Isoporous and mesoporous asymmetric block copolymer material with macropores and method for producing the same

Abstract

The mesoporous isoporous asymmetric material comprises at least one diblock or multiblock copolymer, wherein the material has a transition layer having a thickness of at least 300 nm and a low macropore density, and the material has a substructure adjacent to the transition layer, wherein the substructure comprises a high macropore density. A method for producing a mesoporous isoporous asymmetric material having macropores may include: dissolving at least one diblock or multiblock copolymer in a solution having one or more solvents and one or more non-solvents to form a polymer solution; dispensing the polymer solution onto a substrate or mold, or dispensing through a die or template; removing at least a portion of the solvent and / or non-solvent from the polymer solution to form a concentrated polymer solution; and exposing the concentrated polymer solution to a non-solvent to precipitate at least a portion of the polymer from the concentrated polymer solution.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of U.S. Provisional Application No. 62 / 641,637, filed on March 12, 2018, which is incorporated herein by reference in its entirety. Technical Field

[0003] Embodiments relate to isoporous and mesoporous asymmetric materials based on diblock or multiblock copolymers including macropores. Background Art

[0004] Mesoporous and homoporous block copolymer materials are known and useful due to their small, uniform pores. Combining an asymmetric structure with a mesoporous and homoporous structure makes the material very useful for high-resolution, high-throughput separations, where the mesoporous and homoporous "skin" enables high-resolution separations and the asymmetric structure enables high throughput. However, manufacturing these materials typically produces macropores, which are considered undesirable. It is widely taught that macropores in membranes are undesirable because they cause mechanical weaknesses and can damage the skin, causing defects.

[0005] Abetz 2014a and Abetz 2015 teach self-assembled diblock copolymer membranes made from solvent mixtures based primarily on tetrahydrofuran (THF) and dimethylformamide (DMF) in varying ratios and various poly(styrene-block-4-vinylpyridine) polymers at various concentrations (19 wt% to 35 wt%) and short evaporation windows (5 s to 10 s). In the library of conditions developed, no macropores were shown in the structure of the materials. Abetz 2014b also characterized the adsorption of lysozyme protein near its isoelectric point (11.4). However, these membranes showed a pore size greater than 120 μg / cm 2 and it is taught that lysozyme adsorption is independent of the membrane pore size and the polymer used for membrane formation.

[0006] In addition to the well-known general DMF / THF solvent composition, Abetz 2012, Abetz 2014b, Abetz 2015, Abetz 2017, Peinemann 2010, Peinemann 2011 and Peinemann 2014a also teach diblock copolymer membranes from the following solvent combinations: 1,4-dimethoxybenzene; alkane (DOX) / THF, DOX / DMF, DOX / THF / DMF.

[0007] Peinemann & Abetz 2007 (also see the '694 application) describes a method for forming a homoporous membrane with a sponge-like structure based on the self-assembly of block copolymers. However, none of the structures include macropores. Furthermore, in Peinemann & Nunes 2012, paragraph

[0011] states that "the method (the '694 application) is difficult to reproduce. When the process described in the '694 application is applied to commercially available purified block copolymers, it fails to produce a homoporous membrane." Peinemann & Nunes 2012 also does not include a macroporous structural feature. Although the '694 application states that "optionally, in addition to the solvent, the casting solution may also contain one or more non-solvents for the block copolymer," there is no discussion of the expected effect.

[0008] Peinemann 2014b teaches a DMF / DOX / acetone (24 wt% / 42 wt% / 16 wt%) solvent composition for making diblock copolymer membranes. However, the membranes made from this solution did not include macropores or a transition layer.

[0009] Table of related technologies

[0010] BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Figure 1 is a scanning electron microscope (SEM) image of the disclosed material of Example 1. Figure 1 a, 1c, 1e: 1,4-diol Materials made from SV168 in a polymer solution in dane / acetone (80 wt% / 20 wt% solvent composition). Figure 1 b, 1d, 1f: 1,4-diol Materials made from SV168 in a polymer solution in dane / acetone (60 wt% / 40 wt% solvent composition). Figure 1 a, 1b: homoporous mesoporous materials; Figure 1 c, 1d: Cross-sectional structures near the homoporous mesoporous surface layer; Figure 1 e, 1f: Overall cross-sectional structure.

[0012] Figure 2 is a scanning electron microscope (SEM) image of the disclosed material of Example 1. Figure 2 a and 2d show films in which: SV168 was dissolved in DOX / ACE (70 wt % / 30 wt % solvent composition) at a polymer concentration of 10 wt % with a 60 s evaporation time; Figure 2b and 2e show films where: SV221 was dissolved in DOX / ACE (60 wt% / 40 wt% solvent composition) at a polymer concentration of 10 wt% with a 45 s evaporation time; Figure 2 c and 2f show films where SV273 was dissolved in DOX / ACE (60 wt% / 40 wt% solvent composition) at a polymer concentration of 10 wt% with a 45 second evaporation time. Figure 2 a, 2b, 2c: homoporous and mesoporous surface layer; Figure 2 d, 2e, 2f: Cross-sectional structures near the homoporous mesoporous surface layer.

[0013] Figure 3 is a scanning electron microscope (SEM) image of a comparative example of Example 1 (lacking both macrovoids and transition layer). Figure 3 3a and 3c show films where SV168 was cast from a polymer concentration of 17 wt% in DMF / THF / DOX (33.3 wt% / 33.3 wt% / 33.3 wt% solution composition) and evaporated for 40 seconds. Figure 3 3b and 3d show films where SV168 was cast from a polymer concentration of 19 wt% in DMF / THF (40 wt% / 60 wt% solution composition) and evaporated for 20 seconds. Figure 3 a and 3b: superficial layer; Figure 3 c and 3d: overall cross-sectional structure.

[0014] Figure 4 are photographs of the disclosed and comparative examples from Example 1. Innovative Example Materials with Macropores and Transition Layers Incorporated into a Porous Support ( Figure 4 a) Comparative example of VS without macropores or transition layer ( Figure 4 b) Materials.

[0015] Figure 5 is a graph showing the amount of protein adsorption by materials according to aspects of the present disclosure. DETAILED DESCRIPTION

[0016] The following description of the embodiment(s) is merely exemplary in nature and is in no way intended to limit the disclosed subject matter, its application, or uses.

[0017] As used throughout, ranges are used as shorthand for describing each and every value that is within the range. Any value within the range can be selected as the terminus of the range.

[0018] For the purposes of this specification and the appended claims, unless otherwise indicated, all numbers representing amounts, percentages or ratios and other numerical values used in this specification and the claims should be understood to be modified by the term "about" in all cases. Whether or not explicitly indicated, the use of the term "about" applies to all numerical values. The term generally refers to a numerical range that one of ordinary skill in the art would consider to be a reasonable deviation (i.e., having equivalent functions or results) for the values listed. For example, the term can be interpreted as including deviations of ±10%, or ±5%, or ±1% of a given numerical value, provided that such deviations do not change the final function or result of the value. Therefore, unless otherwise indicated, the numerical parameters set forth in this specification and the appended claims are approximate values that can vary depending on the desired properties that are attempted to be obtained by the present invention.

[0019] It should be noted that, as used in this specification and the appended claims, unless clearly and clearly limited to an object, the expression of the singular form includes plural objects. As used herein, the term "comprises" and its grammatical variants are intended to be non-restrictive, so that the enumeration of items in the list does not exclude other similar items that can replace or be added to the listed items. For example, as used in this specification and the following claims, the terms "comprises", "comprising" and "having" (has) are inclusive (i.e. open-ended), and do not exclude other elements or steps. Therefore, these terms are not only intended to cover the elements or steps of enumeration, but can also include other elements or steps that are not clearly enumerated. In addition, as used herein, when used in combination with element, the use of the term in the singular form can mean "one / kind", but it is also consistent with the meaning of "one / kind or more / kind", "at least one / kind" and "one / kind or more than one / kind". Therefore, in the absence of more constraints, the element limited by the singular form does not exclude the presence of other identical elements.

[0020] The present disclosure relates to homoporous mesoporous block copolymer asymmetric materials comprising a transition layer and also macropores. Embodiments disclosed herein also relate to methods for producing the materials. The disclosed materials exhibit significantly low protein adsorption and bind to porous supports. Comparative materials lacking both macropores and a transition layer exhibit much higher protein adsorption and do not bind to porous supports, both of which are undesirable.

[0021] In the context of the present disclosure, isoporous means having a substantially narrow pore size distribution. For example, a narrow pore size distribution. In the context of the present disclosure, mesoporous means having pore sizes between 1 nm and 200 nm. One surface of the disclosed materials comprises isoporous mesopores, and the one surface is the selective layer or "skin layer." In the context of the present disclosure, macroporous or macroporous means having at least two pore dimensions greater than 1 micron. In the context of the present disclosure, self-supporting means not integrally connected to a porous support material.

[0022] In some embodiments, the material comprises at least one diblock copolymer or multiblock copolymer having a structure of the form AB, BA, BAB, ABAB, BABA, or ABA, wherein A and B represent two different types of block chemistries. In a preferred embodiment, A is a hydrophilic and / or hydrogen-bonding block and B is a hydrophobic block. Suitable hydrogen-bonding and / or hydrophilic blocks include, but are not limited to, polyvinylpyridine, polyethylene oxide, polyacrylic acid, poly(hydroxystyrene), polyacrylates and polymethacrylates, substituted polyacrylates and polymethacrylates. More specific examples of hydrophilic blocks include: poly(acrylic acid), poly(acrylamide), poly(vinylpyridine), poly(vinylpyrrolidone), poly(vinyl alcohol), naturally derived polymers (e.g., cellulose and chitosan), poly(ether), poly(maleic anhydride), poly(N-isopropylacrylamide), poly(styrene sulfonate), poly(allyl hydrochloride), poly(sulfone), poly(ethersulfone), poly(ethylene glycol), poly(2-hydroxyethyl methacrylate). More specific examples of hydrogen bonding blocks include poly(vinylpyridine), poly(ethylene oxide), poly(methacrylate), poly(methyl methacrylate), poly(dimethylethylaminoethyl methacrylate), poly(dimethylaminoethyl methacrylate), poly(acrylic acid), poly(hydroxystyrene), poly(dimethylacrylamide). Suitable hydrophobic blocks may include, but are not limited to, polystyrenes such as polystyrene and poly(alkyl-substituted styrenes), such as poly(α-methylstyrene), polypropylene, poly(vinyl chloride), polybutadiene, poly(isoprene), poly(ethylene-stat-butylene), poly(ethylene-alt-propylene), and polytetrafluoroethylene. In addition, substituted analogs of the above are suitable.

[0023] The cross-sectional structure of the material is asymmetric, wherein the average pore size increases with increasing distance from the surface layer. More specifically, in some embodiments, the surface layer of the material comprises mesoporous and mesoporous pores, and the average pore size increases with increasing distance from the layer. The pore density can be at least 10 13 holes / m 2 to at least 10 14 holes / m 2 within the range.

[0024] Macropores or macropores are pores having at least one characteristic length that is substantially greater than the general size of the surrounding pores. For the purposes of describing the disclosed invention, we define macropores or macropores as pores having at least one characteristic length that is greater than about 0.5 microns. The general shape of the macropores can be, but is not limited to, the following:

[0025] a. spherical: An approximately spherical pore structure having an approximate diameter of at least about 0.5 microns.

[0026] b. tear-shaped : A pore structure having at least two distinct characteristic lengths and at least two characteristic lengths greater than 0.5 micrometers. These pore structures include, but are not limited to, teardrop-like, pear-shaped or pear-shaped, and bell-shaped structures.

[0027] c. Finger-like : A porous structure having at least two dimensions greater than 0.5 micrometers and an aspect ratio greater than 3.

[0028] The isoporous mesoporous material also includes a transition layer having a thickness of at least about 300 nm, wherein a low macropore density exists and one surface comprises a mesoporous isoporous "skin layer". The low macropore density means that the ratio of macropores to mesopores is at most 2×10 -9 For example, for 10 14 holes / m 2 The surface pore density of a general mesoporous homoporous diblock material corresponds to 2×10 5 Macropores / m 2 The transition layer extends to the adjacent substructure with a thickness of about 1 micron to about 500 microns. The macropores are present in a high density in the substructure layer compared to the transition layer. High macropore density means at least 10 6 Macropores / m 2 This high macropore density is significantly higher than the low macropore density of the transition layer. Due to the low macropore density within the surface layer of at least about 300 nm, it will reduce fractures caused by macropores and enhance the overall mechanical integrity. In addition, the distance from the mesoporous homoporous surface layer can mitigate top surface defects caused by the intersection of macropores with the surface layer and prevent any surface defects from propagating into the substructure.

[0029] In at least one embodiment, the transition layer is at least about 300 nm. In at least one embodiment, the transition layer is at least about 350 nm. In at least one embodiment, the transition layer is at least about 400 nm. In at least one embodiment, the transition layer is at least about 450 nm. In at least one embodiment, the transition layer is at least about 500 nm.

[0030] In some embodiments of the material, the mesopores are in the range of about 1 nm to about 200 nm. In some embodiments, the mesopores are in the range of about 5 nm to about 200 nm. In some embodiments, the mesopores are in the range of about 5 nm to about 100 nm. In some embodiments, the mesopores are in the range of about 5 nm to about 50 nm.

[0031] In some applications, large pores may also be desired to reduce the amount of polymer required for the material, making large-scale synthesis more practical while using less starting material. In some embodiments, the mesoporous homoporous material is self-supporting and has a density of less than about 0.26 g / cm 3 In some embodiments, the mesoporous homoporous material is self-supporting and has a dry density of less than about 0.22 g / cm 3 In some embodiments, the mesoporous homoporous material is self-supporting and has a dry density of less than about 0.20 g / cm 3 In some embodiments, the mesoporous homoporous material is self-supporting and has a dry density of less than about 0.18 g / cm 3 In some embodiments, the mesoporous homoporous material is self-supporting and has a dry density of less than about 0.10 g / cm 3 The dry density of the material can be measured by measuring the area and mass of the material on the dry material, and the drying can be carried out by heating in an oven at 65°C for 48 hours.

[0032] In some cases, materials according to the present disclosure can be produced by a method comprising the following steps:

[0033] 1. dissolving at least one diblock or multiblock copolymer in a solution comprising at least one solvent and at least one non-solvent to form a polymer solution;

[0034] 2. Dispensing the polymer solution onto a substrate or mold, or dispensing through a die or template;

[0035] 3. removing at least a portion of the solvent and / or non-solvent from the polymer solution for at least 20 seconds to form a concentrated polymer solution;

[0036] 4. exposing the concentrated polymer solution to a non-solvent such that at least partially dissolved polymer precipitates from the concentrated polymer solution; and

[0037] 5. Optionally, wash the precipitated polymer product.

[0038] In some cases, materials according to the present disclosure can be produced by a method comprising the following steps:

[0039] 1. dissolving at least one diblock or multiblock copolymer in a solution comprising at least 33 wt% of a solvent or combination of solvents and at least 18 wt% of a non-solvent or combination of non-solvents to form a polymer solution;

[0040] 2. Dispensing the polymer solution onto a substrate or mold, or dispensing through a die or template;

[0041] 3. removing at least a portion of the solvent and / or non-solvent from the polymer solution to form a concentrated polymer solution;

[0042] 4. exposing the concentrated polymer solution to a non-solvent such that at least partially dissolved polymer precipitates from the concentrated polymer solution; and

[0043] 5. Optionally, wash the precipitated polymer product.

[0044] In some cases, a mesoporous homoporous asymmetric material comprising macropores and a transition layer can be produced by a method comprising the following steps:

[0045] 1. dissolving at least one diblock or multiblock copolymer in a solution comprising at least 33 wt% of a solvent or combination of solvents and at least 18 wt% of a non-solvent or combination of non-solvents to form a polymer solution;

[0046] 2. Dispensing the polymer solution onto a substrate or mold, or dispensing through a die or template;

[0047] 3. removing at least a portion of the solvent and / or non-solvent from the polymer solution to form a concentrated polymer solution;

[0048] 4. exposing the concentrated polymer solution to a non-solvent to precipitate at least a portion of the polymer from the concentrated polymer solution; and

[0049] 5. Optionally, wash the precipitated polymer product.

[0050] In some cases, a mesoporous homoporous asymmetric material comprising macropores and a transition layer can be produced by a method comprising the following steps:

[0051] 1. dissolving at least one diblock or multiblock copolymer in a solution comprising at least one non-solvent and at least one solvent at a polymer concentration of up to 16 wt % to form a polymer solution;

[0052] 2. Dispensing the polymer solution onto a substrate or mold, or dispensing through a die or template;

[0053] 3. removing at least a portion of the solvent and / or non-solvent from the polymer solution to form a concentrated polymer solution;

[0054] 4. exposing the concentrated polymer solution to a non-solvent such that at least partially dissolved polymer precipitates from the concentrated polymer solution; and

[0055] 5. Optionally, wash the precipitated polymer product.

[0056] In some cases, materials according to the present disclosure can be produced by a method comprising the following steps:

[0057] 1. dissolving at least one diblock or multiblock copolymer in a solution comprising at least one non-solvent and at least one solvent at a polymer concentration of up to 16 wt % to form a polymer solution;

[0058] 2. Dispensing the polymer solution onto a substrate or mold, or dispensing through a die or template;

[0059] 3. removing at least a portion of the solvent and / or non-solvent from the polymer solution to form a concentrated polymer solution;

[0060] 4. exposing the concentrated polymer solution to a non-solvent such that at least partially dissolved polymer precipitates from the concentrated polymer solution; and

[0061] 5. Optionally, wash the precipitated polymer product.

[0062] In some cases, a mesoporous homoporous asymmetric material comprising macropores and a transition layer can be produced by a method comprising the following steps:

[0063] 1. dissolving at least one diblock or multiblock copolymer in a solution comprising at least one solvent and at least one non-solvent to form a polymer solution;

[0064] 2. Dispensing the polymer solution onto a substrate or mold, or dispensing through a die or template;

[0065] 3. removing at least a portion of the solvent and / or non-solvent from the polymer solution for at least 20 seconds to form a concentrated polymer solution;

[0066] 4. exposing the concentrated polymer solution to a non-solvent to precipitate at least a portion of the polymer from the concentrated polymer solution; and

[0067] 5. Optionally, wash the precipitated polymer product.

[0068] In some embodiments, the concentration of the polymer in the polymer solution is from about 3% to 16% by weight. In at least one embodiment, the concentration of the polymer in the polymer solution is from about 5% to about 16% by weight. In at least one embodiment, the concentration of the polymer in the polymer solution is from about 10% to about 16% by weight. In at least one embodiment, the concentration of the polymer in the polymer solution is from about 8% to about 16% by weight. In at least one embodiment of the above materials or methods, at least one diblock copolymer or multiblock copolymer is dissolved in step 1 of one of the above embodiments. In at least one embodiment, the polymer solution and / or material comprises more than one diblock or multiblock copolymer.

[0069] In some embodiments, at least a portion of the solvent and / or non-solvent is removed from the polymer solution for at least about 20 seconds. In at least one embodiment, at least a portion of the solvent and / or non-solvent is removed from the polymer solution for at least about 25 seconds. In at least one embodiment, at least a portion of the solvent and / or non-solvent is removed from the polymer solution for at least about 30 seconds. In at least one embodiment, at least a portion of the solvent and / or non-solvent is removed from the polymer solution for at least about 35 seconds. In at least one embodiment, at least a portion of the solvent and / or non-solvent is removed from the polymer solution for at least about 40 seconds. In at least one embodiment, at least a portion of the solvent and / or non-solvent is removed from the polymer solution for at least about 45 seconds. In at least one embodiment, at least a portion of the solvent and / or non-solvent is removed from the polymer solution for at least about 50 seconds. In at least one embodiment, at least a portion of the solvent and / or non-solvent is removed from the polymer solution for at least about 55 seconds. In at least one embodiment, at least a portion of the solvent and / or non-solvent is removed from the polymer solution for at least about 60 seconds. In at least one embodiment, at least a portion of the solvent and / or non-solvent is removed from the polymer solution for at least about 65 seconds. In some embodiments, for example, solvent and / or non-solvent are removed from polymer solution by evaporative process. In some cases, evaporative process can be carried out under ambient pressure (1 atmospheric pressure). In some cases, evaporative process can be carried out under reduced pressure. In some cases, evaporative process can be carried out in an inert atmosphere such as nitrogen or argon.

[0070] In some embodiments, the polymer solution according to the present disclosure comprises at least one solvent for one or more block copolymers and at least one non-solvent for one or more block copolymers. Any solvent and / or non-solvent in the polymer solution should be miscible with each other. The indication of the solubility or insolubility of the block copolymer or block in a given chemical or mixture of chemical substances depends on the polymer chemical substance and / or composition. In some embodiments, at least one solvent is an ether, such as 1,4-dimethoxybenzene. In some embodiments, the at least one non-solvent is one of the following: ketone, ester, alcohol, sulfoxide, sulfone. Some examples of non-solvents include: acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, dimethyl ketone, cyclohexanone, acetone, ethyl acetate, propyl acetate, ethanol, isopropanol, benzyl alcohol, butanol, dimethyl sulfoxide, and sulfolane.

[0071] In some embodiments, polymer solutions according to the present disclosure comprise at least about 33% of one solvent or a combination of solvents and at least about 18% by weight of one non-solvent or a combination of non-solvents. In some embodiments of the materials or methods, the polymer solution comprises at least 33% of one solvent or a combination of solvents and from about 18% to about 64% by weight of one non-solvent or a combination of non-solvents. In some embodiments, polymer solutions according to the present disclosure comprise from about 33% to about 79% of one solvent or a combination of solvents and from about 18% by weight of one non-solvent or a combination of non-solvents. In some embodiments, polymer solutions according to the present disclosure comprise at least about 50% of one solvent or a combination of solvents and at least about 20% by weight of one non-solvent or a combination of non-solvents. In some embodiments, polymer solutions according to the present disclosure comprise at least about 50% of one solvent or a combination of solvents and at least about 18% by weight of one non-solvent or a combination of non-solvents.

[0072] The solvent / non-solvent percentages totaling 100% may be referred to as "solution composition" and are by weight and include only the weight of the solvent / weight of the non-solvent (i.e., before adding the polymer to the solution to form the polymer solution). In some embodiments, the solution composition according to the present disclosure comprises about 60% of a solvent or a combination of solvents and about 40% by weight of a non-solvent or a combination of non-solvents. In some embodiments, the solution composition according to the present disclosure comprises about 70% of a solvent or a combination of solvents and about 30% by weight of a non-solvent or a combination of non-solvents. In some embodiments, the solution composition according to the present disclosure comprises about 80% of a solvent or a combination of solvents and about 20% by weight of a non-solvent or a combination of non-solvents. In some embodiments of the above methods and materials, at least one diblock copolymer or multi-block copolymer is dissolved in step 1 of one of the above embodiments. In some embodiments of the above methods and materials, the polymer solution or material comprises more than one diblock or multi-block copolymer.

[0073] The radius of curvature of the fracture can be measured on a self-supporting material in a wet state. More specifically, to measure the radius of curvature of the fracture, the wet material is bent around a steel rod or other similar rod or tube of known diameter, thereby forming a "C" shape around the rod. The material is then unfolded and macroscopic cracking is observed along the fold. This test can be performed with the surface facing the rod or away from the rod. The contact length of the material with the rod is about 1 cm. In at least one embodiment, the material according to various aspects of the present disclosure can be folded and spread around a rod with a diameter of up to about 0.020 inches according to the above process without cracking. In at least one embodiment, the material according to various aspects of the present disclosure can be folded and spread around a rod with a diameter of up to about 0.028 inches according to the above process without cracking. In at least one embodiment, the material according to various aspects of the present disclosure can be folded and spread around a rod with a diameter of up to about 0.030 according to the above process without cracking. In at least one embodiment, the material according to various aspects of the present disclosure can be folded and spread around a rod with a diameter of up to about 0.032 inches according to the above process without cracking. In at least one embodiment, the material according to aspects of the present disclosure can be folded and spread according to the above process around a rod up to about 0.035 inches in diameter without cracking. In at least one embodiment, the material according to aspects of the present disclosure can be folded and spread according to the above process around a rod up to about 0.05 inches in diameter without cracking. In at least one embodiment, the material according to aspects of the present disclosure can be folded and spread according to the above process around a rod up to about 0.1 inches in diameter without cracking.

[0074] In some cases, the homoporous mesoporous material according to aspects of the present disclosure is self-supporting. In some cases, the homoporous mesoporous material according to aspects of the present disclosure also includes a porous support or is placed on a porous support. In some cases, the homoporous mesoporous material according to aspects of the present disclosure also includes a plurality of porous supports or is placed on a plurality of porous supports or some combination thereof. The porous support material can be used as a mechanical substrate and provide other mechanical properties such as stability or biocompatibility or other other functionality. The porous support material can include various materials or physical properties for different layers, thicknesses of different layers and variations in pore size and structure. Suitable materials can include braided materials, woven materials or nonwoven materials, such as yarn, cotton, cellulose-based fabrics, rayon, polyester, polyethylene, graphene, graphene oxide, carbon foam, open-cell foam (such as polyurethane base), polystyrene, rayon, metal, metal oxide, or semiconductor mesh support structure. It may be desirable to combine the mesoporous homoporous material with the aforementioned porous support. For example, one or more mesoporous and homoporous materials can be combined with one or more porous support materials to prevent delamination or cracking of the materials, whereas comparable mesoporous and homoporous materials without a transition layer are susceptible to delamination and cracking. While it is recognized that different modes of operation work within the scope of the present invention, in many embodiments, the mechanism of bonding of the materials to the porous support is that the macropores relieve stress at the interface of the porous support, preventing delamination and cracking.

[0075] In some embodiments, at least one of the copolymers comprises an A block and a B block, wherein the A block is hydrophilic and / or hydrogen bonding, and the B block is hydrophobic. In some embodiments, the block structure is a combination of A blocks and B blocks, such as AB, BA, BAB, ABA, BABA, ABAB, and the like. In at least one embodiment, at least one copolymer comprises an A block and a B block, wherein the A block is hydrophilic and / or hydrogen bonding, the B block is hydrophobic, and the A block is poly(vinyl pyridine). In at least one embodiment, at least one copolymer comprises an A block and a B block, wherein the A block is hydrophilic and / or hydrogen bonding, the B block is hydrophobic, and the A block is poly(vinyl pyridine), and the B block is poly(styrene). In at least one embodiment, at least one copolymer comprises an A block and a B block, wherein the A block is hydrophilic and / or hydrogen bonding, the B block is hydrophobic, and the A block is poly(4-vinyl pyridine), and the B block is poly(styrene). In at least one embodiment, at least one copolymer comprises an A block and a B block, wherein the A block is hydrophilic and / or hydrogen bonding, the B block is hydrophobic, and the A block is poly(2-vinylpyridine) and the B block is poly(styrene). In at least one embodiment, at least one copolymer comprises an A block and a B block, wherein the A block is hydrophilic and / or hydrogen bonding, the B block is, the B block is a modified / or substituted poly(styrene), such as poly(hydroxystyrene) or poly(tert-butylstyrene). In at least one embodiment, at least one copolymer comprises an A block and a B block, wherein the A block is hydrophilic and / or hydrogen bonding, the B block is hydrophobic, and the A block is poly(ethylene oxide). Additional embodiments are contemplated from the suitable blocks listed throughout this disclosure.

[0076] If the material is to be used in bio-related applications, it is desirable to have low protein fouling properties. A general method for measuring protein adsorption of membrane materials is by exposing the membrane to a protein solution at a pH near the isoelectric point (IEP) of the protein. The overall charge of the protein is neutral at / around the IEP, so electrostatic interactions between the protein and the membrane can be excluded from the measurement. In the context of the present disclosure, "low protein fouling" is defined as an adsorption of less than 100 μg / cm as measured using the following procedure 2 Lysozyme (Lys) and / or less than 375 μg / cm 2 In some embodiments, the mesoporous homoporous material is a low protein contamination material. In at least one embodiment, the Lys adsorption of the low protein contamination mesoporous homoporous material according to the present disclosure is less than about 80 μg / cm 2In at least one embodiment, the IgG adsorption of the low protein contamination mesoporous homoporous material according to the present disclosure is less than about 300 μg / cm 2 In at least one embodiment, the Lys adsorption of the low protein contamination mesoporous homoporous material according to the present disclosure is less than about 70 μg / cm 2 In at least one embodiment, the IgG adsorption of the low protein contamination mesoporous homoporous material according to the present disclosure is less than about 200 μg / cm 2 .

[0077] The procedure for determining whether a material is low in protein contamination is as follows: Lys (lysozyme, IEP around 11.4, lysozyme from chicken egg white, lyophilized powder, protein ≥90%, ≥40,000 units / mg protein, Sigma-Aldrich) and IgG (immunoglobulin G, IEP around 7.4, gamma-globulin from bovine blood, ≥99% (agarose gel electrophoresis), Sigma-Aldrich) are prepared at room temperature in phosphate buffered saline (PBS, 1X, pH=7.4, Quality Biological, VWR) at a concentration of 1.0 mg / mL at a pH around the IEP of the protein (for Lys, the pH is adjusted by slowly adding sodium hydroxide). 4 mL of a given protein solution is placed in a small closed petri dish with a 4.9 cm 2 area of each material. A separate 4 mL of a given protein solution was placed in a small closed culture dish without material ("control group"). The culture dish was shaken at 80 rpm at 23°C for 16 hours. The material was soaked in 4 mL of the aforementioned PBS buffer solution for 20 minutes. The culture dish containing the original protein solution was labeled "Ads" and the rinsed solution was labeled "Wash". The protein concentration was measured by UV-Vis at 280 nm, and a standard curve for each protein solution was used to correlate UV-Vis adsorption and protein concentration. Protein adsorption on the material can be calculated as follows: Protein adsorption = m (ads,蛋白质) / Material area = ([“Control” concentration g / mL] - [“Ads” concentration g / mL] - [“Washing” concentration g / mL]) * (4.0 mL) / 4.9 cm 2 .

[0078] If the above dimensions are not appropriate (for example, there is not enough area to use the 4.9 cm 2 ), the test process can be adjusted according to the material area. Adsorption tests are performed on different samples of the material, with one measurement for each protein.

[0079] The material can be used as a separation medium in which solutes are separated from a liquid. For example, the material can be used as a membrane for separating solutes by a filtration mechanism.

[0080] Examples of Preferred Embodiments

[0081] Block copolymer poly(styrene-block-4-vinylpyridine) (SV) having the polymer properties shown in Table 1 below was synthesized by anionic polymerization:

[0082]

[0083] Table 1. Polymer properties

[0084] Example 1.

[0085] The polymer SV168 was dissolved in 1,4-dimethoxybenzyl alcohol at a polymer concentration of 10 wt %. Polymer solutions were prepared by mixing dioxane (DOX) / acetone (ACE) (80 wt% / 20 wt% solution composition) and DOX / ACE (60 wt% / 40 wt% solution composition). The polymer solutions were spread onto a porous woven PET support approximately 60 μm thick on top of a glass slide. The film was evaporated at room temperature for 45 seconds and immersed in a water bath. The separator was precipitated in water. Figure 1 The homoporous mesoporous structure of the membrane is shown in Figure 1 a and 1b), cross-sectional structure near the homoporous mesoporous structure ( Figure 1 c and 1d), overall structure ( Figure 1 e and 1f).

[0086] SV168 was dissolved in DOX / ACE (70 wt% / 30 wt% solution) at a polymer concentration of 10 wt%, SV221 was dissolved in DOX / ACE (60 wt% / 40 wt% solution) at a polymer concentration of 10 wt%, and SV273 was dissolved in DOX / ACE (60 wt% / 40 wt% solution) at a polymer concentration of 10 wt%. The polymer solutions were spread on a glass plate with a gate height of approximately 260 μm on a PET woven support with a thickness of approximately 60 μm on top of a glass slide. The films were evaporated at room temperature for 60, 45, and 45 seconds, respectively, and immersed in a water bath. The membranes were precipitated in water. Figure 2 The homoporous mesoporous structure is shown in Figure 2 a, 2b, 2c) and the cross-sectional structure near the homoporous mesoporous surface ( Figure 2 d, 2e, 2f).

[0087] Comparative Example: Polymer SV168 was dissolved in dimethylformamide (DMF) / tetrahydrofuran (THF) / 1,4-dihydrofuran (DMF) at a polymer concentration of 17 wt%. The polymer solution was prepared by dissolving DOX (33.3 wt% / 33.3 wt% / 33.3 wt% solution composition) and DMF / THF (40 wt% / 60 wt% solution composition) at a polymer concentration of 20 wt% to provide a polymer solution. These conditions are consistent with the generally reported casting conditions. The polymer solution was spread on a glass plate with a groove height of about 260 μm on a PET woven support with a thickness of about 60 μm on top of a glass slide. The film was evaporated at room temperature for 40 seconds and 30 seconds, respectively, and the film was immersed in a water bath. Figure 3 As shown, some of the surface structures of the materials are not homoporous, and both lack both macropores and a transition layer. In addition, these comparative example materials tend to delaminate from the porous support and break during handling. The innovative examples successfully bonded to the porous support, while the comparative examples delaminated from the porous support and failed to bond to the support. Figure 4 A macroscopic image is shown in .

[0088] Example 2.

[0089] SV168 was dissolved in 1,4-dimethoxybenzyl alcohol at a polymer concentration of 10 wt %. The polymer was dissolved in dimethylformamide (DMF) / tetrahydrofuran (THF) / 1,4-dihydrofuran (DFU) (70 wt% / 30 wt% solution composition) at a polymer concentration of 17 wt% and in dimethylformamide (DMF) / tetrahydrofuran (THF) / 1,4-dihydrofuran (DFU) (1,4-dihydrofuran (DFU)). The polymer solution was prepared by adding dioxane (DOX) (33.3 wt% / 33.3 wt% / 33.3 wt% solution composition). The polymer solution was spread on a glass plate with a groove height of about 210 μm. There was no porous support material on the glass plate. The film was evaporated at room temperature for 20 seconds and 40 seconds, and the film was immersed in a water bath. After immersion, the film was peeled off from the glass slide and formed into a self-supporting polymer film. The film in Example 3 was cast under the same conditions.

[0090] Measure and record the thickness of the film. The film was punched into an area of 4.9 cm 2 The film was cast into a circle and dried in an oven at 60°C for more than 24 hours. The dry film mass was recorded and the density was calculated (density = mass / volume). Three identical film groups were cast and the average and standard deviation were reported.

[0091]

[0092] Table 2. Density of different membranes

[0093] Example 3.

[0094] Examples of the present disclosure. The same material set as in Example 2 was used in the protein adsorption experiment. The protein adsorption experiment was a modified known procedure (Abetz 2014b) using two different proteins. The protein adsorption test is described in detail above.

[0095] The results are summarized in Figure 5 For each protein, adsorption was much lower in the inventive examples (grey) compared to the comparative examples (black). Lys adsorption in the comparative examples, which lack macropores or a transition layer, is consistent with previous literature (Abetz 2014b). In contrast, both Lys and IgG adsorption were much lower in the homoporous mesoporous asymmetric membranes with macropores and a transition layer.

[0096] Example 4.

[0097] The disclosed membranes were also prepared using mixtures of SV block copolymers. SV142 and SV221 were dissolved in 1,4-dimethoxybenzyl alcohol at different SV ratios at a total polymer concentration of 10 wt%. The polymer solution was spread on a glass plate with a groove height of about 210 μm. There was no porous support material on the glass plate. The film was evaporated at room temperature for 40 seconds and immersed in a water bath. IgG adsorption test and density measurement were performed similarly to the above examples. The results are summarized in Table 3.

[0098]

[0099] Table 3. Density and IgG adsorption of SV mixture membranes.

Claims

1. A mesoporous homoporous asymmetric material comprising macropores and at least one diblock or multiblock copolymer, wherein: a. The material has a transition layer having a thickness of at least 300 nm and a low macropore density, wherein the low macropore density is a ratio of macropores to mesopores of at most 2×10 -9 to define; b. The material has a substructure adjacent to the transition layer, and the substructure comprises a thickness of 1 micron to 500 microns and a high macropore density, wherein the high macropore density means at least 10 6 Macropores / m 2 , and said macropores are defined as pores having at least one characteristic length greater than 0.5 micrometers; as well as c. The surface of the transition layer that does not intersect with the substructure comprises a mesoporous and homoporous surface layer.

2. The material of claim 1, wherein the material exhibits a relative humidity of less than 0.26 g / cm 3 dry density.

3. The material of claim 1 or 2, wherein at least one copolymer comprises A blocks and B blocks, wherein the A blocks are hydrophilic and / or hydrogen bonding, and the B blocks are hydrophobic.

4. The material of claim 3, wherein the A block is poly(vinylpyridine).

5. The material of claim 1 or 2, wherein the material exhibits low protein contamination.

6. The material of claim 1 or 2, wherein the macropores comprise at least one of finger-shaped macropores, spherical macropores, and tear-shaped macropores.

7. The material of claim 1 or 2, wherein at least one copolymer comprises A blocks and B blocks, wherein the A blocks are hydrophilic and / or hydrogen bonding and the B blocks are hydrophobic, and the copolymer further has the following structure: AB, BA, ABA, BAB, ABAB, or BABA.

8. A composite material comprising: porous support; and The material according to any one of claims 1 to 7 provided on the porous support.

9. The composite material according to claim 8, wherein the porous support is selected from woven materials and non-woven materials.

10. The composite material of claim 8, wherein the porous support is a woven material.

11. A method comprising separating a solute from a liquid, the method using a material according to any one of claims 1 to 10 as a separation medium.

12. A method for producing a material according to any one of claims 1 to 7, comprising the steps of: a. dissolving at least one diblock or multiblock copolymer in a solution comprising at least 33 wt % of a solvent or a combination of solvents and at least 18 wt % of a non-solvent or a combination of non-solvents to form a polymer solution; b. distributing the polymer solution onto the mold or distributing it through a template; c. removing at least a portion of the solvent and / or non-solvent from the polymer solution to form a concentrated polymer solution; as well as d. exposing the concentrated polymer solution to a non-solvent to precipitate at least a portion of the polymer from the concentrated polymer solution.

13. The method according to claim 12, wherein in step b, the polymer solution is dispensed onto a substrate or dispensed through a die.

14. The method according to claim 12, further comprising: e. Washing the precipitated polymer product.

15. The method according to any one of claims 12 to 14, wherein at least one block copolymer comprises a hydrophilic and / or hydrogen-bonding A block and a hydrophobic B block.

16. The method of claim 15, wherein the A block is poly(vinylpyridine).

17. The material according to any one of claims 12 to 14, wherein the concentration of the polymer in the polymer solution is from 3% to 30% by weight.

18. The method according to any one of claims 12 to 14, wherein the concentration of the polymer in the polymer solution is from 3% to 16% by weight.

19. The method according to any one of claims 12 to 14, wherein at least part of the solvent and / or non-solvent is removed for at least 20 seconds.

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