CN105521715A - Blend polyvinylidene fluoride hollow fiber film and making method thereof - Google Patents

Blend polyvinylidene fluoride hollow fiber film and making method thereof Download PDF

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Publication number
CN105521715A
CN105521715A CN201510996430.8A CN201510996430A CN105521715A CN 105521715 A CN105521715 A CN 105521715A CN 201510996430 A CN201510996430 A CN 201510996430A CN 105521715 A CN105521715 A CN 105521715A
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hollow fiber
polyvinylidene fluoride
copolymer
fiber membrane
blending
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CN105521715B (en
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陈莉
安子韩
赵义平
冯倩倩
薛高建
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Tianjin Polytechnic University
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Tianjin Polytechnic University
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    • 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
    • B01D69/08—Hollow fibre membranes
    • 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
    • B01D61/24—Dialysis ; Membrane extraction
    • B01D61/243—Dialysis
    • 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
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride
    • 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
    • B01D71/78—Graft polymers

Abstract

The invention belongs to the field of hollow fiber films, and especially relates to a blend polyvinylidene fluoride hollow fiber film used for hemodialysis, and a making method thereof. The method concretely comprises the following steps: blending dried polyvinylidene fluoride, polyvinylidene fluoride grafted polypropylene morpholide and argatroban copolymer, a pore forming agent and a cosolvent to prepare a film casting liquid; carrying out air bath on nascent hollow fibers formed after extruding the film casting liquid through a spinning head, allowing the obtained hollow fibers to enter a coagulation bath, coagulating and regenerating the hollow fibers, and reeling the hollow fibers to obtain a hollow fiber film; and immersing and cleaning the obtained hollow fiber film in pure water, taking out the cleaned hollow fiber film, and immersing the obtained hollow fiber film in a solution containing a pore keeping agent to obtain the finished blend modified polyvinylidene fluoride hollow fiber film. Blending is carried out to realize the hydrophilic modification purpose in order to finally improve the pollution resistance, the blood compatibility and the anticoagulant performance of the film. The hollow fiber film obtained in the invention has the advantages of high strength, high flux, good removal effect of toxic substances with a low molecular weight in blood, and wide application prospect.

Description

A kind of blending polyvinylidene fluoride hollow fiber membrane and preparation method thereof
Technical field:
The invention belongs to blending polyvinylidene fluoride hollow fiber membrane field, particularly relate to the preparation of the blending polyvinylidene fluoride hollow fiber membrane for haemodialysis.
Background technology:
In recent years, along with the increase of End-stage Renal Disease Patients quantity, blood purification technology has become the Main Means of kidney treatment and one of mode be most widely used.Along with the universal of blood purification technology and development. the life cycle of uremic patient obviously extends, and quality of life significantly improves, but has also occurred many long term complications, as renal osteodystrophy, dialysis related amyloidosis, angiocardiopathy etc. thereupon.At present, the Hollow-fibre membranes material being applied to haemodialysis is treated as foreign matter, when contacting with blood in vivo, inevitably cause a series of defense reaction of body, wherein platelet adhesion reaction, activates blood coagulation system, and generation blood coagulation and thrombus are the most serious reactions.Kynoar (PVDF) is a kind of macromolecular material of function admirable, and its outstanding chemical stability, radiation hardness characteristic and heat resistance etc. make it be widely used in UF membrane field.Pvdf membrane material surface is smooth, and surface energy is low, and protein adsorption quantity is lower, and material itself is nontoxic, prepared milipore filter flux is higher, and compared with the current polyether sulphone hollow fibre film for high flux hemodialysis membrane material, ultrasiltrated rate decay is little, is expected to the new material becoming haemodialysis.But because PVDF has strong hydrophobicity, it still can produce the problems such as protein adsorption, platelet adhesion reaction, blood coagulation when field application such as bio-medicals.Therefore, the key factor of PVDF improves its biocompatibility and anticoagulant further.Therefore, blending and modifying is carried out to PVDF blend film biocompatibility and anticoagulant are improved jointly, and then be significant as bio-medical material.
In recent years, with regard to raising PVDF blood compatibility and anticoagulant, mainly introduce functional groups on pvdf membrane surface, comprise hydroaropic substance (such as polyethylene glycol, amphion etc.) and there is the monomer (such as heparin, Phosphorylcholine) of anticoagulant effect, and this method changes the excellent performance of PVDF self, limit application.At present, adopt blending method modification, simple, the defect of surface-modification method can be overcome to a certain extent, and cost of material can be reduced, save the energy, can the advantage such as synchronously practical function modification in film-forming process, just becoming the study hotspot of people.
Adopt blending and modifying to prepare Pvdf Microporous Hollow Fiber Membrane material and have many documents and patent is reported.The blend heating and melting of gained is made perforated membrane by more than the fusing point of polyvinylidene fluoride resin and organic liquid and inorganic grain phenolphthalein polyethersulfone ester 60 DEG C or higher temperature by CN1265048A.CNZO0510110757.7 is by polyvinylidene fluoride resin and polyethersulfone blended and prepare hollow-fibre membrane.CN101596416A, CN101596417A respectively by polyvinylidene fluoride resin and methyl methacrylate and phenolphthalein polyethersulfone blended and prepare the hollow-fibre membrane being used for blood purification albumen noxious material in blood to good rejection effect.CN1579601A is by polyvinylidene fluoride resin and the polyethylene glycol blending Pvdf Microporous Hollow Fiber Membrane for the preparation of haemodialysis.But these researchs after to PVDF blending and modifying, may produce the problem such as blood coagulation or erythrocyte haemolysis, platelet adhesion reaction for hollow-fibre membrane during haemodialysis and contacting blood, bring certain difficulty to the Application and Development that clinical blood is dialysed.
The application patent inventor once adopted the method for alkali treatment to carry out graft modification to PVDF hollow-fibre membrane surface, prepared blood compatibility respectively better and anticoagulation PVDF diffusion barrier (ZL201410325639.7; ZL201410325836).Research finds, adopt hydrophilic, nontoxic, immunogenicity is low, biocompatibility is splendid, protein adsorption cell adhesion is had to the acryloyl morpholine (ACMO) of repulsive interaction carries out graft modification to PVDF, film demonstrates the absorption of good anti-protein, antiplatelet sticks and the characteristic such as anti-hemolysis; And small molecule thrombin inhibitor---the pvdf membrane of argatroban (argatroban) graft modification can the generation of Trombin inhibiting and fibrinous generation, has played very strong anti-freezing, antithrombotic effect.
Therefore, acryloyl morpholine and argatroban are grafted on PVDF by the present invention simultaneously, obtain the graft copolymer with PVDF with compatibility, then by this copolymer and PVDF blended, prepared the blended doughnut hemodialysis membrane with good biocompatibility and anticoagulant by dry-wet spinning technology.
Summary of the invention:
The problem with less effective is not had concurrently for existing PVDF hollow-fibre membrane and contacting blood blood compatibility and anticoagulant, the invention provides a kind of blending polyvinylidene fluoride hollow fiber membrane for haemodialysis and preparation method thereof, this membrane preparation method is simple, be suitable for suitability for industrialized production, gained hollow-fibre membrane has high strength, high-throughout feature, and in blood, low-molecular-weight noxious material has good removal effect, can be used for haemodialysis field.
The preparation method of the described blending polyvinylidene fluoride hollow fiber membrane for haemodialysis comprises the following steps: (1) prepares Kynoar graft polypropylene morpholide and argatroban copolymer; (2) by obtained copolymer and polyvinylidene blending, after adding pore former and solvent, preparation spinning casting solution; (3) blend hollow fiber membrane is prepared.
The preparation method of described step (1) Kynoar graft polypropylene morpholide and argatroban copolymer is: first the Kynoar powder containing carbon-carbon double bond obtained through alkali treatment is joined 5-15 doubly in the solvent of PVDF powder quality, be mixed with Kynoar solution, then, add the initator accounting for PVDF powder quality 1-10%, add again with Kynoar mol ratio be 1: 1: 4-1: 1: 2 acryloylmorpholine monomer (ACMO) and acrylic monomers (AA), under inert atmosphere protection, react at 50-100 DEG C, time is 8-24 hour, reacted solution precipitates in excessive methanol, suction filtration, suction filtration after sediment distilled water flushing, put into 60 DEG C of oven dryings, obtain Kynoar graft polypropylene morpholide and acrylic copolymer, then, by the copolymer of gained and argatroban monomer with 20: 1-20: 10 mass ratio be dissolved in quality 5-15 doubly in the solvent of copolymer quality, add the initator accounting for copolymer quality 5-30% again, reaction condition and solution post processing the same, obtain Kynoar graft polypropylene morpholide and argatroban copolymer.
Described alkali treatment, be specially: in 1-10mol/L NaOH or potassium hydroxide solution, additional proportion is the PVDF powder of 100g/L-180g/L, and in above-mentioned aqueous slkali, add the absolute ethyl alcohol of 10ml/L-50ml/L, stirring reaction in 40-100 DEG C of water bath with thermostatic control, the time is 5-20 minute; After after stirring, suction filtration also washs, it is dry that gained PVDF pulverulent solids product puts into 60 DEG C of baking ovens;
Constantly wash with distilled water in described suction filtration product process, to remove fluoride in product and ethanol.
Described initator is at least one in azodiisobutyronitrile (AIBN), dimethylamino naphthyridine (DMAP), 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDC).
Described solvent is all selected from dimethyl sulfoxide (DMSO) (DMSO), dimethyl formamide (DMF), dimethylacetylamide (DMAC), at least one in 1-METHYLPYRROLIDONE (NMP).
In described step (2), copolymer and PVDF blending ratio are 0: 100-100: 0, the two accounts for spinning casting solution mass percent is 10%-20%, pore former accounts for 5%-10%, solvent accounts for 70%-85%, above-mentioned substance is joined in there-necked flask, in 40-100 DEG C of water bath with thermostatic control, stir 3-6 hour, stop until completely dissolved stirring, standing and defoaming 3-5 hour, obtains spinning casting solution.
Described step (2) pore former is selected from least one in polyvinylpyrrolidone, polyethylene glycol, lithium chloride, ammonium chloride.
Described step (2) solvent is selected from dimethyl sulfoxide (DMSO) (DMSO), dimethyl formamide (DMF), dimethylacetylamide (DMAC), at least one in 1-METHYLPYRROLIDONE (NMP).
It is by the filtration of spinning casting solution, deaeration that described step (3) prepares blend hollow fiber membrane, under 0.1-0.4MPa spinning pressure, extrudes with the spinning head of the speed of 5-20r/min from Φ 0.4-0.8mm; Nascent doughnut is after 5-40cm air bath, solvent volume percentage be 0%-30%, temperature is solidify in the aqueous solution of 25-50 DEG C, reel with the speed of 10-60m/min, afterwards successively through the pure water of 24-72h soak and 24-72h be soak in the aqueous solution of 30% containing guarantor's hole agent volume fraction, get product hollow-fibre membrane; The solvent that the same step of described solvent (2) is used;
Described guarantor hole agent is at least one in methyl alcohol, ethanol, ethylene glycol, glycerine.
The blending polyvinylidene fluoride hollow fiber membrane pure water ultrafiltration permeate flux 80-300mL/m of described step (3) gained 2kPah, bovine serum albumin(BSA) rejection>=90%, hemolysis rate≤5.0%, recalcification time>=200s, urea clearance>=70%, daltonian medium molecular substance clearance rate>=60% of relative molecular mass 10000-20000, proof pressure>=0.1MPa.
The principle of the invention is: acryloyl morpholine can with alkali treatment after with the Kynoar generation Raolical polymerizable of double bond, gained copolymer and Kynoar have good compatibility, in order to pore-forming, add again the good polyvinylpyrrolidone of biocompatibility, blended rear spinning, obtained have excellent hydrophilic and biocompatibility, and have the hollow-fibre membrane of higher elimination effect to low in blood, middle molecular substance.
Beneficial effect:
The present invention will have hydrophily, good biocompatibility first, nontoxic, immunogenicity is low, the Small molecular argatroban of acryloyl morpholine and the efficient anticoagulation repelling performance is had to carry out modification to pvdf membrane to protein adsorption, cell adherence, by the copolymer that obtains and PVDF blended, the object of hydrophilic modifying is reached by the preparation of dry-wet spinning technology, finally improve the resistance tocrocking of film, blood compatibility and anti-freezing performance, obtain the blended doughnut hemodialysis membrane with good biocompatibility and anticoagulant.The present invention have technique simple, be easy to realize the features such as industrialization, can be applicable to haemodialysis field.
The blending polyvinylidene fluoride hollow fiber membrane pure water ultrafiltration permeate flux 80-300mL/m of gained 2kPah, bovine serum albumin(BSA) rejection>=90%, hemolysis rate≤5.0%, recalcification time>=200s, urea clearance>=70%, daltonian medium molecular substance clearance rate>=60% of relative molecular mass 10000-20000, proof pressure>=0.1MPa, this thickness is 100-200 μm, and internal diameter is 100-300 μm.
Specific embodiments:
Embodiment 1:
(1) preparation of Kynoar graft polypropylene morpholide and argatroban copolymer:
In the sodium hydroxide solution of 2.5mol/L, additional proportion is the PVDF powder of 100g/L, and in above-mentioned aqueous slkali, add the absolute ethyl alcohol of 10ml/L, stirring reaction in 60 DEG C of waters bath with thermostatic control, and the time is 10 minutes.Suction filtration products therefrom, after washing, gained PVDF pulverulent solids product puts into 60 DEG C of baking ovens dryings.
The PVDF powder of 16g alkali treatment is joined in the there-necked flask containing 120gDMF, be mixed with uniform solution, then, add the AIBN of 0.2g, add again with PVDF mol ratio be 1: 1: 2 ACMO monomer and AA monomer, under nitrogen atmosphere protection, react at 70 DEG C, the time is 12 hours, reacted solution precipitates in excessive methanol, suction filtration, suction filtration after sediment distilled water flushing, puts into 60 DEG C of oven dryings, obtains Kynoar graft polypropylene morpholide and acrylic copolymer; Then, the copolymer of 5g gained and 1g argatroban monomer are dissolved in the there-necked flask containing 50gDMF, add the DMAP of EDC and 0.5g of 1g again, reaction condition and solution post processing the same, obtain Kynoar graft polypropylene morpholide and argatroban copolymer.
(2) preparation of spinning casting solution:
Kynoar 10%; Kynoar graft polypropylene morpholide and argatroban copolymer 0%; Polyvinylpyrrolidone (PVPk15) 7%; Dimethyl formamide (DMF) 83%, is more than mass percent.Above-mentioned raw materials is added in molten material still, at 60 DEG C of temperature, make spinning casting solution through stirring 4h dissolving, standing and defoaming 3h.
(3) preparation of hollow-fibre membrane:
By above-mentioned casting solution filtration, deaeration, under 0.2MPa spinning pressure, extrude with the spinning head of the speed of 10r/min from Φ 0.4-0.8mm; Nascent doughnut is after 5crn air bath, DMF percent by volume be 30%, temperature is solidify in the aqueous solution of 40 DEG C, reel with the speed of 10m/min, soaking 48h at pure water and contain glycerine volume fraction successively is afterwards soak 48h in the aqueous solution of 30%, obtains finished product hollow-fibre membrane.
The blending polyvinylidene fluoride hollow fiber membrane pure water ultrafiltration permeate flux of gained is 90mL/m 2kPah, bovine serum albumin(BSA) rejection is 97%, and hemolysis rate is 9.87%, and recalcification time is 170s, and urea clearance is 72%, and the daltonian medium molecular substance clearance rate of relative molecular mass 10000-20000 is 52%, and proof pressure is 0.2MPa.
Embodiment 2:
(1) preparation of Kynoar graft polypropylene morpholide and argatroban copolymer:
In the sodium hydroxide solution of 10mol/L, additional proportion is the PVDF powder of 180g/L, and in above-mentioned aqueous slkali, add the absolute ethyl alcohol of 30ml/L, stirring reaction in 60 DEG C of waters bath with thermostatic control, and the time is 10 minutes.Suction filtration products therefrom, after washing, gained PVDF pulverulent solids product puts into 60 DEG C of baking ovens dryings.
The PVDF powder of 16g alkali treatment is joined in the there-necked flask containing 80gDMSO, be mixed with uniform solution, then, add the AIBN of 1.6g, add again with PVDF mol ratio be 1: 1: 4 ACMO monomer and AA monomer, under nitrogen atmosphere protection, react at 70 DEG C, the time is 12 hours, reacted solution precipitates in excessive methanol, suction filtration, suction filtration after sediment distilled water flushing, puts into 60 DEG C of oven dryings, obtains Kynoar graft polypropylene morpholide and acrylic copolymer; Then, the copolymer of 5g gained and 2.5g argatroban monomer are dissolved in the there-necked flask containing 25gDMSO, add the DMAP of EDC and 0.25g of 0.5g again, reaction condition and solution post processing the same, obtain Kynoar graft polypropylene morpholide and argatroban copolymer.
(2) preparation of spinning casting solution:
Kynoar 14.4%; Kynoar graft polypropylene morpholide and argatroban copolymer 1 .6%; Polyethylene glycol 8%; Dimethyl sulfoxide (DMSO) (DMSO) 76%, is more than mass percent.Added by above-mentioned raw materials in molten material still, at 60 DEG C of temperature, through stirring 6h, dissolving, deaeration 5h makes spinning casting solution.
(3) preparation of hollow-fibre membrane:
By above-mentioned casting solution filtration, deaeration, under 0.4MPa spinning pressure, extrude from spinning head with the speed of 20r/min; Nascent doughnut is after 10crn air bath, DMSO percent by volume be 10%, temperature is solidify in the aqueous solution of 40 DEG C, reel with the speed of 60m/min, soaking 24h at pure water and contain methyl alcohol volume fraction successively is afterwards soak 24h in the aqueous solution of 30%, obtains finished product hollow-fibre membrane.
The blending polyvinylidene fluoride hollow fiber membrane pure water ultrafiltration permeate flux of gained is 125mL/m 2kPah, bovine serum albumin(BSA) rejection is 96%, and hemolysis rate is 5.0%, and recalcification time is 270s, and urea clearance is 78%, and the daltonian medium molecular substance clearance rate of relative molecular mass 10000-20000 is 56%, and proof pressure is 0.2MPa.
Embodiment 3:
(1) preparation of Kynoar graft polypropylene morpholide and argatroban copolymer:
In the sodium hydroxide solution of 5mol/L, additional proportion is the PVDF powder of 180g/L, and in above-mentioned aqueous slkali, add the absolute ethyl alcohol of 10ml/L, stirring reaction in 60 DEG C of waters bath with thermostatic control, and the time is 10 minutes.Suction filtration products therefrom, after washing, gained PVDF pulverulent solids product puts into 60 DEG C of baking ovens dryings.
The PVDF powder of 16g alkali treatment is joined in the there-necked flask containing 240gDMAC, be mixed with uniform solution, then, add the AIBN of 0.8g, add again with PVDF mol ratio be 1: 1: 2 ACMO monomer and AA monomer, under nitrogen atmosphere protection, react at 70 DEG C, the time is 12 hours, reacted solution precipitates in excessive methanol, suction filtration, suction filtration after sediment distilled water flushing, puts into 60 DEG C of oven dryings, obtains Kynoar graft polypropylene morpholide and acrylic copolymer; Then, the copolymer of 5g gained and 1g argatroban monomer are dissolved in the there-necked flask containing 75gDMAC, add the DMAP of EDC and 0.5g of 1g again, reaction condition and solution post processing the same, obtain Kynoar graft polypropylene morpholide and argatroban copolymer.
(2) preparation of spinning casting solution:
Kynoar 8%; Kynoar graft polypropylene morpholide and argatroban copolymer 8%; Lithium chloride 10%; Dimethylacetylamide (DMAC) 74%, is more than mass percent.Above-mentioned raw materials is added in molten material still, at 60 DEG C of temperature, make spinning casting solution through stirring, dissolving.
(3) preparation of hollow-fibre membrane:
By above-mentioned casting solution filtration, deaeration, under 0.2MPa spinning pressure, extrude from spinning head with the speed of 10r/min; Nascent doughnut is after 10crn air bath, DMAC percent by volume be 20%, temperature is solidify in the aqueous solution of 40 DEG C, reel with the speed of 30m/min, soaking 72h at pure water and contain volume fraction of ethanol successively is afterwards soak 72h in the aqueous solution of 30%, obtains finished product hollow-fibre membrane.
The blending polyvinylidene fluoride hollow fiber membrane pure water ultrafiltration permeate flux of gained is 170mL/m 2kPah, bovine serum albumin(BSA) rejection is 95%, and hemolysis rate is 3.64%, and recalcification time is 340s, and urea clearance is 80%, and the daltonian medium molecular substance clearance rate of relative molecular mass 10000-20000 is 60%, and proof pressure is 0.2MPa.
Embodiment 4:
(1) preparation of Kynoar graft polypropylene morpholide and argatroban copolymer:
In the sodium hydroxide solution of 10mol/L, additional proportion is the PVDF powder of 180g/L, and in above-mentioned aqueous slkali, add the absolute ethyl alcohol of 50ml/L, stirring reaction in 60 DEG C of waters bath with thermostatic control, and the time is 10 minutes.Suction filtration products therefrom, after washing, gained PVDF pulverulent solids product puts into 60 DEG C of baking ovens dryings.
The PVDF powder of 16g alkali treatment is joined in the there-necked flask containing 120gNMP, be mixed with uniform solution, then, add the AIBN of 1.6g, add again with PVDF mol ratio be 1: 1: 2 ACMO monomer and AA monomer, under nitrogen atmosphere protection, react at 70 DEG C, the time is 12 hours, reacted solution precipitates in excessive methanol, suction filtration, suction filtration after sediment distilled water flushing, puts into 60 DEG C of oven dryings, obtains Kynoar graft polypropylene morpholide and acrylic copolymer; Then, the copolymer of 5g gained and 1g argatroban monomer are dissolved in the there-necked flask containing 50gNMP, add the DMAP of EDC and 0.25g of 0.5g again, reaction condition and solution post processing the same, obtain Kynoar graft polypropylene morpholide and argatroban copolymer.
(2) preparation of spinning casting solution:
Kynoar 0%; Kynoar graft polypropylene morpholide and argatroban copolymer 20%; Ammonium chloride 10%; NMP70%, is more than mass percent.Above-mentioned raw materials is added in molten material still, at 60 DEG C of temperature, make spinning casting solution through stirring, dissolving.
(3) preparation of hollow-fibre membrane:
By above-mentioned casting solution filtration, deaeration, under 0.1MPa spinning pressure, extrude from spinning head with the speed of 20r/min; Nascent doughnut is after 10crn air bath, NMP percent by volume be 5%, temperature is solidify in the aqueous solution of 40 DEG C, reel with the speed of 60m/min, soaking 48h at pure water and contain ethylene glycol volume fraction successively is afterwards soak 48h in the aqueous solution of 30%, obtains finished product hollow-fibre membrane.
The blending polyvinylidene fluoride hollow fiber membrane pure water ultrafiltration permeate flux of gained is 200mL/m 2kPah, bovine serum albumin(BSA) rejection is 91%, and hemolysis rate is 1.94%, and recalcification time is 400s, and urea clearance is 82.5%, and the daltonian medium molecular substance clearance rate of relative molecular mass 10000-20000 is 62%, and proof pressure is 0.2MPa.

Claims (10)

1. for a blending polyvinylidene fluoride hollow fiber membrane for haemodialysis, it is characterized in that, the preparation method of described hollow-fibre membrane comprises the steps:
(1) Kynoar graft polypropylene morpholide and argatroban copolymer is prepared; (2) by obtained copolymer and polyvinylidene blending, after adding pore former and solvent, preparation spinning casting solution; (3) blend hollow fiber membrane is prepared.
2. a kind of blending polyvinylidene fluoride hollow fiber membrane for haemodialysis according to claim 1, is characterized in that: the preparation method of described step (1) Kynoar graft polypropylene morpholide and argatroban copolymer is as follows:
1. the Kynoar powder containing carbon-carbon double bond obtained through alkali treatment is joined 5-15 doubly in the solvent of PVDF powder quality, be mixed with Kynoar solution;
2. in above-mentioned solution, add the initator accounting for PVDF powder quality 1-10%, add acryloylmorpholine monomer and acrylic monomers again, Kynoar: acryloylmorpholine monomer: acrylic monomers mol ratio is 1: 1: 4-1: 1: 2, under inert atmosphere protection, react at 50-100 DEG C, the time is 8-24 hour;
3. reacted solution precipitate in excessive methanol, suction filtration, suction filtration after sediment distilled water flushing, puts into 60 DEG C of oven dryings, obtains Kynoar graft polypropylene morpholide and acrylic copolymer;
4. by the copolymer of above-mentioned gained and argatroban monomer with 20: 1-20: 10 mass ratio be dissolved in 5-15 doubly in the solvent of copolymer quality, add the initator accounting for copolymer quality 5-30% again, 2. reaction condition and solution post-processing step, obtain Kynoar graft polypropylene morpholide and argatroban copolymer.
3. a kind of blending polyvinylidene fluoride hollow fiber membrane for haemodialysis according to claim 2, is characterized in that:
Described alkali treatment, be specially: in 1-10mol/L NaOH or potassium hydroxide solution, additional proportion is the PVDF powder of 100g/L-180g/L, and in above-mentioned aqueous slkali, add the absolute ethyl alcohol of 10ml/L-50ml/L, stirring reaction in 40-100 DEG C of water bath with thermostatic control, in time, ask as 5-20 minute; After after stirring, suction filtration also washs, it is dry that gained PVDF pulverulent solids product puts into 60 DEG C of baking ovens.
4. a kind of blending polyvinylidene fluoride hollow fiber membrane for haemodialysis according to claim 2, is characterized in that: described solvent is selected from dimethyl sulfoxide (DMSO), dimethyl formamide, dimethylacetylamide, at least one in 1-METHYLPYRROLIDONE.
5. a kind of blending polyvinylidene fluoride hollow fiber membrane for haemodialysis according to claim 2, is characterized in that: described reaction initiator is at least one in azodiisobutyronitrile, dimethylamino naphthyridine, 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride.
6. a kind of blending polyvinylidene fluoride hollow fiber membrane for haemodialysis according to claim 1, it is characterized in that: described step (2) copolymer is 0-100: 100-0 with polyvinylidene blending ratio, the two accounts for casting solution mass percent is 10%-20%, pore former accounts for 5%-10%, solvent accounts for 70%-85%, above-mentioned substance is joined in there-necked flask, 3-6 hour is stirred in 40-100 DEG C of water bath with thermostatic control, stop until completely dissolved stirring, standing and defoaming 3-5 hour, obtains spinning casting solution.
7. a kind of blending polyvinylidene fluoride hollow fiber membrane for haemodialysis according to claim 1, is characterized in that: the pore former of described step (2) is selected from least one in polyvinylpyrrolidone, polyethylene glycol, lithium chloride, ammonium chloride.
8. a kind of blending polyvinylidene fluoride hollow fiber membrane for haemodialysis according to claim 1, its characteristic is: described step (2) solvent is selected from dimethyl sulfoxide (DMSO), dimethyl formamide, dimethylacetylamide, at least one in 1-METHYLPYRROLIDONE.
9. a kind of blending polyvinylidene fluoride hollow fiber membrane for haemodialysis according to claim 1, its characteristic is: the concrete steps that described step (3) prepares blend hollow fiber membrane are as follows:
By the filtration of spinning casting solution, deaeration, under 0.1-0.4MPa spinning pressure, extrude with the spinning head of the speed of 5-20r/min from Φ 0.4-0.8mm; Nascent doughnut is after 5-40cm air bath, solvent volume percentage be 0%-30%, temperature is solidify in the aqueous solution of 25-50 DEG C, reel with the speed of 10-60m/min, afterwards successively through the pure water of 24-72h soak and 24-72h be the aqueous solution soaking of 30% containing guarantor's hole agent volume ratio, get product hollow-fibre membrane, the same step of described solvent (2) solvent for use; Described guarantor hole agent is at least one in methyl alcohol, ethanol, ethylene glycol, glycerine.
10. the application of a kind of blending polyvinylidene fluoride hollow fiber membrane for haemodialysis according to claim 1.
CN201510996430.8A 2015-12-29 2015-12-29 A kind of blending polyvinylidene fluoride hollow fiber membrane and preparation method thereof Active CN105521715B (en)

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Publication number Priority date Publication date Assignee Title
CN105854636A (en) * 2016-05-15 2016-08-17 东北电力大学 Preparation method of high-hydrophobicity polyvinylidene fluoride hollow fiber membrane
CN106310970A (en) * 2016-09-23 2017-01-11 天津工业大学 Modified polyvinylidene fluoride hollow fiber membrane for hematodialysis
CN106310970B (en) * 2016-09-23 2019-03-05 天津工业大学 A kind of modified polyvinilidene fluoride hollow-fibre membrane for haemodialysis
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CN107602740B (en) * 2017-10-31 2019-12-31 北京化工大学 Modified dielectric fluorine-containing polymer and film material thereof, and preparation method thereof
CN109529637A (en) * 2018-12-18 2019-03-29 曲靖师范学院 A kind of preparation method of resisting microbial contamination polyvinylidene fluoride separation membrane
CN112588132A (en) * 2020-10-28 2021-04-02 健帆生物科技集团股份有限公司 Hollow fiber membrane and preparation method thereof
CN112588132B (en) * 2020-10-28 2022-11-11 健帆生物科技集团股份有限公司 Hollow fiber membrane and preparation method thereof

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