Polyquinoline membrane

Abstract

This application relates to poly(quinoline) membranes. In general, this disclosure provides certain membranes used as filter materials in removing metal ions, metal particles, and / or organic contaminants from liquid compositions, particularly those used in the microelectronics industry. The membranes of this disclosure are porous membranes comprising a poly(quinoline) polymer. Advantageously, the poly(quinoline) membranes are thermally and hydrolyzably stable, and therefore can be cleaned with acidic materials such as dilute hydrochloric acid between uses without significant degradation. The poly(quinoline) polymer can be designed to be soluble in certain solvents, thereby enabling the fabrication of the corresponding porous membranes using dip-casting techniques.

Description

Technical Field

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

[0002] Filters are essential tools in modern industry, used to remove unwanted substances from useful fluid streams. Useful fluids treated with filters include water used for manufacturing or processing (e.g., in semiconductor manufacturing), liquid industrial solvents and processing fluids, as well as liquids with medical or pharmaceutical applications. Unwanted substances removed from fluids include impurities and contaminants such as particles, microorganisms, and dissolved chemicals. Specific applications of filters include their use with liquid substances used in the manufacture of semiconductors and microelectronic devices.

[0003] Filters can remove unwanted substances in a variety of ways, such as through size exclusion or through chemical and / or physical interactions with the substances. Some filters are defined by structural materials that provide a porous structure to the filter, and the filter is able to trap particles of a certain size that cannot pass through the pores. Some filters are defined as having structural materials or chemical substances associated with the structural materials that can associate with and interact with substances that pass through the filter. For example, the chemical features of a filter can achieve association with unwanted substances in the material stream that passes through or crosses the filter, trapping those unwanted substances, for example, through ionic, coordination, chelation, or hydrogen bonding interactions. Some filters can remove substances from the filtered material stream using both size exclusion and chemical interaction features simultaneously.

[0004] In some cases, to perform filtration, a filter includes a filter membrane responsible for removing unwanted substances from the fluid passing through it. Where necessary, the filter membrane can be in the form of a flat sheet, and can be wound (e.g., spiral), flat, folded, or disc-shaped. Alternatively, the filter membrane can be in the form of hollow fibers. The filter membrane can be housed within a housing or otherwise supported such that the fluid to be filtered enters through the filter inlet and must pass through the filter membrane before passing through the filter outlet.

[0005] Removing ionic substances (such as dissolved anions or cations) from solutions is important in many industries, including the microelectronics industry, where even minute concentrations of ionic contaminants and particles can adversely affect the quality and performance of microprocessors and memory devices. More specifically, it may be necessary to remove metal-containing substances, including metal ions, from liquid compositions used in device manufacturing. Metal-containing substances can be found in various types of liquids used in microelectronics manufacturing.

[0006] Removing metal-containing substances from liquid compositions remains a variety of unresolved technical challenges. In microelectronic device processing, a wide range of different types of liquid substances are used as processing solvents, cleaning agents, and other processing solutions. Many (if not most) of these substances require extremely high levels of purity. For example, liquid substances (e.g., solvents) used in the photolithography process of microelectronic devices must have very high purity. Specific examples of liquids used in microelectronic device processing include process solutions for techniques such as spin-on glass (SOG), bottom anti-reflective coating (BARC), photolithography, wet chemical etching, and cleaning operations following chemical mechanical polishing, ashing, and etching. Summary of the Invention

[0007] In summary, this disclosure provides certain membranes for use as filter materials in the removal of particulate matter, metal ions, and organic contaminants from liquid compositions, particularly those used in the microelectronics industry. The membranes disclosed herein are porous membranes comprising a polyquinoline polymer. The polyquinoline polymer has a relatively high glass transition temperature (T0). g The temperature range is approximately 200°C to 400°C, and it exhibits excellent thermal stability (approximately 300°C to 500°C). Advantageously, polyquinoline membranes are hydrolytically stable and therefore can be cleaned with acidic detergents such as dilute hydrochloric acid between uses without suffering unwanted degradation. Polyquinoline polymers can be designed to be soluble in certain solvents, thereby enabling the fabrication of corresponding porous membranes via dip-casting techniques. Attached Figure Description

[0008] Figure 1 This is a scanning electron micrograph (SEM) of the membrane in Example 4, showing the porosity of the membrane cross-section at 800x magnification.

[0009] Figure 2 This is a SEM image of the membrane in Example 4, showing the porosity of the membrane surface at 200x magnification. Detailed Implementation

[0010] Unless otherwise expressly stated, the singular forms “a / an” and “the” as used herein include the plural form. Unless otherwise expressly stated, the term “or” as used herein is generally used in its sense to include “and / or”.

[0011] The term "approximately" typically refers to a range of numbers considered equivalent to the value (e.g., having the same function or result). In many cases, the term "approximately" may include numbers rounded to the nearest significant figure.

[0012] Numerical ranges expressed using endpoints include all numbers that fall into the range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

[0013] Filter membranes can be constructed from porous structures having an average pore size that can be selected based on the intended use of the filter (i.e., the type of filtration). Typical pore sizes are in the micrometer or submicrometer range, for example, from about 0.001 μm to about 10 μm. Membranes with an average pore size of about 0.001 μm to about 0.05 μm are sometimes classified as ultrafiltration membranes. Membranes with pore sizes from about 0.05 μm to 10 μm are sometimes called microporous membranes.

[0014] Filter membranes (or simply “membranes”) with pore sizes in the micrometer or submicrometer range can effectively remove unwanted substances from a fluid flow by sieving mechanisms, non-sieving mechanisms, or both. A sieving mechanism is a filtration mode that removes particles from a liquid flow by mechanically retaining them on the surface of the filter membrane. The filter membrane acts by mechanically interfering with particle movement and trapping particles within the filter, thereby mechanically preventing particle flow through the filter. Typically, the particles can be larger than the filter pores. A “non-sieving” filtration mechanism is a filtration mode in which the filter membrane traps suspended particles or dissolved substances contained in the liquid flow passing through the filter membrane in a partially mechanical manner, including, for example, electrostatic mechanisms that attract and trap particles or dissolved impurities on the filter surface and remove them from the liquid flow by electrostatic attraction. The particles can be dissolved or can be solids with a particle size smaller than the pore size of the filter medium.

[0015] In some embodiments of the filtration membranes and methods disclosed herein, the filter comprises a porous filtration membrane in the form of a polymer membrane comprising certain polyquinoline. As used herein, a "porous filtration membrane" is a porous polymer solid comprising porous (e.g., micropore) interconnected channels extending from one surface of the membrane to an opposite surface of the membrane. These channels generally provide tortuous tunnels or pathways through which the filtered liquid must pass.

[0016] The filtration membrane and method disclosed herein can also be used to prevent any particles larger than the pore size (e.g., metal particles) present in a liquid composition from entering the microporous membrane, or to trap particles within the pores of the microporous membrane (i.e., wherein the particles are removed by a sieving-type filtration mechanism).

[0017] Liquid compositions requiring purification can be effectively filtered by the membranes of this disclosure to remove metallic and / or organic contaminants to levels suitable for the desired application. One application in which the filtration materials and methods of this disclosure can be utilized is semiconductor manufacturing, for example, for purifying metals from solutions used for etching and cleaning semiconductor materials. Given the selectivity of their purification capabilities, the filtration membranes and methods of this disclosure are generally particularly useful in photolithography. Advantageously, the filtration membranes and methods of this disclosure are contemplated to effectively remove unwanted amounts of particulate material, such as metal particles, ions, and / or organic contaminants, from these fluids.

[0018] In one embodiment, the metallic contaminants to be removed using the filtration materials and methods of this disclosure include Li, B, Na, K, Mg, Al, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Mo, Cd, Sn, Ba, and Pb ions, individually or in combination of two or more thereof.

[0019] In one embodiment, the metal ions to be removed are selected from iron, chromium, manganese, aluminum, and nickel cations.

[0020] Therefore, in a first aspect, this disclosure provides a porous membrane comprising a polyquinoline polymer, said membrane having a thickness of about 40 μm to about 300 μm. In some embodiments, the membrane has an average pore size of about 10 nm to about 200 nm, or about 10 nm to about 100 nm. Typically, the polyquinoline polymer has a number-average molecular weight (M... n The glass transition temperature is approximately 20,000 to approximately 200,000 Daltons. In some embodiments, the polyquinoline polymer of this disclosure will have a glass transition temperature of approximately 250°C to approximately 350°C.

[0021] In one embodiment, the polyquinoline polymer comprises the portion of formula (I):

[0022]

[0023] Each R is independently selected from hydrogen, phenyl, substituted phenyl, thiophene, or C1-C6 alkyl. In another embodiment, the polyquinoline polymer comprises the portion of formula (II):

[0024]

[0025] Each R is independently selected from hydrogen, phenyl, thiophene (i.e., thiophene group), substituted phenyl or C1-C6 alkyl.

[0026] In another embodiment, the polyquinoline polymer comprises repeating units of formula (III):

[0027]

[0028] Where Y is

[0029] a. oxygen

[0030] b. The divalent ketone portion of the following formula:

[0031]

[0032] c. The divalent sulfone portion of the following formula:

[0033] or

[0034] d. The divalent group in the following formula

[0035]

[0036] Each R is independently selected from hydrogen, phenyl, thiophene (i.e., thiophene group), substituted phenyl or C1-C6 alkyl, and each R 1 It is independently selected from C1-C6 alkyl groups or C1-C6 alkyl groups substituted with one or more fluorine atoms.

[0037] As used herein, the term "substituted phenyl" refers to a phenyl group having one or more substituents selected from halogens; hydroxyl; nitro; C1-C6 alkoxy; C1-C6 alkyl; and a C1-C6 alkyl group substituted one or more times with a group selected from halogens, hydroxyl, or nitro.

[0038] In one embodiment, R is a phenyl group. In another embodiment, -Y- is a divalent group of the following formula.

[0039]

[0040] And R 1 Each is a trifluoromethyl group.

[0041] In some embodiments, the material of the filter membrane may have chemical properties suitable for incorporating chelation or ion exchange functions. This function can be introduced via a coating that can be applied to the membrane, such a coating having functional groups suitable for chelation and / or ion exchange mechanisms to remove impurities. Alternatively, the “R” group in formulas (I), (II), and (III) above can be modified to include such functional groups that can subsequently be used in non-sieving purification mechanisms without applying a coating or other surface treatment to the membrane, such as sulfonic acid groups or other groups used in ion exchange purification methods. Examples of various methods for grafting or otherwise attaching desired functional groups to the surface of a polymer membrane for non-sieving filtration purposes can be found in U.S. Patent No. 10,792,620 (incorporated herein by reference) and U.S. Patent Publications Nos. 2020 / 0406201, 2020 / 0254398, 2020 / 0206691, 2019 / 0329185, and 2018 / 0185835, which are incorporated herein by reference.

[0042] The polyquinolines available in this disclosure can be prepared by known synthetic methods. In this regard, see U.S. Patent Nos. 5,786,071, 5,247,050; 5,648,448 and 6,462,148, which are incorporated herein by reference, and Hong Ma et al., Chem. Mater, 1999, 11, 2218-2225.

[0043] In one example, the polyquinoline of this disclosure as described above in formula (III), wherein each R is a phenyl group and Y is a group of the following formula.

[0044]

[0045] And each R 1 It is trifluoromethyl, that is, a polymer containing repeating units of the following formula:

[0046]

[0047] The monomer can be obtained through formula (A):

[0048]

[0049] Monomer of formula (B):

[0050]

[0051] The preparation is achieved by copolymerization of diphenyl phosphate in a solvent such as m-cresol at elevated temperatures in the presence of diphenyl phosphate.

[0052] The monomer of formula (A) can be prepared in two steps by reacting phenylacetonitrile and 4,4'-dinitrophenyl ether in the presence of sodium hydroxide to form the intermediate of formula (C):

[0053]

[0054] The compound of formula (C) can then be hydrogenated in tetrahydrofuran, for example in the presence of a catalyst such as Pd / C, to provide the compound of formula (A) above.

[0055] The compound of formula (B), namely 2,2-bis(4-acetylphenyl)hexafluoropropane, can be prepared by reacting 2,2-bis(4-carboxyphenyl)hexafluoropropane with methyllithium in tetrahydrofuran and then hydrolyzing it with hydrochloric acid.

[0056] As described above, the membranes disclosed herein can be prepared by an infiltration casting process. In this process, polyquinoline is dissolved in a water-miscible solvent. A suitable solvent for a particular polyquinoline used for this purpose can be determined using Hansen solubility parameter analysis or empirically through repeated trials. In some embodiments, such solvents include water-miscible solvents such as tetrahydrofuran, N-methylpyrrolidone (NMP), N,N-dimethylformamide (DMF), dimethylacetamide (DMAC), dimethyl sulfoxide (DMSO), dioxane, or tetrahydropyran. Polymer nonsolvents are another class of materials that are typically added to polymer solutions to alter their phase separation behavior and produce the desired membrane morphology. In the formation of this membrane, liquids such as water and certain water-miscible organic materials can be used as nonsolvents alone, in combination of nonsolvents, or sequentially. Once in solution, these polymer solutions can be cast into membranes and immersed in nonsolvents / coagulants to induce phase separation and form the porous membranes of this disclosure.

[0057] In one embodiment, water-miscible nonsolvents include C1-C14. 10 Alkyl alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, etc. Additionally, non-solvents can be selected from glycols and glycol ethers, C2-C... 10 Diols and C2-C 10Triol, Tetrahydrofurfuryl alcohol, Ethyl benzoate, Acetonitrile, Acetone, Ethylene glycol, Propylene glycol, 1,3-Propane glycol, Butyryl lactone, Butyl carbonate, Ethyl carbonate, Propylene carbonate, Dipropylene glycol, Diethylene glycol monomethyl ether, Triethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, Triethylene glycol monoethyl ether, Ethylene glycol monopropyl ether, Ethylene glycol monobutyl ether, Diethylene glycol monobutyl ether, Triethylene glycol monohexyl ether, Diethylene glycol monohexyl ether, Ethylene glycol phenyl ether, Propylene glycol methyl ether, Dipropylene glycol Methyl ethers, tripropylene glycol methyl ethers, dipropylene glycol dimethyl ethers, dipropylene glycol ethyl ethers, propylene glycol n-propyl ethers, dipropylene glycol n-propyl ethers, tripropylene glycol n-propyl ethers, propylene glycol n-butyl ethers, dipropylene glycol n-butyl ethers, tripropylene glycol n-butyl ethers, propylene glycol phenyl ethers, ethylene glycol monophenyl ethers, diethylene glycol monophenyl ethers, hexaethylene glycol monophenyl ethers, dipropylene glycol methyl ether acetate, tetraethylene glycol dimethyl ether diester, glycerol carbonates, N-formylmorpholine, triethyl phosphate, and combinations thereof.

[0058] When adding a non-solvent, the formation of the membrane morphology is considered to determine the desired microstructure based on porosity, average pore size, and pore size distribution. Therefore, the desired morphology is provided by selecting the non-solvent, concentration, temperature, etc. In one embodiment, a polyquinoline polymer is dissolved in tetrahydrofuran, blended with isopropanol, cast into a membrane, and then immersed in water to induce phase separation and form a porous filtration membrane.

[0059] Therefore, in another aspect, this disclosure provides a porous membrane comprising a polyquinoline polymer, said membrane having:

[0060] A thickness of approximately 40 μm to approximately 300 μm.

[0061] Average pore size from approximately 10 nm to approximately 200 nm

[0062] The membrane is prepared as follows: a polyquinoline polymer is dissolved in an aqueous miscible solvent to form a solution, then at least one first non-solvent is added, the solution is then cast onto a flat surface to form a coated surface, and the coated surface is then immersed in at least one second non-solvent to achieve the formation of a porous membrane.

[0063] In one embodiment of this aspect, when measured at 14.2 psi, the membrane exhibits an isopropanol flow time greater than about 200 seconds / 500 mL and less than about 50,000 seconds / 500 mL, and when measured with ethoxynonfluorobutane HFE 7200 at a temperature of about 22 °C, the membrane exhibits a bubble point of about 5 to about 400 psi.

[0064] In another embodiment, when measured using ethoxynonfluorobutane HFE 7200 at a temperature of about 22°C, the bubble point is about 5 to about 180 psi.

[0065] In one embodiment, the first non-solvent is isopropanol and the second non-solvent is water.

[0066] In another embodiment, the above-described polyquinoline solution can be filtered through an ion exchange resin or membrane to remove trace metal ions that may be entrained in the polyquinoline raw material. For example, a tetrahydrofuran solution of polyquinoline can be passed through an ion exchange membrane or column containing ion exchange resin beads to remove trace metal ions before forming the membrane of this disclosure.

[0067] As used in this article, "filter" refers to an article having a structure that includes a filter membrane.

[0068] In some embodiments, the filter of this disclosure includes a composite filter configuration. For example, a filter having a composite configuration may comprise two or more filter materials, such as two or more filter articles. For example, the filter may include a first porous polymer membrane comprising the membrane of this disclosure, and a second filter material that does not comprise the membrane of this disclosure or is different from the membrane of this disclosure in some way. The second filter material may also be in the form of a porous membrane, or may be different, for example, having a non-porous form, or other filter materials, such as woven or non-woven materials. The second filter material can be made of the same or different polymer material as the first membrane.

[0069] Therefore, in another aspect, this disclosure provides a composite filter comprising:

[0070] A first filter material and a second filter material, wherein the output-facing surface of the first filter material is in contact with the input-facing surface of the second filter material.

[0071] The first filter material comprises a membrane as set forth herein;

[0072] Furthermore, the second filter material is different from the first filter material.

[0073] As described above, filter membranes can be used to remove particulate materials (such as metal particles) and metal ions or organic contaminants from liquid compositions such as organic solvents. Some specific, non-limiting examples of solvents for photolithography that can be filtered using filter membranes as described herein include: n-butyl acetate (nBA), isopropanol (IPA), ethyl 2-ethoxyacetate (2EEA), cyclohexanone, ethyl lactate, γ-butyrolactone, isopentyl ether, methyl-2-hydroxyisobutyrate, methyl isobutyl methanol (MIBC), methyl isobutyl ketone (MIBK), isopentyl acetate, propylene glycol methyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), and a mixture of propylene glycol monomethyl ether (PGME) and PGMEA (7:3) (i.e., OK73 solvent, with a mixed specific surface tension of 27.7 mN / m).

[0074] For example, in some practical modes, solvents containing metal ions and / or metal impurities (i.e., particulate matter) and / or organic contaminants, such as cleaning solvents or solvents used for resist stripping applications in photolithography, can be obtained in amounts higher than required for the target application to form integrated circuits. For example, metal impurities may be present in the solvent in total amounts at ppm or ppb levels. The solvent is then passed through a filter membrane of this disclosure to remove the metal contaminants, providing a filtered solvent with a metal concentration or amount lower than that in the starting solvent. In certain practical modes, the filter membrane of this disclosure can remove about 25% (wt) or more, about 30% (wt) or more, about 35% (wt) or more, about 40% (wt) or more, about 45% (wt) or more, about 50% (wt) or more, about 55% (wt) or more, about 60% (wt) or more, about 65% (wt) or more, about 70% (wt) or more, about 75% (wt) or more, about 80% (wt) or more, about 85% (wt) or more, about 90% (wt) or more, or about 95% (wt) or more of any one or more metals from the starting solvent.

[0075] Solvents treated to remove metal contaminants can be passed through a filter under desired conditions (e.g., conditions that enhance the removal of metal contaminants from a liquid stream). In some practical models, the solvent is passed through the filter at a temperature of about 120°C or lower, 80°C or lower, or 40°C or lower.

[0076] The solvent is not limited to any particular flow rate through the filter membrane of this disclosure.

[0077] When referring to porous polymer filtration membranes as described herein, such membranes can be characterized based on physical characteristics including pore size, bubble point, and porosity. In this regard, porous polymer filtration membranes can have any pore size that allows the membrane to effectively function as a filtration membrane, such as those described herein, including pores of a certain pore size (average pore size) that are sometimes considered microporous or ultrafiltration membranes. In some embodiments, the porous membrane may have an average pore size in the range of about 10 nm to about 200 nm, or about 10 nm to about 100 nm, wherein the pore size is selected based on one or more factors, including: the particle size or type of impurities to be removed, pressure and pressure drop requirements, and the viscosity requirements of the liquid being processed by the filter. Pore size is often reported as the average pore size of porous materials, which can be measured using known techniques, such as mercury porosimetry (MP), scanning electron microscopy (SEM), liquid displacement microscopy (LLDP), or atomic force microscopy (AFM).

[0078] Bubble point is also a known characteristic of porous membranes. According to the bubble point test method, a sample of a porous polymer filter membrane is immersed in and wetted with a liquid having a known surface tension, and air pressure is applied to one side of the sample. The air pressure is gradually increased. The minimum pressure at which gas flows through the sample is called the bubble point. To determine the bubble point of porous materials, a sample of the porous material is immersed in and wetted with ethoxyne-nonfluorobutane HFE 7200 (available from 3M) at a temperature of 20-25°C (e.g., 22°C). Air pressure is applied to one side of the sample (the side with the larger pore size) using compressed air, and the air pressure is gradually increased. When the membrane is asymmetrical, air pressure is applied to the side of the membrane sample with the larger pore size. Unless otherwise specified, all bubble point values ​​provided herein are measured using the above procedure and are initial bubble points. Examples of useful or preferred porous polymer filter membranes measured using the above procedure according to this specification can be found in all ranges and subranges between about 5 to about 400 psi, about 5 to about 350 psi, about 5 to about 300 psi, about 5 to about 250 psi, about 5 to about 225 psi, about 5 to about 200 psi, about 5 to about 180 psi, about 5 to about 150 psi, about 30 to about 400 psi, about 30 to about 350 psi, about 30 to about 300 psi, about 30 to about 250 psi, about 30 to about 225 psi, about 30 to about 200 psi, about 30 to about 180 psi, about 30 to about 150 psi, about 50 to about 400 psi, about 50 to about 350 psi, about 50 to about 300 psi, about 50 to about 250 psi, about 50 to about 225 psi, about 50 to about 200 psi, about 50 to about 180 psi, and so on. The porous polymer filter layer described herein may have any porosity that allows it to function effectively as described herein. Example porous polymer filter layers can have relatively high porosities, such as at least 60, 70, or 80%. As used herein and in the field of porous materials, the “porosity” (sometimes also referred to as void fraction) of a porous material is a measure of the percentage of void (i.e., “empty”) space in the total volume of the material, and is calculated as the fraction of the void volume of the material to the total volume of the material. A material with zero percentage porosity is entirely solid.

[0079] Advantageously, the balance between bubble point and IPA flow time (affected by aperture and interconnectivity (i.e., morphology)) is optimized according to the desired overall performance.

[0080] The described porous polymer filter membrane can be in the form of a sheet or hollow fiber having any available thickness (e.g., in the range of about 40 μm to about 300 μm, about 80 μm to about 250 μm, or about 120 μm to about 200 μm, or about 140 μm to 180 μm).

[0081] In some embodiments, the membranes of this disclosure are asymmetric.

[0082] The isopropanol (IPA) flow time reported in this paper was measured by passing 500 mL of isopropanol fluid through a membrane with an effective surface area of ​​13.8 cm² at 14.2 psi and 21 °C. 2 The time taken to process the membrane in the 47mm membrane disc is determined.

[0083] The filter membrane can be housed within a larger filter structure, such as a multilayer filter assembly or cartridge in a filtration system. The filter membrane in the filtration system is positioned within a filter housing, for example as part of a multilayer filter assembly or as part of a cartridge, to expose the filter membrane to the flow path of the liquid chemical substance, thereby causing at least a portion of the liquid chemical substance flow to pass through the filter membrane, so that the filter membrane removes a certain amount of impurities or contaminants from the liquid chemical substance. The structure of the multilayer filter assembly or cartridge may include one or more of a variety of additional materials and structures within the filter assembly or cartridge to support the filter membrane, allowing fluid to flow in from the filter inlet, through the membrane (including the filter layer), and through the filter outlet, thereby passing through the filter membrane as it passes through the filter. As described above, the filter membrane supported by the filter assembly or cartridge can be any useful shape, such as a folded cylinder, a cylindrical pad, one or more non-folded (flat) cylindrical sheets, folded sheets, etc.

[0084] Furthermore, as described, the filtration membrane can be characterized by membrane flux, defined as the volumetric flow rate of liquid passing through a unit area of ​​membrane at a given pressure. The membrane flux must be high enough so that a membrane filtration device with a given membrane area can deliver the liquid flow rate necessary for a given application. The flow characteristics of the membrane can also be measured by membrane flow time, which can be considered as the membrane resistance to liquid flow and is defined as the flow of 500 mL of liquid through a membrane with a diameter of 13.8 cm² at 21°C and a pressure of 14.2 psi. 2The time required for a 47 mm effective surface area disc membrane. In some embodiments, the filter membrane described herein may have a relatively low flow time, for example, combined with a relatively high bubble point, and exhibit good filtration performance (e.g., as measured by particle retention). In some embodiments, the isopropanol flow time is greater than about 200 seconds / 500 mL when measured at 14.2 psi. In other embodiments, when measured at 14.2 psi, the isopropanol flow times were greater than about 200 seconds / 500 mL and less than about 50,000 seconds / 500 mL, greater than about 200 seconds / 500 mL and less than about 20,000 seconds / 500 mL, greater than about 200 seconds / 500 mL and less than about 15,000 seconds / 500 mL, greater than about 200 seconds / 500 mL and less than about 8,000 seconds / 500 mL, greater than about 200 seconds / 500 mL and less than about 1,000 seconds / 500 mL, greater than about 500 seconds / 500 mL and less than about 50,000 seconds / 500 mL, and greater than about 500 seconds / 500 mL and less than about 20,000 seconds / 500 mL. 500 mL, greater than about 500 seconds / 500 mL and less than about 15,000 seconds / 500 mL, greater than about 200 seconds / 500 mL and less than about 8,000 seconds / 500 mL, greater than about 500 seconds / 500 mL and less than about 1,000 seconds / 500 mL, greater than about 1,000 seconds / 500 mL and less than about 50,000 seconds / 500 mL, greater than about 1,000 seconds / 500 mL and less than about 20,000 seconds / 500 mL, greater than about 1,000 seconds / 500 mL and less than about 15,000 seconds / 500 mL, greater than about 200 seconds / 500 mL and less than about 8,000 seconds / 500 mL, and any range and subranges therein.

[0085] Therefore, in another aspect, this disclosure provides a method for removing one or more particulate materials and / or metal ions and / or organic contaminants from a liquid composition, said liquid composition comprising at least one particulate material and / or metal ions, said method comprising:

[0086] (i) passing the liquid composition through the membrane of this disclosure, and

[0087] (ii) Reducing the amount of one or more particulate materials and / or metal ions and / or organic contaminants in the liquid composition, thereby providing a purified liquid composition.

[0088] Example

[0089] Example 1 - 5,5'-Oxadiazine (phenyl-2,1-benzisoxazole) (2a):

[0090] Phenylacetonitrile (27.4 mL, 29.70 g, 0.20 mol) was added dropwise to a solution of sodium hydroxide (21.60 g, 0.54 mol) in 120 mL anhydrous methanol and 340 mL tetrahydrofuran (THF) under vigorous stirring in an ice bath. Then, 4,4'-dinitrodiphenyl ether (13.00 g, 0.05 mol) was slowly added in four equal portions, and the mixture was stirred in an ice bath for 5 minutes. The resulting dark green slurry was heated at reflux temperature for 20 hours. After cooling in an ice bath, the resulting dark precipitate was filtered and washed with cold methanol until the methanol wash was clear, yielding a yellow powder (12.60 g, 54%).

[0091] Example 2 - 4,4'-Diamino-3,3'-Di(benzoyl)diphenyl ether (2)

[0092] A total of 0.56 g of 10% palladium on carbon was added to a suspension of compound (C) of formula above (4.00 g, 8.60 mmol) in 35 mL of anhydrous THF and 1.0 mL of triethylamine. The suspension was purged with hydrogen and stirred at room temperature for 27 hours under a hydrogen atmosphere. An additional 0.28 g of 10% palladium on carbon in 10 mL of THF was added to the reaction mixture, and hydrogenation was continued for another 14 hours. The catalyst was removed by filtration, and the solvent was removed by rotary evaporation under reduced pressure. The resulting oil was purified by passing it through a silica gel column with hexane / ethyl acetate (1:1) as the eluent to give yellow crystals (2.80 g, 70%).

[0093] Example 3 – Synthesis of a representative polyquinoline polymer

[0094] A mixture of compound (A) (2.00 mmol), compound (B) (2.00 mmol), diphenyl phosphate (DPP) (12.51 g, 50.0 mmol), and freshly distilled m-cresol (2.40 mL, 23.0 mmol) was placed in a three-necked flask. The reaction mixture was purged with nitrogen for about 20 minutes with stirring, and then heated from room temperature to 135–140 °C in an oil bath over about 30 minutes. This mixture was maintained at this temperature under a nitrogen atmosphere for 48 hours.

[0095] After cooling, the resulting viscous solution was added dropwise to a stirred solution of 400 mL methanol containing 10% v / v triethylamine. The precipitated polymer was redissolved in 30 mL chloroform or tetrahydrofuran and reprecipitated by slowly adding it to a stirred solution of 400 mL methanol containing 10% v / v triethylamine. The polymer was collected by filtration and continuously extracted with a methanol solution containing 10% v / v triethylamine in a Soxhlet extractor for 24 hours, followed by vacuum drying at 100 °C for 24 hours to obtain a grayish-white polymer (1.51 g) with a yield of 96%.

[0096] Example 4 – Preparation of Filter Membranes

[0097] A 6.8 g sample of polyquinoline (PQ) polymer in powder form, typically prepared as in Example 3, was added to 50 g of tetrahydrofuran (THF) solvent with stirring using a top-mounted stirrer. After the polymer was completely dissolved, 15.5 g of isopropanol (IPA) was added to the solution as a non-solvent. The PQ membrane was prepared by casting a polymer solution film of approximately 150 to 200 micrometers thickness onto glass and then immersing it in a water bath at room temperature. The formed membrane was dried at room temperature for 24 hours. The IPA flow time and bubble point of the membrane were then measured, and the results are shown in the table below.

[0098] Material weight ratio IPA Flow Time Initial bubble point ASTM average bubble point (psi) *PQ / THF / IPA = 6.8 / 50 / 15.5 780 seconds / 500mL 3.57psi 12.6psi

[0099] aspect

[0100] Therefore, in a first aspect, this disclosure provides a porous membrane comprising a polyquinoline polymer having a thickness of about 40 μm to about 300 μm.

[0101] In a second aspect, this disclosure provides a membrane of the first aspect, wherein the membrane exhibits a bubble point of about 5 to about 400 psi when measured using ethoxynonfluorobutane HFE 7200 at a temperature of about 22°C.

[0102] In a third aspect, this disclosure provides a membrane of the first or second aspect, wherein the membrane has an average pore size of about 10 to about 200 nm.

[0103] In a fourth aspect, this disclosure provides a membrane according to any one of the first to third aspects, wherein the polyquinoline polymer comprises a portion of the following formula:

[0104]

[0105] Each R is independently selected from hydrogen, phenyl, substituted phenyl, thiophene, or C1-C6 alkyl.

[0106] In a fifth aspect, this disclosure provides a membrane according to any one of the first to fourth aspects, wherein the polyquinoline polymer comprises a portion of the following formula:

[0107]

[0108] Each R is independently selected from hydrogen, phenyl, thiophene, substituted phenyl, or C1-C6 alkyl.

[0109] In a sixth aspect, this disclosure provides a membrane for either the fifth or sixth aspect, wherein each R is hydrogen.

[0110] In a seventh aspect, this disclosure provides a membrane of the fifth or sixth aspect, wherein one R is hydrogen and the other R is phenyl.

[0111] In an eighth aspect, this disclosure provides a membrane according to any one of the first to seventh aspects, wherein the polyquinoline polymer comprises repeating units of formula (III):

[0112]

[0113] Where Y is selected from:

[0114] a) Oxygen,

[0115] b) The divalent ketone portion of the following formula:

[0116]

[0117] c) The divalent sulfone portion of the following formula:

[0118] or

[0119] d) The divalent group in the following formula

[0120]

[0121] Each R is independently selected from hydrogen, phenyl, thiophene, substituted phenyl, or C1-C6 alkyl, and each R 1 It is independently selected from C1-C6 alkyl groups or C1-C6 alkyl groups substituted with one or more fluorine atoms.

[0122] In the ninth aspect, this disclosure provides a membrane of the eighth aspect, wherein R is a phenyl group.

[0123] In a tenth aspect, this disclosure provides a membrane according to an eighth or ninth aspect, wherein Y is a group of the following formula.

[0124]

[0125] And each R 1 It is trifluoromethyl.

[0126] In the eleventh aspect, this disclosure provides a membrane according to any one of the first to tenth aspects, wherein when measured at 14.2 psi, the membrane exhibits an isopropanol flow time greater than about 200 seconds / 500 mL and less than about 50,000 seconds / 500 mL, and when measured at a temperature of about 22 °C using ethoxynonfluorobutane HFE 7200, the membrane exhibits a bubble point of about 5 to about 300 psi.

[0127] In a twelfth aspect, this disclosure provides a porous membrane comprising a polyquinoline polymer, the membrane having:

[0128] A thickness of approximately 40 μm to approximately 300 μm, and

[0129] Average pore size from approximately 10 nm to approximately 200 nm

[0130] The preparation is as follows: a polymer is dissolved in an aqueous miscible solvent to form a solution, then at least one first non-solvent is added, the solution is then cast onto a flat surface to form a coated surface, and the coated surface is then immersed in at least one second non-solvent to achieve the formation of a porous membrane.

[0131] In a thirteenth aspect, this disclosure provides a membrane of the twelfth aspect, wherein when measured at 14.2 psi, the membrane exhibits an isopropanol flow time greater than about 200 seconds / 500 mL and less than about 50,000 seconds / 500 mL, and when measured at a temperature of about 22 °C using ethoxynonfluorobutane HFE 7200, the membrane exhibits a bubble point of about 5 to about 400 psi.

[0132] In the fourteenth aspect, this disclosure provides a membrane of the twelfth or thirteenth aspect, which further includes the step of purifying the solution by means of ion exchange resin or membrane filtration before casting the solution onto a flat surface, thereby removing trace metal ion contaminants.

[0133] In the fifteenth aspect, this disclosure provides a membrane of any one of aspects 12 to 14, wherein the first non-solvent comprises isopropanol.

[0134] In a sixteenth aspect, this disclosure provides a membrane of any one of aspects twelfth to fifteenth, wherein the second non-solvent comprises water.

[0135] In a seventeenth aspect, this disclosure provides a membrane of any one of aspects twelve to sixteen, wherein the water-miscible solvent is selected from tetrahydrofuran, N-methylpyrrolidone, N,N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, dioxane, or tetrahydropyran.

[0136] In the eighteenth aspect, this disclosure provides a membrane according to any one of the twelfth to seventeenth aspects, wherein the water-miscible solvent comprises tetrahydrofuran.

[0137] In a nineteenth aspect, this disclosure provides a method for removing one or more particulate materials and / or metal ions and / or organic contaminants from a liquid composition, said liquid composition comprising at least one particulate material and / or metal ions and / or organic contaminants, said method comprising:

[0138] (i) passing the liquid composition through a membrane according to any one of aspects 1 to 18, and

[0139] (ii) Reducing the amount of one or more particulate materials and / or metal ions and / or organic contaminants in the liquid composition, thereby providing a purified liquid composition.

[0140] In a twentieth aspect, this disclosure provides a method of the nineteenth aspect, wherein the liquid composition comprises a solvent selected from the group consisting of: n-butyl acetate, isopropanol, ethyl 2-ethoxyacetate, cyclohexanone, ethyl lactate, γ-butyrolactone, isopentyl ether, methyl-2-hydroxyisobutyrate, methyl isobutyl methanol, methyl isobutyl ketone, isopentyl acetate, propylene glycol methyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, and combinations thereof.

[0141] In its twenty-first aspect, this disclosure provides a filter comprising a membrane comprising any one of the first to eighteenth aspects.

[0142] In a twenty-second aspect, this disclosure provides a composite filter comprising:

[0143] A first filter material and a second filter material, wherein the output-facing surface of the first filter material is in contact with the input-facing surface of the second filter material.

[0144] The first filter material comprises a membrane according to any one of aspects 1 to 18.

[0145] Furthermore, the second filter material is different from the first filter material.

[0146] Several illustrative embodiments of this disclosure have been described thus; it will be readily understood by those skilled in the art that other embodiments can still be made and used within the scope of this application. Many advantages of this disclosure as covered herein have been set forth in the foregoing description. However, it should be understood that this disclosure is illustrative in many respects only. Of course, the scope of the invention is defined in the language expressed herein.

Claims

1. A porous membrane comprising a polyquinoline polymer, said membrane having a thickness of 40 μm to 300 μm; The polyquinoline polymer described herein comprises repeating units of formula (III): Where Y is selected from: a. oxygen b. The divalent ketone portion of the following formula: c. The divalent sulfone portion of the following formula: or d. The divalent group in the following formula Each R is independently selected from hydrogen, phenyl, thiophene, substituted phenyl, or C1-C6 alkyl, and each R 1 It is independently selected from C1-C6 alkyl groups or C1-C6 alkyl groups substituted with one or more fluorine atoms.

2. The porous membrane according to claim 1, wherein R is a phenyl group.

3. The porous membrane according to claim 1, wherein Y is a group of the following formula. And each R 1 It is trifluoromethyl.

4. The porous membrane according to claim 1, wherein the membrane comprises: Average pore size from 10 nm to 200 nm The membrane is prepared by dissolving the polymer in an aqueous miscible solvent to form a solution, then adding at least one first non-solvent, then casting the solution onto a flat surface to form a coated surface, and then immersing the coated surface in at least one second non-solvent to achieve the formation of the porous membrane.

5. A method for removing one or more particulate materials and / or metal ions and / or organic contaminants from a liquid composition, said liquid composition comprising at least one particulate material and / or metal ions and / or organic contaminants, said method comprising: (i) passing the liquid composition through the porous membrane according to claim 1, and (ii) Reducing the amount of one or more particulate materials and / or metal ions and / or organic contaminants in the liquid composition, thereby providing a purified liquid composition.

6. A filter comprising the porous membrane according to claim 1.

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