CN104437138A - Polysulfonate separation membrane and preparation method thereof - Google Patents
Polysulfonate separation membrane and preparation method thereof Download PDFInfo
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- CN104437138A CN104437138A CN201410652309.9A CN201410652309A CN104437138A CN 104437138 A CN104437138 A CN 104437138A CN 201410652309 A CN201410652309 A CN 201410652309A CN 104437138 A CN104437138 A CN 104437138A
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Abstract
The invention discloses a polysulfonate separation membrane and a preparation method thereof. Casting solution of the polysulfonate separation membrane is prepared from the following components in mass ratio: the mass ratio of membrane preparation raw material, solvent, nonsolvent and modified additive is (10-20):(50-85):(5-25):(0-15). The preparation method of the polysulfonate separation membrane comprises the following steps: preparing the casting solution; preparing the membrane by a nonsolvent-induced phase separation method, solidifying in a coagulating bath, rinsing and drying. In the preparation process of the polysulfonate separation membrane, the casting solution, the coagulating bath, the temperature of the environment atmosphere, the environment humidity and the standing time can be accurately controlled to realize a spongy gradient structure of membrane pores. The preparation method of the polysulfonate separation membrane has simple process and can realize industrial scale production.
Description
Technical field
The present invention relates to diffusion barrier field, particularly relate to a kind of polyethers diffusion barrier and preparation method thereof.
Background technology
Membrane separation technique take pressure as driving force, carries out Selective Separation by membrane aperture size and surperficial compatibility to mixing material, and compared with traditional separation method, UF membrane has selective height, energy consumption is low, separative efficiency is high and be convenient to realize the advantages such as automation.Thermally induced phase separation (hot method) and phase separation method (wet method) are the methods of two kinds of common preparative separation membrane materials, and wet spinning technology is simple, and process flexible is controlled, and energy consumption is low, industrially applies more extensive.The macroporous structure that the diffusion barrier structure of wet-layer preparation is uneven often, this heterogeneity structure can cause film mechanical strength low, and permeance property and cutoff performance are difficult to improve simultaneously.The diffusion barrier structure of spongelike structure is homogeneous, and micro-nano networked pore structures support strength is good, and in dry run, membrane micropore degree of caving in is little, and dry state flux is large; Film mechanical strength is relatively high, surface abrasion, and permeance property and cutoff performance can control as required, can meet complicated treatment media and treatment process; The polyether sulfone structure of spongelike structure has better blood compatibility.Gradient pore spongelike structure is a kind of novel single separating layer membrane pore structure, and on film cross section, the separation aperture of UF membrane cortex is minimum, and along with the increase separating absciss layer distance, aperture increases.In filter process, permeating medium is by after selective separating, and flow resistance reduces gradually, and separating rate is fast, and membrane flux is high; The aperture particle suitable with fenestra, through after separating layer, can be taken out of under filter medium washes away, and effectively avoids blocking fenestra to cause flux depression, has certain resistance tocrocking.
Publication number is the preparation method that the Chinese patent application of 103191655A discloses a kind of compound Pvdf Microporous Hollow Fiber Membrane, at Pvdf Microporous Hollow Fiber Membrane surface coating maleic anhydride cross-linked polyethylene glycol.Because polyethylene glycol is hydrophilic, in water, solidify the composite membrane top layer prepared after crosslinked and there is spongelike structure.Publication number is that the Chinese patent application of 102131566A discloses the polyolefin micropore filter membrane being prepared unsymmetric structure by ultraviolet initiation situ aggregation method.In fabricated in situ process, the one-shot forming in the process of synthesis of masking macromolecular material, forms spongelike structure.These two kinds of method film preparation processes are simple, but are difficult to realize large-scale production.
Publication number is the preparation method that the Chinese patent application of 101484234A and 103608092A Chinese patent application disclose a kind of gradient spongy hole Nomex (polysulfones, polyether sulfone) milipore filter, realize fenestra by hydrophilic additive in casting solution and non-solvent to be changed to spongy pore structure by macropore, hydrophilic additive is the necessary additive that membrane structure changes, being the key factor causing membrane structure to change, still there is part macroporous structure in the film cross section zone line of preparation.
Publication number is the preparation method that the Chinese patent application of 101623605A discloses a kind of high flux and high retention ratio spongy polyvinylidene fluoride film having.It fills Kynoar casting solution with inorganic nano-particle, by controlling solvent-nonsolvent exchange velocity in pre-evaporation and coagulation bath temperature adjustment casting solution solidification process, prepares the Pvdf Microporous Hollow Fiber Membrane with full spongelike structure.
Publication number is that the Chinese patent application of 101890307A discloses a kind of Pvdf Microporous Hollow Fiber Membrane and the method for making thereof with Graded Density.It prepares the Pvdf Microporous Hollow Fiber Membrane with graded pore structure by hydrophilic polymer and diluent propane diols or ethylene acetate by thermally induced phase separation, the thermograde controlling the formation solidification of the casting solution aerial time of staying is poor, to form goal gradient pore structure diffusion barrier.
Publication number is that the Chinese patent application of 103816818A discloses hollow-fibre membrane of a kind of super hydrophilic gradient pore structure and preparation method thereof.Except containing except masking macromolecular material in casting solution, also additionally with the addition of amphipathic block polyether modified organic silicon material, size and the Density Distribution of fenestra is controlled by the length and relative scale regulating and controlling hydrophilic block and hydrophobic block in amphipathic nature block polymer, realize membrane structure with water or other non-solvents regulation and control casting solution state and be transformed into homogeneous spongelike structure by perforation structure, pore-size distribution radially gradually changes.
From above, in prior art, the structure of wet process film is difficult to control, and the film properties of preparation is difficult to significantly improve.Therefore, diffusion barrier and preparation method thereof all needs to be improved further.
Summary of the invention
In view of this, be necessary for above-mentioned problem, a kind of polysulfones diffusion barrier and preparation method thereof is provided.
In order to realize foregoing invention object, the present invention adopts following technical scheme:
A kind of polysulfones diffusion barrier, its casting solution is made up of the component of following mass ratio: the mass ratio of masking raw material, casting solution, non-solvent, property-modifying additive is 10-25:50-85:5-25:0-15.
Preferably, the mass ratio of masking raw material, casting solution, non-solvent, property-modifying additive is 10-20:50-70:10-20:5-12.
Preferably, described masking raw material are a kind of in polysulfones and polyether sulfone or both mixtures.
Preferably, described casting solution is one or several the mixture in nitrogen methyl pyrrolidone, dimethyl formamide and dimethylacetylamide.
Preferably, described property-modifying additive is polyethylene glycol, poly-methyl pyrrole alkane ketone, class 80 of department or other amphipathic block polymers.
Preferably, described non-solvent is LiCl solution, HCl solution, NaOH solution, the H of mass fraction 0.5-3%
2sO
4solution, ammoniacal liquor or sodium dodecyl sulfate aqueous solution, or be a kind of or two kinds of mixtures according to mass ratio 1:1-1:3 in class 40 of department, acetic acid, acetone, oxolane, citric acid, ethanol, isopropyl alcohol, butyric acid, n-octyl alcohol or polysorbas20.
A preparation method for polysulfones diffusion barrier, comprises the following steps:
1) masking raw material, casting solution, non-solvent and property-modifying additive are mixed, stirring and dissolving under 10-120 DEG C of condition, the weight ratio of described masking raw material and casting solution, non-solvent, property-modifying additive is 10-20:50-85:5-25:0-15;
2) by phase separation method, above-mentioned mixed solution is passed through membrane equipment film extrusion in the constant air humidity atmosphere of 20%-100%; Preferably, at 25-50 DEG C, the constant saturated humidity of 60%-85% prepares above-mentioned diffusion barrier;
3) time of staying is 0-600s or stops distance for 0-50cm film in atmosphere, then enters film-forming in coagulating bath; Preferably, the time of staying is 0-100s or stops distance for 0-30cm film in atmosphere;
4) film solidified is processed by aftertreatment fluid before rinsing or after rinsing, then naturally dries at ambient temperature.
Preferably, described polysulfones diffusion barrier is spongy graded pore structure polysulfones diffusion barrier.
Preferably, described aftertreatment fluid is NaCl, HCl, NaOH, dimethyl formamide, methyl pyrrolidone, oxolane, ethanol, sodium acetate, class of department 40, KAl (SO
4)
212H
2the aqueous solution of one or several mixtures in O, acetic acid, citric acid, NaClO, HClO, polysorbas20, glycerine and dodecyl sodium sulfate.
Preferably, described coagulating bath is ethanol, the casting solution aqueous solution or pH are the aqueous solution of 4-10.Described pH is the aqueous solution that the aqueous solution of 4-10 comprises that any pH of being dissolved in the water is the chemical substance of 4-10, as sodium bicarbonate aqueous solution.
Preferably, described polysulfones diffusion barrier can be Flat Membrane, tubular membrane or hollow-fibre membrane, or from the film of hollow-fibre membrane, tubular membrane, other shape any that Flat Membrane is different with spherical film.
More preferably, described polysulfones diffusion barrier is spherical.
Preferably, described polysulfones diffusion barrier has supporting layer or without supporting layer.
Preferably, the thickness of described polysulfones diffusion barrier is 50-5000 micron.Preferred, the thickness of described polysulfones diffusion barrier is 100-500 micron.
Described spongelike structure diffusion barrier cross section is asymmetrical continuous net-shaped micro-nano pore structure, and described gradient pore is along the side of film to the cavernous structure that the netted micro-nano hole diameter of opposite side increases gradually or reduces.A certain amount of non-solvent is added in described diffusion barrier preparation liquid.By the pH difference of solvent in the non-solvent of acidity and property-modifying additive regulation and control casting solution to structure adaptability state or casting solution and coagulating bath, casting solution phase separation speed and phase separation can be controlled accurately, film cross section is avoided to form finger-like pore and macroporous structure defect, realize membrane pore structure and become the netted micro-nano hole of continuous print sponge by the typical discontinuous finger-like pore Structure Transformation of phase separation method, the netted micro-nano hole pore size of sponge is radially uniform gradient distribution in cross section.And be transformed into homogeneous phase structure by non-homogeneous phase due to membrane pore structure, effectively reduce the defect on film surface, improve mechanical strength and mar proof, increase the service life.Because film hole diameter increases gradually by retaining layer, diameter and film retain the suitable particle in aperture in use successfully can enter into penetrating fluid through rete after retaining layer under the washing away of current, effective reduction Pore Blocking degree, improves film treatment effeciency.
Compared with prior art, the present invention has following beneficial effect:
(1) described polysulfones diffusion barrier prepares the diffusion barrier with spongy graded pore structure by the content and kind regulating and controlling non-solvent in casting solution.In described diffusion barrier casting solution, non-solvent content is different in different polymer, and different solvents non-solvent addition is different, and the similar polymers of the different trade mark is also different.Index (viscosity is dissolved exactly by casting solution, turbidity or pH) the raw-material film formulation of the different trade mark is finely tuned, accurate control parameters of preparation, guarantee that film that different batches is produced has the structures and characteristics of stable uniform, conveniently can realize the strict control of film quality, significant to production.
(2) preparation method of described polysulfones diffusion barrier has spongy graded pore structure polysulfones diffusion barrier by non-solvent and the preparation of spinning technique control casting solution phase separation.In the preparation process of described polysulfones diffusion barrier, by accurately controlling casting solution, the temperature of coagulating bath and environment and ambient humidity and the time of staying, to realize fenestra be spongy gradient-structure.This preparation method's technique is simple, is convenient to industrial-scale production.It provides another kind of mode that is alternative, cheap and that easily realize for wet process film structure regulating and directed transformation, solves that wet process film structure described in the prior art is difficult to control, the film properties of preparation is difficult to the problem that significantly improves.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of polyether sulfone Flat Membrane prepared by the embodiment of the present invention 1.
Detailed description of the invention
Formula of polysulfones diffusion barrier of the present invention and preparation method thereof, also for Flat Membrane, tubular membrane, hollow-fibre membrane and the film of any other shape with different geometrical construction, includes supporting layer and without support tunic.Because it when without prejudice to carrying out many possible detailed description of the invention when the spirit and scope of the present invention, can it should be understood that all situations all unrestricted scope of the invention as illustrating enumerated herein.The reagent used in the present invention, apart from outside specified otherwise, be all commercially available AR, cross section structure is by surface sweeping Electronic Speculum (JSM-6390, company of NEC) test, test flat membrane casting equipment, water flux/rejection testing arrangement laboratory self-control; Viscosity of sludge is by rotation viscometer (NDJ-8S, Shanghai Ping Xuan scientific instrument Co., Ltd) test; Rejection test bovine serum albumin for retaining material, by UV-1800 type ultraviolet-uisible spectrophotometer (Shanghai Mei Puda Instrument Ltd.) quantitative analysis.
Embodiment 1
By the mixture (mass ratio of acetic acid and glycerine is 1:1) of polyether sulfone, dimethyl formamide, acetic acid and glycerine and PVPK30 15:60:12:13 mixing in mass ratio, stir in 85 DEG C of oil baths and be prepared into clear transparent solutions in 24 hours, reduce mixing speed and continue stirring deaeration in 2 hours.Control the moisture stable of knifing atmosphere 55%, the gap arranging flat membrane casting equipment scraper is 0.2 micron, the casting solution prepared is laid in substrate of glass side, start flat membrane casting equipment, scraper runs with the speed of 100mm/s, 25s is stopped in atmosphere after scraper is out of service, then transfer in the sodium bicarbonate aqueous solution coagulating bath of 0.1mol/L, prepare polyether sulfone Flat Membrane, rinsing 48 hours in pure water, within in rinse cycle every 2-5 hour, change a water, then at NaOH, soak 4h in the mixed solution of citric acid and glycerine and carry out post processing, the poly (ether sulfone) film prepared at room temperature is placed and is dried in the shade for 24 hours.
Embodiment 2
By polysulfones, dimethylacetylamide, PEG6000 18:68:15 mixing in mass ratio, stir in 60 DEG C of oil baths and be prepared into clear transparent solutions in 24 hours, reduce mixing speed and continue stirring deaeration in 2 hours, then dropwise add hydrochloric acid until casting solution pH is between 4-5, now in casting solution, the mass ratio of polysulfones, dimethylacetylamide, PEG6000, hydrochloric acid is 17:66:14:3.Control the moisture stable of knifing atmosphere 100%, the gap arranging dull and stereotyped biofilm machine scraper is 0.5 micron, the casting solution prepared is laid in substrate of glass side, start flat membrane casting equipment, scraper runs with the speed of 100mm/s, 1min is stopped in atmosphere after scraper is out of service, then transfer in the sodium bicarbonate aqueous solution coagulating bath of 0.1mol/L, prepare polyether sulfone Flat Membrane, rinsing 48 hours in pure water, within in rinse cycle every 2-5 hour, change a water, then at dodecyl sodium sulfate, soak 4h in the mixed solution of citric acid and glycerine and carry out post processing, the poly (ether sulfone) film prepared at room temperature is placed and is dried in the shade for 24 hours.
Embodiment 3
By the 20:75:5 mixing in mass ratio of polyether sulfone, methyl pyrrolidone, butyric acid, stir in 30 DEG C of oil baths and be prepared into clear transparent solutions in 24 hours, reduce mixing speed and continue stirring deaeration in 2 hours, then in casting solution, dropwise isopropyl alcohol is added, and the viscosity B coefficent of Real-Time Monitoring casting solution, stop adding until the viscosity of casting solution reaches minimum, now in casting solution, the mass ratio of polyether sulfone, methyl pyrrolidone, butyric acid and isopropyl alcohol is 17:66:5:12.Control the moisture stable of knifing atmosphere 55%, the gap arranging flat membrane casting equipment scraper is 0.2 micron, the casting solution prepared is laid in substrate of glass side, start flat membrane casting equipment, scraper runs with the speed of 100mm/s, transfer to immediately after scraper is out of service in the sodium bicarbonate aqueous solution coagulating bath of 0.1mol/L, prepare polyether sulfone Flat Membrane, rinsing 48 hours in pure water, within in rinse cycle every 2-5 hour, change a water, then in class 40 of department, soak 4h in the mixed solution of citric acid and glycerine and carry out post processing, the poly (ether sulfone) film prepared at room temperature is placed and is dried in the shade for 24 hours.
Embodiment 4
By polysulfones, dimethylacetylamide, PEG6000 17:68:15 mixing in mass ratio, stir at ambient temperature and be prepared into clear transparent solutions in 24 hours, reduce mixing speed and continue stirring deaeration in 2 hours, then dropwise add butyric acid until casting solution pH is between 4-5, now in casting solution, the mass ratio of polysulfones, dimethylacetylamide, PEG6000, butyric acid is 17:66:14:3.Select
hollow tunica fibrosa spinneret, hollow fiber spinning machine prepares hollow-fibre membrane, the inner liquid of spinning is the sodium bicarbonate aqueous solution of 0.1mol/L, coagulating bath is water, inner liquid and coagulating bath are normal temperature, spinning head is a dried up 30cm, control the moisture stable of knifing atmosphere 85%, start spinning-drawing machine, wire vent speed is 80cm/min, the rinsing 48 hours in pure water of preparation ps hollow fiber uf membrane, within in rinse cycle every 2-5 hour, change a water, then in the mixed solution of hydrochloric acid/hypochlorous acid and glycerine, soak 4h and carry out post processing, the poly (ether sulfone) film prepared at room temperature is placed and is dried in the shade for 24 hours.
Embodiment 5
Polyether sulfone, dimethyl formamide and PEG6000 are pressed the mass ratio mixing of 17:70:13, stir in 85 DEG C of oil baths and be prepared into clear transparent solutions in 24 hours, reduce mixing speed and continue stirring deaeration in 2 hours.Control the moisture stable of knifing atmosphere 55%, the gap arranging dull and stereotyped biofilm machine scraper is 0.2 micron, the casting solution prepared is laid in substrate of glass side, start dull and stereotyped biofilm machine, scraper runs with the speed of 100mm/s, 1.5min is stopped in atmosphere after scraper is out of service, then transfer in the sodium bicarbonate aqueous solution coagulating bath of 0.1mol/L, prepare polyether sulfone Flat Membrane, rinsing 48 hours in pure water, within in rinse cycle every 2-5 hour, change a water, then at NaOH, soak 4h in the mixed solution of citric acid and glycerine and carry out post processing, the poly (ether sulfone) film prepared at room temperature is placed and is dried in the shade for 24 hours.
The poly (ether sulfone) film that each embodiment above-mentioned obtains metal spraying after liquid nitrogen brittle failure, observes its cross section structure by SEM, by homemade permeation flux tester test pure water flux, with the BSA phosphate buffer solution of 1000ppm for penetrating fluid tests rejection.Fig. 1 is the cross-sectional scans Electronic Speculum figure (SEM) of polysulfones Flat Membrane in embodiment 1.Polysulfones diffusion barrier of the present invention prepares the diffusion barrier with complete spongy graded pore structure by the content of non-solvent in regulation and control casting solution and kind or the pH gradient between casting solution and coagulating bath, and this preparation method's technique is simple, the structure of easy controlling diaphragm.Gained Flat Membrane cross-sectional aperture is diminished to opposite gradually by a surface, distribution gradient, and dense face surface apertures minimum-value aperture is about 0.1 μm, and loose face surface apertures is about 2.5 μm, and surface apertures is than being about 25:1, and pure water flux can reach 3000L/m
2about hatm.
The performance test results of table 1 each embodiment gained polysulfones diffusion barrier
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a polysulfones diffusion barrier, is characterized in that, its casting solution is made up of the component of following mass ratio: the mass ratio of masking raw material, casting solution, non-solvent, property-modifying additive is 10-20:50-85:5-25:0-15.
2. polysulfones diffusion barrier according to claim 1, is characterized in that, the mass ratio of described masking raw material, casting solution, non-solvent, property-modifying additive is 10-20:50-70:10-20:5-12.
3. polysulfones diffusion barrier according to claim 1, is characterized in that, described masking raw material are a kind of in polysulfones and polyether sulfone or both mixtures; Described casting solution is one or several the mixture in nitrogen methyl pyrrolidone, dimethyl formamide and dimethylacetylamide; Described property-modifying additive is polyethylene glycol, poly-methyl pyrrole alkane ketone, class 80 of department or other amphipathic block polymers; Described non-solvent is the LiCl solution of mass fraction 0.5-3%, HCl solution, NaOH solution, H2SO4 solution, ammoniacal liquor or sodium dodecyl sulfate aqueous solution, or is a kind of or two kinds of mixtures according to mass ratio 1:1-1:3 in class 40 of department, acetic acid, acetone, oxolane, citric acid, ethanol, isopropyl alcohol, n-butanol, n-octyl alcohol or polysorbas20.
4. a preparation method for polysulfones diffusion barrier, is characterized in that, comprises the following steps:
1) masking raw material, casting solution, non-solvent and property-modifying additive are mixed, stirring and dissolving under 10-120 DEG C of condition, the mass ratio of described masking raw material and casting solution, non-solvent, property-modifying additive is 10-20:50-85:5-25:0-15;
2) by phase separation method, above-mentioned mixed solution is passed through membrane equipment film extrusion in the constant air humidity atmosphere of 20%-100%;
3) time of staying is 0-600s or stops distance for 0-50cm film in atmosphere, then enters film-forming in coagulating bath;
4) film solidified is processed by aftertreatment fluid before rinsing or after rinsing, then naturally dries at ambient temperature.
5. the preparation method of polysulfones diffusion barrier according to claim 4, it is characterized in that, described post-treatment solution is by NaCl, HCl, NaOH, dimethyl formamide, methyl pyrrolidone, oxolane, ethanol, sodium acetate, class of department 40, KAl (SO
4)
212H
2the aqueous solution of one or several mixtures in O, acetic acid, citric acid, NaClO, HClO, polysorbas20, glycerine and dodecyl sodium sulfate; Described coagulating bath is ethanol, the casting solution aqueous solution or pH are the aqueous solution of 4-10.
6. the preparation method of polysulfones diffusion barrier according to claim 4, is characterized in that, described polysulfones diffusion barrier is spongy graded pore structure polysulfones diffusion barrier.
7. the preparation method of polysulfones diffusion barrier according to claim 4, it is characterized in that, described polysulfones diffusion barrier can be Flat Membrane, tubular membrane or hollow-fibre membrane, or from the film of hollow-fibre membrane, tubular membrane, other shape any that Flat Membrane is different with spherical film.
8. the preparation method of polysulfones diffusion barrier according to claim 7, is characterized in that, described polysulfones diffusion barrier is spherical.
9. the preparation method of polysulfones diffusion barrier according to claim 4, is characterized in that, described polysulfones diffusion barrier has supporting layer or without supporting layer.
10. the preparation method of polysulfones diffusion barrier according to claim 4, is characterized in that, the thickness of described polysulfones diffusion barrier is 50-5000 micron.
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