embodiment is in which the carbonaceous material is in the form of a powder, particulate material, fibers, or sheets.

[0081] A fourth embodiment according to any of the above embodiments is one in which the G25 particle retention rate is approximately 65% ​​to approximately 80% in a 5% single layer.

[0082] A fifth embodiment according to any of the above embodiments is one in which the film exhibits a bubble point of about 10 psi to about 40 psi.

[0083] A sixth embodiment, according to any of the above embodiments, is one in which the membrane exhibits an isopropanol flow time of approximately 845 seconds / 500 ml to approximately 1665 seconds / 500 ml when measured at 14.2 psi.

[0084] A seventh embodiment according to any of the above embodiments is one in which the polymer contains less than about 65 μg / g of extractable organic compounds and / or metal ions.

[0085] An eighth embodiment according to any of the embodiments described above is one in which the polymer is other than polysulfone or poly(tetrafluoroethane).

[0086] A ninth embodiment according to any of the aforementioned embodiments is one in which the polymer is mixed with approximately 10 to approximately 80% (by weight) of carbonaceous material.

[0087] A tenth embodiment according to any of the above embodiments is one in which the film has a thickness of about 35 to about 400 μm.

[0088] An eleventh embodiment according to any of the above embodiments is in which the polymer is selected from the group consisting of polyamide, polyimide, polyolefin, polyethersulfone, polyacrylate, polyester, cellulose, cellulose ester, polycarbonate, poly(phenylene oxide), poly(styrene), halogenated polymer, and combinations thereof.

[0089] In the twelfth embodiment, the filter includes the porous polymer membrane described in claim 1.

[0090] In the 13th embodiment, the composite film includes a first porous polymer film and a second porous polymer film. The outer surface of the first porous polymer film is in contact with the outer surface of the second porous polymer film. The first porous polymer film contains a first polymer in which a first carbonaceous material is mixed in a quantity greater than 0 and less than approximately 80% (by weight). The second porous polymer membrane is different from the first porous polymer membrane.

[0091] In the 14th aspect according to the 13th aspect, the outer surface of the first porous polymer film is the output-facing surface, and the outer surface of the second porous polymer film is the input-facing surface.

[0092] A 15th aspect according to the 13th or 14th aspect is a composite film in which the composite film is a co-cast film of a first porous polymer film and a second porous polymer film.

[0093] In the sixteenth embodiment, the filter includes the composite film described in claim 13.

[0094] In the seventeenth aspect, a method for preparing a porous polymer film containing a polymer mixed with a carbonaceous material is: a. Combining a carbonaceous material with a flowable form of a polymer, wherein the polymer is (i) mixed with at least one solvent and / or dispersant in an effective amount to provide a flowable form; and / or (ii) heated to a temperature sufficient to provide a flowable form; b. To provide a polymer composition in which a carbonaceous material is mixed by dispersing the carbonaceous material in the polymer; and c. Removing the solvent or dispersant if present, and / or cooling the polymer composition to form a porous polymer film.

[0095] The 18th aspect according to the 17th aspect is characterized in that the polymer is selected from polyamides, polyimides, polyolefins, polyethersulfones, polyacrylates, polyesters, cellulose, cellulose esters, polycarbonates, poly(phenylene oxide), poly(styrene), halogenated polymers, or combinations thereof.

[0096] A 19th aspect according to the 17th or 18th aspect is one in which the polymer contains a mixture of carbonaceous material that is greater than 0 and less than about 80% (by weight).

[0097] In the 20th aspect, a method for removing impurities from a liquid composition is: A liquid composition containing a drug solution and one or more impurities is brought into contact with the porous polymer film described in claim 1, This includes forming a purified liquid composition containing a drug solution and a reduced amount of one or more impurities.

[0098] The 21st aspect according to the 20th aspect is that the drug solution is a ketone or an alcohol.

[0099] A 22nd aspect according to the 20th or 21st aspect is an organic material selected from the group consisting of methyl amyl ketone, ethyl-3-ethoxypropionate, propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), a mixed solution of propylene glycol monomethyl ether (PGME) and PGMEA (e.g., 7:3), methanol, ethyl acetate, ethyl lactate, n-butyl acetate (nBA), isopropyl alcohol (IPA), 2-ethoxyethyl acetate (2EEA), xylene, cyclohexanone, methyl isobutylcarbinol (MIBC), methyl isobutyl ketone (MIBK), isoamyl acetate, undecane, and combinations thereof.

[0100] The 23rd aspect according to the 20th to 22nd aspects is an amine solvent selected from the group consisting of aqueous ammonia, hydroxylamine, monoethanolamine (MEA), triethanolamine (TEA), morpholine, N-methyldiethanolamine (MDEA), N-monomethylethanolamine (MMEA), N-ethylaminoethoxyethanol, 2-(2-aminoethoxy)ethanol, tetraethylammonium hydroxide (TEAH), tetrabutylammonium hydroxide (TBAH), and combinations thereof.

[0101] The 24th embodiment according to the 20th to 23rd embodiments is one in which the chemical solution is deionized water, hydrogen peroxide, hydrochloric acid, sulfuric acid, or a combination thereof.

[0102] The 25th aspect according to the 20th to 24th aspects is one or more impurities being metal ions, acids, bases, peroxides, or organic contaminants.

[0103] A 26th aspect according to the 20th to 25th aspects is one in which the purified liquid composition contains 99.99% by weight or more of the chemical solution and one or more impurities totaling about 2000 ppb or less.

[0104] A 27th aspect according to the 20th to 26th aspects comprises one or more organic amine impurities selected from triethylamine, N,N-diisopropylamine, heptylamine, and 3,3,5,5-tetramethylbenzylidene.

[0105] A 28th aspect according to the 20th to 27th aspects is one or more impurities containing metal ions, and the purified liquid composition contains a total of about 12 ppb or less of metal ions.

[0106] A 29th aspect according to the 28th aspect is characterized in which the metal ion is selected from cations of the group consisting of magnesium, aluminum, titanium, vanadium, manganese, nickel, copper, zinc, molybdenum, silver, cadmium, tin, lead, and combinations thereof.

[0107] In the 30th aspect, the purified liquid composition is purified according to the method of claim 20.

Claims

1. A porous polymer membrane containing ultra-high molecular weight polyethylene mixed with a carbonaceous material greater than 0 and less than 80% by weight, wherein the carbonaceous material is one or more of activated carbon, carbon black, carbon nanotubes, and graphene, and the porous polymer membrane is (a) When measured using ethoxynonafluorobutane HFE7200 at a temperature of 22°C, the bubble point ranges from 2 psi to 200 psi. (b) Isopropanol flow times of 20 seconds / 500 ml to 10,000 seconds / 500 ml when measured at 14.2 psi, and (c) A porous polymer film exhibiting a G25 particle retention rate of 25% to 100%.

2. The G25 particle retention rate is 65% to 80% in a 5% single layer. The porous polymer film exhibits bubble points of 10 psi to 40 psi. The porous polymer membrane according to claim 1, wherein the porous polymer membrane exhibits an isopropanol flow time of 845 seconds / 500 ml to 1665 seconds / 500 ml when measured at 14.2 psi.

3. The polymer of the porous polymer film contains less than 65 μg / g of extractable organic compounds and / or metal ions. The porous polymer film according to claim 1, wherein the ultra-high molecular weight polyethylene is mixed with a carbonaceous material in an amount of 10 to less than 80% by weight.

4. The porous polymer film according to claim 1, wherein the porous polymer film has a thickness of 35 to 400 μm.

5. A filter comprising a porous polymer membrane as described in claim 1.

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