WO2015153574A1 - Membrane filtrante poly(amide-imide) thermiquement réticulée - Google Patents

Membrane filtrante poly(amide-imide) thermiquement réticulée Download PDF

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WO2015153574A1
WO2015153574A1 PCT/US2015/023538 US2015023538W WO2015153574A1 WO 2015153574 A1 WO2015153574 A1 WO 2015153574A1 US 2015023538 W US2015023538 W US 2015023538W WO 2015153574 A1 WO2015153574 A1 WO 2015153574A1
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membrane
linked
psi
thermally cross
microporous membrane
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PCT/US2015/023538
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English (en)
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Sina BONYADI
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Entegris, Inc.
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Publication of WO2015153574A1 publication Critical patent/WO2015153574A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
    • B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
    • B01D71/641—Polyamide-imides
    • 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
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0083—Thermal after-treatment
    • 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
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0093—Chemical modification
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/30—Cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B01D2325/022—Asymmetric membranes
    • B01D2325/023—Dense layer within the membrane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/30—Chemical resistance

Definitions

  • the invention includes embodiments that relate to membranes. Particularly, the invention includes embodiments that are directed to thermally cross-linked polyamide-imide membranes, method of making such, and devices using such.
  • PAI poly(amide-imide)
  • An embodiment of the invention provides a thermally cross-linked microporous membrane.
  • the thermally cross-linked microporous membrane includes a thermally cross- linked polyamide-imide polymer.
  • the thermally cross-linked microporous membrane has an HFE bubble point from about 25 psi to about 200 psi and an IPA flow-time from about 400 seconds to about 40,000 seconds.
  • a second embodiment of the invention provides another thermally cross-linked poly(amide-imide) membrane.
  • the thermally cross-linked membrane has anHFE bubble point from about 25 psi to about 200 psi.
  • the thermally cross-linked membrane is microporous; asymmetric and has a tight layer with a thickness of less than or equal to 10 microns.
  • a third embodiment of the invention provides a microporous membrane.
  • the microporous membrane includes a chemically resistant polyamide-imide polymer.
  • the microporous membrane has an HFE bubble point from about 25 psi to about 200 psi and an IPA flow-time from about 400 seconds to about 40,000 seconds.
  • a fourth embodiment of the invention provides another membrane.
  • the membrane comprises a chemically resistant polyamide-imide polymer.
  • the membrane has an HFE bubble point from about 25 psi to about 200 psi.
  • the membrane is microporous;
  • a fifth embodiment of the invention provides a filtration device.
  • the filtration device includes a filter incorporating a thermally cross-linked microporous membrane.
  • the thermally cross-linked microporous membrane includes a thermally cross-linked polyamide- imide polymer, wherein the thermally cross-linked microporous membrane has a bubble point and an IPA flow-time.
  • the thermally cross-linked microporous membrane has an HFE bubble point from about 25 psi to about 200 psi and an IPA flow-time from about 400 seconds to about 40,000 seconds.
  • a sixth embodiment of the invention provides another filtration device.
  • the filtration device includes a filter incorporating a microporous membrane.
  • the microporous membrane includes a chemically resistant polyamide-imide polymer, wherein the microporous membrane has a bubble point and an IPA flow-time.
  • the microporous membrane has an HFE bubble point from about 25 psi to about 200 psi and an IPA flow-time from about 400 seconds to about 40,000 seconds.
  • FIG. 1 is a schematic representation of a membrane in accordance with an embodiment of the invention.
  • FIG. 2A is an SEM image of a Torlon® membrane that can be employed in manufacturing a cross-linked membrane described herein.
  • FIG. 2B is an SEM image of a cross-linked Torlon® membrane described herein.
  • FIG. 3 is a flow chart of a method of making a membrane in accordance with embodiments of the invention.
  • FIGs. 4A and 4B are bar plots showing tensile strength and tensile stress, respectively, of the non-cross-linked poly(amide-imide) (Torlon®) membranes following exposure to 10% aqueous hydrochloric acid.
  • FIGs. 5A and 5B are bar plots showing tensile strength and tensile stress, respectively, of the thermally cross-linked poly(amide-imide) (Torlon®) membranes following exposure to 10% aqueous hydrochloric acid.
  • FIG. 6 is a plot showing the percent of retention of 25 nm polystryrene (G25) nanoparticles as a function of monolayer concentration by the cross-linked PAI membrane.
  • alkyl as used herein, unless otherwise indicated, means straight or branched saturated monovalent hydrocarbon radicals of formula C n H 2n+ i. In some embodiments, n is from 1 to 18. In other embodiments, n is from 1 to 12. Preferably, n is from 1 to 6. In some embodiments, n is 1-1000, for example, n is 1 -100. Alkyl can optionally be substituted with -OH, -SH, halogen, amino, cyano, nitro, a C - C 12 alkyl, Ci- C 12 haloalkyl, Ci- C 12 alkoxy, Q- Q 2 haloalkoxy or C C 12 alkyl sulfanyl.
  • alkyl can optionally be substituted with one or more halogen, hydroxyl, Ci- Q 2 alkyl, C 2 - Ci 2 alkenyl or C 2 - C 12 alkynyl group, Q- Ci 2 alkoxy, or C C 12 haloalkyl.
  • the term alkyl can also refer to cycloalkyl.
  • an "alkenyl group”, alone or as a part of a larger moiety is preferably a straight chained or branched aliphatic group having one or more double bonds with 2 to about 12 carbon atoms, e.g., ethenyl, 1-propenyl, 1-butenyl, 2-butenyl, 2 -methyl- 1-propenyl, pentenyl, hexenyl, heptenyl or octenyl, or a cycloaliphatic group having one or more double bonds with 3 to about 12 carbon atoms.
  • an "alkynyl” group is preferably a straight chained or branched aliphatic group having one or more triple bonds with 2 to about 12 carbon atoms, e.g., ethynyl, 1-propynyl, 1-butynyl, 3-methyl-l-butynyl, 3, 3 -dimethyl- 1-butynyl, pentynyl, hexynyl, heptynyl or octynyl, or a cycloaliphatic group having one or more triple bonds with 3 to about 12 carbon atoms.
  • cycloalkyl means saturated cyclic hydrocarbons, i.e. compounds where all ring atoms are carbons.
  • a cycloalkyl comprises from 3 to 18 carbons.
  • a cycloalkyl comprises from 3 to 6 carbons.
  • Examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.
  • cycloalkyl can optionally be substituted with one or more halogen, hydroxyl, Ci- C 12 alkyl, C 2 - C 12 alkenyl or C 2 - C 12 alkynyl group, Ci- C 12 alkoxy, or Ci- C 12 haloalkyl.
  • haloalkyl includes an alkyl substituted with one or more F, CI, Br, or I, wherein alkyl is defined above.
  • alkoxy means an "alkyl-O-" group, wherein alkyl is defined above.
  • alkoxy group include methoxy or ethoxy groups.
  • aryl refers to a carbocyclic aromatic group.
  • an aryl comprises from 6 to 18 carbons.
  • aryl groups include, but are not limited to phenyl and naphthyl.
  • aryl groups include optionally substituted groups such as phenyl, biphenyl, naphthyl, phenanthryl, anthracenyl, pyrenyl, fluoranthyl or fluorenyl.
  • An aryl can be optionally substituted.
  • Suitable substituents on an aryl include halogen, hydroxyl, Ci- C 12 alkyl, C 2 - C 12 alkene or C 2 - C 12 alkyne, C 3 - C 12 cycloalkyl, Ci- C 12 haloalkyl, C C 12 alkoxy, aryloxy, arylamino or aryl group.
  • a C 6 -C 18 aryl selected from the group consisting of phenyl, indenyl, naphthyl, azulenyl, heptalenyl, biphenyl, indacenyl, acenaphthylenyl, fluorenyl, phenalenyl, phenanthrenyl, anthracenyl, cyclopentacyclooctenyl or benzocyclooctenyl.
  • a C6-Ci4 aryl selected from the group consisting of phenyl, naphthalene, anthracene, lH-phenalene, tetracene, and pentacene.
  • aryloxy means an "aryl-O-" group, wherein aryl is defined above.
  • Examples of an aryloxy group include phenoxy or naphthoxy groups.
  • hetero)arylamine means an "(hetero)aryl-NH-", an "(hetero)aryl-N(alkyl)-", or an "((hetero)aryl) 2 -N-" groups, wherein (hetero)aryl and alkyl are defined above.
  • heteroaryl refers to aromatic groups containing one or more heteroatoms (O, S, or N).
  • a heteroaryl group can be monocyclic or polycyclic, e.g. a monocyclic heteroaryl ring fused to one or more carbocyclic aromatic groups or other monocyclic heteroaryl groups.
  • the heteroaryl groups of this invention can also include ring systems substituted with one or more oxo moieties.
  • heteroaryl groups include, but are not limited to, pyridinyl, pyridazinyl, imidazolyl, pyrimidinyl, pyrazolyl, triazolyl, pyrazinyl, quinolyl, isoquinolyl, tetrazolyl, furyl, thienyl, isoxazolyl, thiazolyl, oxazolyl, isothiazolyl, pyrrolyl, quinolinyl, isoquinolinyl, indolyl, benzimidazolyl, benzofuranyl, cinnolinyl, indazolyl, indolizinyl, phthalazinyl, pyridazinyl, triazinyl, isoindolyl, purinyl, oxadiazolyl, thiazolyl, thiadiazolyl, furazanyl, benzofurazanyl, benzothiophenyl,
  • benzotriazolyl benzothiazolyl, benzoxazolyl, quinazolinyl, quinoxalinyl, naphthyridinyl, dihydroquinolyl, tetrahydroquinolyl, dihydroisoquinolyl, tetrahydroisoquinolyl, benzofuryl, furopyridinyl, pyrolopyrimidinyl, and azaindolyl.
  • a 5-14-membered heteroaryl group selected from the group consisting of pyridyl, 1-oxo-pyridyl, furanyl, benzo[l,3]dioxolyl, benzo[l,4]dioxinyl, thienyl, pyrrolyl, oxazolyl, imidazolyl, thiazolyl, a isoxazolyl, quinolinyl, pyrazolyl, isothiazolyl, pyridazinyl, pyrimidinyl, pyrazinyl, a triazinyl, triazolyl, thiadiazolyl, isoquinolinyl, indazolyl, benzoxazolyl, benzofuryl, indolizinyl, imidazopyridyl, tetrazolyl, benzimidazolyl, benzothiazolyl, benzothiadiazolyl,
  • heteroaryl groups may be C- attached or N-attached (where such is possible).
  • a group derived from pyrrole may be pyrrol- 1-yl (N-attached) or pyrrol-3-yl (C-attached).
  • Suitable substituents for heteroaryl are as defined above with respect to aryl group.
  • Suitable substituents for an alkyl, cycloalkyl include a halogen, an alkyl, an alkenyl, a cycloalkyl, a cycloalkenyl, an aryl, a heteroaryl, a haloalkyl, cyano, nitro, haloalkoxy.
  • substituents for a substitutable carbon atom in an aryl, a heteroaryl, alkyl or cycloalkyl include but are not limited to -OH, halogen (-F, -CI, -Br, and -I), -R, -OR, -CH 2 R, -CH 2 OR, -CH 2 CH 2 OR,.
  • Each R is independently an alkyl group.
  • suitable substituents for a substitutable carbon atom in an aryl, a heteroaryl or an aryl portion of an arylalkenyl include halogen, hydroxyl, Cj- Cj 2 alkyl, C 2 - Cj 2 alkenyl or C 2 - Q 2 alkynyl group, Cj- Ci 2 alkoxy, aryloxy group, arylamino group and Cj- Cj 2 haloalkyl.
  • an amino group may be a primary (-NH 2 ), secondary (-NHR P ), or tertiary (-NR p R q ), wherein R p and Rq may be any of the alkyl, alkenyl, alkynyl, alkoxy, cyclo alkyl, cycloalkoxy, aryl, heteroaryl, and a bicyclic carbocyclic group.
  • a (di)alkylamino group is an instance of an amino group substituted with one or two alkyls.
  • thermal cross-linked polyamide-imide refers to a polyamide-imide polymer subjected to the thermal crosslinking procedure, as described herein.
  • thermal crosslinking it has been discovered that the chemical properties of the polyamide-imide porous membranes can be significantly improved by thermal crosslinking.
  • a thermally cross-linked polyamide-imide microporous membrane is compatible with a 10% aqueous HCl solution while a non (thermally) cross-linked polyamide-imide membrane is damaged by the same 10% aqueous HCl solution after being soaked in it for three weeks.
  • the thermally cross linked polyamide-imide membrane has greater strength after soaking in 10% aqueous HCl for three weeks than a polyamide-imide membrane that is not thermally cross linked and also soaked in 10% aqueous HCl for three weeks.
  • the thermally crossed-linked polyaminde-imide membrane is also compatible with TMAH (tetramethyl ammonium hydroxide) solvent and the strength of the thermally cross-linked polyaminde-imide membrane in TMAH is greater than the strength of a non-thermally cross-linked polyamide-imide membrane after extended soaking in TMAH.
  • TMAH tetramethyl ammonium hydroxide
  • the mechanical properties of the thermally cross-linked polyamide-imide membrane can be improved compared to the non-thermally cross-linked polyaminde-imide membrane, and the thermal cross-linking also alters the membrane pore structure in a manner that the membrane IPA flow-time improves while the mean bubble point of the membrane remains almost the same.
  • the present invention is a microporous membrane comprising a chemically resistant polyamide-imide polymer.
  • chemically resistant polymer refers to such a polymer that a numerical value corresponding to a measured mechanical property of the polymer, such as tensile strain or tensile stress, is reduced, within the error of the measurement, by less than or equal to about 50% after the polymer has been exposed to 10% aqueous HCl for three weeks.
  • the reduction in tensile strain or tensile stress is less than or equal to about 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, 5%, or 0%.
  • microporous membranes comprising a chemically resistant polyamide-imide polymer possess physical and technical specifications as described herein with respect to thermally cross-linked polyamide-imide membranes.
  • the thermal crosslinking of polyamide-imide membranes is achieved by raising the polyamide-imide membrane temperature.
  • the results show that the polyamide-imide polymer can be cross-linked by raising its temperature.
  • the degree of cross-linking depends on the temperature. In case of a Torlon® membrane, the highest cross-linking was observed at temperatures in the range of 240 degrees centigrade to 260 degrees Centigrade.
  • Cross- linking can be carried out without adding any cross-linking agent. Accordingly some of the porous membranes as described herein can be considered as consisting essentially of polyamide-imide polymer that is thermally cross-linked.
  • porous membranes as described herein are devoid of additives which make the membrane hydrophilic such as polyethylene glycol and others. Accordingly, some other of the porous membranes as described herein can be considered as consisting essentially of polyamide-imide polymer that is thermally cross-linked and are absent extractable additives like polyethylene glycol.
  • the pore size of the thermally crosslinked porous polyamide-imide membranes is in the range of between 1 nanometer and 20 nanometers, in some cases the pore size of the thermally crosslinked porous polyamide-imide membranes is in the range of between 1 nanometer and 10 nanometers.
  • Porous membranes with small pore sizes that are stable in chemicals like 10% aqueous HC1 and TMAH used in semiconductor manufacturing are advantageous for removing very small particles that can cause defects in manufactured chips and memory devices.
  • the method of fabricating a cross-linked poly(amide-imide) membrane include manufacturing a poly(amide-imide) porous membrane from the polymer, as described in details below, followed by thermally curing the membrane to induce cross-linking.
  • any poly(amide-imide) polymer suitable for manufacturing filter membranes can be employed to manufacture the membranes described herein.
  • a poly(amide- imide) is a polymer having at least one repeat unit represented by the following structural formula:
  • n is 0 or an integer between 1 and 12; for example n is 0. In another example embodiment, n is 2.
  • R is a moiety that includes at least one C 6 -Ci 6 aryl or heteroaryl, optionally substituted with one or more substituents selected from d- C n alkyl, (C 6 -C ] 8 )(hetero)aryl(Ci- Ci 2 )alkyl, (C 6 -C ] 8 )(hetero)aryl (C 2 - Cj 2 )alkene, C 3 -C 12 cycloalkyl, (C 6 -C 1 8)(hetero)aryl(C 3 -Ci 2 ) cycloalkyl, C ⁇ - C 12 haloalkyl, (C 6 -Ci 8 )(hetero)aryl(Ci- Cj 2 )haloalkyl, Ci- C 12 alkoxy, (C
  • An example of a repeat unit of formula (I) is a repeat unit of the following structural formula:
  • group R is a moiety of the following structural formula:
  • Torlon® membranes any of the Torlon® membranes available from various vendors, e.g. from Solvay Plastics.
  • the structures of representative Torlon® polymers are described, for example, in U.S. 4,900,449, the entire teachings of which are incorporated herein by reference.
  • An example chemical structure of a Torlon® membrane can be described as follows:
  • R 1 is represented by structural formula (II).
  • the cross-linked membrane 100 includes one or more polyamide-imide polymers and, in one embodiment, has an HFE bubble point from about 25 psi to about 200 psi and an IPA flow- time from about 400 seconds to about 40,000 seconds.
  • the cross-linked membrane 100 has an open pore 12 structure and the pores 12 are interconnected allowing liquid or gas filtration.
  • the cross-linked membrane 100 includes one or more polyamide-imide polymers, wherein the membrane 100 has an HFE bubble point from about 25 psi to about 200 psi.
  • the membrane is asymrnetric-and microporous and has a tight layer that has a thickness of ⁇ 10 microns.
  • the membrane 100 also has an IP A flow time in a range from about 400 seconds to about 40,000 seconds.
  • cross-linked microporous membrane 100 is not limited by its form or shape unless expressly stated and includes membranes of varying shape, form, and morphology unless expressly limited by the specification.
  • the membrane 100 includes pleated form. In another embodiment, the membrane 100 includes hollow fiber. In yet another embodiment, the membrane 100 is in the form of flat films. In another embodiment, the membrane 100 includes composite form.
  • microporous cross-linked membranes described herein can be incorporated in filtration or purification housings.
  • An embodiment of the invention provides a filtration device 300 as shown in FIG. 1.
  • the filtration device includes one or more filters 200 incorporating a microporous membrane 100.
  • the microporous membrane includes polyamide-imide polymer, has an HFE bubble point, and an IPA flow-time.
  • the microporous membrane has an HFE bubble point from about 25 psi to about 200 psi and has an IPA flow-time from about 400 seconds to about 40,000 seconds.
  • the cross-linked microporous membranes 100 can be pleated and bonded, including potting, to form integral devices that permit filtration and purification of liquids and other fluids that pass through the membrane in the housing.
  • the membranes can be hollow fibers and incorporated to a housing to form integral devices that permit filtration and purification of liquids and other fluids that pass through the membrane in the housing.
  • Example embodiments of the membranes that could be employed in the practice of the present invention are described in PCT/US2014/065699, filed November 14, 2014, the entire teachings of which is incorporated herein by reference.
  • Any poly(amide-imide) membrane described in PCT/US2014/065699 can be subjected to thermal treatment, as described below, resulting in a thermally cross-linked poly( amide-imide) porous membrane.
  • porous poly(amide-imide) membranes that can be subjected to thermal cross-linking are described below. All testing methods used to determine pore sizes and flow times are equally applicable to the cross-linked membranes. Test methods described herein may be used to characterize the bubble point and flow time of the membranes as well as the test conditions for these values.
  • the bubble point used to characterize the membranes 100 refers to a mean bubble point using an air flow porisometer. ASTM F316 - 03(2011 ) Standard Test Methods for Pore Size Characteristics of Membrane Filters by Bubble Point and Mean Flow Pore Test were used to calculate bubble point.
  • microporous membrane bubble points refer to a mean bubble point measured by an HFE-7200 (available from 3MTM, St. Paul, MN). HFE-7200 bubble points can be converted into IPA bubble point values by multiplying the HFE-7200 value measured bubble point by 1.5. HFE-7200 by 3MTM is ethoxy-nonafluorobutane and has a reported surface tension of 13.6 mN/m at 25°C.
  • IPA flow time is the time to flow 500 milliliters of isopropyl alcohol, at a temperature of 21°C and pressure of 97,900 Pa (about 0.1 MPa, or about 1 bar, or about 14.2 psid), through a 47 millimeter disk of the microporous membrane with an area of 12.5 cm 2 .
  • embodiments of the inventions include microporous membranes 100 with varying HFE bubble points.
  • the HFE bubble point ranges from about 25 pounds per square inch pressure to about 150 pounds per square inch pressure.
  • the HFE bubble point ranges from about 53 pounds per square inch pressure to about 99 pounds per square inch pressure.
  • the HFE bubble point ranges from about 38 pounds per square inch pressure to about 75 pounds per square inch pressure.
  • the HFE bubble point ranges from about 32 pounds per square inch pressure to about 38 pounds per square inch pressure.
  • Embodiments of the invention include microporous membranes 100 with various ranges of IPA flow times.
  • the IPA flow time ranges from about 4225 seconds to about 7535 seconds.
  • the IPA flow time ranges from about 4090 seconds to about 5580 seconds.
  • the IPA flow time ranges from about 3445 seconds to about 4225 seconds.
  • the IPA flow time ranges from about 2860 seconds to about 3445 seconds.
  • NMP stands for N-methyl-2-pyrrolidone
  • EG for ethylene glycol
  • TEG for tri-ethylene glycol
  • Another embodiment includes a microporous membrane 100 with an HFE bubble point between 25 psi and 32 psi and an IPA flow time between 2860 seconds and 3445 seconds.
  • Another embodiment of the microporous membrane 100 includes an HFE bubble point between 32 psi and 38 psi and an IPA flow time of between 3445 seconds and 4245 seconds.
  • Yet another embodiment of the microporous membrane 100 includes an HFE Bubble point between 38 psi and 75 psi and an IPA flow time between 4245 seconds and 5580 seconds.
  • Another embodiment includes a microporous membrane 100 with an HFE bubble point between 53 psi and 99 psi and an IPA flow time between 4090 seconds and 7535 seconds.
  • microporous membranes 100 that are symmetric or asymmetric as (as shown in FIG. 1).
  • Symmetric membranes refer to porous membranes where the pore 12 size and/or structure are
  • asymmetric refers to a porous membrane in which the pore 12 size and/or structure are not the same from one side of the membrane to the other side as in FIG. 1.
  • the asymmetric microporous membranes 100 have a tight layer 10 (bottom) and an open layer 20 (top).
  • Examples la- Id of the polyamide-imide microporous membranes 100 made from the dope formulation are shown in Table 1.
  • the polyamide-imide (PAI) polymer dope formulation includes one or more polyamide-imide (PAI) polymers, one or more solvents, and one or more non-solvents.
  • PAI polyamide-imide
  • the formulation includes N- methylpyrrolidone (NMP) as the solvent, ethylene glycol (EG) as a non-solvent, and polyamide-imide polymer.
  • NMP N- methylpyrrolidone
  • EG ethylene glycol
  • polyamide-imide polymer polyamide-imide polymer.
  • the membrane 100 also includes the reaction product of the one or more solvents with each other, the reaction product of the one or more non-solvents with the each other, the reaction product of the one or more PAI polymers with each other, and the reaction product of the one or more solvents, one or more non-solvents, and one or more PAI polymers with each other.
  • Examples 2a-2d are examples with dope formulations differing from Examples 1 a-d as shown in Table 1 with increased amount of water in the coagulation bath.
  • Example 2a-d as in Examples la-d, the HFE bubble point of the membrane 100 increased as the amount of water in the coagulation bath increased as shown in Table 1. It should be appreciated that is it within the scope of invention to make microporous membranes 100 with a combination of one or more parameters such as range of IPA flow times, HFE bubble points, as well as varying the amount of water in the coagulation bath, etc.
  • Step 310 includes providing polyamide-imide (PAI) polymer dope formulation.
  • the polyamide-imide (PAI) polymer dope formulation includes one or more polyamide-imide (PAI) polymers, one or more solvents, and one or more non-solvents.
  • the polyamide-imide (PAI) polymer dope formulation includes N- methylpyrrolidone (NMP) as the solvent, ethylene glycol (EG) as a non-solvent, and polyamide-imide polymer in a ratio range of 79(NMP)/8(EG)/13(PAI) weight% to
  • the dope formulation includes a plurality of polyamide- imides which differ from each other.
  • the plurality of polyamide-imides may have various characteristics which are similar or vary from each other.
  • the pluralities of differing polyamide-imides are in various ranges.
  • the dope formulation includes a plurality of solvents which are similar or vary from each other.
  • the pluralities of differing solvents are in various ranges.
  • the dope formulation includes a plurality of non-solvents which are similar or vary from each other.
  • the plurality of differing non- solvents are in various ranges.
  • Step 320 includes phase separating the polyamide-imide (PAI) polymer dope formulation with a coagulant.
  • the coagulant includes NMP and water in a ratio of 80(NMP)/20(water) weight% to 65(NMP)/35(water) weight %.
  • Step 330 includes thermally treating the microporous membrane obtained in step 320 to induce cross-linking.
  • the pre-formed membranes are placed into an oven and heated to 250 ' C for 6 hours.
  • Example 1 Fabrication and characterization of thermally cross-linked poly(amide-imide microporous membranes
  • microporous poly(amide-imide) membranes were pre-fabricated as described above, in Table 1 , Example 2d, using Torlon® poly(amide-imide) polymer, with the following modification: the coagulant used to phase-seprate the polymer was NMP/Water (60/40 weight %).
  • Asymmetric flat sheet poly(amide-imide) membranes with a HFE-7200 bubble point of 100 psi and Isopropyl Alcohol (IP A) flow-time of 4500 sec were placed and hold onto frames of 20cm* 15cm dimensions. The frames were placed into an oven and heated up to 250 ' C for 6 hours. The outcome was cross-linked poly(amide-imide) membrane with slightly darker color compared with the original yellowish color of the uncross-linked membrane.
  • FIG. 2A and 2B are SEM images showing the P AI (Torlon®) membrane before (FIG. 2A) and after (FIG. 2B) thermal cross-lining.
  • the mechanical properties of the non- crosslinked membrane is significantly affected by the contact with acid solution as the membrane tensile strain and tensile stress at break were both dropped drastically.
  • a three- week long exposure to 10% aqueous HCl reduced the tensile strain of untreated Torlon® membrane from about 0.08 to about 0.02, representing a 75%) reduction on tensile strain.
  • the tensile stress of untreated Torlon® membrane was reduced from 8.41 MPa to 3.37 MPa, representing approximately 60% reduction.
  • FIG. 5 A a three-week long exposure to 10% aqueous HCl reduced the tensile strain of a thermally cross-linked Torlon® membrane from about 0.07 to about 0.05, representing a mere 29% reduction on tensile strain.
  • FIG. 5B the tensile stress of a thermally cross-linked Torlon® membrane showed no significant reduction (7.79 to 8.9 MPa).

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  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

Membranes poly(amide-imide) microporeuses thermiquement réticulées présentant une haute résistance chimique; et leurs procédés de fabrication. Cette membrane microporeuse thermiquement réticulée présente un point de bulle HFE d'environ 25 psi à environ 200 psi et un temps d'écoulement IPA d'environ 400 secondes à environ 40 000 secondes. Une autre membrane poly(amide-imide) microporeuse thermiquement réticulée comprend un polymère polyamide-imide, ladite membrane présentant un point de bulle HFE d'environ 25 psi à environ 200 psi. La membrane est asymétrique et comporte une couche serrée dont l'épaisseur est inférieure ou égale à 10 microns. L'invention concerne également des dispositifs de filtration et de purification comprenant de tels dispositifs.
PCT/US2015/023538 2014-04-02 2015-03-31 Membrane filtrante poly(amide-imide) thermiquement réticulée WO2015153574A1 (fr)

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Citations (3)

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US4900449A (en) * 1987-05-20 1990-02-13 Gelman Sciences Filtration membranes and method of making the same
EP1672011A1 (fr) * 2003-09-25 2006-06-21 Daicel Chemical Industries, Ltd. Film poreux resistant aux agents chimiques
WO2015073820A1 (fr) * 2013-11-14 2015-05-21 Entegris, Inc. Membranes microporeuses en polyamide-imide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4900449A (en) * 1987-05-20 1990-02-13 Gelman Sciences Filtration membranes and method of making the same
EP1672011A1 (fr) * 2003-09-25 2006-06-21 Daicel Chemical Industries, Ltd. Film poreux resistant aux agents chimiques
WO2015073820A1 (fr) * 2013-11-14 2015-05-21 Entegris, Inc. Membranes microporeuses en polyamide-imide

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
QIU W ET AL: "Dehydration of ethanol-water mixtures using asymmetric hollow fiber membranes from commercial polyimides", JOURNAL OF MEMBRANE SCIENCE, ELSEVIER, vol. 327, no. 1-2, 5 February 2009 (2009-02-05), pages 96 - 103, XP025917502, ISSN: 0376-7388, [retrieved on 20081127], DOI: 10.1016/J.MEMSCI.2008.11.029 *

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