WO2024089493A1 - Membranes polymères poreuses comprenant un réseau à motifs de trous traversants et leurs procédés de fabrication - Google Patents

Membranes polymères poreuses comprenant un réseau à motifs de trous traversants et leurs procédés de fabrication Download PDF

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Publication number
WO2024089493A1
WO2024089493A1 PCT/IB2023/059543 IB2023059543W WO2024089493A1 WO 2024089493 A1 WO2024089493 A1 WO 2024089493A1 IB 2023059543 W IB2023059543 W IB 2023059543W WO 2024089493 A1 WO2024089493 A1 WO 2024089493A1
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pores
micrometers
porous polymeric
polymeric membrane
protrusions
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PCT/IB2023/059543
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English (en)
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Neelakandan Chandrasekaran
Jr. Olester Benson
Rajendra H. VISHNUMURTHY
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3M Innovative Properties Company
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Publication of WO2024089493A1 publication Critical patent/WO2024089493A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/08—Flat membrane modules
    • B01D63/081—Manufacturing thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/52—Use of a mould
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/08—Patterned membranes

Definitions

  • the present disclosure generally relates to porous polymeric membranes.
  • a porous polymeric membrane in a first aspect, includes a) a first outer surface having a patterned array of first pores having irregularly shaped perimeters; b) an opposing second outer surface having a plurality of second pores; and c) a polymeric matrix extending between the first outer surface and the second outer surface.
  • the polymeric matrix defines a plurality of through holes that extend between the first pores and the second pores.
  • a method in a second aspect, includes applying a casting solution to a tooling structure having a major surface and a patterned array of protrusions extending orthogonally therefrom, to form a layer of the casting solution.
  • the casting solution includes a polymer component and a solvent system.
  • the method further includes contacting the layer of the casting solution with a nonsolvent fluid to solidify the polymer component and form a porous polymeric membrane; and removing the porous polymeric membrane from the tooling structure, thereby providing a porous polymeric membrane.
  • the porous polymeric membrane includes 1) a first outer surface having a patterned array of first pores having irregularly shaped perimeters that do not correspond to a shape of a top of the plurality of protrusions; 2) an opposing second outer surface having a plurality of second pores; and 3) a polymeric matrix extending between the first outer surface and the second outer surface.
  • the polymeric matrix defines a plurality of through holes that extend between the first pores and the second pores.
  • FIG. 1 is a schematic perspective view of an exemplary porous polymeric membrane according to the present disclosure.
  • FIG. 2A is a scanning electronic microscopy (SEM) image of a portion of a first surface of an exemplary infiltrated three-dimensional article according to the present disclosure.
  • FIG. 2B is an SEM image of a portion of a second surface of the exemplary infiltrated three-dimensional article of FIG. 2A.
  • FIG. 3 is a flow chart of an exemplary method according to the present disclosure
  • FIG. 4 is a schematic cross-sectional schematic of a porous polymeric membrane formed on a tooling structure in which pores on a surface of the membrane do not correspond to a shape of a top of the tooling structure protrusions.
  • FIG. 5 is a schematic cross-sectional schematic of a tooling structure having protrusions with a stem and a head for use in methods according to the present disclosure.
  • the term “diameter” refers to the longest distance measurable along a cross-section of an element (e.g., pore, through hole, protrusion head, protrusion stem).
  • An average diameter is the average of 25 or more measured diameters.
  • microporous refers to having multiple pores that have an average dimension (in some cases, diameter) of up to 500 micrometers. At least some of the multiple pores should have a dimension on the order of or larger than the wavelength of visible light. For example, at least some of the pores should have a dimension (in some cases, diameter) of at least 400 nanometers. Pore size is measured by measuring bubble point according to ASTM F-316-80.
  • the thickness of a membrane should be understood to be its smallest dimension. It is generally referred to as the “z” dimension and refers to the distance between the major surfaces of the membrane.
  • the term “upstanding” with regard to the tooling protrusions refers to posts that protrude from a major surface and includes posts that stand perpendicular to the major surface and posts that are at an angle to the major surface other than 90 degrees.
  • aliphatic group means a saturated or unsaturated linear, branched, or cyclic hydrocarbon group. This term is used to encompass alkyl, alkenyl, and alkynyl groups, for example.
  • Alkyl means a linear or branched, cyclic or acyclic, saturated monovalent hydrocarbon having from one to thirty-two carbon atoms, e.g., methyl, ethyl, 1 -propyl, 2-propyl, pentyl, and the like.
  • Alkylene means a linear saturated divalent hydrocarbon having from one to twelve carbon atoms or a branched saturated divalent hydrocarbon radical having from three to twelve carbon atoms, e.g., methylene, ethylene, propylene, 2-methylpropylene, pentylene, hexylene, and the like.
  • alkenyl and ene refers to a monovalent linear or branched unsaturated aliphatic group with one or more carbon-carbon double bonds, e.g., vinyl.
  • (meth)acrylate is a shorthand reference to acrylate, methacrylate, or combinations thereof
  • (meth)acrylic is a shorthand reference to acrylic, methacrylic, or combinations thereof
  • (meth)acryl is a shorthand reference to acryl and methacryl groups.
  • Acryl refers to derivatives of acrylic acid, such as acrylates, methacrylates, acrylamides, and methacrylamides.
  • (meth)acryl is meant a monomer or oligomer having at least one acryl or methacryl groups, and linked by an aliphatic segment if containing two or more groups.
  • (meth)acrylate-functional compounds are compounds that include, among other things, a (meth)acrylate moiety.
  • micro refers to at least one dimension defining a structure or shape being in a range from 1 micrometer to 1 millimeter.
  • a microstructure may have a height or a width that is in a range from 1 micrometer to 1 millimeter.
  • a “resin” contains all polymerizable components (monomers, oligomers and/or polymers) being present in a hardenable composition.
  • the resin may contain only one polymerizable component compound or a mixture of different polymerizable compounds.
  • glass transition temperature (T g ), of a polymer refers to the transition of a polymer from a glassy state to a rubbery state and can be measured using Differential Scanning Calorimetry (DSC), such as at a heating rate of 10 °C per minute in a nitrogen stream.
  • DSC Differential Scanning Calorimetry
  • a suitable DSC method and mode of analysis is as described in Matsumoto, A. et. al., J. Polym. Sci. A., Polym. Chem. 1993, 31, 2531-2539.
  • thermoplastic refers to a polymer that flows when heated sufficiently above its glass transition point and become solid when cooled.
  • thermoset refers to a polymer that permanently sets upon curing and does not flow upon subsequent heating.
  • Thermoset polymers are typically crosslinked polymers.
  • the term “generally”, unless otherwise specifically defined, means that the property or attribute would be readily recognizable by a person of ordinary skill but without requiring absolute precision or a perfect match (e.g., within +/- 20 % for quantifiable properties).
  • the term “substantially”, unless otherwise specifically defined, means to a high degree of approximation (e.g., within +/- 10% for quantifiable properties) but again without requiring absolute precision or a perfect match. Terms such as same, equal, uniform, constant, strictly, and the like, are understood to be within the usual tolerances or measuring error applicable to the particular circumstance rather than requiring absolute precision or a perfect match.
  • CAP cast and precipitate
  • NIPS nonsolvent induced phase separation
  • CAP allows etch-free single step continuous fabrication.
  • CAP processes are generally compatible with any ternary pairs of polymer-solvent-nonsolvent, which can be a significant advantage from each of a commercialization and scale-up perspective.
  • a suitable tooling surface can include protrusions that have both a head and a stem, wherein the formed porous polymeric membrane can be removed from the protrusions without walls of the through holes being destroyed by the head, as discussed in greater detail below.
  • porous polymeric membrane comprises:
  • a porous polymeric membrane 100 comprises a first outer surface 110 having a patterned array of first pores 120 having irregularly shaped perimeters; an opposing second outer surface 130 having a plurality of second pores 140; and a polymeric matrix 150 extending between the first outer surface 110 and the second outer surface 130.
  • the polymeric matrix 150 defines a plurality of through holes 160 that extend between the first pores 120 and the second pores 140, the through holes being bound by walls 170.
  • the patterned array comprises a grid of pores that are spaced (approximately) equally from adjacent pores, located in rows and columns. Any deliberate pattern useful for filtration is suitable for the array.
  • the plurality of second pores 140 have regularly shaped perimeters, e.g., circular perimeters.
  • the first pores 120 have a size (e.g., diameter) that is smaller than the size (e.g., diameter) of the second pores 140 and generally include a group of four small pores instead of one larger pore.
  • the term “irregular” with respect to the perimeter of a pore refers to the perimeter having a shape that is uneven or unbalanced. Often, the perimeter of an irregularly shaped pore is asymmetric due to the lack of evenness or balance in an otherwise symmetric shape (e.g., equilateral triangle, circle, square, etc.). For instance, an irregular circular pore has a perimeter that is not a perfect circle, see, e.g., the pore indicated by reference number 224 in FIG. 2A.
  • Pore shape and/or size can be determined using any commonly known microscopic methods. For example, optical microscopy or scanning electron microscopy can be used in combination with any image analysis software. For example, software commercially available as free ware under the trade designation “IMAGE J” from NIH, Bethesda, MD.
  • a tooling surface used in cast and precipitate processes can include protrusions that have both a head and a stem and that the formed porous polymeric membrane can be removed from the protrusions without walls of the through holes being destroyed by the heads of the protrusions.
  • removal of the porous polymeric membrane does form a tear in the perimeter of at least some of the pores on the first outer surface or the second outer surface as the membrane passes over the heads.
  • FIG. 2A shows a tear 222 in the perimeter of a pore 220 on a surface 210 of a porous polymeric membrane 200.
  • An advantage of employing protrusions that have both a head and a stem is that the head can assist in securing the layer of casting solution in place on the tooling structure during the precipitation process to form the porous polymeric membrane (e.g., if submerged in a nonsolvent fluid), thus decreasing the chance that the membrane will separate from the tooling structure undesirably early.
  • the first pores and the second pores have perimeters that are different from each other in at least one of shape (e.g., regular versus irregular) or size.
  • FIGS. 2A- 2B provide an example of first pores 220 and second pores 240 that have different pore sizes. More particularly, FIG. 2A is a scanning electron microscope (SEM) image of a portion of a first surface 210 of a porous polymeric membrane 200 formed of polyethersulfone including a plurality of first pores 220 having irregularly shaped perimeters. Through holes 260 and the polymeric matrix 250 are visible through at least some of the first pores 220.
  • SEM scanning electron microscope
  • FIG. 2B is an SEM image of a portion of a second surface 230 of the polymeric membrane 200 including a plurality of second pores 240.
  • the plurality of second pores 240 have both a different shape (irregular ovals) and a different size (smaller) than the plurality of first pores 220 in FIG. 2A. This was achieved by applying a layer of casting solution on a tooling structure that had a thickness greater than the height of the protrusions.
  • the protrusions had a shape of a head on a stem, in particular a T-shape, and outer edges of the head tended to form the second pores 240. For instance, the four second pores 240 indicated in FIG.
  • the second pores 240 each correspond to a location of four edges of the head (e.g., the top of the “T”) of one stem.
  • the second pores 240 have an average area that is less than half of an average area of the first pores 220.
  • the first pores optionally have an average area that is less than half of an average area of the second pores.
  • the polymeric matrix 250 that is located adjacent to the through holes 260 and extends between the first surface 210 and the second surface 230 is porous.
  • the polymeric matrix located adjacent to the through holes is nonporous.
  • the distance between adjacent through holes affects whether or not the polymeric matrix is porous, with small distances (e.g., less than 10 micrometers) being more likely to have nonporous polymeric matrices.
  • first pores and second pores may have similar pore sizes but different pore shapes.
  • a plurality of first pores can have irregularly shaped perimeters (e.g., irregular circles), whereas a plurality of second pores can have a different shape (e.g., regular circles) than the plurality of first pores.
  • This can be achieved by applying a layer of casting solution on a tooling structure that has a thickness smaller than the height of the protrusions.
  • the protrusions may have a shape of a head on a stem, and removal of the porous polymeric membrane from the tooling structure tends to deform the perimeters of at least some of the first pores to result in them having irregularly shaped perimeters.
  • At least one of the through holes, first pores, or second pores of a porous polymeric membrane have an average diameter of 1 micrometer or greater, 2 micrometers or greater, 3 micrometers, 5 micrometers, 7 micrometers, 10 micrometers, 12 micrometers, 15 micrometers, 20 micrometers, 25 micrometers, 30 micrometers, 35 micrometers, 40 micrometers, 45 micrometers, 50 micrometers, 60 micrometers, 70 micrometers, 80 micrometers, 90 micrometers, 100 micrometers, 110 micrometers, 120 micrometers, 120 micrometers, 140 micrometers, or 150 micrometers or greater; and 500 micrometers or less, 475 micrometers, 450 micrometers, 425 micrometers, 400 micrometers, 375 micrometers, 350 micrometers, 325 micrometers, 300 micrometers, 275 micrometers, 250 micrometers, 225 micrometers, 200 micrometers, 190 micrometers, 180 micrometers, 170 micrometer
  • the through holes have an average diameter of 1 micrometer to 500 micrometers or 10 micrometers to 300 micrometers.
  • the average diameter of the through holes is typically determined at either the first outer surface or the second outer surface of the porous polymeric membrane.
  • the diameter of the through holes may vary between the first outer surface and the second outer surface through the thickness of the porous polymeric membrane, e.g., when a tooling structure has protrusions with cross-sections that vary along the height of the protrusions.
  • the through holes are isoporous. Isoporous through holes may be provided by employing a tooling structure that has protrusions of the same size.
  • the porous polymeric membrane has a thickness between the first outer surface and the second outer surface of 1 micrometer or greater, 2 micrometers, 5 micrometers, 7 micrometers, 10 micrometers, 12 micrometers, 15 micrometers, 20 micrometers, 25 micrometers, 30 micrometers, 35 micrometers, 40 micrometers, 45 micrometers, 50 micrometers, 60 micrometers, 70 micrometers, 80 micrometers, 90 micrometers, 100 micrometers, 125 micrometers, 150 micrometers, 175 micrometers, 200 micrometers, 225 micrometers, 250 micrometers, 275 micrometers, 300 micrometers, 325 micrometers, 350 micrometers, 400 micrometers, 450 micrometers, or 500 micrometers or greater; and 5 millimeters (mm) or less, 4.5 mm, 4 mm, 3.5 mm, 3 mm, 2.5 mm, 2 mm, 1.5 mm, 1 mm, 950 micrometers, 900 micrometers, 850
  • the through holes/first pores have a density on the first outer surface imparted by the density of protrusions on a major surface of the tooling structure employed to prepare the porous polymeric membrane.
  • the density of the first pores and through holes on the first outer surface is 50 per square centimeter (cm 2 ) or greater, 75 per cm 2 , 100 per cm 2 , 125 per cm 2 , 150 per cm 2 , 175 per cm 2 , 200 per cm 2 , 225 per cm 2 , or 250 per cm 2 or greater.
  • An upper maximum of density of through holes and first pores is limited by the diameters of the heads of the protrusions on the tooling structure. More particularly, if the heads of the protrusions get too close together (or touch) it will be difficult to successfully remove the porous polymeric matrix from the tooling structure with intact through holes and/or pores.
  • the polymeric matrix comprises polyethersulfone, polypropylene, polysulfone, polyacrylonitrile, a cellulose ester, a polyimide, a polyamide, poly(vinylidene fluoride), or poly (tetrafluoroethylene).
  • the polymeric matrix comprises polyethersulfone or amorphous nylon.
  • Suitable commercially available polyethersulfones are from BASF (Wyandotte, MI) under the trade designation “ULTRASON E6020” and “ULTRASON E7020”.
  • a suitable commercially available amorphous nylon is from Evonik Industries (Essen, Germany) under the trade designation “TROGAMID CX9704”.
  • the present disclosure provides a method comprising:
  • Step 310 to apply a casting solution to a tooling structure comprising a major surface and a patterned array of protrusions extending orthogonally therefrom, to form a layer of the casting solution, the casting solution comprising a polymer component and a solvent system.
  • the layer of the casting solution has a thickness smaller than the height of the protrusions while in other embodiments, the layer of the casting solution has a thickness equal to the height of the protrusions.
  • the layer of the casting solution typically employing a casting solution layer thickness of equal or smaller height than the protrusion height results in a precipitated membrane having a thickness smaller than the protrusion height due to shrinkage during the precipitation process.
  • the layer of the casting solution has a thickness larger than the height of the protrusions.
  • a casting solution layer having a thickness larger than the height of the protrusions can result in a porous polymeric membrane having pores that are smaller than the size of the top of the protrusions (e.g., the size of heads of the protrusions), such as shown in FIG. 2B and described above.
  • the casting solution may be applied to the tooling structure by any suitable means, for instance and without limitation, roller coating, flow coating, dip coating, spin coating, spray coating, knife coating, or die coating.
  • the casting solution comprises a solids content of 5 percent by weight (wt.%) or greater, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%, 11 wt.%, 12 wt.%, 13 wt.%, 14 wt.%, or 15 wt.% or greater; and 50 wt.% or less, 47 wt.%, 45 wt.%, 42 wt.%, 40 wt.%, 37 wt.%, 35 wt.%, 32 wt.%, 30 wt.%, 29 wt.%, 28 wt.%, 27 wt.%, 26 wt.%, 25 wt.%, 24 wt.%, 23 wt.%, 22 wt.%, 21 wt.%, 20 wt.%, 19 wt.%, 18 wt.%, 17 w
  • the resulting porous polymeric membrane tends to shrink to such an extent that the through holes are substantially larger than the size of the protrusions of the tooling structure.
  • a solids content of greater than 50 wt.% tends to result in too high of a viscosity to successfully cast on the tooling structure.
  • any polymer-solvent-nonsolvent combination that forms a polymeric membrane in a cast and precipitate process is suitable for use in methods according to the present disclosure.
  • the polymer component optionally comprises polyethersulfone, polypropylene, polysulfone, polyacrylonitrile, a cellulose ester, a polyimide, a polyamide (e.g., an amorphous nylon), poly(vinylidene fluoride), or poly(tetrafluoroethylene).
  • the polymer component comprises polyethersulfone or amorphous nylon
  • the solvent system comprises dimethyl sulfoxide
  • the nonsolvent fluid comprises water.
  • solvents for the casting solution may include water, dimethyl formamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidinone, tetramethylurea, acetone, methyl ethyl ketone, methyl acetate, ethylacetate and other alkyl acetates, dimethylsulfoxide and combinations thereof.
  • the solvent may be oligomeric or polymeric in nature forming a polymer blend with the polymer component.
  • the solvent may comprise more than one solvent, a blend of solvents, or a nonsolvent for phase inversion.
  • a nonsolvent is a material that is miscible in the solvent of the dope formulation, but which, by itself, is insoluble with the polymer or may cause coagulation of the polymer.
  • the nonsolvent may be added to a solvent to influence the rate of a phase inversion or aid in the development of a microstructure.
  • Polymer solvents may be categorized as good solvents, nonsolvents, and poor solvents.
  • Good solvents are those in which the interactions (forces) between the polymer molecules and solvent molecules are greater than the forces of attraction between one polymer molecule and another polymer molecule. The reverse is true for nonsolvents.
  • Poor solvents are those in which the interactions between the polymer and solvent are equal to the forces of attraction between one polymer and another polymer molecule.
  • Good solvents dissolve substantial amounts of polymer and may be miscible with the polymer at concentrations of at least 5 weight percent, whereas poor solvents may or may not be miscible, depending upon the molecular weight of the polymer and the type of solvent.
  • examples of good solvents for polyethersulfone include dimethylacetamide, dioxane, dimethylsulfoxide, N-methyl-2- pyrrolidinone, chloroform, tetramethylurea, formic acid, and tetrachloroethane.
  • Another method for evaluating solvents for polymer solubility includes Hildebrand solubility parameters.
  • solubility parameters refer to a solubility parameter represented by the square root of the cohesive energy density of a material, having units of (pressure) 1 2 , and being equal to (AH-RT) 1/2 V 1/2 where AH is the molar vaporization enthalpy of the material, R is the universal gas constant, T is the absolute temperature, and V is the molar volume of the solvent.
  • Hildebrand solubility parameters are tabulated for solvents in: Barton, A. F. M., “Handbook of Solubility and Other Cohesion Parameters”, 2nd Ed., CRC Press, Boca Raton, FL. (1991); for monomers and representative polymers in “Polymer Handbook”, 4th Ed., J. Brandrup & E. H. Immergut, Eds.
  • the method also comprises Step 320 to contact the layer of the casting solution with a nonsolvent fluid to solidify the polymer component and form a porous polymeric membrane. Suitable nonsolvents can be determined as described above in detail. Additionally, the method comprises Step 330 to remove the porous polymeric membrane from the tooling structure (e.g., by peeling off the tooling structure), thereby providing a porous polymeric membrane.
  • the porous polymeric membrane comprises 1) a first outer surface having a patterned array of first pores having irregularly shaped perimeters that do not correspond to a shape of a top of the plurality of protrusions; 2) an opposing second outer surface having a plurality of second pores; and 3) a polymeric matrix extending between the first outer surface and the second outer surface. Further, the polymeric matrix defines a plurality of through holes that extend between the first pores and the second pores.
  • the porous polymeric membrane may be according to any embodiment of the first aspect described in detail above.
  • FIG. 4 a schematic cross-sectional schematic illustration is provided of a porous polymeric membrane 400 formed on a tooling structure 490 in which pores on a first outer surface 410 of the membrane 400 do not correspond to a shape of a top 484 of the tooling structure 490 protrusions 480. Rather, the pores correspond to a shape of a stem 482 of the protrusions 480 and the stem 482 has a different shape than the top (e.g., head) 484.
  • the pores in the illustration of FIG. 4 are filled with the protrusions 480 because the porous polymeric membrane 400 has yet to be removed from the tooling structure 490.
  • a second, opposing outer surface 430 of the membrane 400 is located adjacent to the tooling structure 490.
  • the protrusions of a tooling structure comprise a stem (e.g., post) and a head, in which the stem extends generally orthogonally from the major surface of the tooling structure and the head is disposed distal to the major surface of the tooling structure.
  • the protrusions comprise a head on a stem
  • the first pores of the resulting porous polymeric membrane have an average pore size that is smaller than the head of the protrusions.
  • the protrusions comprise a T-shape, a nail shape, a mushroom shape (e.g., with a circular or oval head enlarged with respect to the stem), or combinations thereof.
  • the tooling structure 510 may comprise a backing 514 having a first side 516 and a second side 518 opposite the first side 516. Upstanding stems 520 extend from the first side 516 of the backing 514, such that each stem 520 has a proximal end 522 contiguous with the first side 516 of the backing 514 and a distal end (i.e., head) 524 opposite the proximal end 522.
  • the distal ends 24 of the posts 20 need not all be the same shape and/or orientation within a given tooling structure 510.
  • the stems 520 in FIG. 5 are arranged perpendicular to the backing 514, the stems 520 could also be slanted at an angle to the backing 514, e.g., an angle between 45 and 90 degrees, between 60 and 90 degrees, or between 75 and 90 degrees.
  • the material composition of the tooling structure includes an organic polymer.
  • the organic polymer is not particularly limiting and comprise either a thermoplastic polymer or a thermoset polymer.
  • exemplary thermoplastic polymers include polyolefin homopolymers such as polyethylene, polypropylene, and polybutylene, copolymers of ethylene, propylene and/or butylenes, and copolymers and blends thereof; copolymers containing ethylene such as ethylene vinyl acetate and ethylene acrylic acid; polyesters such as polyethylene terephthalate), polyethylene butyrate and polyethylene napthalate; polyamides such as poly(hexamethylene adipamide); polyurethanes; polycarbonates; poly(vinyl alcohol); ketones such as polyetheretherketone; polyphenylene sulfide; and mixtures thereof.
  • the thermoplastic is a polyolefin (e.g., polyethylene, polypropylene, polybutylene, ethylene copolymers, propylene copolymers, butylene copolymers, and copolymers and blends of these materials), a polyester and combinations thereof.
  • the tooling structure is formed of polypropylene or a crosslinked (meth)acrylate polymer.
  • any number of current methods can be used to make the tooling structure, such as by feeding a molten resin containing the organic polymer and any additional ingredients between a nip formed by two rolls or a nip formed between a die face and roll surface, with at least one of the rolls having cavities.
  • the cavities may be the inverse shape of a protrusion having a stem and a head or may be the inverse shape of a post without a head.
  • Pressure provided by the nip forces the resin into the cavities.
  • a vacuum can be used to evacuate the cavities for easier filling.
  • the nip is typically sufficiently wide such that a continuous backing is formed over the cavities.
  • the mold surface and cavities can optionally be air or water cooled before stripping the integrally formed backing and posts from the mold, such as by a stripper roll. If the protrusions formed upon exiting the cavities do not have heads, heads can be subsequently formed by a capping method as described in U.S. Pat. No. 5,077,870 (Melbye et al.). Typically, the capping method includes deforming the tip portions of the protrusions using heat and/or pressure. The heat and pressure, if both are used, could be applied sequentially or simultaneously.
  • suitable tool rolls include those formed from a series of plates defining a plurality of protrusion-forming cavities about its periphery such as those described, for example, in U.S. Pat. No. 4,775,310 (Fischer). Cavities may be formed in the plates by drilling or photoresist technology, for example. Still other suitable tool rolls may include wire-wrapped rolls, which are disclosed along with their method of manufacturing, for example, in U.S. Pat. No. 6,190,594 (Gorman et al.). Another exemplary method for forming a thermoplastic backing with protrusions includes using a flexible mold belt defining an array of post-shaped cavities as described in U.S. Pat. No. 7,214,334 (Jens et al.). Yet other useful methods for forming a thermoplastic backing with protrusions can be found in U.S. Pat. Nos. 6,287,665 (Hammer); 7,198,743 (Tuma); and 6,627,133 (Tuma).
  • thermoplastic flow stream is passed through a patterned die lip (e.g., cut by electron discharge machining) to form a web having ridges that extend in the machine direction, slicing the ridges in a direction perpendicular to the machine direction, and stretching the web in the machine direction to form separated projections.
  • the ridges may form protrusion precursors and exhibit the cross-sectional shape of stems with heads to be formed.
  • the thermoplastic backing of the tooling structure made by this method has stretch-induced molecular orientation.
  • thermoset polymers for the tooling structure include for instance and without limitation, crosslinked acrylate such as mono- or multi-functional acrylates or acrylated epoxies, acrylated polyesters, and acrylated urethanes blended with mono- and multifunctional monomers are typically preferred. These polymers are typically preferred for one or more of the following reasons: high thermal stability, environmental stability, and clarity, plus excellent release from a tooling or mold.
  • materials suitable for forming the tooling structure are reactive resin systems capable of being crosslinked by a free radical polymerization mechanism by exposure to actinic radiation, for example, electron beam, ultraviolet light, or visible light. Additionally, these materials may be polymerized by thermal means with the addition of a thermal initiator such as benzoyl peroxide. Radiation-initiated cationically polymerizable resins also may be used.
  • Reactive resins suitable for forming the tooling structure may be blends of photoinitiator and at least one compound bearing an acrylate group. Preferably the resin blend contains a monofunctional, a difunctional, or a polyfunctional compound to ensure formation of a crosslinked polymeric network upon irradiation.
  • Illustrative examples of resins that are capable of being polymerized by a free radical mechanism that can be used herein include acrylic-based resins derived from epoxies, polyesters, polyethers, and urethanes, ethylenically unsaturated compounds, aminoplast derivatives having at least one pendant acrylate group, isocyanate derivatives having at least one pendant acrylate group, epoxy resins other than acrylated epoxies, and mixtures and combinations thereof.
  • the term acrylate is used here to encompass both acrylates and methacrylates.
  • U.S. Pat. 4,576,850 discloses examples of crosslinked resins that may be used in tooling structures of the present disclosure. Further, polymerizable resins of the type disclosed in, for example, U.S. Patent 7,61 1,251 (Thakkar) may be used in tooling structures of the present disclosure.
  • Ethylenically unsaturated resins include both monomeric and polymeric compounds that contain atoms of carbon, hydrogen and oxygen, and optionally nitrogen, sulfur, and the halogens may be used herein. Oxygen or nitrogen atoms, or both, are generally present in ether, ester, urethane, amide, and urea groups.
  • Ethylenically unsaturated compounds preferably have a molecular weight of less than about 4,000 and preferably are esters made from the reaction of compounds containing aliphatic monohydroxy groups, aliphatic polyhydroxy groups, and unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, iso-crotonic acid, maleic acid, and the like. Such materials are typically readily available commercially and can be readily cross linked.
  • trimethylolpropane triacrylate typically tend to provide faster penetration of the material of the overlay fdm and difunctional and polyfunctional compounds typically tend to provide more crosslinked, stronger bonds at the interface between the cube comer elements and overlay fdm.
  • ethylenically unsaturated compounds and resins include styrene, divinylbenzene, vinyl toluene, N-vinyl formamide, N-vinyl pyrrolidone, N-vinyl caprolactam, monoallyl, polyallyl, and polymethallyl esters such as diallyl phthalate and diallyl adipate, and amides of carboxylic acids such as N,N-diallyladipamide.
  • Illustrative examples of photopolymerization initiators that can be blended with acrylic compounds in tooling structures of the present disclosure include the following: benzil, methyl o- benzoate, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc., benzophenone/tertiary amine, acetophenones such as 2,2-diethoxyacetophenone, benzyl methyl ketal, 1 -hydroxy cyclohexylphenyl ketone, 2- hydroxy-2-methyl-l-phenylpropan-l-one, l-(4- isopropylphenyl)-2 -hydroxy-2 -methylpropan- 1 -one, 2-benzyl-2-N,N-dimethylamino- 1 -(4- morpholinophenyl)-l-butanone, 2, 4, 6-trimethylbenzoyl -diphenylphosphine oxide
  • Cationically polymerizable materials including but are not limited to materials containing epoxy and vinyl ether functional groups may be used herein. These systems are photoinitiated by onium salt initiators, such as triarylsulfonium, and diaryliodonium salts.
  • the thickness of the backing of the tooling structure is up to about 400, 250, 150, 100, 75 or 50 micrometers, such as 30 to 225 micrometers, 50 to 200 micrometers, or 100 to 150 micrometers.
  • the stems have a maximum height (above the backing) of up to 5 mm, 3 mm, 1.5 mm, 1 mm, 500 micrometers, 400 micrometers, 300 micrometers, 200 micrometers, or 100 micrometers, and, in some embodiments a minimum height of at least about 5 micrometers, 10 micrometers, 25 micrometers, 50 micrometers, 75 micrometers, 100 micrometers, 125 micrometers, 150 micrometers, 175 micrometers, or 200 micrometers.
  • the stems have an aspect ratio (that is, a ratio of height to width at the widest point) of at least about 2: 1, 3: 1, or 4: 1.
  • the protrusions may have an average diameter of 1 micrometer or greater, 2 micrometers or greater, 3 micrometers, 5 micrometers, 7 micrometers, 10 micrometers, 12 micrometers, 15 micrometers, 20 micrometers, 25 micrometers, 30 micrometers, 35 micrometers, 40 micrometers, 45 micrometers, 50 micrometers, 60 micrometers, 70 micrometers, 80 micrometers, 90 micrometers, 100 micrometers, 110 micrometers, 120 micrometers, 120 micrometers, 140 micrometers, or 150 micrometers or greater; and 500 micrometers or less, 475 micrometers, 450 micrometers, 425 micrometers, 400 micrometers, 375 micrometers, 350 micrometers, 325 micrometers, 300 micrometers, 275 micrometers, 250 micrometers, 225 micrometers, 200 micrometers, 190 micrometers, 180 micrometers, 170 micrometers, or 160 micro
  • the present disclosure provides a porous polymeric membrane.
  • the porous polymeric membrane comprises a) a first outer surface having a patterned array of first pores having irregularly shaped perimeters; b) an opposing second outer surface having a plurality of second pores; and c) a polymeric matrix extending between the first outer surface and the second outer surface.
  • the polymeric matrix defines a plurality of through holes that extend between the first pores and the second pores.
  • the present disclosure provides a porous polymeric membrane according to the first embodiment, wherein the through holes have an average diameter of 1 micrometer to 500 micrometers or 10 micrometers to 300 micrometers.
  • the present disclosure provides a porous polymeric membrane according to the first embodiment or the second embodiment, wherein the plurality of second pores have regularly shaped perimeters.
  • the present disclosure provides a porous polymeric membrane according to any of the first through third embodiments, wherein the polymeric matrix located adjacent to the through holes is porous.
  • the present disclosure provides a porous polymeric membrane according to any of the first through third embodiments, wherein the polymeric matrix located adjacent to the through holes is nonporous.
  • the present disclosure provides a porous polymeric membrane according to any of the first through fifth embodiments, wherein the through holes are isoporous.
  • the present disclosure provides a porous polymeric membrane according to any of the first through sixth embodiments, having a thickness between the first outer surface and the second outer surface of 1 micrometer or greater.
  • the present disclosure provides a porous polymeric membrane according to any of the first through seventh embodiments, wherein the through holes have a density on the first outer surface of 50 per square centimeter or greater.
  • the present disclosure provides a porous polymeric membrane according to any of the first through eighth embodiments, wherein the polymeric matrix comprises polyethersulfone, polypropylene, polysulfone, polyacrylonitrile, a cellulose ester, a polyimide, a polyamide, poly(vinylidene fluoride), or polytetrafluoroethylene).
  • the present disclosure provides a porous polymeric membrane according to any of the first through ninth embodiments, wherein the polymeric matrix comprises polyethersulfone or amorphous nylon.
  • the present disclosure provides a porous polymeric membrane according to any of the first through tenth embodiments, wherein the first pores have an average area that is less than half of an average area of the second pores.
  • the present disclosure provides a method.
  • the method comprises applying a casting solution to a tooling structure comprising a major surface and a patterned array of protrusions extending orthogonally therefrom, to form a layer of the casting solution.
  • the casting solution comprises a polymer component and a solvent system.
  • the method further comprises contacting the layer of the casting solution with a nonsolvent fluid to solidify the polymer component and form a porous polymeric membrane; and removing the porous polymeric membrane from the tooling structure, thereby providing a porous polymeric membrane.
  • the porous polymeric membrane comprises 1) a first outer surface having a patterned array of first pores having irregularly shaped perimeters that do not correspond to a shape of a top of the plurality of protrusions; 2) an opposing second outer surface having a plurality of second pores; and 3) a polymeric matrix extending between the first outer surface and the second outer surface.
  • the polymeric matrix defines a plurality of through holes that extend between the first pores and the second pores.
  • the present disclosure provides a method according to the twelfth embodiment, wherein the protrusions comprise a stem and a head, in which the stem extends orthogonally from the major surface of the tooling structure and the head is disposed distal to the major surface of the tooling structure.
  • the present disclosure provides a method according to the thirteenth embodiment, wherein the protrusions comprise a T-shape, a nail shape, a mushroom shape, or combinations thereof.
  • the present disclosure provides a method according to the thirteenth embodiment or the fourteenth embodiment, wherein the first pores have an average pore size that is smaller than the head of the protrusions.
  • the present disclosure provides a method according to any of the twelfth through fourteenth embodiments, wherein the layer of the casting solution has a thickness smaller than the height of the protrusions.
  • the present disclosure provides a method according to any of the twelfth through fourteenth embodiments, wherein the layer of the casting solution has a thickness equal to the height of the protrusions.
  • the present disclosure provides a method according to any of the twelfth through fifteenth embodiments, wherein the layer of the casting solution has a thickness larger than the height of the protrusions.
  • the present disclosure provides a method according to any of the twelfth through eighteenth embodiments, wherein the casting solution comprises a solids content of 5 percent by weight to 50 percent by weight.
  • the present disclosure provides a method according to any of the twelfth through eighteenth embodiments, wherein the polymer component comprises polyethersulfone, polypropylene, polysulfone, polyacrylonitrile, a cellulose ester, a polyimide, a polyamide, poly(vinylidene fluoride), or polytetrafluoroethylene).
  • the polymer component comprises polyethersulfone, polypropylene, polysulfone, polyacrylonitrile, a cellulose ester, a polyimide, a polyamide, poly(vinylidene fluoride), or polytetrafluoroethylene).
  • the present disclosure provides a method according to any of the twelfth through twentieth embodiments, wherein the polymer component comprises polyethersulfone or amorphous nylon, the solvent system comprises dimethyl sulfoxide, and the nonsolvent fluid comprises water.
  • the present disclosure provides a method according to any of the twelfth through twenty-first embodiments, wherein the tooling structure is formed of polypropylene or a crosslinked (meth)acrylate polymer.
  • the present disclosure provides a method according to any of the twelfth through twenty-second embodiments, wherein the protrusions have an average diameter of 1 micrometer to 500 micrometers or 10 micrometers to 300 micrometers.
  • the present disclosure provides a method according to any of the twelfth through twenty-third embodiments, wherein the porous polymeric membrane is according to any of the first through eleventh embodiments.
  • PES polyethersulfone
  • NMP N-Methyl pyrrolidone
  • Deionized water was selected as a non-solvent. 10 wt.% of PES was dissolved in NMP using a speed mixer at room temperature until a homogeneous clear solution was obtained. After that the solution was left standing overnight at 60 °C to remove any entrapped bubbles.
  • the structured surface used to make the membrane was a mechanical fastener strip prepared from an ethylene-propylene copolymer available from Dow Chemical Company, Midland, MI, under the trade designation “C700-35N” using the method described in U.S. Pat. No. 5,845,375 (Miller et al.).
  • the mechanical fastener strips were arranged in a staggered array.
  • the posts were conical in shape.
  • the distal tips of the posts were deformed with a textured heated surface to form grooved caps such as that disclosed in U.S. Pat. No. 6,708,378 (Parellada et al.) or U.S. Pat. No. 5,868,987 (Kampfer et al.).
  • the membranes were prepared by casting the homogeneous PES solution on to the structured surface using a doctor blade such that the scraping action touched the top of the caps and excess PES solution above the caps was wiped off.
  • the structured surface coated with the PES solution was then immersed into deionized water at 25 °C immediately. Upon immersion, the PES solution slowly solidified into an opaque film that was still attached to the structured surface. The solidified film was slowly peeled from the structured surface and stored in deionized water at 25 °C until further analysis.
  • the structured surface had a height of 350 micrometers where the PES solution could be cast. Note that the initial casting thickness of the membrane was dependent on the height of the structured surface itself and other structured surfaces with a higher or a lower height are also thought to be useful to prepare membranes of varying thicknesses.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)

Abstract

L'invention concerne des membranes polymères poreuses. Une membrane polymère poreuse comprend une première surface externe comprenant un réseau à motifs de premiers pores présentant des périmètres de forme irrégulière ; une seconde surface externe opposée comprenant une pluralité de seconds pores ; et une matrice polymère s'étendant entre la première surface externe et la seconde surface externe. La matrice polymère définit une pluralité de trous traversants qui s'étendent entre les premiers pores et les seconds pores. Un procédé de fabrication de membranes polymères poreuses comprend l'application d'une solution de coulée à une structure d'outillage présentant une surface principale et un réseau à motifs de saillies s'étendant orthogonalement à partir de celle-ci, pour former une couche de la solution de coulée. La solution de coulée comprend un composant polymère et un système de solvant. Le procédé comprend en outre la mise en contact de la couche de la solution de coulée avec un fluide non solvant pour solidifier le composant polymère et former une membrane polymère poreuse ; et le retrait de la membrane polymère poreuse de la structure d'outillage, fournissant ainsi une membrane polymère poreuse.
PCT/IB2023/059543 2022-10-27 2023-09-26 Membranes polymères poreuses comprenant un réseau à motifs de trous traversants et leurs procédés de fabrication WO2024089493A1 (fr)

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