CN106310970A - Modified polyvinylidene fluoride hollow fiber membrane for hematodialysis - Google Patents
Modified polyvinylidene fluoride hollow fiber membrane for hematodialysis Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M1/00—Suction or pumping devices for medical purposes; Devices for carrying-off, for treatment of, or for carrying-over, body-liquids; Drainage systems
- A61M1/14—Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis
- A61M1/16—Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis with membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The invention belongs to the technical field of membranes, and in particular relates to a modified polyvinylidene fluoride (PVDF) hollow fiber membrane for hematodialysisa, and a preparation method thereof. A PVDF body is modified by using acryloyl morpholine with rejecting performance on protein adsorption and cell adhesion and acrylic acid with high hydrophilic performance to prepare a hollow fiber membrane; the surface of the membrane is subjected to surface modification by L-arginine with an anticoagulation effect; and the anti-pollution performance, the blood compatibility and the anticoagulation performance of the membrane are finally improved, and a modified hollow fiber hemodialysis membrane with high biocompatibility and anticoagulation performance is obtained. The process provided by the invention is simple and can be applied to the field of hemodialysis.
Description
Technical field:
The invention belongs to technical field of membrane, particularly to a kind of modified polyvinilidene fluoride doughnut for hemodialysis
Film, with and preparation method thereof.
Background technology:
At present, the Hollow-fibre membranes material being applied to hemodialysis is treated as foreign body in vivo, when contacting with blood, no
Can avoid causing a series of defense reaction of body, wherein platelet adhesion, activate blood coagulation system, produce blood coagulation and thrombosis is
The most serious reaction.Kynoar (PVDF) is the macromolecular material of a kind of function admirable, its prominent chemical stability, resistance to
Radiation characteristic and thermostability etc. make it be widely used in membrance separation field.Pvdf membrane material surface is smooth, and surface can be low, and material
Itself is nontoxic, and prepared ultrafilter membrane flux is higher, and with in the polyether sulfone being currently used for high flux hemodialysis membrane material
Hollow fiber film is compared, and ultrasiltrated rate decay is little, is expected to become the new material of hemodialysis.But owing to PVDF has strong hydrophobic
Property, it still can produce the problems such as protein adsorption, platelet adhesion, blood coagulation when field application such as bio-medicals.Therefore,
PVDF is to improve its biocompatibility and anticoagulant further as the key factor of hemodialysis film.Therefore, pvdf membrane is changed
Property its biocompatibility and anticoagulant are improved jointly, and then be used as bio-medical material be significant.
In recent years, for improving pvdf membrane blood compatibility and anticoagulant, mainly introduce function on pvdf membrane surface
Property group, including hydroaropic substance (such as Polyethylene Glycol, amphion etc.) and have anticoagulant effect monomer (such as heparin,
Phosphorylcholine), make film surface-functionalized, modified effect is obvious, with strong points, is just becoming the study hotspot of people.
Use surface modification to prepare the existing many documents of Pvdf Microporous Hollow Fiber Membrane material and patent is reported.
KH570 is grafted on the surface of polyvinylidene fluoride film by CN104857866A, prepares the preparation of hydrophilic modifying polyvinylidene fluoride film.
CN104548961A uses atomic radicals transfer polymerization method at Kynoar film surface grafting hydrophilic anti-pollution monomer, obtains
To hydrophilic anti-pollution polyvinylidene fluoride film.CN102558595A uses atomic radicals transfer polymerization method by sulfobetaines first
Base acrylic acid methyl ester. or allyl polyglycol graft on polyvinylidene fluoride film surface, improve its hydrophilic and antipollution energy
Power.CN103357281A is first by polyvinylidene fluoride resin pretreatment, then carries out altogether with the ascorbic acid crossed by nitrogen deoxidation treatment
Poly-, preparing can the modified PVDF micro-filtration membrane of the most anti-protein contamination.But these researchs are at the blood compatibility modified to PVDF
Property and may to produce the problem such as blood coagulation or erythrocyte haemolysis, platelet adhesion reaction the most not mentioned with contacting blood, to clinical blood
The exploitation application of liquid dialysis brings certain difficulty.
The method that the application patent inventor once used alkali to process carries out graft modification to PVDF body, prepares hemorrhage respectively
Liquid phase capacitive preferably separates film (ZL201410325639.7 with anticoagulation PVDF；ZL201410325836).Research finds, uses
Hydrophilic, nontoxic, immunogenicity is low, biocompatibility is splendid, have the acryloyl of repulsive interaction to protein adsorption cell adhesion
Morpholine carries out graft modification to PVDF, and film demonstrates that the absorption of preferable anti-protein, antiplatelet are sticked and the characteristic such as anti-hemolysis；
And the pvdf membrane of small molecule thrombin inhibitor argatroban graft modification can anticoagulant enzyme generation and fiber egg
White generation, has played the strongest anticoagulant, antithrombotic effect.The present inventor applies for a patent (application number as result of study
201510996430.8), it is grafted on PVDF obtain graft copolymer by acryloyl morpholine and argatroban simultaneously, then should
Copolymer and PVDF blending and modifying, prepared by dry-wet spinning technology and have good biocompatibility and anticoagulant
Modified doughnut hemodialysis membrane.
Owing to argatroban is relatively costly, attempt using the people that structure is similar to it, has antiplatelet aggregation and sticks
Body essential amino acids L-arginine carries out surface modification to PVDF hollow-fibre membrane, gives film surface-functionalized anticoagulant base
Group, the good blood compatibility of the PVDF hollow-fibre membrane the most prepared, obtain having good biocompatibility and anticoagulant
Modified PVDF doughnut hemodialysis membrane.
Summary of the invention:
For existing PVDF hollow-fibre membrane and contacting blood blood compatibility with anticoagulant does not has concurrently and less effective
Problem, the present invention provides a kind of modified polyvinilidene fluoride hollow-fibre membrane for hemodialysis and preparation method thereof, this film system
Preparation Method is simple, and repeatable usability is high, and gained hollow-fibre membrane has high intensity, high-throughout feature, and in blood
In, the noxious substance of low-molecular-weight there is good removal effect, can be used for hemodialysis field.
The described modified polyvinilidene fluoride hollow-fibre membrane for hemodialysis, its preparation method is as follows:
(1) Kynoar graft polypropylene morpholide and acrylic acid copolymer are prepared；(2) by prepared copolymer with
Polyvinylidene blending, adds pore former and solvent mixing preparation spinning casting solution；(3) hollow-fibre membrane is prepared, i.e. PVDF/
PVDF-g-(PACMO-PAA) fibrous membrane；(4) by prepared hollow-fibre membrane at surface grafting L-arginine.
Described step (1) Kynoar (PVDF) graft polypropylene morpholide and the preparation method of acrylic copolymer
For: first join 5-15 times of PVDF powder matter by processing, through alkali, the Kynoar powder containing carbon-carbon double bond obtained
In the solvent of amount, it is configured to Kynoar solution, then, adds the initiator accounting for PVDF powder quality 1-10%, then by third
Dimethomorph monomer (ACMO): acrylic monomers (AA): Kynoar mol ratio is 1: 1: 4-1: 1: 2 addition ACMO and AA,
Under inert atmosphere protection, reacting at 50-100 DEG C, the time is 8-24 hour, and reacted solution is heavy in excessive methanol
Shallow lake, sucking filtration, sucking filtration after precipitate distilled water flushing, put into 60 DEG C of oven dryings, obtain Kynoar graft polypropylene acyl
Morpholine and acrylic copolymer.
Described alkali processes, particularly as follows: add final concentration of in 1-10mol/L sodium hydroxide or potassium hydroxide solution
The PVDF powder of 100g/L-180g/L, and press 10mL/L-50mL/L addition dehydrated alcohol, stir in 40-100 DEG C of water bath with thermostatic control
Mixing reaction, the time is 5-20 minute；After stirring sucking filtration and wash after, gained PVDF pulverulent solids product is put in 60 DEG C of baking ovens
It is dried；
Constantly wash with distilled water during described sucking filtration, to remove the fluoride in product and ethanol.
Described initiator is azodiisobutyronitrile (AIBN), dimethylamino naphthyridine (DMAP), 1-(3-dimethylamino third
Base) at least one in-3-ethyl-carbodiimide hydrochloride (EDC)；
Preferably, described initiator is azodiisobutyronitrile；
Described solvent is selected from dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethyl acetylamide
(DMAC), at least one in N-Methyl pyrrolidone (NMP)；
Preferably, described solvent is dimethylformamide or dimethyl acetylamide；
In described step (2), copolymer and PVDF ratio are 1: 9-9: 1, and the two accounts for spinning casting solution mass percent and is
10%-20%, pore former accounts for 5%-10%, and solvent accounts for 70%-85%, is joined by above-mentioned substance in there-necked flask, at 40-
100 DEG C of waters bath with thermostatic control are stirred 3-6 hour, stop stirring, standing and defoaming 3-5 hour until completely dissolved, obtain spinning casting film
Liquid；
Preferably, described copolymer and PVDF ratio are 1: 1；
Described step (2) pore former is selected from least in polyvinylpyrrolidone, Polyethylene Glycol, lithium chloride, ammonia chloride
Kind；
Preferably, described pore former is Polyethylene Glycol or polyvinylpyrrolidone；
Described step (2) solvent is selected from dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethyl acetylamide
(DMAC), at least one in N-Methyl pyrrolidone (NMP)；
Preferably, described solvent is dimethylformamide or dimethyl acetylamide；
Described step (3) prepare modified hollow fibre membrane be the spinning casting solution of step (2) gained is filtered, deaeration,
Under 0.1-0.4MPa spinning pressure, extrude from the spinning head of Φ 0.4-0.8mm with the speed of 5-20r/min；Nascent doughnut
After 5-40cm air bath, solvent volume percentage ratio be 0%-30%, temperature be the aqueous solution of 25-50 DEG C in solidify, with 10-
The speed winding of 60m/min, the hole agent volume fraction containing guarantor of the pure water immersion and 24-72h that sequentially pass through 24-72h afterwards is
Soaking in the aqueous solution of 30%, get product hollow-fibre membrane PVDF/PVDF-g-(PACMO-PAA)；
Described solvent is selected from dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethyl acetylamide (DMAC), N-
At least one in methyl pyrrolidone (NMP)；
Described hole agent of protecting is at least one in methanol, ethanol, ethylene glycol, glycerol；
Preferably, described guarantor hole agent is glycerol；
Concretely comprising the following steps of described step (4) doughnut film surface grafting L-arginine: first, uses deionized water rinsing
PVDF/PVDF-g-(PACMO-PAA) fibrous membrane surface, then with nitrogen purging film surface to being dried；Then, film is immersed in contains
Have in 2-(N-morpholine) ethyl sulfonic acid (MES) buffer of 0.02-0.10M EDC (pH=4), stand 10-30min；Afterwards, directly
Connect the N-hydroxysuccinimide (NHS) adding EDC mass half in above-mentioned buffer solution, and slowly rock and make NHS complete
Dissolve, and at 2-10 DEG C, activate 1-5h；Finally, the film after activation is respectively placed in containing 5mg/mL-30mg/mL L-essence ammonia
In the borate buffer solution (pH=9.7) of acid, and at 25 DEG C, react 12-24h；By formed by L-arginine and acryloyl morpholine
The common PVDF hollow-fibre membrane modified, by pure water rinsing to remove unreacted monomer and by-product, and soaks in water
More than two days, postlyophilization, standby.
The principle of the invention is: acryloyl morpholine and acrylic acid can process with alkali after with the Kynoar of double bond occur from
Obtained copolymer by base polyreaction, for pore-forming, add again the good pore former of biocompatibility, modified spinning, prepare
Hollow-fibre membrane；Utilize on film surface acrylic acid carboxyl and arginic amino to carry out amidation process again, prepare tool
There are good biocompatibility and anticoagulant, and low in blood, middle molecular substance are had the doughnut of higher elimination effect
Film.
Beneficial effect:
1, the present invention will have hydrophilic, good biocompatibility first, and nontoxic, immunogenicity is low, to protein adsorption, carefully
Born of the same parents be stained with repel the acryloyl morpholine of performance and hydrophilic preferable acrylic acid that PVDF body is modified prepare hollow is fine
Dimension film, and then carries out surface modification on film surface with the L-arginine with anticoagulation, finally improve film resistance tocrocking,
Blood compatibility and anticoagulant performance, obtain the modified doughnut hemodialysis membrane with good biocompatibility and anticoagulant.
Present invention process is simple, can be applicable to hemodialysis field.
2, have that document reports at film surface grafting aminoacid, be first film forming, then on film surface by various modification sides
Method fixes acrylic acid, then recycles amidation process, and aminoacid introduces film surface.Although improve the antipollution on film surface
Property, but utilize this kind of method meeting blocking portion fenestra after the fixed amino acid of film surface, cause the permeance property of film matrix to decline.
For solving this problem, and giving film surface blood compatibility and anticoagulant, this patent is first by acryloyl morpholine and propylene simultaneously
Acid monomers is grafted on PVDF powder, then film forming.Film forming procedure utilizes surface segregation effect, acryloyl morpholine and acrylic acid
Hydrophilic group in strand is to film surface enrichment.The acryloyl morpholine hydrophilic segment on surface provides good hydrophilic in film surface
Property, resistance tocrocking, the most preferably blood compatibility (relatively low platelet adhesion reaction amount and hemolysis rate)；The carboxylic of surface acrylic
Base activated heel arginine carries out amidation process, and the arginine of grafting is that film surface provides good anticoagulant, residue
Unreacted carboxyl ensures the hydrophilic that film surface is good.Use such method can also be grafted other amino as required
Acid, such as at film surface grafting lysine, improves the biocompatibility on film surface, cultivates PC12 cell on film surface, to promote
The regeneration etc. of nervous tissue.By dual modification, on the premise of not affecting the permeance property that film matrix is good, give film
Blood compatibility that surface is good and anticoagulant property.
3, the modified polyvinilidene fluoride hollow-fibre membrane pure water ultrafiltration permeation flux 80-300mL/m of gained2KPa h,
Bovine serum albumin rejection >=90%, initial water contact angle value≤50 °, flux recovery rate >=90%, bovine serum albumin is inhaled
Attached amount≤60 μ g/cm2, the erythrocyte amount of sticking≤3 × 105, hemolysis rate≤5.0%, blood plasma recalcification time >=250s, activation portion
Dividing zymogen time >=70s, urea clearance rate >=80%, the daltonian medium molecular substance of relative molecular mass 10000-20000 is clear
Except rate >=70%, proof pressure >=0.1MPa.
Specific embodiments:
Embodiment 1: a kind of modified polyvinilidene fluoride hollow-fibre membrane and preparation method thereof
(1) Kynoar graft polypropylene morpholide and the preparation of acrylic copolymer:
The PVDF powder of final concentration of 100g/L is added in the potassium hydroxide solution of 2.5mol/L, and at above-mentioned aqueous slkali
In press 10mL/L add dehydrated alcohol, in 100 DEG C of waters bath with thermostatic control stirring reaction, the time is 5 minutes.Sucking filtration products therefrom is pure
After water purification washing, gained PVDF pulverulent solids product is put in 60 DEG C of baking ovens and is dried.
The PVDF powder that above-mentioned for 16g alkali processes is joined in the there-necked flask containing 120g DMF, is configured to homogeneous molten
Liquid, then, adds the AIBN of 0.2g, then by ACMO: AA: PVDF mol ratio is 1: 1: 2 addition ACMO monomer and AA monomer, at nitrogen
Under gas atmosphere protection, reacting at 50 DEG C, the time is 24 hours, and reacted solution precipitates in excessive methanol, sucking filtration, precipitation
Sucking filtration after thing distilled water flushing, puts into 60 DEG C of oven dryings, obtains Kynoar graft polypropylene morpholide and acrylic acid
Copolymer；
(2) preparation of spinning casting solution:
Kynoar 9%；Kynoar graft polypropylene morpholide and acrylic copolymer 1%；Polyvinyl pyrrole
Alkanone (PVPk15) 7%；Dimethylformamide (DMF) 83%, is more than mass percent.Above-mentioned raw materials is added molten material still
In, at a temperature of 60 DEG C, agitated 4h dissolves, standing and defoaming 3h makes spinning casting solution.
(3) preparation of hollow-fibre membrane:
Above-mentioned casting solution is filtered, deaeration, under 0.2MPa spinning pressure, with the speed of 10r/min from Φ 0.4-0.8mm
Spinning head extrusion；Nascent doughnut after 5cm air bath, DMF percent by volume be 30%, temperature be 40 DEG C water-soluble
Liquid solidifies, winds with the speed of 10m/min, soak 48h at pure water the most successively and be 30% containing glycerol volume fraction
Aqueous solution soaks 48h, obtains PVDF-g-(PACMO-PAA) hollow-fibre membrane.
(4) doughnut film surface grafting L-arginine
First, with deionized water rinsing PVDF/PVDF-g-(PACMO-PAA) fibrous membrane surface, then purge film table with nitrogen
Face is to being dried；Then, film is immersed in (pH=4) in the MES buffer containing 0.02M EDC, stands 10min；Afterwards, directly
In above-mentioned buffer solution, add the NHS of EDC mass half, and slowly rock and make NHS be completely dissolved, and at 2 DEG C, activate 1h；
Finally, the film after activation is placed in the borate buffer solution (pH=9.7) containing 5mg/mL L-arginine, and anti-at 25 DEG C
Answer 12h；By the PVDF hollow-fibre membrane pure water rinsing jointly modified by L-arginine and acryloyl morpholine formed to remove
Unreacted monomer and by-product, and in water soak two days, postlyophilization, standby.
The modified polyvinilidene fluoride hollow-fibre membrane pure water ultrafiltration permeation flux 210mL/m of gained2KPa h, Ox blood serum
Albumin rejection is 92.5%, and initial water contact angle value is 50 °, and flux recovery rate is 94%, bovine serum albumin adsorbance
It is 60 μ g/cm2, the erythrocyte amount of sticking is 2.35 × 105, hemolysis rate is 3.76%, and blood plasma recalcification time is 250s, activation portion
Dividing zymogen time is 70s, and urea clearance rate is 80%, and the daltonian medium molecular substance of relative molecular mass 10000-20000 is clear
Except rate is 70%, proof pressure is 0.2MPa
Embodiment 2: a kind of modified polyvinilidene fluoride hollow-fibre membrane and preparation method thereof
(1) Kynoar graft polypropylene morpholide and the preparation of acrylic copolymer:
The PVDF powder of final concentration of 180g/L is added in the sodium hydroxide solution of 10mol/L, and at above-mentioned aqueous slkali
In press 30mL/L add dehydrated alcohol, in 50 DEG C of waters bath with thermostatic control stirring reaction, the time is 20 minutes.Sucking filtration products therefrom is pure
After water purification washing, gained PVDF pulverulent solids product is put in 60 DEG C of baking ovens and is dried.
The PVDF powder that above-mentioned for 16g alkali processes is joined in the there-necked flask containing 80g DMSO, is configured to homogeneous molten
Liquid, then, adds the AIBN of 1.6g, then by ACMO: AA: PVDF mol ratio is 1: 1: 4 addition ACMO monomer and AA monomer, at nitrogen
Under gas atmosphere protection, reacting at 70 DEG C, the time is 12 hours, and reacted solution precipitates in excessive methanol, sucking filtration, precipitation
Sucking filtration after thing distilled water flushing, puts into 60 DEG C of oven dryings, obtains Kynoar graft polypropylene morpholide and acrylic acid
Copolymer；；
(2) preparation of spinning casting solution:
Kynoar 14.4%；Kynoar graft polypropylene morpholide and acrylic copolymer 1.6%；Poly-second two
Alcohol 8%；Dimethyl sulfoxide (DMSO) 76%, is more than mass percent.Above-mentioned raw materials is added in molten material still, 60 DEG C of temperature
Under degree, agitated 6h, dissolving, deaeration 5h makes spinning casting solution.
(3) preparation of hollow-fibre membrane:
By the filtration of above-mentioned casting solution, deaeration, under 0.4MPa spinning pressure, extrude from spinning head with the speed of 20r/min；
Nascent doughnut after 10cm air bath, DMSO percent by volume be 10%, temperature be the aqueous solution of 40 DEG C in solidify, with
The speed winding of 60m/min, soaks 24h at pure water the most successively and contains immersion in the aqueous solution that methanol volume fraction is 30%
24h, obtains PVDF-g-(PACMO-PAA) hollow-fibre membrane；
(4) doughnut film surface grafting L-arginine
First, with deionized water rinsing PVDF/PVDF-g-(PACMO-PAA) fibrous membrane surface, then purge film table with nitrogen
Face is to being dried；Then, film is immersed in (pH=4) in the MES buffer containing 0.10M EDC, stands 30min；Afterwards, directly
In above-mentioned buffer solution, add the NHS of EDC mass half, and slowly rock and make NHS be completely dissolved, and activate at 10 DEG C
5h；Finally, the film after activation is respectively placed in the borate buffer solution (pH=9.7) containing 30mg/mL L-arginine, and
24h is reacted at 25 DEG C；The PVDF hollow-fibre membrane pure water jointly modified by L-arginine and acryloyl morpholine formed is rushed
Wash to remove unreacted monomer and by-product, and soak more than two days in water, postlyophilization, standby.
The modified polyvinilidene fluoride hollow-fibre membrane pure water ultrafiltration permeation flux 260mL/m of gained2KPa h, Ox blood serum
Albumin rejection is 91.3%, and initial water contact angle value is 32.8 °, and flux recovery rate is 96.5%, and bovine serum albumin is inhaled
Attached amount is 42 μ g/cm2, the erythrocyte amount of sticking is 1.56 × 105, hemolysis rate is 0.96%, and blood plasma recalcification time is 300s, lives
Changing part zymogen time is 90s, and urea clearance rate is 89%, relative molecular mass 10000-20000 daltonian Middle molecule thing
Matter clearance rate is 78%, and proof pressure is 0.2MPa.
Embodiment 3: a kind of modified polyvinilidene fluoride hollow-fibre membrane and preparation method thereof
(1) Kynoar graft polypropylene morpholide and the preparation of acrylic copolymer:
The PVDF powder of final concentration of 180g/L is added in the sodium hydroxide solution of 5mol/L, and in above-mentioned aqueous slkali
Adding dehydrated alcohol by 10mL/L, stirring reaction in 60 DEG C of waters bath with thermostatic control, the time is 10 minutes.Sucking filtration products therefrom is pure
After water washing, gained PVDF pulverulent solids product is put in 60 DEG C of baking ovens and is dried.
The PVDF powder that above-mentioned for 16g alkali processes is joined in the there-necked flask containing 240g DMAC, is configured to homogeneous molten
Liquid, then, adds the EDC of 0.8g, then by ACMO: AA: PVDF mol ratio is 1: 1: 2 addition ACMO monomer and AA monomer, at nitrogen
Under gas atmosphere protection, reacting at 70 DEG C, the time is 12 hours, and reacted solution precipitates in excessive methanol, sucking filtration, precipitation
Sucking filtration after thing distilled water flushing, puts into 60 DEG C of oven dryings, obtains Kynoar graft polypropylene morpholide and acrylic acid
Copolymer；
(2) preparation of spinning casting solution:
Kynoar 8%；Kynoar graft polypropylene morpholide and acrylic copolymer 8%；Lithium chloride 10%；
Dimethyl acetylamide (DMAC) 74%, is more than mass percent.Above-mentioned raw materials is added in molten material still, 100 DEG C of temperature
Under, agitated 5h, dissolving, deaeration 4h makes spinning casting solution.
(3) preparation of hollow-fibre membrane:
By the filtration of above-mentioned casting solution, deaeration, under 0.2MPa spinning pressure, extrude from spinning head with the speed of 10r/min；
Nascent doughnut after 10cm air bath, DMAC percent by volume be 20%, temperature be the aqueous solution of 50 DEG C in solidify, with
The speed winding of 30m/min, soaks 72h at pure water the most successively and contains immersion in the aqueous solution that volume fraction of ethanol is 30%
72h, obtains PVDF-g-(PACMO-PAA) hollow-fibre membrane；
(4) doughnut film surface grafting L-arginine
First, with deionized water rinsing PVDF/PVDF-g-(PACMO-PAA) fibrous membrane surface, then purge film table with nitrogen
Face is to being dried；Then, film is immersed in (pH=4) in the MES buffer containing 0.05M EDC, stands 15min；Afterwards, directly
In above-mentioned buffer solution, add the NHS of EDC mass half, and slowly rock and make NHS be completely dissolved, and at 5 DEG C, activate 2h；
Finally, the film after activation is respectively placed in the borate buffer solution (pH=9.7) containing 15mg/mL L-arginine, and at 25 DEG C
Lower reaction 18h；By formed the PVDF hollow-fibre membrane pure water rinsing jointly modified by L-arginine and acryloyl morpholine with
Remove unreacted monomer and by-product, and soak more than two days in water, postlyophilization, standby.
The modified polyvinilidene fluoride hollow-fibre membrane pure water ultrafiltration permeation flux 230mL/m of gained2KPa h, Ox blood serum
Albumin rejection is 93.3%, and initial water contact angle value is 40.5 °, and flux recovery rate is 93.7%, and bovine serum albumin is inhaled
Attached amount is 51 μ g/cm2, the erythrocyte amount of sticking is 2.31 × 105, hemolysis rate is 2.46%, and blood plasma recalcification time is 286s, lives
Changing part zymogen time is 81s, and urea clearance rate is 85%, relative molecular mass 10000-20000 daltonian Middle molecule thing
Matter clearance rate is 75%, and proof pressure is 0.2MPa.
Embodiment 4: a kind of modified polyvinilidene fluoride hollow-fibre membrane and preparation method thereof
(1) Kynoar graft polypropylene morpholide and the preparation of acrylic copolymer:
The PVDF powder of final concentration of 150g/L is added in the potassium hydroxide solution of 10mol/L, and at above-mentioned aqueous slkali
In press 50mL/L add dehydrated alcohol, in 40 DEG C of waters bath with thermostatic control stirring reaction, the time is 20 minutes.Sucking filtration products therefrom is pure
After water purification washing, gained PVDF pulverulent solids product is put in 60 DEG C of baking ovens and is dried.
The PVDF powder that above-mentioned for 16g alkali processes is joined in the there-necked flask containing 120g NMP, is configured to homogeneous molten
Liquid, then, adds the DMAP of 1.6g, then by ACMO: AA: PVDF mol ratio is 1: 1: 3 addition ACMO monomer and AA monomer, at nitrogen
Under gas atmosphere protection, reacting at 100 DEG C, the time is 8 hours, and reacted solution precipitates in excessive methanol, sucking filtration, precipitation
Sucking filtration after thing distilled water flushing, puts into 60 DEG C of oven dryings, obtains Kynoar graft polypropylene morpholide and acrylic acid
Copolymer；
(2) preparation of spinning casting solution:
Kynoar 2%；Kynoar graft polypropylene morpholide and acrylic copolymer 18%；Ammonium chloride
10%；NMP70%, is more than mass percent.Above-mentioned raw materials is added in molten material still, at a temperature of 40 DEG C, agitated 3h
Dissolving, standing and defoaming 3h makes spinning casting solution.
(3) preparation of hollow-fibre membrane:
By the filtration of above-mentioned casting solution, deaeration, under 0.1MPa spinning pressure, extrude from spinning head with the speed of 20r/min；
Nascent doughnut after 40cm air bath, NMP percent by volume be 5%, temperature be the aqueous solution of 25 DEG C in solidify, with
The speed winding of 60m/min, soaks 48h at pure water the most successively and contains immersion in the aqueous solution that ethylene glycol volume fraction is 30%
48h, obtains PVDF-g-(PACMO-PAA) hollow-fibre membrane；
(4) doughnut film surface grafting L-arginine
First, with deionized water rinsing PVDF/PVDF-g-(PACMO-PAA) fibrous membrane surface, then purge film table with nitrogen
Face is to being dried；Then, film is immersed in (pH=4) in the MES buffer containing 0.08M EDC, stands 20min；Afterwards, directly
In above-mentioned buffer solution, add the NHS of EDC mass half, and slowly rock and make NHS be completely dissolved, and at 8 DEG C, activate 3h；
Finally, the film after activation is respectively placed in the borate buffer solution (pH=9.7) containing 25mg/mL L-arginine, and at 25 DEG C
Lower reaction 20h；By formed the PVDF hollow-fibre membrane pure water rinsing jointly modified by L-arginine and acryloyl morpholine with
Remove unreacted monomer and by-product, and soak more than two days in water, postlyophilization, standby.
The modified polyvinilidene fluoride hollow-fibre membrane pure water ultrafiltration permeation flux 250mL/m of gained2KPa h, Ox blood serum
Albumin rejection is 91.3%, and initial water contact angle value is 38.5 °, and flux recovery rate is 93.1%, and bovine serum albumin is inhaled
Attached amount is 55 μ g/cm2, the erythrocyte amount of sticking is 2.89 × 105, hemolysis rate is 3.05%, and blood plasma recalcification time is 277s, lives
Changing part zymogen time is 79s, and urea clearance rate is 82%, relative molecular mass 10000-20000 daltonian Middle molecule thing
Matter clearance rate is 73%, and proof pressure is 0.2MPa.
Claims (10)
1. the modified polyvinilidene fluoride hollow-fibre membrane for hemodialysis, it is characterised in that described hollow-fibre membrane system
Preparation Method is as follows: (1) prepares Kynoar graft polypropylene morpholide and acrylic acid copolymer；(2) by prepared copolymerization
Thing and polyvinylidene blending, add pore former and solvent mixing preparation spinning casting solution；(3) hollow is prepared by spinning casting solution
Fibrous membrane；(4) by prepared hollow-fibre membrane at surface grafting L-arginine.
A kind of modified polyvinilidene fluoride hollow-fibre membrane for hemodialysis, it is characterised in that
The preparation method of described step (1) Kynoar graft polypropylene morpholide and acrylic copolymer is: first will be through alkali
Process in the solvent that the Kynoar powder containing carbon-carbon double bond obtained joins 5-15 times of PVDF powder quality, preparation
Become Kynoar solution, then, add the initiator accounting for PVDF powder quality 1-10%, then press acryloylmorpholine monomer: third
Acrylic monomer: Kynoar mol ratio is 1: 1: 4-1: 1: 2 addition acryloylmorpholine monomer and acrylic monomerss, at indifferent gas
Under atmosphere protection, reacting at 50-100 DEG C, the time is 8-24 hour, and reacted solution precipitates in excessive methanol, sucking filtration, heavy
Sucking filtration after the thing distilled water flushing of shallow lake, puts into 60 DEG C of oven dryings, obtains Kynoar graft polypropylene morpholide and propylene
Acid copolymer；
Described alkali processes, particularly as follows: add final concentration of in 1-10mol/L sodium hydroxide or potassium hydroxide solution
The PVDF powder of 100g/L-180g/L, and press 10mL/L-50mL/L addition dehydrated alcohol, stir in 40-100 DEG C of water bath with thermostatic control
Mixing reaction, the time is 5-20 minute；After stirring sucking filtration and wash after, gained PVDF pulverulent solids product is put in 60 DEG C of baking ovens
It is dried.
A kind of modified polyvinilidene fluoride hollow-fibre membrane for hemodialysis, it is characterised in that
Described initiator is azodiisobutyronitrile, dimethylamino naphthyridine, 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide hydrochloride
At least one in salt.
A kind of modified polyvinilidene fluoride hollow-fibre membrane for hemodialysis, it is characterised in that
Preparing of described spinning casting solution is as follows: Kynoar graft polypropylene morpholide and acrylic copolymer with PVDF ratio are
1: 9-9: 1, the two accounts for spinning casting solution mass percent is 10%-20%, and pore former accounts for 5%-10%, and solvent accounts for 70%-
85%, above-mentioned substance is joined in there-necked flask, stirring 3-6 hour in 40-100 DEG C of water bath with thermostatic control, until completely dissolved
Stop stirring, standing and defoaming 3-5 hour, obtain spinning casting solution.
A kind of modified polyvinilidene fluoride hollow-fibre membrane for hemodialysis, it is characterised in that
At least one in polyvinylpyrrolidone, Polyethylene Glycol, lithium chloride, ammonia chloride of described pore former.
A kind of modified polyvinilidene fluoride hollow-fibre membrane for hemodialysis, it is characterised in that
The preparation method of described hollow-fibre membrane is as follows: by the spinning casting solution filtration of step (2) gained, deaeration, at 0.1-0.4MPa
Under spinning pressure, extrude from the spinning head of Φ 0.4-0.8mm with the speed of 5-20r/min；Nascent doughnut is empty through 5-40cm
After gas bath, solvent volume percentage ratio be 0%-30%, temperature be the aqueous solution of 25-50 DEG C in solidify, with 10-60m/min's
Speed winds, and sequentially passes through the pure water immersion of 24-72h afterwards and the hole agent volume fraction containing guarantor of 24-72h is the aqueous solution of 30%
Middle immersion, get product hollow-fibre membrane.
A kind of modified polyvinilidene fluoride hollow-fibre membrane for hemodialysis, it is characterised in that
Described guarantor hole agent is at least one in methanol, ethanol, ethylene glycol, glycerol.
A kind of modified polyvinilidene fluoride hollow-fibre membrane for hemodialysis, it is characterised in that
Concretely comprising the following steps of described doughnut film surface grafting L-arginine: first, by deionized water rinsing step (3) gained hollow
Fibrous membrane surface, then with nitrogen purging film surface to being dried；Then, film is immersed in the 2-(N-containing 0.02-0.10M EDC
Morpholine) in ethanesulfonic acid buffer, pH of buffer=4, stand 10-30min；Afterwards, state directly up in buffer solution and add
The N-hydroxysuccinimide of EDC mass half, and slowly rock and make NHS be completely dissolved, and at 2-10 DEG C, activate 1-5h；?
After, the film after activation is placed in the borate buffer solution containing 5mg/mL-30mg/mL L-arginine, pH of buffer=9.7, and
12-24h is reacted at 25 DEG C；The PVDF hollow-fibre membrane jointly modified by L-arginine and acryloyl morpholine that will be formed, uses
Pure water rinsing is to remove unreacted monomer and by-product, and soaks more than two days in water, postlyophilization, standby.
9. a kind of modified polyvinilidene fluoride doughnut for hemodialysis as described in claim 2,4,6 any one
Film, it is characterised in that described solvent is dimethyl sulfoxide, dimethylformamide, and dimethyl acetylamide, in N-Methyl pyrrolidone
At least one.
A kind of application of the modified polyvinilidene fluoride hollow-fibre membrane for hemodialysis.
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