EP2838647A1 - Aus sulfonierten polyphenylensulfonen hergestellte ultrafiltrierungsmembranen - Google Patents

Aus sulfonierten polyphenylensulfonen hergestellte ultrafiltrierungsmembranen

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Publication number
EP2838647A1
EP2838647A1 EP13720290.9A EP13720290A EP2838647A1 EP 2838647 A1 EP2838647 A1 EP 2838647A1 EP 13720290 A EP13720290 A EP 13720290A EP 2838647 A1 EP2838647 A1 EP 2838647A1
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EP
European Patent Office
Prior art keywords
membrane
polymer
sulfonated
membranes
anyone
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP13720290.9A
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English (en)
French (fr)
Inventor
Martin Weber
Christian Maletzko
Natalia Widjojo
Peishan ZHONG
Tai-Shung Chung
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BASF SE
National University of Singapore
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BASF SE
National University of Singapore
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Priority to EP13720290.9A priority Critical patent/EP2838647A1/de
Publication of EP2838647A1 publication Critical patent/EP2838647A1/de
Withdrawn legal-status Critical Current

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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
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/80—Block polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/145—Ultrafiltration
    • 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
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/106—Membranes in the pores of a support, e.g. polymerized in the pores or voids
    • 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
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/107—Organic support material
    • 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
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • 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
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • 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
    • B01D2325/0283—Pore size
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention is directed to ultrafiltration membranes comprising a membrane substrate layer (S) based on a sulfonated polyaryleneethersulfone polymer, in particu- lar sulfonated polyphenylenesulfone (sPPSU) polymer and to a method for their preparation. Furthermore, the present invention is directed to ultrafiltration processes making use of said membrane.
  • S membrane substrate layer
  • sPPSU sulfonated polyaryleneethersulfone
  • Ultrafiltration is a membrane process which lies between microfiltration (MF) and nanofiltration (NF).
  • MF microfiltration
  • NF nanofiltration
  • the pore sizes of such membranes are typically within the range of about 2 to 100nm [1].
  • the ideal UF membranes should have the characteristics of: (1 ) hydrophilicity and high water flux; (2) highly porous with sponge-like (no macrovoid) and interconnected pore structures; (3) sufficient mechanical strength with good long term membrane stability.
  • UF membranes are prepared via the phase inversion process to form asymmetric membranes from materials such as polysulfone (PSU) [5], poly(vinylidene) fluoride (PVDF) [6], cellulose acetate (CA) [7] and polyimide (PI) [8].
  • PSU polysulfone
  • PVDF poly(vinylidene) fluoride
  • CA cellulose acetate
  • PI polyimide
  • polyaryl- sulfones are known for their chemical and mechanical resistance, thermal stability as well as ability to withstand wide ranges of temperature and corrosive environment [9].
  • UF membranes made from these polymers are subject to poor wettability by an aqueous media, macrovoids formation as well as fouling tendency.
  • the above problem is, in particular, solved by providing ultrafiltration (UF) integrally asymmetric membranes with fully porous and sponge-like morphology via the phase inversion process using sulfonated polyphenylenesulfone (sPPSU) synthesized via direct sulphonation route.
  • sPPSU sulfonated polyphenylenesulfone
  • the methods described in this invention can be extended to produce integrally skinned asymmetric hollow fiber membranes from the aforementioned polymer materials for various applications in the membrane industry.
  • these newly developed UF membranes have the potential to be applied in processes like hemodialysis, protein separa- tion/fractionation, virus removal, recovery vaccines and antibiotics from fermentation broths, wastewater treatment, milk/dairy product concentration, clarification of fruit juice, etc.
  • the negative charge in these UF asymmetric membranes also can enhance the separation performance for specific protein pairs/mixtures.
  • Such membranes can also be applied as membrane substrates with some modifications for other membrane applications such as nanofiltration and forward osmosis.
  • the methods described in this invention can be extended to produce integrally skinned UF asymmetric hollow fiber membranes.
  • sPPSU directly sulfonated polyphenylenesulfone
  • 5,5 ' -Di-sulfonate-4,4'-dichlorodiphenyl sul- fone sDCDPS monomer
  • Fig. 1 shows the morphology of as-cast membranes: (a) PPSU; (b) sPPSU-2,5%; (c) sPPSU-5%
  • Fig. 2 shows the probability density curve of UF membranes with different sulfonation contents: (a) PPSU; (b) sPPSU-2,5%; (c) sPPSU-5%
  • Membranes for water treatment are generally semi-permeable membranes which allow for separation of dissolved and suspended particles of water, wherein the separation process itself can be either pressure-driven or electrically driven.
  • membrane applications are pressure-driven membrane technologies such as microfiltration (MF; pore size about 0.08 to 2 ⁇ , for separation of very small, suspended particles, colloids, bacteria), ultrafiltration (UF; pore size about 0.005 to 0.2 ⁇ ; for separation of organic particles > 1000 MW, viruses, bacteria, colloids), nanofiltration (NF, pore size 0.001 to 0.01 ⁇ , for separation of organic particles > 300 MW Trihalo- methan (THM) precursors, viruses, bacteria, colloids, dissolved solids) or reverse osmosis (RO, pore size 0.0001 to 0.001 ⁇ , for separation of ions, organic substances > 100 MW).
  • MF microfiltration
  • UF ultrafiltration
  • NF nanofiltration
  • NF pore size 0.001 to 0.01 ⁇
  • RO reverse osmosis
  • Molecular weights of polymers are, unless otherwise stated as Mw values, in particular determined via GPC in DMAc (dimethylacetamide).
  • DMAc dimethylacetamide
  • Polyester copolymers were used as column material. The calibration of the columns was performed with narrowly distributed PMMA standards. As flow rate 1 ml / min was selected, the concentration of the injected polymer solution was 4 mg / ml.
  • Partially sulfonated in the context of the present invention refers to a polymer, wherein merely a certain proportion of the monomeric constituents is sulfonated and contains at least one sulfo group residue. In particular about 0,5 to 4,5 mol-% or about 1 to 3,5 mol-% of the monomeric constituents or repeating units of the polymer carry at least one sulfo group.
  • the sulfonated monomeric unit may carry one or more, as for example 2, 3, 4 , in particular 2 sulfo groups.
  • sulfo content is below 0,5 mol.-% then no improvement of the hydrophilicity can be seen, if the sulfo content is above 5 mol.-% then a membrane with macrovoids and low mechanical stability is obtained.
  • whoArylene represents bivalent, mono- or polynucleated, in particular mono-, di- or tri- nucleated aromatic ring groups which optionally may be mono- or poly-substituted, as for example mono-, di- or tri-substituted, as for example by same or different, in particular same lower alkyl, as for example Ci-C 8 or CrC 4 alkyl groups, and contain 6 to 20, as for example 6 to 12 ring carbon atoms.
  • Two or more ring groups may be condensed or, more preferably non-condensed rings, or two neighboured rings may be linked via a group R selected from a C-C single bond or an ether (-0-) or an alkylene bridge, or halogenated alkylene bridge or sulfono group (-S0 2 -).
  • Arylene groups may, for example, be selected from mono-, di- and tri-nucleated aromatic ring groups, wherein, in the case of di- and tri-nucleated groups the aromatic rings are optionally condensed; if said two or three aromatic rings are not condensed, then they are linked pairwise via a C-C- single bond, -0-, or an alkylene or halogenated alkylene bridge.
  • phenylenes like hydroquinone; bisphenylenes; naphthylenes; phenan- thrylenes as depicted below:
  • R represents a linking group as defined above like -0-, alkylene, or fluorinated or chlorinated alkylene or a chemical bond and which may be further substituted as defined above.
  • HandAlkylene represents a linear or branched divalent hydrocarbon group having 1 to 10 or 1 to 4 carbon atoms, as for example CrC 4 -alkylene groups, like -CH 2 -, -(CH 2 )2-, (CH 2 ) 3 -,-(CH 2 ) 4 -, -(CH 2 ) 2 -CH(CH 3 )-, -CH 2 -CH(CH 3 )-CH 2 - , (CH 2 ) 4 -.
  • “Lower alkyl” represents an “alkyl” residue which is linear or branched having from 1 to 8 carbon atoms. Examples thereof are: CrC 4 -alkyl radicals selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl or ie f-butyl, or d-C 6 -alkyl radicals selected from Ci-C 4 -alkyl radicals as defined above and additionally pentyl, 1 -methylbutyl, 2- methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 -ethyl propyl, hexyl, 1 ,1 -dimethylpropyl, 1 ,2-dimethylpropyl, 1 -methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1 -dimethylbutyl, 1 ,2-d
  • An "Asymmetric membrane” (or anisotropic membrane) has a thin porous or non- porous selective barrier, supported by a much thicker porous substructure (see also H. Susanto, M. Ulbricht, Membrane Operations, Innovative Separations and Transformations, ed. E. Driolo, L. Giorno, Wiley-VCH-Verlag GmbH, Weinheim, 2009, p. 21 ) B. Particular embodiments
  • a sponge-like, asymmetric membrane, in particular applicable as UF membrane, comprising at least one asymmetric membrane substrate layer (S) comprising at least one partially sulfonated polyphenylenesulfone polymer (P1 ).
  • Ar represents a divalent aromatic residue
  • At least one monomeric unit selected from M1 and M2 is sulphonated
  • aromatic rings of M1 and / or M2 may further carry one or more same or different substituents (different from sulfo residues of the type -S0 3 H, or the corresponding metal salt form thereof of the type -S0 3 " M + ), in particular those suitable for improving the feature profile (like mechanical strength, or permeability) of said substrate layer.
  • substituents may be lower alkyl substituents, like methyl or ethyl.
  • the membrane of one of the preceding embodiments wherein in said partially sulfonated polyarylenesulfone polymer (in particular polyphenylenesulfone polymer) (P1 ) about 0,5 to 5 or 1 to 3,5 mol-% of the monomeric constituents or repeating units of the polymer carry at least one sulfo group. 4.
  • said partially sulfonated polyarylenesulfone polymer (in particular polyphenylenesulfone polymer) (P1 ) is obtainable by
  • Hal is F, CI, Br or J as for example the M1 a monomer:
  • M2a Monomer as for example the M2a Monomer : and wherein the aromatic rings of M1 a and / or M2a may further carry one or more substituents as described above for M1 and M2; and at least one sulphonated monomer of the general formulae M1 b and M2b
  • aromatic rings of M1 b and / or M2b may further carry one or more substituents as described above for M1 and M2, and in particular wherein the molar proportion of sulfonated monomers M1 b and/ or M2b is in the range of 0,5 to 5 mol-% based on the total mole number of M1 a, M1 b, M2a and M2b. and wherein the molar ratio of (M1 a +M1 b) : (M2a +M2b) is about 0,95 to 1.05, in particular 0,97 to 1 ,03.
  • a method of preparing a membrane of any one of the preceding claims comprises preparing at least one substrate layer (S) by applying a polymer solution comprising at least one partially sulphonated polyarylenesulfone polymer (in particular polyphenylenesulfone polymer) (P1 ) as defined in anyone of the embodiments 1 to 7.
  • the polymer solution contains at least one solvent selected from N-methylpyrrolidone (NMP), N-dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), dimethylformamide (DMF), tri- ethylphosphate, tetrahydrofuran (THF), 1 ,4-dioxane, methyl ethyl ketone (MEK), or a combination thereof; and, additionally may contain at least one further additive selected from ethylene glycol, diethylene glycol, polyethylene glycol, glycerol, methanol, ethanol, isopropanol, polyvinylpyrrolidone, or a combination there- of, wherein said additive is contained in said polymer solution in a range of 0 to
  • An ultrafiltration membrane comprising at least one membrane of anyone of the claims 1 to 1 1 or prepared according to anyone of the embodiments 13 to 17. 19.
  • the ultrafiltration membrane of embodiment 18 in the form of a flat sheet, hollow fiber or tubule.
  • An ultrafiltration method making use of a membrane of embodiment 18 or 19.
  • polymer P1 Unless otherwise stated, preparation of polymers is generally performed by applying standard methods of polymer technology. In general, the reagents and monomeric constituents as used herein are either commercially available or well known from the prior art or easily accessible to a skilled reader via disclosure of the prior art. According to a first particular embodiment the partially sulfonated polyarylene sulfone polymer (in particular polyphenylenesulfone polymer) P1 is produced by reacting a mixture of monomers comprising monomers of the type M1 a and M2a and at least one sulfonated variant of the Type M1 b and M2b.
  • the sulfonated polyarylene sulfone polymer (in particular polyphenylenesulfone polymer) P1 can be synthesized, for example by reacting a dialkali metal salt of an aromatic diol and an aromatic dihalide as taught, for example by [20] R.N. Johnson et al., J. Polym. Sci. A-1 , Vol. 5, 2375 (1967).
  • Suitable aromatic dihalides (M1 a) include: bis(4-chlorophenyl)sulfone, bis(4-fluorophenyl) sulfone, bis(4-bromophenyl) sulfone, bis(4-iodophenyl) sulfone, bis(2-chlorophenyl) sulfone, bis(2-fluorophenyl) sulfone, bis (2-methyl-4-chlorophenyl) sulfone, bis(2-methyl-4-fluorophenyl) sulfone, bis(3,5-dimethyl-4-chlorophenyl) sulfone, bis(3,5-dimethyl-4-flurophenyl) sulfone and corresponding lower alkyl substituted analogs thereof.
  • dihalides are bis(4- chlorophenyl) sulfone (also designated (4,4'-dichlorophenyl) sulfone; DCDPS) and bis(4-fluorophenyl) sulfone.
  • Suitable dihydric aromatic alcohols (M2a) which are to react with the aro- matic dihalide are: hydroquinone, resorcinol, 1 ,5-dihydroxynaphthalene, 1 ,6- dihydroxynaphthalene, 1 ,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 4,4'- bisphenol, 2,2'-bisphenol, bis(4-hydroxyphenyl) ether, bis(2-hydroxyphenyl) ether, 2,2- bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxy-phenyl)propane, 2,2-bis(3,5- dimethyl-4-hydroyphenyl)propane, bis(4-hydroxyphenyl)methane, and 2,2-bis(3,5- dimethyl-4-hydroxypenyl)hexafluoropropane.
  • hydroquinone resorcinol
  • 1 ,5-dihydroxynaphthalene 1 ,6-dihydroxynaphthalene
  • 1 ,7- dihydroxynaphthalene 2,7-dihydroxynaphthalene
  • 4,4'-biphenol bis(4-hydroxyphenyl) ether
  • bis(2-hydroxyphenyl) ether may be used either individually or as a combination of two or more monomeric constituents M2a.
  • dihydric aromatic alcohols are 4,4'-bisphenol and 2,2'-bisphenol.
  • Compounds M1 b and M2b are the mono- or poly-sulfonated equivalents of the above- described non-sulfonated monomeric constituents M1 a and M1 b.
  • Such sulfonated monomeric constituents are either well-known in the art or easily accessible via routine methods of organic synthesis.
  • sulfonated aromatic dihalides such as sodium 5,5'-sulphonyl bis(2-chlorobenzenesulfonate) (the 5,5'-bis sulfonated analog of DCDPS) are, for example, disclosed by [21] M. Ueda et al., J. Polym. Sci., Part A: Polym. Chem. Vol. 31 853 (1993).
  • the dialkali metal salt of said dihydric aromatic phenol is obtainable by the reaction between the dihydric aromatic alcohol and an alkali metal compound, such as potassium carbonate, potassium hydroxide, sodium carbonate or sodium hydroxide.
  • a polar solvent such as dimethyl sulfoxide, sulfolane, N-methyl- 2-pyrrolidone, 1 ,3-dimethyl-2-imidazolidinone, ⁇ , ⁇ -dimethylformamide, N,N- dimethylacetamide, and diphenyl sulfone, or mixtures thereof or mixtures of such polar solvents with apolar organic solvents like toluene may be applied.
  • the reaction temperature is typically in the range of 140 to 320 or in particular 160 to 250°C.
  • the reaction time may be in the range of 0.5 to 100, or in particular 2 to 15 h.
  • either one of the dihydric aromatic alcohol alkali metal salt and the aromatic dihalide in excess results in the formation of end groups that can be utilized for molecular weight control. Otherwise, if the two constituents are used in equimolar amounts, and either one of a monohydric phenol, as for example, phenol, cresol, 4-phenylphenol or 3-phenylphenol, and an aromatic halide, as for example 4-chlorophenyl sulfone, 1 - chloro-4-nitrobenzene, 1 -chloro-2-nitrobenzene, 1 -chloro-3-nitrobenzene, 4- fluorobenzophenone, 1 -fluoro-4-nitrobenzene, 1 -fluoro-2-nitrobenzene or 1 -fluoro-3- nitrobenzene is added for chain termination.
  • a monohydric phenol as for example, phenol, cresol, 4-phenylphenol or 3-phenylphenol
  • an aromatic halide as for example 4-chlorophenyl
  • the degree of polymerization (calculated on the basis of repeating units composed of one monomer (M1 ) and one monomer (M2), as for example repeating units (1 ) and (2) or (1 a) and (2a)) of the thus obtained polymer may be in the range of 40 to 120, in particular 50 to 80 or 55 to 75.
  • Reaction of the monomeric constituents, in particular, of the aromatic dihalides M1 a and M1 b and the dihydric aromatic alcohol alkali metal salts of M2a and optionally M2b may also be performed as described [14] Geise, G.M., et al J. Poly. Sci, Part B: Polym Phys.: Vol 48, (2010), 1685 and literature cross-referenced therein.
  • Preparation of substrate layer (S) Preparation of the sponge-like, macrovoid free substrate layer (S) is performed by applying well-known techniques of membrane formation, as for example described in [15] C.A. Smolders et al J. Membr. Sci.: Vol 73, (1992), 259.
  • phase sinversion method A particular method of preparation is known as phase sinversion method.
  • a first step the partially sulfonated polymer (P1 ) as prepared above is dried, as for example at a temperature in the range of 20 to 80, as for example 60°C under vacuum in order to remove excess liquid.
  • a homogeneous dope solution comprising the polymer in a suitable solvent system is prepared.
  • Said solvent system contains at least one solvent selected from N-methylpyrrolidone (NMP), N-dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), dimethylformamide (DMF), triethylphosphate, tetrahydrofuran (THF), 1 ,4- dioxane, methyl ethyl ketone (MEK), or a combination thereof; and, additionally may contain at least one further additive selected from ethylene glycol, diethylene glycol, polyethylene glycol, glycerol, methanol, ethanol, isopropanol, polyvinylpyrrolidone, or a combination thereof, wherein said additive is contained in said polymer solution in a range of 0 - 50 or 0 - 30 wt.-% per total weight of the polymer solution.
  • NMP N-methylpyrrolidone
  • DMAc dimethylacetamide
  • DMSO dimethylsulfoxide
  • DMF dimethylformamide
  • the polymer content is in the range of 10 to 40, or 16 to 24 wt.-% based on the total weight of the solution.
  • a typical composition comprises sPPSU 2,5%/ethylene glycol/N-methyl pyrrolidone (NMP>99.5%) in a wt%-ratio of 20:16:64.
  • the polymer solution is then cast on a solid support, as for example glass plate using a casting knife suitably of applying a polymer layer of sufficient thick- ness.
  • the polymer layer provided on said support is immersed in a coagulant bath, containing a water-based coagulation liquid, e.g. a tap water coagulant bath at room temperature.
  • a water-based coagulation liquid e.g. a tap water coagulant bath at room temperature.
  • water may be applied in admix- ture with at least one lower alcohol as coagulant bath, in particular methanol, ethanol, isopropanol, and optionally in admixture with at least one solvent as defined above.
  • the as-cast membranes were soaked in water for at least 2 days with constant change of water to ensure complete removal of solvent in order to induce phase inversion.
  • Example 1 Preparation of membrane substrate polymers a) sPPSU 2,5% In a 4 I HWS-vessel with stirrer, Dean-Stark-trap, nitrogen-inlet and temperature control, 1 ,99 mol Dichlorodiphenylsulfone (DCDPS), 2,00 mol 4,4 ' -Dihydroxybiphenyl (DHBP), 0,05 mol 3, 3 ' -Di-sodiumdisulfate-4,4 ' -dichlorodiphenylsulfone und 2,12 mol Potassiumcarbonate (Particle size 36,2 ⁇ ) are suspended under nitrogen atmosphere in 2000 ml NMP. Under stirring the mixture is heated up to 190°C.
  • DCDPS Dichlorodiphenylsulfone
  • DHBP 2,00 mol 4,4 ' -Dihydroxybiphenyl
  • DHBP 2,00 mol 4,4 ' -Dihydroxybiphenyl
  • DHBP 2,00 mol 4,4 '
  • Viscosity number 88,7 ml/g (1 wt.-/vol% solution in N-methylpyrrolidone at 25°C).
  • the content of the sDCDPS monomer was estimated taking the S-content of the polymer to be 2,4 mol-%.
  • Viscosity number 83,2 ml/g (1 wt.-/vol% solution in N-methylpyrrolidone at 25°C).
  • the content of the sDCDPS monomer was estimated taking the S-content of the polymer to be 4,7 mol-%.
  • Example 2 Fabrication of fully sponge-like and hydrophilic UF membranes from sPPSU 2,5% and sPPSU 5% sPPSU 2,5% and sPPSU 5% were synthesized as described above in example 1 and following to the synthesis route developed by McGrath et al. [14].
  • NMP N-methyl-2-pyrrolidone
  • EG ethylene glycol
  • the casting solutions were allowed to degas overnight prior to casting onto a glass plate with a casting knife of 100 ⁇ in thickness.
  • the as-cast membranes were then immersed into a water coagulation bath immediately at room temperature and kept for 1 day to ensure complete precipitation.
  • Fig. 1 shows the SEM images of UF membranes cast with non-sulfonated and sulfonated materials.
  • the membrane from non-sulfonated PPSU (Fig. 1 a) exhibits numerous macrovoids due to instantaneous demixing, while those from sulfonated PPSU of the present invention (Fig. 1 b and 1 c) display a fully sponge-like and interconnected pore structures with no observed macrovoids.
  • Example 3 UF performance testing of sPPSU-2,5% sPPSU-5% and PPSU membranes
  • PWP pure water permeability
  • g is the water permeation volumetric flow rate (L/h)
  • A is the effective filtration area (m 2 )
  • AP is the trans-membrane pressure (bar).
  • the membrane was subjected to neutral solute (polyethylene glycol (PEG) or polyethylene oxide (PEO)) separation tests by flowing them through the membrane's top surface under a pressure of 25 psi (1 .72 bar) on the liquid side.
  • concentrations of the neutral solutes were measured by a total organic carbon analyzer (TOC ASI-5000A, Shimadzu, Japan).
  • TOC ASI-5000A total organic carbon analyzer
  • the measured feed ⁇ C f ) and permeate (C p ) concentrations were used for the calculation of the effective solute rejection coefficient R
  • the radius (r) of a hypothetical solute at a given M w can be calcu- lated.
  • Table 2 represent the PWP and pore size characteristics of UF membranes from non- sulfonated and direct sulfonated PPSU materials. It is interesting to take note that the PWP of these membranes follows the order: non-sulfonated PPSU > sPPSU (2.5 mol% DCDPS) > sPPSU (5 mol% DCDPS). Although the non-sulfonated PPSU membranes are highly hydrophobic, it possesses large number of macrovoids with higher fouling tendency. Hence, this may be the reason why it has the highest PWP among all membrane substrates. Meanwhile, the membrane substrate from 5 mol% DCDPS polymer results in a lower PWP than that containing 2.5 mol% sulphonated monomer. This phenomenon is due to the fact that the former has a higher degree of water- induced swelling than the latter.
  • the MWCO of as-cast membranes is in the following order: sPPSU (2.5 mol% DCDPS) > non-sulfonated PPSU > sPPSU (5 mol% DCDPS).
  • the MWCO in the sPPSU with 2.5 mol% is higher than non-sulfonated PPSU because its sulfonic group induces delayed demixing and results in larger pore size.
  • the MWCO in the sPPSU with 5 mol% is smaller than other membranes due to the effect of larger swelling behavior in the highly sulfonated materials.
  • Example 4 Mechanical strength properties of PPSU, sPPSU 2,5% and sPPSU 5% membranes
  • Table 3 summarizes mechanical strengths of the fabricated UF membranes. Young's modulus decreases, while elongation at break increases with an increase in sulfonation degree of membrane substrates. For sulfonated PPSU with 5 mol% sDCDPS, it shows lower mechanical strength.
  • the fabricated UF membranes were immersed in the glycerol/water 50/50wt% mixture for 2 days followed by drying in the air before carrying out the mechanical test. The mechanical properties of membrane substrates were then measured by an Instron 5542 tensile testing equipment. The flat sheet membranes were cut into stripes with 5 mm width and clamped at the both ends with an initial gauge length of 25 mm and a testing rate of 10 mm/min. At least three stripes were tested for each casting condition to obtain the average values of tensile stress, extension at break and Young's modulus of the membranes.
  • PPSU non-sulfonated
  • 241 .0 ⁇ 16.2 7.89 ⁇ 0.29 18.4 ⁇ 3.77 sPPSU (2.5 mol% DCDPS) 75.7 ⁇ 2.72 3.67 ⁇ 0.10 37.2 ⁇ 4.45 sPPSU (5 mol% DCDPS) 14.2 ⁇ 0.77 0.97 ⁇ 0.05 43.9 ⁇ 2.34

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
EP13720290.9A 2012-04-20 2013-04-19 Aus sulfonierten polyphenylensulfonen hergestellte ultrafiltrierungsmembranen Withdrawn EP2838647A1 (de)

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EP12165060 2012-04-20
PCT/EP2013/058173 WO2013156598A1 (en) 2012-04-20 2013-04-19 Ultrafiltration membranes fabricated from sulfonated polyphenylenesulfones
EP13720290.9A EP2838647A1 (de) 2012-04-20 2013-04-19 Aus sulfonierten polyphenylensulfonen hergestellte ultrafiltrierungsmembranen

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US20160089629A1 (en) * 2014-09-26 2016-03-31 Uop Llc Asymmetric integrally-skinned flat sheet membranes for h2 purification and natural gas upgrading
US10814289B2 (en) 2014-10-07 2020-10-27 Toyobo Co., Ltd. Separation membrane, separation membrane element and separation membrane module
DE102016102782A1 (de) 2016-02-17 2017-09-14 B. Braun Avitum Ag Dialysemembran und Verfahren zu ihrer Herstellung
US11001673B2 (en) 2016-05-26 2021-05-11 University Of Florida Research Foundation, Incorporated Aliphatic polysulfones with improved mechanical integrity
US10894864B2 (en) 2016-05-26 2021-01-19 University Of Florida Research Foundation, Inc. Aliphatic polysulfones with improved mechanical integrity
CN106178684B (zh) * 2016-07-28 2018-02-13 上海超高环保科技股份有限公司 易去污的聚砜过滤组合物
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WO2019157377A1 (en) * 2018-02-09 2019-08-15 Board Of Regents, The University Of Texas System Sulfonated poly(arylene ether) membranes with high monovalent salt rejection even in the presence of mixed salt feeds that contain multivalent salts
CN109499371B (zh) * 2018-11-12 2021-10-15 苏州富淼膜科技有限公司 一种聚亚苯基砜内衬膜及其制备方法
CN112029103A (zh) * 2020-08-05 2020-12-04 杭州晟聚环保科技有限公司 一种酸碱离子改性聚合物及其多孔膜的制备
KR102525810B1 (ko) 2021-04-21 2023-04-26 한국화학연구원 다공성 불소계 분리막 및 이의 제조 방법
CN114864978B (zh) * 2022-06-16 2023-05-05 电子科技大学 高增湿氢燃料电池增湿器中空纤维膜材料及其制备方法和应用

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WO2013156598A1 (en) 2013-10-24
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CN104411388A (zh) 2015-03-11
KR20150023277A (ko) 2015-03-05
JP6211059B2 (ja) 2017-10-11

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