CN102512997B - Hydrophilic polyethersulfone with cardo alloy ultrafiltration membrane and preparation method thereof - Google Patents
Hydrophilic polyethersulfone with cardo alloy ultrafiltration membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a novel hydrophilic polyethersulfone with cardo alloy ultrafiltration membrane and a preparation method thereof. According to the invention, hydrophilic polyethersulfone with cardo (PES-C) and hydrophilic polyvinylpyrrolidone (PVP) with a high molecular weight are blended, and a flat or hollow fiber ultrafiltration membrane is prepared by using an immersion-precipitation process or a dry/wet phase inversion process; and then the PES-C/PVP alloy ultrafiltration membrane with permanent hydrophilicity is prepared through hydrophilic long-lasting aftertreatment. The preparation method provided in the invention is simple, convenient, highly efficient and economy and is favorable for realization of industrial application. The prepared ultrafiltration membrane has good high temperature resistance, chemical solvent resistance, acidic and alkaline corrosion resistance and osmotic separation performance and excellent anti-pollution ability and can be used in the fields of purification of water quality, treatment of industrial waste water, recycling of domestic sewage, purification and separation of biological medicine products, etc.
Description
Technical field
The present invention relates to milipore filter separation field, particularly a kind of polyethersulfone with cardo alloy ultrafiltration membrane with permanent hydrophilic and preparation method thereof.
Background technology
China is that a serious scarcity of freshwater resources and water pollute quite serious country, and therefore how effectively administering environment, fully develop water resource is the key subjects that are related to national economy.Under the background of increasingly sharpening at current water resources crisis, membrane separation technique is efficient with it, the feature of energy-saving and environmental protection is widely applied in water resource recycling fields such as desalinization, Industrial Wastewater Treatment and municipal wastewater improvement.Yet present stage; film pollution problem in use remains the maximum bottleneck of the isolation technics development of restriction liquid film and scale application; and development has hydrophily, resistant to pollution membrane material is acknowledged as the effective way addressing this problem; for improving film separative efficiency, prolonging service lifetime of film, reduce operating cost significant.
In recent years, along with the range of application of ultrafiltration membrane technique is constantly widened, in fields such as petrochemical industry, smelting processing, biological product purification separation, medical production high-temperature sterilizations, not only need membrane material to there is good hydrophily and contamination resistance, the heat resistance of material, chemical stability and mechanical mechanics property etc. are all had higher requirement simultaneously.Generally the commercialization milipore filter of application mostly is hydrophobic film material at present, as polysulfones, polyether sulfone, Kynoar etc., the serviceability temperature of these milipore filters is all no more than 70 ℃, therefore greatly limited the application of membrane separation technique, developed that novel fire resistant, chemically-resistant solvent, separating property well have the hydrophily of lasting stability concurrently and the milipore filter of excellent contamination resistance has become the task of top priority simultaneously.
Polyethersulfone with cardo is a kind of novel high-performance engineering plastics that China researches and develops voluntarily.In the molecular structure of polyether sulfone, introduced phenolphthalein group, make the polyether sulfone of this " modification " show good heat endurance, its vitrification point is the highest a kind of (Tg=263 ℃) of vitrification point in polysulfones series, and it also has high temperature resistant hydrolysis, chemical stability and the dimensional stability of good mechanical performance, excellence in addition.Thereby polyethersulfone with cardo has higher serviceability temperature than conventional membrane materials such as polysulfones, polyether sulfones, all there is good application potential in the field that need to bear for a long time high temperature, resistance to chemical attack at the oily waste water processing of petrochemical industry, metallurgical waste water processing, biological medicine industry high-temperature sterilization etc.
In view of polyethersulfone with cardo is the same with the commercial milipore filter of most, it is all the special engineered macromolecular material of hydrophobicity.If will keep in actual applications the original heat resistance of material, chemical stability and the higher advantages such as mechanical strength, overcome again its defect hydrophobic, that easily cause film to pollute, just must carry out modification to membrane material.
At present, the hydrophilic modifying of milipore filter material mainly comprises chemical modification and the large class of physical modification two:
(1) chemical modification can realize by methods such as copolymerization, grafting, plasma surface polymerization and interfacial polycondensations, yet confirms that by practice chemical modification method exists many limitation: comprising that film forming and hydrophilic modifying can not be synchronizeed carries out; Reaction condition is often comparatively harsh, with high costs; Chemical reaction easily exerts an influence to porous membrane structure and intensity, and heavy metal ion also can be brought environmental issue etc.
(2) physical modification comprises high polymer alloy technology (being blending and modifying technology) and surface coating modified etc.Surface coating modified is very common a kind of in physical modification method, its method is simple, easy to operate, but the hydrophilic layer forming by physical absorption easily and primer peel off even and come off, cause the hydrophily of membrane material to be difficult to lastingly, and the chemical substance coming off can be polluted separating medium.
High polymer alloy refers to by multiple macromolecule and forms a kind of new polymer composite by blending and modifying.Not only can retain the premium properties of original material, also can overcome the defect separately of original material, thereby realize, have complementary advantages, improve membrane material characteristic; There is simple and convenient, with low cost, to be easy to control feature simultaneously.Adopt polymer blended technology to carry out the hydrophilic modifying of milipore filter, its outstanding advantage applies exists: hydrophilic modifying is synchronizeed and carried out with film forming procedure; Hydrophilic modifying uniform fold is to surface and the fenestra inwall of film; Owing to being physical modification method, it is stable that the structure of modification caudacoria and performance all keep.
In existing bibliographical information, polyethersulfone with cardo is successfully prepared milipore filter (as the people such as Lu Xueren have prepared flat plate ultrafiltration membrane at use for laboratory polyether sulphone) as membrane material, but mainly concentrates on the research of preparation method, heat resistance and the chemical stability of milipore filter.For polyethersulfone with cardo, carrying out the preparation of hydrophilic modifying and application study rarely has and relates to.
Chinese patent CN. 1308060C discloses a kind of preparation method of polyethersulfone with cardo hollow fiber ultrafiltration membrane, by inversion of phases technique, prepared polyethersulfone with cardo hollow fiber ultrafiltration membrane, and confirmed that by embodiment it has the premium properties of high temperature resistant, resistance to solvent, acid-alkali-corrosive-resisting.Chinese patent CN. 101036862A discloses a kind of polyethersulfone with cardo and PAEK blending hollow fiber ultrafiltration membrane and preparation method thereof, and method and the corresponding film properties of two kinds of high temperature resistant, hydrophobicity engineering plastics blend maskings is provided.Yet above-mentioned two patents have only proposed to prepare the basic skills of polyethersulfone with cardo hollow fiber ultrafiltration membrane, and the hydrophily of membrane material is explained, the anti-pollution ability that is applied to actual separation system is also not mentioned.
At present, the research of preparing the polyethersulfone with cardo milipore filter with permanent hydrophilic by polymer blended mode has no report.
Summary of the invention
The problem that the object of the invention is to and hydrophilic long-time stability deficiency not good enough for heat resistance in existing membrane material, provides a kind of novel hydrophilic polyethersulfone with cardo alloy ultrafiltration membrane and preparation method thereof.Adopt the method for two kinds of high polymer blend, through hydrophilic holding effect post processing, can prepare the milipore filter that high temperature resistant, chemically-resistant solvent and acid and alkali corrosion, permeability and separation are functional, have permanent hydrophilic and the controlled excellent combination property of structure.In fields such as petrochemical industry, metallurgical industry, medicine, food, bioengineering, all there is good application potential.
For achieving the above object, the technical solution adopted in the present invention is:
Selecting polyethersulfone with cardo (PES-C) and HMW, hydrophilic polyvinylpyrrolidone (PVP) is filmogen, adopt the mode of solution blending to prepare casting solution, by immersion precipitation or dry-wetting phase conversion process, prepare polyethersulfone with cardo alloy plate or hollow fiber ultrafiltration membrane, after this pass through hydrophilic holding effect post processing, give the hydrophily of PES-C/PVP alloy ultrafiltration membrane lasting stability.By changing content and the filming technology condition of the high molecular proportioning of blend, additive in casting solution, can realize the regulation and control of film morphosis.
A hydrophilic polyethersulfone with cardo alloy ultrafiltration membrane, comprises the raw material of following weight portion proportioning: polyethersulfone with cardo 5-30 part, polyvinylpyrrolidone 0.1-20 part, additive 0-20 part, solvent 30-95 part.
Further, described hydrophilic polyethersulfone with cardo alloy ultrafiltration membrane, is characterized in that, comprises the raw material of following weight portion proportioning: polyethersulfone with cardo 15-25 part, polyvinylpyrrolidone 1-10 part, additive 0.5-10 part, solvent 55-85 part.
Further, described hydrophilic polyethersulfone with cardo alloy ultrafiltration membrane, the intrinsic viscosity scope 0.5～1.0 of described polyethersulfone with cardo; Described polyvinylpyrrolidone is a kind of or its any combination in PVP (K85), PVP (K90) or PVP (K120).
A method of preparing hydrophily polyethersulfone with cardo alloy plate milipore filter, comprises as follows step in sequence:
1) preparation of casting solution: first according to weight portion proportioning, weigh polyethersulfone with cardo, polyvinylpyrrolidone, solvent and additive, after this successively each component is positioned in proportion container,
In 20～110 ℃ of temperature ranges, fully stirring and dissolving 12～36 hours until form homogeneous phase solution, after stainless steel filtering net filtration, vacuum or standing and defoaming, is placed " slaking " and is made blend macromolecule casting solution;
2) immersion precipitation is prepared flat plate ultrafiltration membrane: the method that adopts immersion precipitation film forming, used thickness is stainless steel or the glass slicker of 5～500 microns, the casting solution making in step 1) is coated on glass plate or backing material, in air, place and stop after 1～30 second, the coagulation bath that immerses 5～60 ℃ divides solidifying, makes nascent state without supporting layer or has the flat plate ultrafiltration membrane of supporting layer;
3) milipore filter sizing, clean: by step 2) in the flat plate ultrafiltration membrane that makes be soaked in sizing in 24-72 hour in the deionized water of 10～30 ℃, and carry out rinsing with clear water, to remove residual solvent and additive, form sizing milipore filter;
4) hydrophilic holding effect post processing: it is in 0.1～20% post-treatment solution that the sizing milipore filter making in step 3) is soaked in to mass concentration, at 20～95 ℃, react 0.5～48 hour, carry out hydrophilic holding effect post processing, obtain having the polyethersulfone with cardo alloy ultrafiltration membrane of permanent hydrophilic.
A method of preparing hydrophily polyethersulfone with cardo alloy hollow fiber ultrafiltration membrane, comprises as follows step in sequence:
1) preparation of casting solution: first according to weight portion proportioning, weigh polyethersulfone with cardo, polyvinylpyrrolidone, solvent and additive, after this successively each component is positioned in proportion container,
In 20～110 ℃ of temperature ranges, fully stirring and dissolving 12～36 hours until form homogeneous phase solution, after stainless steel filtering net filtration, vacuum or standing and defoaming, is placed " slaking " and is made blend macromolecule casting solution;
2) dry-wet method spinning hollow fiber ultrafiltration membrane: adopt dry-wet method inversion of phases technique to prepare hollow fiber ultrafiltration membrane, the casting solution making in step 1) is extruded through spinning head with measuring pump, behind the air gap of 1～50cm, the coagulation bath that is dipped vertically into 5～60 ℃ divides solidifying, the wire wrapping wheel that is 5～50m/min through winding speed again imports to be received in silk groove, its SMIS liquid consists of pure water or is the aqueous solution of 5～90% organic solvents containing mass concentration, forms the hollow fiber ultrafiltration membrane of nascent state;
3) milipore filter sizing, clean: by step 2) in the hollow fiber ultrafiltration membrane that makes be soaked in sizing in 24-72 hour in the deionized water of 10～30 ℃, and carry out rinsing with clear water, to remove residual solvent and additive, form sizing milipore filter;
4) hydrophilic holding effect post processing: it is in 0.1～20% post-treatment solution that the sizing milipore filter making in step 3) is soaked in to mass concentration, at 20～95 ℃, react 0.5～48 hour, carry out hydrophilic holding effect post processing, obtain having the polyethersulfone with cardo alloy ultrafiltration membrane of permanent hydrophilic.
Further, the described method of preparing hydrophily polyethersulfone with cardo alloy plate milipore filter is N with preparing solvent used in the method for hydrophily polyethersulfone with cardo alloy hollow fiber ultrafiltration membrane, one or more in N-dimethylacetylamide, DMF, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE.
Further, the described method of preparing hydrophily polyethersulfone with cardo alloy plate milipore filter and to prepare additive therefor in the method for hydrophily polyethersulfone with cardo alloy hollow fiber ultrafiltration membrane be one or more in pure water, polyethylene glycol, oxalic acid, water-soluble inorganic salt; Described water-soluble inorganic salt is at least one in lithium chloride, lithium nitrate.
Further, in the hydrophilic holding effect post processing of described step 4), described post-treatment reagents comprises hydrogen peroxide and persulfate; Described persulfate comprises one or more in sodium peroxydisulfate, ammonium persulfate, potassium peroxydisulfate, and post-treatment reagents mass concentration is 0.1～20%, preferably 1～10%; Post-processing temperature scope is 20～95 ℃, preferably 25～90 ℃; Finishing time 0.5～48 hour, preferably l～24 hour.
The structural formula of described polyethersulfone with cardo PES-C is as shown below, intrinsic viscosity scope 0.5～1.0, preferably 0.6～0.8.
The structural formula of described polyvinylpyrrolidone PVP is as shown below, comprises PVP (K85), PVP (K90), the PVP (K120) of HMW, preferably PVP (K90).
The polyvinylpyrrolidone the present invention relates to is a kind of hydrophilic high molecular material, is commonly used for pore-foaming agent and develops macroporous polymer film.Not only the hydrophily of membrane material be can increase, and the porosity of film and the connectedness in hole are conducive to improve.
The present invention program's key and innovative point are to adopt polyvinylpyrrolidone (comprising PVP(K85), the PVP(K90 of long-chain, HMW), PVP(K120) etc.) with polyethersulfone with cardo blend, through hydrophilic holding effect post processing, prepare novel fire resistant, chemically-resistant solvent, there is permanent hydrophilic and the good milipore filter of separating property.
Its know-why is: on the one hand, the polyvinylpyrrolidone of polyethersulfone with cardo and HMW has good comixing compatibility.For polymer blended, comixing compatibility is that preparation macroscopic view is even, the material modified basis of function admirable preferably.The method test glass transition temperature Tg of blend and the Tg of pure material contrast by Instrumental Analysis are the effective means of judging compatibility quality between macromolecule.If the Tg after polymer blended is between the Tg of two kinds of pure components, and only have unique transition point, illustrate that the two is completely compatible.
According to above-mentioned criterion, the present invention adopts DSC instrument test, confirm first all only have single glass transition temperature Tg (referring to Figure of description 1) after the PVP of HMW of different proportion and the blend of PES-C molecule, be that the two can be completely compatible on microcosmic molecular scale, the segment that can form firm stable in its blend solution between two kinds of macromolecule long-chains tangles, and forms homogeneous system.Thereby the latter two are also difficult to separation in film forming procedure and solidifying and setting, milipore filter in use comprises hydrophilic high mol in film surface and membrane pore structure all the time, thereby gives the good hydrophily of alloy ultrafiltration membrane of preparation.
By comparison, conventional masking additive PVP mostly is short chain molecule, as PVP(K15), PVP(K30) etc.Because molecular weight is lower, be difficult to form firmly segment entanglement with the polyethersulfone with cardo of macromolecule, in the preparation and washing solidifying and setting process of milipore filter, water miscible little molecular weight PVP is very easily dissolved, and causes the PVP content remaining in film surface and fenestra very low; In addition when milipore filter is applied in the process of water treatment, the content of little molecular weight PVP also can cause membrane material finally to lose hydrophily along with the prolongation of service time is constantly run off, and contamination resistance also reduces greatly.
On the other hand, in milipore filter structure, the PVP molecule of HMW is met water and can be produced strong swelling effect, causes the flux of film extremely low, performance degradation.Therefore must adopt suitable aftertreatment technology to eliminate the swelling effect of PVP, improve film properties.The hydrophilic holding effect post processing that the present invention adopts, by oxidation cross-linked processing mode, makes to form stable covalent structure between hydrophilic macromolecule, not only weakened PVP molecule swelling effect, increase substantially membrane flux; PVP molecule after being simultaneously cross-linked is difficult to be dissolved in water and is difficult for causing run off more, and the hydrophily of membrane material also can keep for a long time.
In the present invention, the hydrophily of milipore filter characterizes with the contact angle numerical value of membrane material, permeability and separation performance is by being 25 ℃ in temperature, transmembrane pressure is under the condition of 0.1MPa, and the rejection of the bovine serum albumin BSA that the pure water flux of test membrane and investigation film are 67000 to molecular weight is evaluated.Milipore filter structure is to observe by ESEM.
The contamination resistance of PES-C/PVP alloy ultrafiltration membrane during mainly by the separated bovine serum albumen solution of test milipore filter separating property attenuation in time determine; Defined in addition this parameter of fouling degree of membrane MF, before and after using by film, the reduction degree of pure water flux shows indirectly.
The size of fouling degree of membrane numerical value represents the quality of the anti-fouling performance of film.Be worth littlely, show that the anti-fouling performance of this film is better.It is defined as:
Wherein: J
0the initial pure water flux of-film, the pure water flux after J-film is used.
Compared to prior art, distinguishing feature and beneficial effect that the present invention has are as follows:
1, adopt the material modification mode of hydrophobic polyethersulfone with cardo (PES-C) and HMW, hydrophilic polyvinylpyrrolidone (PVP) blend, based on the two good comixing compatibility, can on microcosmic molecular scale, form stable firmly segment and tangle, thereby realize, have complementary advantages.Prepared novel polyether sulphone alloy ultrafiltration membrane has two kinds of macromolecules excellent properties separately concurrently, has both had good heat resistance, physical and mechanical properties and chemical stability, and hydrophily and the contamination resistance of membrane material significantly improve simultaneously.
2, the blended ultrafiltration membrane that adopts the inventive method to prepare has good separating property and excellent contamination resistance, and not only the permeation flux of milipore filter is high, and effluent quality is good, and extends the service life of film, reduces cleaning frequency membrane, and operating cost reduces.
3, for eliminating the swelling effect of hydrophilic macromolecule PVP, prevent the loss of PVP molecule in long-term use procedure simultaneously, the present invention is after casting solution film-forming, adopt specific hydrophilic holding effect post processing, by the chemical reaction between group, make to form stable covalent structure between hydrophilic macromolecule, not only weakened PVP molecule swelling effect, significantly improved the flux of film, the hydrophily of membrane material also can keep for a long time simultaneously.
4, the present invention, by changing formula and the filming technology condition of casting solution, can realize the regulation and control of milipore filter morphosis.Can be according to the needs of practical application, the polyether sulphone blended ultrafiltration membrane structure of appropriate design.
What 5, the present invention prepared polyethersulfone with cardo alloy ultrafiltration membrane employing is the mode of physical blending, avoided physics coating or absorption floating coat material the coming off of film surface, and the infringement of chemical modification method (as plasma, radiation etc.) to membrane structure and performance; And milipore filter surface and fenestra inside all obtain uniform hydrophilic modifying, and technique is simple, efficiently convenient, economical and practical, be conducive to realize industry amplification and scale application.
6, the hydrophilic polyethersulfone with cardo alloy ultrafiltration membrane that prepared by the present invention is applicable to the processes such as purification separation of purification of water quality, Industrial Wastewater Treatment, sewage reuse, biomedical product, especially serviceability temperature require high, separation system pollutes the fields such as obvious petrochemical industry, metallurgical industry, medicine, biology, food good application potential.
Accompanying drawing explanation
Fig. 1 is the glass transition temperature Tg variation diagram that polyethersulfone with cardo (PES-C) and polyvinylpyrrolidone PVP (K90) adopt DSC test blend under different proportion;
Wherein, curve 1:PVP (K90); Curve 2:PES-C/PVP (K90) (20/80wt%); Curve 3:PES-C/PVP (K90) (40/60wt%); Curve 4:PES-C/PVP (K90) (50/50wt%); Curve 5:PES-C/PVP (K90) (60/40wt%); Curve 6:PES-C/PVP (K90) (80/20wt%); Curve 7:PES-C;
Fig. 2 is the ESEM cross-section structure of the prepared polyethersulfone with cardo alloy hollow fiber ultrafiltration membrane of embodiment 4;
Fig. 3 is the ESEM cross-section structure of the prepared polyethersulfone with cardo alloy hollow fiber ultrafiltration membrane of embodiment 6.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is further detailed explanation, but the present invention is not limited to specific embodiment.
20 grams of polyethersulfone with cardo PES-C, 3 grams of polyvinylpyrrolidone PVP (K90), add respectively in 95 grams of 1-METHYLPYRROLIDONEs and 2 grams of pure water and 1 gram of oxalic acid mixed solvent, at 60 ℃, stir 24 hours, form the blend macromolecule casting solution of homogeneous phase.After this, casting solution being positioned over after stainless steel filtering net filters to temperature is to carry out vacuum defoamation in the batch can of 60 ℃.After bubble removes completely, employing thickness is the glass slicker of 200 microns, and casting solution is coated on glass plate, stops after approximately 5 seconds and immerse minute solidifying in 40 ℃ of deionized waters in air, forms the milipore filter of nascent state.After this film is soaked in to sizing in 48 hours in the deionized water of 25 ℃, and cleans to remove residual solvent and additive.It is, in 1% hydrogenperoxide steam generator, under 30 ℃ of conditions, to react and within 24 hours, carry out hydrophilic holding effect post processing that membrane material after cleaning is dipped into concentration, obtains having the polyethersulfone with cardo alloy ultrafiltration membrane of permanent hydrophilic.The performance of the PES-C/PVP alloy plate milipore filter measuring afterwards, is 25 ℃ in temperature, and under the condition that transmembrane pressure is 0.1MPa, the pure water flux of film is 378L/m
2.hr, to the rejection of bovine serum albumin (BSA), be 89.1%.It is 102L/m that BSA filters membrane flux after 4 hours
2.hr, fouling degree of membrane MF is 0.35.Scanning electron microscopic observation film surface is fine and close cortex, and the supporting layer being connected is finger-like pore structure.Film surface contact angle is 38 ° through measuring mean value.Be soaked in the aqueous solution and retest after 2 months, contact angle is substantially constant.
Polyethersulfone with cardo PES-C20 gram, 8 grams of polyvinylpyrrolidone PVP (K90), add respectively in 95 grams of dimethyl sulfoxide (DMSO)s and 3 grams of polyethylene glycol (600) mixed solvent, stir 36 hours at 80 ℃, form the blend macromolecule casting solution of homogeneous phase.After this, casting solution being positioned over after stainless steel filtering net filters to temperature is to carry out vacuum defoamation in the batch can of 80 ℃.After bubble removes completely, employing thickness is the stainless steel scraper of 300 microns, and casting solution is coated on glass plate, stops after approximately 10 seconds and immerse minute solidifying in 40 ℃ of deionized waters in air, forms the milipore filter of nascent state.After this film is soaked in to sizing in 24 hours in the deionized water of 30 ℃, and cleans to remove residual solvent and additive.It is, in 10% sodium peroxydisulfate solution, under 60 ℃ of conditions, to react and within 6 hours, carry out hydrophilic holding effect post processing that membrane material after cleaning is dipped into concentration, obtains having the polyethersulfone with cardo alloy ultrafiltration membrane of permanent hydrophilic.Measuring afterwards its performance, is 25 ℃ in temperature, and under the condition that transmembrane pressure is 0.1MPa, the pure water flux of film is 242L/m
2.hr, to the rejection of bovine serum albumin (BSA), be 92.6%.It is 95L/m that BSA filters membrane flux after 4 hours
2.hr, fouling degree of membrane MF is 0.2.Scanning electron microscopic observation film surface is fine and close cortex, and supporting layer is the sponge pore structure interconnecting.Film surface contact angle is 27 ° through measuring mean value.Be soaked in the aqueous solution and retest after 2 months, contact angle is substantially constant.
16 grams of polyethersulfone with cardo PES-C, 5 grams of polyvinylpyrrolidone PVP (K85), add respectively in 65 grams of DMFs and 4 grams of polyethylene glycol (400) mixed solvent, at 80 ℃, stir 12 hours, form the blend macromolecule casting solution of homogeneous phase.After this, casting solution being positioned over after stainless steel filtering net filters to temperature is to carry out standing and defoaming in the batch can of 80 ℃.After bubble removes completely, employing thickness is the stainless steel scraper of 250 microns, and casting solution is coated on glass plate, stops after approximately 5 seconds and immerse minute solidifying in 40 ℃ of deionized waters in air, forms the milipore filter of nascent state.After this film is soaked in to sizing in 48 hours in the deionized water of 25 ℃, and cleans to remove residual solvent and additive.It is, in 0.5% potassium persulfate solution, under 40 ℃ of conditions, to react and within 24 hours, carry out hydrophilic holding effect post processing that membrane material after cleaning is dipped into concentration, obtains having the polyethersulfone with cardo alloy ultrafiltration membrane of permanent hydrophilic.Measuring afterwards its performance, is 25 ℃ in temperature, and under the condition that transmembrane pressure is 0.1MPa, the pure water flux of film is 317L/m
2.hr, to the rejection of bovine serum albumin (BSA), be 91.2%.It is 106L/m that BSA filters membrane flux after 4 hours
2.hr, fouling degree of membrane MF is 0.38.Scanning electron microscopic observation film surface is fine and close cortex, and supporting layer is the sponge pore structure interconnecting.Film surface contact angle is 33 ° through measuring mean value.Be soaked in the aqueous solution and retest after 2 months, contact angle is substantially constant.
Embodiment 4
100 grams of polyethersulfone with cardo PES-C, 20 grams of polyvinylpyrrolidone PVP (K90), add respectively in the mixed solvent of 430 grams of DMAs and 15 grams of pure water, at 60 ℃, stir 24 hours, form the blend macromolecule casting solution of homogeneous phase.After this, casting solution being positioned over after stainless steel filtering net filters to temperature is to carry out vacuum defoamation in the batch can of 60 ℃.After bubble removes completely, adopt dry-wetting phase conversion process to prepare hollow fiber ultrafiltration membrane.Casting solution is extruded through spinning head, and behind the air gap of one section of 2cm, the coagulation bath that is dipped vertically into 40 ℃ divides solidifying, then in the wire wrapping wheel that is 8m/min through speed importing receipts silk groove, core liquid consists of pure water, forms the hollow fiber ultrafiltration membrane of nascent state.The hollow-fibre membrane of nascent state is soaked in to sizing in 48 hours in the deionized water of 25 ℃, and cleans to remove residual solvent and additive with clear water.It is, in 4% ammonium persulfate solution, under 60 ℃ of conditions, to react and within 6 hours, carry out hydrophilic holding effect post processing that membrane material after cleaning is dipped into concentration, obtains having the polyethersulfone with cardo alloy hollow fiber ultrafiltration membrane of permanent hydrophilic.Measuring afterwards its performance, is 25 ℃ in temperature, and under the condition that transmembrane pressure is 0.1MPa, the pure water flux of film is 526L/m
2.hr, to the rejection of bovine serum albumin (BSA), be 91.3%.It is 192L/m that BSA filters membrane flux after 4 hours
2.hr, fouling degree of membrane MF is 0.31.Scanning electron microscopic observation film section structure is for arranging compact double finger-like pore, and surfaces externally and internally is dense layer surface.Film surface contact angle is 32 ° through measuring mean value.Be soaked in the aqueous solution and retest after 2 months, contact angle is substantially constant.
Formula of casting according to embodiment 4 is prepared hollow fiber ultrafiltration membrane.Spinning process condition is: the air gap is 2cm, and spinning speed is 10m/min, and coagulation bath temperature is 60 ℃, and core liquid consists of the aqueous solution that mass concentration is 80% DMA.The hollow-fibre membrane of nascent state is soaked in to sizing in 48 hours in the deionized water of 25 ℃, and cleans with clear water.It is, in 8% sodium peroxydisulfate solution, under 80 ℃ of conditions, to react and within 5 hours, carry out hydrophilic holding effect post processing that membrane material after cleaning is dipped into concentration, obtains having the polyethersulfone with cardo alloy hollow fiber ultrafiltration membrane of permanent hydrophilic.The performance of the PES-C/PVP alloy hollow fiber ultrafiltration membrane measuring, is 25 ℃ in temperature, and under the condition that transmembrane pressure is 0.1MPa, the pure water flux of film is 757L/m
2.hr, to the rejection of bovine serum albumin (BSA), be 81.6%.It is 223L/m that BSA filters membrane flux after 4 hours
2.hr, fouling degree of membrane MF is 0.29.Scanning electron microscopic observation film section structure is for arranging compact double finger-like pore, and exodermis is fine and close, and endodermis has part open-celled structure.Film surface contact angle is 30 ° through measuring mean value.Be soaked in the aqueous solution and retest after 2 months, contact angle is substantially constant.
100 grams of polyethersulfone with cardo PES-C, 35 grams of polyvinylpyrrolidone PVP (K90), add respectively in 400 grams of DMAs and 15 grams of pure water mixed solvents, stir 24 hours at 60 ℃, form the blend macromolecule casting solution of homogeneous phase.After this, casting solution being positioned over after stainless steel filtering net filters to temperature is to carry out vacuum defoamation in the batch can of 60 ℃.After bubble removes completely, adopt dry-wetting phase conversion process to prepare hollow fiber ultrafiltration membrane.Casting solution is extruded through spinning head, and behind the air gap of one section of 5cm, the coagulation bath that is dipped vertically into 60 ℃ divides solidifying, then in the wire wrapping wheel that is 10m/min through speed importing receipts silk groove, core liquid consists of pure water, forms the hollow fiber ultrafiltration membrane of nascent state.The hollow-fibre membrane of nascent state is soaked in to sizing in 48 hours in the deionized water of 25 ℃, and cleans to remove residual solvent and additive with clear water.It is, in 10% potassium persulfate solution, under 60 ℃ of conditions, to react and within 4 hours, carry out hydrophilic holding effect post processing that membrane material after cleaning is dipped into concentration, obtains having the polyethersulfone with cardo alloy hollow fiber ultrafiltration membrane of permanent hydrophilic.Measuring afterwards its performance, is 25 ℃ in temperature, and under the condition that transmembrane pressure is 0.1MPa, the pure water flux of film is 312L/m
2.hr, to the rejection of bovine serum albumin (BSA), be 93.4%.It is 171L/m that BSA filters membrane flux after 4 hours
2.hr, fouling degree of membrane MF is 0.18.Scanning electron microscopic observation film section structure is the sponge pore structure being interconnected, and interior exodermis is fine and close pore structure.Film surface contact angle is 24 ° through measuring mean value.Be soaked in the aqueous solution and retest after 2 months, contact angle is substantially constant.
120 grams of polyethersulfone with cardo PES-C, 50 grams of polyvinylpyrrolidone PVP (K120), add respectively in the mixed solvent of 500 grams of 1-METHYLPYRROLIDONEs and 12 grams of pure water and 3 grams of lithium nitrates, at 90 ℃, stir 12 hours, form the blend macromolecule casting solution of homogeneous phase.After this, casting solution being positioned over after stainless steel filtering net filters to temperature is to carry out vacuum defoamation in the batch can of 80 ℃.After bubble removes completely, adopt dry-wetting phase conversion process to prepare hollow fiber ultrafiltration membrane.Casting solution is extruded through spinning head, and behind the air gap of 10cm, the coagulation bath that is dipped vertically into 80 ℃ divides solidifying, then imports in receipts silk groove through the wire wrapping wheel of 15m/min, and its SMIS liquid consists of pure water, forms the hollow fiber ultrafiltration membrane of nascent state.The hollow-fibre membrane of nascent state is soaked in to sizing in 24 hours in the deionized water of 25 ℃, and cleans to remove residual solvent and additive with clear water, form sizing milipore filter.It is, in 5% hydrogenperoxide steam generator, under 30 ℃ of conditions, to react and carry out post processing in 12 hours that membrane material after cleaning is dipped into concentration, obtains having the polyethersulfone with cardo alloy ultrafiltration membrane of permanent hydrophilic.The performance of the PES-C/PVP alloy hollow fiber ultrafiltration membrane measuring afterwards, is 25 ℃ in temperature, and under the condition that transmembrane pressure is 0.1MPa, the pure water flux of film is 294L/m
2.hr, to the rejection of bovine serum albumin (BSA), be 95.7%.It is 165L/m that BSA filters membrane flux after 4 hours
2.hr, fouling degree of membrane MF is 0.15.Scanning electron microscopic observation film section structure is the sponge pore structure being interconnected, and interior exodermis is fine and close pore structure.Film surface contact angle is 22 ° through measuring mean value.Be soaked in the aqueous solution and retest after 2 months, contact angle is substantially constant.
Comparative example 1
120 grams of polyethersulfone with cardo PES-C, add in 445 grams of DMA solvents, stir 24 hours at 60 ℃, form the macromolecule casting solution of homogeneous phase.After this, casting solution being positioned over after stainless steel filtering net filters to temperature is to carry out vacuum defoamation in the batch can of 60 ℃.After bubble removes completely, adopt dry-wetting phase conversion process to prepare hollow fiber ultrafiltration membrane.Spinning process condition is identical with embodiment 4.The hollow-fibre membrane of nascent state is soaked in to 48 hours sizing and solidifyings in the deionized water of 25 ℃, and cleans to remove residual solvent and additive.The performance of the polyethersulfone with cardo hollow fiber ultrafiltration membrane measuring afterwards, is 25 ℃ in temperature, and under the condition that transmembrane pressure is 0.1MPa, the pure water flux of film is 278L/m
2.hr, to the rejection of bovine serum albumin (BSA), be 94.3%.It is 42 L/m that BSA filters membrane flux after 4 hours
2.hr, fouling degree of membrane MF is 0.76.Film surface contact angle is 67 ° through measuring mean value.
When this comparative example shows not add hydrophilic macromolecule, the polyethersulfone with cardo milipore filter of preparation presents obvious hydrophobicity, and not only membrane flux is lower, and contamination resistance is poor during filtration protein solution.
Comparative example 2
100 grams of polyethersulfone with cardo PES-C, 20 grams of polyvinylpyrrolidone PVP (K30), add respectively in the mixed solvent of 430 grams of DMAs and 15 grams of pure water, at 60 ℃, stir 24 hours, form the blend macromolecule casting solution of homogeneous phase.After this, casting solution being positioned over after stainless steel filtering net filters to temperature is to carry out vacuum defoamation in the batch can of 60 ℃.After bubble removes completely, adopt dry-wetting phase conversion process to prepare hollow fiber ultrafiltration membrane.Spinning technology parameter is identical with embodiment 4.Through solidifying and setting with after cleaning, the performance of the hollow fiber ultrafiltration membrane measuring.In temperature, be 25 ℃, under the condition that transmembrane pressure is 0.1MPa, the pure water flux of film is 296L/m
2.hr, to the rejection of bovine serum albumin (BSA), be 91.6%.It is 87L/m that BSA filters membrane flux after 4 hours
2.hr, fouling degree of membrane MF is 0.45.Film surface contact angle is 48 ° through measuring mean value.Be soaked in the aqueous solution and retest after 2 months, contact angle becomes 55 °.
This comparative example shows when adding micromolecular polyvinylpyrrolidone PVP (K30), in blended ultrafiltration membrane preparation process, the PVP molecule of short chain is very easily water-soluble and cause the content of PVP molecule to reduce, and in use also easily there is leakage, cause PES-C/PVP (K30) the alloy hollow fiber ultrafiltration membrane hydrophily of preparation poor, contamination resistance reduces, and membrane material does not have permanent hydrophily.
Comparative example 3
PES-C/PVP (K90) blended ultrafiltration membrane of preparing according to the formula in embodiment 4 and spinning condition, removes after residual solvent through solidifying and setting cleaning, directly measures the performance of milipore filter without post processing.In temperature, be 25 ℃, under the condition that transmembrane pressure is 0.1MPa, the pure water flux of film is 36L/m
2.hr, to the rejection of bovine serum albumin (BSA), be 95.7%.
This comparative example shows PES-C/PVP (K90) the alloy hollow fiber ultrafiltration membrane of preparation, as directly used without post processing,, because the strong swelling effect of PVP molecule can stop up fenestra, causes the flux of film extremely low, and performance degradation, does not possess actual application value.Therefore must carry out hydrophilic holding effect post processing to it, improve membrane flux, give the hydrophily of membrane material lasting stability simultaneously.
The above; it is only the preferably specific embodiment of the present invention; but protection scope of the present invention is not limited to this; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; according to technical scheme of the present invention and inventive concept thereof, be equal to replacement or changed, within all should being encompassed in protection scope of the present invention.
Claims (1)
1. a hydrophilic polyethersulfone with cardo alloy ultrafiltration membrane, is characterized in that, comprises the raw material of following weight portion proportioning: polyethersulfone with cardo 5-30 part, polyvinylpyrrolidone 0.1-20 part, additive 0-20 part, solvent 30-95 part;
The intrinsic viscosity scope of described polyethersulfone with cardo is 0.5～1.0; Described polyvinylpyrrolidone is a kind of or its any combination in PVP (K85), PVP (K90), PVP (K120);
Described solvent is one or more in DMA, DMF, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE;
Described additive is one or more in pure water, polyethylene glycol, oxalic acid, water-soluble inorganic salt; Described water-soluble inorganic salt is at least one in lithium chloride, lithium nitrate.
2. hydrophilic polyethersulfone with cardo alloy ultrafiltration membrane according to claim 1, it is characterized in that, comprise the raw material of following weight portion proportioning: polyethersulfone with cardo 15-25 part, polyvinylpyrrolidone 1-10 part, additive 0.5-10 part, all the other components are solvent 55-85 part.
3. a method of preparing hydrophily polyethersulfone with cardo alloy plate milipore filter, is characterized in that, comprises as follows step in sequence:
1) preparation of casting solution: first weigh polyethersulfone with cardo, polyvinylpyrrolidone, solvent and additive according to the weight portion proportioning in a kind of hydrophilic polyethersulfone with cardo alloy ultrafiltration membrane claimed in claim 1, after this successively each component is positioned in proportion container, in 20～110 ℃ of temperature ranges, abundant stirring and dissolving 12～36 hours is until form homogeneous phase solution, after stainless steel filtering net filtration, vacuum or standing and defoaming, place " slaking " and make blend macromolecule casting solution;
2) immersion precipitation is prepared flat plate ultrafiltration membrane: the method that adopts immersion precipitation film forming, used thickness is stainless steel or the glass slicker of 5～500 microns, the casting solution making in step 1) is coated on glass plate or backing material, in air, stop after 1～30 second, the coagulation bath that immerses 5～60 ℃ divides solidifying, makes nascent state without supporting layer or has the flat plate ultrafiltration membrane of supporting layer;
3) milipore filter sizing, clean: by step 2) in the flat plate ultrafiltration membrane that makes be soaked in sizing in 24～72 hours in the deionized water of 10～30 ℃, and carry out rinsing with clear water, to remove residual solvent and additive, form sizing milipore filter;
4) hydrophilic holding effect post processing: it is in 0.1～20% post-treatment solution that the sizing milipore filter making in step 3) is soaked in to mass concentration, at 20～95 ℃, react and within 0.5～48 hour, carry out hydrophilic holding effect post processing, obtain having the polyethersulfone with cardo alloy ultrafiltration membrane of permanent hydrophilic.
4. a method of preparing hydrophily polyethersulfone with cardo alloy hollow fiber ultrafiltration membrane, is characterized in that, comprises as follows step in sequence:
1) preparation of casting solution: first weigh polyethersulfone with cardo, polyvinylpyrrolidone, solvent and additive according to the weight portion proportioning in a kind of hydrophilic polyethersulfone with cardo alloy ultrafiltration membrane claimed in claim 1, after this successively each component is positioned in proportion container, in 20～110 ℃ of temperature ranges, abundant stirring and dissolving 12～36 hours is until form homogeneous phase solution, after stainless steel filtering net filtration, vacuum or standing and defoaming, place " slaking " and make blend macromolecule casting solution;
2) dry-wet method spinning hollow fiber ultrafiltration membrane: adopt dry-wetting phase conversion process to prepare hollow fiber ultrafiltration membrane, the casting solution making in step 1) is extruded through spinning head with measuring pump, behind the air gap of 1～50cm, the coagulation bath that is dipped vertically into 5～60 ℃ divides solidifying, the wire wrapping wheel that is 5～50m/min through winding speed again imports to be received in silk groove, its SMIS liquid consists of pure water or is the aqueous solution of 5～90% organic solvents containing mass concentration, forms the hollow fiber ultrafiltration membrane of nascent state;
3) milipore filter sizing, clean: by step 2) in the hollow fiber ultrafiltration membrane that makes be soaked in sizing in 24～72 hours in the deionized water of 10～30 ℃, and carry out rinsing with clear water, to remove residual solvent and additive, form sizing milipore filter;
4) hydrophilic holding effect post processing: it is in 0.1～20% post-treatment solution that the sizing milipore filter making in step 3) is soaked in to mass concentration, at 20～95 ℃, react 0.5～48 hour, carry out hydrophilic holding effect post processing, obtain having hydrophilic polyethersulfone with cardo alloy ultrafiltration membrane.
5. according to the method described in claim 3 or 4, it is characterized in that, in the hydrophilic holding effect post processing of described step 4), described post-treatment reagents comprises hydrogen peroxide and persulfate; Described persulfate comprises one or more in sodium peroxydisulfate, ammonium persulfate, potassium peroxydisulfate, and post-treatment reagents mass concentration is 0.1～20%; Post-processing temperature scope is 20～95 ℃; Finishing time 0.5～48 hour.
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| CN103071402B (en) * | 2012-12-21 | 2015-03-04 | 天邦膜技术国家工程研究中心有限责任公司 | Hydrophilic polyaryletherketone blended hollow fiber ultrafilter membrane and preparation method thereof |
| CN104607068B (en) * | 2015-01-20 | 2017-04-12 | 苏州信望膜技术有限公司 | Bio-adhesion-resistant porous separation membrane as well as preparation method and application thereof |
| CN108479432B (en) * | 2018-02-08 | 2020-10-27 | 东华大学 | Preparation method of hydrophilic phenolphthalein polyether sulfone composite nanofiber ultrafiltration membrane |
| CN112619432A (en) * | 2019-09-24 | 2021-04-09 | 中国石油化工股份有限公司 | Ultrafiltration membrane and preparation method thereof |
| CN113244791B (en) * | 2021-05-12 | 2022-06-17 | 佳木斯大学 | Preparation method of emodin-blended phenolphthalein polyethersulfone ultrafiltration membrane |
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