CN104411388B - The ultrafiltration membrane prepared by sulfonated polyphenylene sulfone - Google Patents

The ultrafiltration membrane prepared by sulfonated polyphenylene sulfone Download PDF

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CN104411388B
CN104411388B CN201380032253.0A CN201380032253A CN104411388B CN 104411388 B CN104411388 B CN 104411388B CN 201380032253 A CN201380032253 A CN 201380032253A CN 104411388 B CN104411388 B CN 104411388B
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film
polymer
sulfonated
sulfonation
polyether sulfone
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CN104411388A (en
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M·韦伯
C·马莱茨科
N·维佐约
P·钟
泰-尚·钟
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BASF SE
National University of Singapore
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National University of Singapore
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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

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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)

Abstract

The present invention relates to ultrafiltration membranes and their preparation method comprising the film basal layer (S) based on sulfonated polyarylenes ether sulfone polymer.In addition, the present invention relates to the use of the hyperfiltration process that the film carries out.

Description

The ultrafiltration membrane prepared by sulfonated polyphenylene sulfone
Technical field
The present invention relates to comprising being based on sulfonated polyether sulfone polymer, especially sulfonated polyphenylene sulfone (sPPSU) polymer Film basal layer (S) ultrafiltration membrane and their preparation method.In addition, the present invention relates to the use of the ultrafiltration that the film carries out Method.
Background technique
Ultrafiltration (UF) is a kind of membrane process between micro-filtration (MF) and nanofiltration (NF).The aperture of such film is usually about In the range of 2 to 100nm [1].When applying 1-3 bars of driving force, this membrane process can retain macromolecular and colloid.At these While bigger molecule is rejected by, compared with small molecule can together with solvent free permeation.Similarly, the principle of UF depends primarily on Size exclusion.This method has been widely used for a variety of industries, for example, fruit juice and beverage [2,3] dialysis [4] and water it is net Change.
Ideal UF film should have characteristics that (1) hydrophily and high water flux；(2) spongy highly porous (without big Hole) and connection pore structure；(3) sufficient mechanical strength and good long-term membrane stability.
Most of UF film is by phase inversion by such as polysulfones (PSU) [5], polyvinylidene fluoride (PVDF) [6], second The material of acid cellulose (CA) [7] and polyimides (PI) [8] forms asymmetric membrane to prepare.In these materials, polyarylsulfone (PAS) Class is because of its chemistry and mechanical resistance, thermal stability and is able to bear the temperature of wide scope and the ability of corrosive environment has been big Known to family [9].However, it is contemplated that the hydrophobic property of certain above-mentioned polymer (that is, PSU and PVDF), by these polymer shapes At UF film have difference aqueous medium wettability, macroporous structure formation and fouling tendency.Therefore, it is necessary to be used for such Addition generally acts as hydrophilic agent and pore-foaming agent (that is, polyethylene glycol (PEG) [10,11], polyethylene in the polymer material of UF application Pyrrolidones (PVP)) additive.
It needs to utilize the advanced UF isolation technics with excellent chemical resistance and the film of thermal stability.
In the prior art, sulfonation PPSUs [12] and CA with 0.8 to 2.5meq/g degree of functionality are with sulfonation PPSU's Blend polymer [13] has been used for electrodialysis.However, by Direct Sulfonation without being mixed with other polymeric materials The UF film that is constituted of the material with low degree of functionality will be very desirable.
Summary of the invention
Particularly, the above problem can pass through phase by providing the sulfonated polyphenylene sulfone (sPPSU) synthesized by Direct Sulfonation Ultrafiltration (UF) the densification anisotropic membrane with highly porous sponge like morphology that conversion method is formed solves.By sulfonation list Body, film newly developed show high water-permeability.The hydrophily of UF film with negative electrical charge may reduce fouling tendency.In this hair Method described in bright can be expanded to the dense skin to be served many purposes in film industry by the preparation of above-mentioned polymer material Layer asymmetric hollow fiber membrane.Particularly, these UF films newly developed, which have, is applied to such as haemodialysis, protein point From/fractionation, virus sweep, recycling vaccine and antibiotic, sewage treatment, milk/dairy produce concentration, juice clarification from fermentation liquid Etc. processes potential.Negative electrical charge in these UF anisotropic membranes also can be improved to specific protein confrontation/mixture separating property. Such film is alternatively arranged as that there are certain improved film substrates to be applied to other films using such as nanofiltration and forward osmosis.According to film knot Structure, the method for the invention can be expanded to preparing dense layer surface UF asymmetric hollow fiber membrane.
More specifically, two kinds of new materials, that is, 5 containing 2.5mol% and 5.0mol%, 5 '-two-sulfonate groups- 4,4 '-dichloro diphenyl sulfones (5,5 '-Di-sulfonate-4,4 '-dichlorodiphenyl sulfone) sDCDPS monomer The polyphenylsulfone (sPPSU) of Direct Sulfonation, be used to study influence of the water-wet behavior to UF performance.The PPSU conduct of unsulfonated Benchmark be used to compare performance.
Detailed description of the invention
Fig. 1 shows casting (as-cast) film: (a) PPSU；(b) sPPSU-2,5%；(c) form of sPPSU-5%
Fig. 1 (Continued) shows the form of casting (as-cast) film PPSU, sPPSU-2,5%, sPPSU-5%
Fig. 2 shows the UF film with different sulfonation contents: (a) PPSU；(b) sPPSU-2,5%；(c) sPPSU-5% Probability density curve
Specific embodiment
A. general definition:
" film for water process " is usually the semi-permeable film of dissolubility particle and suspended particulate in separable water, wherein Separation process itself can be pressure-driven or be driven by electricity.
The example of film application is pressure-driven membrane technology such as micro-filtration (MF；About 0.08 to 2 μm of aperture, for separating very Small suspended particulate, colloid, bacterium), ultrafiltration (UF；About 0.005 to 0.2 μm of aperture；For separate > organic granular of 1000MW, Virus, bacterium, colloid), nanofiltration (NF, 0.001 to 0.01 μm of aperture, for separating > organic granular the haloform of 300MW (THM) precursor (Trihalo-methan (THM) precursors), virus, bacterium, colloid, soluble solid) or it is reverse osmosis (0.0001 to 0.001 μm of RO, aperture, for separating the organic substance of ion, > 100MW).
The molecular weight of polymer is unless otherwise defined weight average molecular weight Mw, particularly by GPC in DMAc (dimethyl Acetamide) in measurement.Particularly, gpc measurement be in the dimethyl acetamide (DMAc) containing 0.5 weight-% lithium bromide into Capable.Polyester copolymer is used as column material.Column is calibrated using narrow ditribution PMMA standard items.When selection 1ml/min's When flow velocity, the concentration of the polymer solution injected is 4mg/ml.
" sulfonation " molecule has at least one-SO3Sulphonic acid ester (or specified sulfo group) residue of H type, or formed by it Corresponding-SO3 -M+The metal salt of type, such as the alkali metal salt formed with M=Na, K or Li.
" partly sulfonated " in the context of the present invention means that only certain partial monosomy ingredient is sulfonated and includes at least one The polymer of sulfo group residue.Especially about 0.5 to 4.5mol-% or about 1 to 3.5mol% polymer monomer ingredient repeats single Member has at least one sulfo group.Sulfonated monomer unit can have one or more, such as 2,3,4, especially 2 sulfo groups.If Sulfo group content is lower than 0.5mol.-%, then will be unable to see hydrophilic improvement, can if sulfo group content is higher than 5mol.-% Obtain the film with macropore and low mechanical stability.
" arlydene " represents divalent, single or multiple core, the especially aromatic ring group of mono-, di- or three cores, optional coverlet Replace or polysubstituted, such as is replaced by mono-, di- or three, such as by identical or different, especially identical low alkyl group, such as C1-C8Or C1-C4Alkyl replaces, and contains 6 to 20, such as 6 to 12 ring carbon atoms.2 or multiple ring group (ring It groups can be) that condensed ring or more preferably non-condensed ring or 2 adjacent loops (neighboured rings) can be by mono- selected from C-C Key or ehter bond (- O-) or alkylidene bridge or halogeno alkylen bridge or sulfo group (sulfono) (- SO2) R group connection.Sub- virtue Base for example can be selected from the aromatic ring group of mono-, di- and three cores, wherein in the case where two cores and three core groups, aromatic rings can be optional It is condensed；If described 2 or 3 aromatic rings are not condensed, they pass through C-C- singly-bound ,-O- or alkylidene or halogenated Alkylidene bridge connects two-by-two.Mentioned example: phenylene, such as hydroquinone (hydroquinone)；Double phenylenes (biphenylenes)；Naphthylene (naphthylenes)；Phenanthrylene (phenanthrylenes) is described as follows:
Wherein R, which is represented, has linking group as defined above, for example,-O-, alkylidene or fluoro or chloro alkylidene or Chemical bond, and it can be according to being further substituted as defined above.
" alkylidene " represents the bivalent hydrocarbon radical with 1 to 10 or 1 to 4 carbon atom of linear chain or branched chain, such as C1-C4- Alkylidene, such as-CH2-、-(CH2)2-、(CH2)3-、-(CH2)4-、-(CH2)2-CH(CH3)-、-CH2-CH(CH3)-CH2-、 (CH2)4-。
" low alkyl group " represents a kind of " alkyl " residue with 1 to 8 carbon atom of linear chain or branched chain.Their example Are as follows: the C selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, 2- butyl, isobutyl group or tert-butyl1-C4Alkyl residue；Or Selected from C as defined above1-C4Alkyl and other amyl, 1- methyl butyl, 2- methyl butyl, 3- methyl butyl, 2, 2- dimethyl propyl, 1- ethyl propyl, hexyl, 1,1- dimethyl propyl, 1,2- dimethyl propyl, 1- methyl amyl, 2- methyl Amyl, 3- methyl amyl, 4- methyl amyl, 1,1- dimethylbutyl, 1,2- dimethylbutyl, 1,3- dimethylbutyl, 2,2- Dimethylbutyl, 2,3- dimethylbutyl, 3,3- dimethylbutyl, 1- ethyl-butyl, 2- ethyl-butyl, 1,1,2- trimethyl third Base, 1,2,2- thmethylpropyl, 1- ethyl -1- methyl-propyl, 1- Ethyl-2-Methyl propyl C1-C6Alkyl residue.
" anisotropic membrane " (or anisotropic membrane) has thin porous or non-porous selective barrier layer (barrier), Its by thicker porous structure support (referring to H.Susanto, M.Ulbricht, Membrane Operations, Innovative Separations and Transformations,ed.E.Driolo,L.Giorno,Wiley-VCH- Verlag GmbH, Weinheim, 2009, page 21).
B. specific embodiment
The present invention provides embodiment in detail below:
1. a kind of spongy, anisotropic membrane, is particularly suitable as UF film, includes at least one part comprising at least one The non-title film basal layer (S) of the polyphenylene sulfone polymer (P1) of sulfonation.
2. the film of embodiment 1, wherein the partly sulfonated polyether sulfone polymer (P1) is polyarylethersulfone polymer, and By the monomer composition of following general formula
Wherein
Ar represents the aromatic residues of divalent,
At least one monomeric unit selected from M1 and M2 is sulfonated,
And wherein the aromatic rings of M1 and/or M2 can be further (different with one or more identical or different substituent groups In-SO3The sulfo group residue of H type or the corresponding-SO formed by it3 -M+The metal salt of type), especially those are suitble to improve institute State the substituent group of basal layer characteristic (such as mechanical strength or permeability).Suitable substituent group can be rudimentary alkyl substituent, Such as methyl or ethyl.
3. the film of one of foregoing embodiments, wherein in the partly sulfonated poly (arylene ether) sulfone (polyarylenesulfone) in polymer (especially polyphenylene sulfone polymer) (P1), about 0.5 to 5 or 1 to 3.5mol-% Polymer monomer ingredient or repetitive unit have sulfo group.
4. the film of one of foregoing embodiments, wherein partly sulfonated poly (arylene ether) sulfone polymer (the especially poly- sub- benzene Base sulfone polymer) (P1) can pass through polymerization formula M 1a and M2a non-sulfonated monomer and at least one formula M 1b and M2b sulphur Change monomer to obtain
HO-Ar-OH (M2a)
Wherein Ar has as defined above, and
Hal is F, Cl, Br or I
Such as M1a monomer:
And
Such as M2a monomer:
And wherein the aromatic rings of M1a and/or M2a can further have one or more as above described in the M1 and M2 Substituent group；
Wherein Ar and Hal has as defined above, and n and m independently are 0,1 or 2, and condition is that n and m are not simultaneously 0；
Such as M1b monomer:
And
Such as M2b monomer:
Such as
And wherein the aromatic rings of M1b and/or M2b can further have one or more as above described in the M1 and M2 Substituent group, especially wherein the molar ratio of sulfonated monomer M1b and/or M2b in the range of 0.5 to 5mol-%, based on M1a, M1b, The molal quantity meter of M2a and M2b.And wherein (M1a+M1b): the molar ratio of (M2a+M2b) is about 0.95 to 1.05, in particular 0.97 to 1.03.
5. the film of one of foregoing embodiments, wherein partly sulfonated poly (arylene ether) sulfone polymer (the especially poly- sub- benzene Base sulfone polymer) (P1) be block copolymer or statistical copolymer.
6. the film of one of foregoing embodiments, wherein partly sulfonated poly (arylene ether) sulfone polymer (the especially poly- sub- benzene Base sulfone polymer) (P1) include formula (1) non-sulfonated repetitive unit and formula (2) sulfonation repetitive unit:
7. the film of embodiment 3, wherein (especially polyphenylsulfone polymerize the partly sulfonated poly (arylene ether) sulfone polymer Object) (P1) include formula (1a) non-sulfonated repetitive unit and formula (2a) sulfonation repetitive unit:
8. the film of embodiment 6 or 7, the sulfonation repetitive unit 2a wherein included with 0.1 to 20,0.2 to 10, it is outstanding Its 0.5 to 5 or 1 to 3.5mol% molar ratio is each based on repetitive unit (1) and (2) or the total mole number of (1a) and (2a) Meter.
9. the film of one of foregoing embodiments, wherein the weight average molecular weight (Mw) of the polymer P 1 is 50,000 to 150, In the range of 000, especially 70,000 to 100,000g/mol, measured in DMAc by GPC.If Mw 150,000 or more, Then the solution viscosity of polymer is too high.If Mw 50,000 hereinafter, if film obtained show limited mechanical strength.
10. the film of any one of foregoing embodiments, wherein at least one basal layer (S) represents one kind fully, that is, base Throughout the spongy of entire cross section and without the structure of macropore in sheet.
11. the film of any one of foregoing embodiments, wherein basal layer (S) have 30 to 400,50 to 250 or 80 to Thickness degree in the range of 150 μm.If thickness degree is at 400 μm or more, permeability of the membrane is lower, if thickness degree is at 30 μm Hereinafter, then defect will reduce selectivity.
12. the film of any one of foregoing embodiments, wherein sulfonated polymer (P1) can be by the M1b type comprising sulfonation It is prepared by the monomer mixture of monomer.
13. the method for preparing the film of any one of foregoing embodiments, wherein this method comprises: by application comprising at least A kind of partly sulfonated poly (arylene ether) sulfone polymer (especially polyphenylsulfone polymerization defined such as any one of embodiment 1 to 7 Object) polymer solution of (P1) prepares at least one basal layer (S).
14. the method for embodiment 13, wherein the polymer content of the solution is in 10 to 40,12 to 30 or 16 to 24 weights In the range of amount %.If the polymer content is on above range, the solution of the coating solution for spinning process Viscosity can be too high, and if it is under the range, film is formed too slow in fibre spinning.
15. the method for embodiment 14, wherein polymer solution includes at least one selected from following solvents: N- methyl pyrrole Pyrrolidone (NMP), N- dimethyl acetamide (DMAc), dimethyl sulfoxide (DMSO), dimethylformamide (DMF), triethyl phosphate, Tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane, methyl ethyl ketone (MEK) or their combination；In addition, may include at least one choosing From other following additives: ethylene glycol, diethylene glycol, polyethylene glycol, glycerine, methanol, ethyl alcohol, isopropanol, polyethylene pyrrole Pyrrolidone or their combination, wherein the additive include content in the polymer solution 0 to 50,1 to 40 or In the range of 1 to 25 or 5 to 15 weight %, the total weight based on polymer solution.
16. the method in 13 to 14 any one of embodiment, wherein at least one basal layer (S) can be by phase inversion simultaneously It is prepared using water as coagulating bath.
17. the method for embodiment 16, wherein water optionally at least one lower alcohol, especially methanol, ethyl alcohol, isopropanol into Row mixing, and optionally mixed at least one solvent as defined in embodiment 21, with for flocculating agent.
18. including the film of any one of at least one embodiment 1 to 11 or according to any one of embodiment 13 to 17 The ultrafiltration membrane of the film of preparation.
19. embodiment 18 in the form of plate, doughnut or tubule existing for ultrafiltration membrane.
20. a kind of hyperfiltration process that the film using embodiment 18 or 19 carries out.
21. embodiment 20 can be used for haemodialysis, Separation of Proteins/fractionation, virus sweep, recycle from fermentation liquid The method of vaccine and antibiotic, sewage treatment, milk/dairy produce concentration, juice clarification etc..
22. the film of any one of embodiment 1 to 12 or the film prepared according to any one of embodiment 13 to 7 are in conduct For producing the purposes being suitable in the basal layer of the film of other application such as FO or NF.
C. other embodiments of the invention
The film such as production of UF film and their purposes in different structure filtering module can be known from the prior art that. See, for example, [19] MC Porter et al.in Handbook of Industrial Membrane Technology (William Andrew Publishing/Noyes,1990)。
1. the preparation of hydrophilic film basal layer (S)
The preparation of 1.1 polymer Ps 1
Unless otherwise indicated, the preparation of polymer is usually carried out by using the standard method of polymer technology.In general, This reagent used and monomer component are disclosures that is commercially available or being known from the prior art that or passing through the prior art Easily there is the reader of technical background to obtain.
According to the first specific embodiment, partly sulfonated poly (arylene ether) sulfone polymer (especially polyphenylene polymers) P1 It can be by reacting the monomer mixture comprising the monomer of M1a and M2a type and the sulfonation variant of at least one M1b and M2b type It is prepared.
In general, poly (arylene ether) sulfone polymer (especially polyphenylene polymers) P1 of sulfonation can be for example, by reaction fragrance two Two alkali metal salts and aromatic dihalide compound of alcohol (such as are described in [20] R.N.Johnson et al., J.Polym.Sci.A- Volume 1,5, the introduction in 2375 (1967)) it is synthesized.
The example of suitable aromatic dihalide compound (M1a) includes: bis- (4- chlorphenyl) sulfones, bis- (4- fluorophenyl) sulfones, bis- (4- Bromophenyl) sulfone, bis- (4- iodophenyl) sulfones, bis- (2- chlorphenyl) sulfones, bis- (2- fluorophenyl) sulfones, bis- (2- methyl -4- chlorphenyl) sulfones, Bis- (2- methyl -4- fluorophenyl) sulfones, bis- (3,5- dimethyl -4- chlorphenyl) sulfones, bis- (3,5- dimethyl -4- fluorophenyl) sulfones, with And the analog that their corresponding low alkyl group replaces.They can be used alone or 2 as them or multiple monomer components Be applied in combination.The specific example of dihalide be bis- (4- chlorphenyl) sulfones (and specify (4,4 '-dichlorophenyl) sulfone； ) and bis- (4- fluorophenyl) sulfones DCDPS.
The example for the aromatic dihydroxy alcohol (M2a) that can be suitably reacted with aromatic dihalide compound are as follows: hydroquinone, isophthalic two It is phenol, 1,5- dihydroxy naphthlene, 1,6- dihydroxy naphthlene, 1,7- dihydroxy naphthlene, 2,7 dihydroxy naphthalene, 4,4 '-bis-phenols, 2,2 '-bis-phenols, double (4- hydroxyphenyl) ether, bis- (2- hydroxyphenyl) ethers, bis- (4- hydroxyphenyl) propane of 2,2-, bis- (the 3- methyl -4- hydroxy-phenies) third of 2,2- Bis- (3, the 5- dimethyl -4- hydroxyphenyl) propane of alkane, 2,2-, bis- (4- hydroxyphenyl) methane and 2, bis- (3, the 5- dimethyl -4- of 2- Hydroxyphenyl) hexafluoropropane.Preferably hydroquinone, resorcinol, 1,5- dihydroxy naphthlene, 1,6- dihydroxy naphthlene, 1,7- dihydroxy Naphthalene, 2,7 dihydroxy naphthalene, 4,4 '-bis-phenols, bis- (4- hydroxyphenyl) ethers, bis- (2- hydroxyphenyl) ethers.They can be used alone or as 2 A or multiple monomer component M2a's is applied in combination.The example of especially such aromatic dihydroxy alcohol is that 4,4 '-bis-phenols and 2,2 '-are bis- Phenol.
Compound M1b and M2b are the equivalent of the above-mentioned non-sulfonated monomer component M1a and M1b of single sulfonation or more sulfonation.This Class sulfonated monomer ingredient is well known in the prior art or is easily obtained by the conventional method of organic synthesis.Such as the aromatics of sulfonation Dihalide, such as bis- (2- chlorobenzenesulfonic acid) sodium of 5,5 '-sulfonyls (analogs of 5,5 '-bis- sulfonation DCDPS) are disclosed in, for example, [21] M.Ueda et al., J.Polym.Sci., Part A:Polym.Chem. volume 31 853 (1993).
Two alkali metal salts of the aromatic dihydroxy phenol can pass through the pure and mild alkali metal compound of aromatic dihydroxy (such as carbonic acid Potassium, potassium hydroxide, sodium carbonate or sodium hydroxide) between reaction obtain.
Two alkali metal salt of aromatic dihydroxy alcohol and aromatic dihalide compound and with anti-between sulfonated monomer as defined above It should can be carried out according to method described in the prior (see, for example, [22] Harrison et al, Polymer preprints (2000)41(2)1239).For example, can be carried out in polar solvent, polar solvent such as dimethyl sulfoxide, sulfolane, N- methyl -2- Pyrrolidones, 1,3- dimethyl -2- imidazolidinone, n,N-Dimethylformamide, n,N-dimethylacetamide, diphenyl sulfone, or The mixture of their mixture or such polar solvent and non-polar organic solvent such as toluene.
Reaction temperature is logical to be produced 140 to 320, or in the range of especially 160 to 250 DEG C.Reaction time 0.5 to 100, or In the range of especially 2 to 15h.
Either aromatic dihydroxy alcohol alkali metal salt or aromatic dihalide compound is excessively used to can lead to and can be used for controlling The formation of the end group of molecular weight processed.In addition, if two kinds of ingredients are used with equimolar amounts, add monohydric phenol (such as phenol, Cresols, 4- phenylphenol or 3- phenylphenol) or aromatic halide (such as the chloro- 4- nitrobenzene of 4- chlorphenyl sulfone, 1-, the chloro- 2- of 1- The chloro- 3- nitrobenzene of nitrobenzene, 1-, 4- fluorine benzophenone, the fluoro- 4- nitrobenzene of 1-, the fluoro- 2- nitrobenzene of 1- or the fluoro- 3- nitrobenzene of 1-) To be used for chain termination.
The degree of polymerization of thus obtained polymer (with the repetitive unit being made of monomer (M1) and monomer (M2), such as weighs Multiple unit (1) and (2) or (1a) and (2a) meter) it can be 40 to 120, in the range of especially 50 to 80 or 55 to 75.
The aromatic dihydroxy alcohol alkali of the reaction of monomer component, especially aromatic dihalide compound M1a and M1b and M2a and optional M2b The reaction of metal salt can be according to being described in [14] Geise, G.M., et al J.Poly.Sci, Part B:Polym Phys.: the Volume 48, (2010), 1685 and wherein method in the document of cross reference carries out.
The preparation of 1.2 basal layers (S)
Preparation spongy, without macropore basal layer (S) can be by using being for example described in [15] C.A.Smolders et Al J.Membr.Sci.: volume 73, (1992), the known film in 259 form technology and carry out.
Specific preparation method is phase inversion.
In the first step, right such as at 60 DEG C in order to remove surplus liquid, such as within the temperature range of 20 to 80 DEG C Partly sulfonated polymer (P1) made above is dried in vacuo.
In second step, preparation includes the homogeneous coating solution of polymer in suitable solvent system.The dicyandiamide solution Following solvent: N-Methyl pyrrolidone (NMP), N- dimethyl acetamide (DMAc), dimethyl sulfoxide is selected from comprising at least one (DMSO), dimethylformamide (DMF), triethyl phosphate, tetrahydrofuran (THF), 1,4- dioxane, methyl ethyl ketone (MEK) or their combination；In addition, may include at least one selected from other following additives: ethylene glycol, gathers diethylene glycol Ethylene glycol, glycerine, methanol, ethyl alcohol, isopropanol, polyvinylpyrrolidone or their combination, wherein the additive is in institute The content in polymer solution is stated in the range of 0-50 or 0-30 weight-%, with the total weight of polymer solution.
Polymer content is in the range of 10 to 40 or 16 to 24 weight-%, with the total weight of solution.Such as a kind of allusion quotation The composition of type include weight %- ratio be 20:16:64 sPPSU2.5%/ethylene glycol/N-Methyl pyrrolidone (NMP > 99.5%).
In the third step, polymer solution is cast in by the casting scraper of suitable application adequate thickness polymeric layer solid On phase carrier such as glass plate.
Immediately later, in the 4th step, the polymeric layer being coated on above-mentioned carrier is immersed in comprising water at room temperature The coagulating bath of property coagulation liquid, such as in tap water coagulating bath.Optionally, water can be used as admixture conduct at least one lower alcohol Coagulating bath, lower alcohol in particular methanol, ethyl alcohol, isopropanol, and optionally there is solvent one defined above at least one It rises and is used as admixture.In order to induce inversion of phases, by cast membrane dipping at least 2 days in water, constantly replacement water was during this period with true Protect fully erased solvent.
Thus process can get and show as spongelike structure and the film substrate without macropore.
Test portion
Embodiment 1: the preparation of film substrate polymer
A) sPPSU 2.5%
There is the 4L HWS- container of blender, Dean-Stark water segregator, nitrogen inlet and temperature controller at one In, in a nitrogen atmosphere, by 1.99mol dichloro diphenylsulfone (DCDPS), 4,4 '-dihydroxybiphenyl (DHBP) of 2.00mol, 3,3 '-two-two sodium sulphate -4,4 ' of 0.05mol-dichloro diphenylsulfone (3,3 '-Di-sodiumdisulfate-4,4 ' - Dichlorodiphenylsulfone it) is suspended in 2000ml NMP with 2.12mol potassium carbonate (36.2 μm of partial size).It is stirring Under heat the mixture to 190 DEG C.30l/h nitrogen is passed through in mixture in the form of being bubbled, and mixture is protected at 190 DEG C Hold 6h.After adding 1000ml NMP, cooling mixture.Under a nitrogen, mixture is cooled to 60 DEG C or less.After filtering, Mixture is precipitated in the water containing 100ml 2M HCl.With the product of hot water (20h, 85 DEG C at) extraction precipitation, and subtracting Under the conditions of pressure for 24 hours in 120 DEG C of dryings.
Viscosity number: 88.7ml/g (at 25 DEG C, 1 weight -/volume % solution) in N-Methyl pyrrolidone.
It is 2.4mol-% by the content that the S- content of polymer estimates sDCDPS monomer.
B) sPPSU 5%
There is the 4L HWS- container of blender, Dean-Stark water segregator, nitrogen inlet and temperature controller at one In, in a nitrogen atmosphere, by 1.90mol dichloro diphenylsulfone (DCDPS), 4,4 '-dihydroxybiphenyl (DHBP) of 2.00mol, 3,3 '-two-two sodium sulphate -4,4 ' of 0.1mol-dichloro diphenylsulfone (sDCDPS) and 2.12mol potassium carbonate (36.2 μm of partial size) It is suspended in 2000ml NMP.190 DEG C are heated the mixture under stiring.30l/h nitrogen is passed through mixing in the form of being bubbled In object, and mixture is kept into 6h at 190 DEG C.After adding 1000ml NMP, cooling mixture.Under a nitrogen, it mixes Object is cooled to 60 DEG C or less.After filtering, mixture is precipitated in the water containing 100ml 2M HCl.With hot water (20h, 85 At DEG C) product of extraction precipitation, and at reduced pressure conditions in 120 DEG C it is dry for 24 hours.
Viscosity number: 83.2ml/g (at 25 DEG C, 1 weight -/volume % solution) in N-Methyl pyrrolidone.
It is 4.7mol-% by the content that the S- content of polymer estimates sDCDPS monomer.
Embodiment 2: completely spongy and hydrophilic UF film is prepared by sPPSU 2.5% and sPPSU 5%
Just as described in Example 1, sPPSU 2.5% and sPPSU 5% are synthesized according to what is developed by McGrath etc. [14] Route is synthesized.
In the preparation of UF film, n-methyl-2-pyrrolidone (NMP) purchased from Merck and purchased from Sigma Aldrich's Ethylene glycol (EG) is respectively used as solvent and additive.
The group of every kind of coating solution becomes polymer/EG/NMP (weight %)=13/16/71.
Before casting solution is cast to glass plate using the casting scraper with a thickness of 100 μm, casting solution was carried out Night degassing.Then cast membrane is immersed in water coagulating bath immediately at room temperature, and is kept for 1 day, to ensure to precipitate completely.
In precipitation process, it can be observed: compared with the UF film cast by non-sulfonated PPSU material, by having 2.5 Hes The UF film that the sPPSU material of 5mol%DCDPS is cast shows lower settling rate.This is a kind of common phenomenon, due to Non-sulfonated material is compared, and sulfonate materials tend to promote delayed demixing.However, with by that need to be mixed to form with other polymers The known sulfonate materials of rear method of sulfonating [16] synthesis of anisotropic membrane are compared, and the polymer of Direct Sulfonation of the invention can be formed Independent anisotropic membrane, without being mixed with other polymers.
Fig. 1 shows the SEM figure for the UF film cast by non-sulfonated material and sulfonate materials.As expected, by non-sulfonated The film that PPSU (Fig. 1 a) is formed shows many macrovoids due to instantaneous demixing, however those are by sulfonation of the invention (Fig. 1 b shows pore structure that is completely spongy and being connected to 1c) to the film that PPSU is formed, and big gap is not observed.
Also can be observed: the bottom surface of the film formed by sulfonate materials is highly porous.The typical case shown such as Fig. 1 b and 1c Film form is very beneficial for UF application, and has the film substrate for being used as other types membrane process such as NF or forward osmosis (FO) Potential.In addition, compared with the film formed by non-sulfonated material, they also show more preferably water-wet behavior and higher porous Property.Table 1, which is shown, is formed by the contact angle of top surface and bottom surface of UF film and porous by non-sulfonated and sulfonation PPSU Property.
Table 1. is formed by the contact angle and porosity of the top surface and bottom surface of UF film by non-sulfonated and sulfonation PPSU
The UF performance test of embodiment 3:sPPSU-2.5%, sPPSU-5% and PPSU film
The pure of the plate membrane substrate of above-mentioned preparation is tested first with the ultrafiltration membrane permeation cell with 5cm sample diameter Water permeability (PWP) is (with L/m2Bar hr) [17,18].
Wherein Q is water penetration volume flow rate (L/h), and A is effective filtration area (m2), Δ P is transmembrane pressure (bar).
Then, Neutral Solute (polyethylene glycol (PEG) or polyethylene oxide (PEO)) separation test is carried out to above-mentioned film, made They flow through the top surface of film under the liquid phase pressure of 25psi (1.72 bars).Utilize total organic carbon analyzer (TOC ASI- 5000A, Shimadzu, Japan) measurement Neutral Solute concentration.Measured charging (Cf) concentration and infiltration (Cp) concentration by with In the effective solution loss coefficients R (%) of estimation:
In the present invention, the solution of PEG or PEO containing 200ppm different molecular weight are used as Neutral Solute, are used for table Levy membrane aperture and pore-size distribution.Stokes (Stokes) radius (r of these Neutral Solutess, nm) and molecular weight (Mw, gmol-1) between relationship may be expressed as:
For r=16.73 × 10 PEG-12×M0.557 (3)
For r=10.44 × 10 PEO-12×M0.587 (4)
Given M can be estimated from equation (3) and (4)wHypothesis solute radius (r).Then according to traditional solute Migration method ignores the space between solute and membrane pores and hydrodynamical interaction, can get average effective pore and Pore-size distribution, average effective pore radius (μp) and geometric standard deviation (σp) can be assumed that and μs(geometry of solute is flat when R=50% Equal radius) and σg(geometric standard deviation is defined as r when R=84.13%sWith r when R=50%sRatio) it is identical.Therefore, Based on μpAnd σp, the pore-size distribution of film is represented by following probability density function:
The PWP characteristic and aperture response for the UF film that table 2. is formed by non-sulfonated and Direct Sulfonation PPSU material are summarized
Table 2 shows the PWP characteristic and aperture response of the UF film formed by non-sulfonated and Direct Sulfonation PPSU material. What is interesting is the PWP that can pay attention to these films to follow following sequence: non-sulfonated PPSU > sPPSU (2.5mol%DCDPS) > sPPSU (5mol%DCDPS).Although non-sulfonated PPSU film has high hydrophobicity, it, which possesses, largely there is higher fouling to incline To macrovoid.Therefore, this may be why it has highest PWP in all film substrates.Meanwhile by 5mol% The film substrate that DCDPS polymer is formed has PWP more lower than the film substrate comprising 2.5mol% sulfonated monomer.This phenomenon is Since the former has the fact that higher water induction swellbility than the latter.
The molecular cut off (MWCO) of cast membrane follows following sequence: sPPSU (2.5mol%DCDPS) > non-sulfonated PPSU > SPPSU (5mol%DCDPS).The MWCO of sPPSU comprising 2.5mol%DCDPS is higher than non-sulfonated PPSU, because of its sulfonation Group is induction of delayed demixing and forms larger aperture.However, the MWCO of the sPPSU comprising 5mol%DCDPS is than other films It is small, this is because in height sulfonate materials larger swelling behavior influence.These are as the result is shown: being formed by Direct Sulfonation material The film with certain sulfonation degree have and be developed as huge potential quality for ultrafiltration membrane, this is because it has good PWP With ant-scaling characteristic and porosity and interconnected pore structure.
The mechanical strength property of 5% film of embodiment 4:PPSU, sPPSU 2.5% and sPPSU
Table 3 summarizes the mechanical strength of prepared UF film.Young's modulus reduces, while with the increasing of film substrate sulfonation degree Add, elongation at break increases.For the sulfonation PPSU containing 5mol%sDCDPS, it shows lower mechanical strength. It is then right before carrying out mechanical test by prepared UF film immersion 2 days in 50/50 weight % mixture of glycerine/water It is dried.Then the mechanical property of 5542 tensile test equipment of Instron measurement film substrate is utilized.Plate membrane is cut It is jammed at the band with 5mm width, and at both ends, initial gage length 25mm, test rate 10mm/min.Extremely 3 bands formed under the conditions of respective casting are tested, less to obtain the tensile stress of film, elongation at break and Young's modulus Average value.
The mechanical property for the UF film that table 3. is formed by non-sulfonated material and sulfonate materials
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The disclosure of document cited herein is included in this specification by way of citation.

Claims (11)

1. a kind of ultrafiltration membrane, it includes at least one film basal layer (S), the film basal layer (S) includes at least one part sulphur The polyether sulfone polymer (P1) of change forms polymer material as single film, wherein the polymer (P1) includes non-sulfonated sum The repetitive unit of sulfonation and wherein in the partly sulfonated polyether sulfone polymer (P1), the polymer of 0.5 to 5 mole of % Monomer component or repetitive unit there is at least one sulfonate group, and wherein
The partly sulfonated polyether sulfone polymer (P1) is poly (arylene ether) sulfone polymer, and its repetitive unit is by following The monomeric unit of general formula forms:
Wherein
Ar represents the Arylene residues of divalent,
At least one monomeric unit selected from M1 and M2 is sulfonated,
And the aromatic rings contained by M1 and M2 optionally and is independently of one another further substituted；
And the wherein monomer and at least that the partly sulfonated polyether sulfone polymer (P1) passes through polymerization formula M 1a and M2a A kind of sulfonated monomer acquisition of formula M 1b and M2b,
HO-Ar-OH (M2a)
Wherein Ar has as defined above, and
Hal is F, Cl, Br or I
Wherein Ar and Hal has as defined above, and n and m independently are 0,1 or 2, and condition is that n and m are not simultaneously 0.
2. the film of claim 1, wherein the partly sulfonated polyether sulfone polymer (P1) is block copolymer or statistics copolymerization Object.
3. the film of one of preceding claims, wherein the partly sulfonated polyether sulfone polymer (P1) includes the non-sulphur of formula (1) Change the sulfonation repetitive unit of repetitive unit and formula (2)
4. the film of claim 3, wherein the molar ratio of the sulfonation repetitive unit contained is 1 to 3.5 mole of %, based on repetition The total mole number meter of unit (1) and (2).
5. the film of claims 1 or 2, wherein the Mw of the polymer (P1) is in the range of 50,000 to 150,000, by solidifying Glue penetration chromatography (GPC) measurement in N- dimethyl acetamide (DMAc).
6. the film of claims 1 or 2, wherein the Mw of the polymer (P1) is in the range of 70,000 to 100,000g/mol, The measurement in N- dimethyl acetamide (DMAc) by gel permeation chromatography (GPC).
7. the film of claims 1 or 2, wherein the basal layer (S) represents a kind of spongy and without macropore structure, and/or
Wherein basal layer (S) has the thickness degree in 50-250 μ m.
8. the preparation method of the film of any one of preceding claims comprising: by application comprising at least one as right is wanted The polymer solution of the partly sulfonated polyether sulfone polymer (P1) of any one of 1 to 6 definition is asked to prepare at least one substrate Layer (S),
Wherein the polymer content of the solution is in the range of 10 to 24 weight %；And
Wherein the polymer solution includes at least one selected from following solvents: N-Methyl pyrrolidone (NMP), N- dimethyl Acetamide (DMAc), dimethyl sulfoxide (DMSO), dimethylformamide (DMF), triethyl phosphate, tetrahydrofuran (THF), 1,4- bis- Six ring of oxygen, methyl ethyl ketone (MEK) or their combination；And furthermore comprising at least one selected from other following additions Agent: ethylene glycol, diethylene glycol, polyethylene glycol, glycerine, methanol, ethyl alcohol, isopropanol, polyvinylpyrrolidone or their group It closes, wherein content of the additive in the polymer solution be in the range of 0-30 weight %, with polymer solution Total weight, and wherein at least one basal layer (S) prepares by phase inversion and using water as coagulating bath.
9. a kind of ultrafiltration membrane, it includes at least one films prepared according to claim 8.
10. a kind of hyperfiltration process utilizes the film of any one of claim 1 to 7 or 9.
11. the film of any one of claims 1 to 7 or the film prepared according to claim 8 are as substrate suitable for producing Purposes in the film of FO or NF.
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