CN105709613B - A kind of nano-fiber composite film and its preparation method and application effectively removing medium biomolecule - Google Patents

A kind of nano-fiber composite film and its preparation method and application effectively removing medium biomolecule Download PDF

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CN105709613B
CN105709613B CN201610049450.9A CN201610049450A CN105709613B CN 105709613 B CN105709613 B CN 105709613B CN 201610049450 A CN201610049450 A CN 201610049450A CN 105709613 B CN105709613 B CN 105709613B
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nano
fiber composite
composite film
biomolecule
membrane
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CN105709613A (en
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王雪芬
于旭峰
朱雅东
王敏
程诚
邓莉
华韦康
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Donghua 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
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • 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
    • 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
    • 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
    • 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
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • 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
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07K—PEPTIDES
    • C07K1/00—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length
    • C07K1/14—Extraction; Separation; Purification
    • C07K1/34—Extraction; Separation; Purification by filtration, ultrafiltration or reverse osmosis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/02—Hydrophilization
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/30—Cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/39—Electrospinning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/36—Hydrophilic membranes

Abstract

The present invention relates to a kind of nano-fiber composite film and its preparation method and application for effectively removing medium biomolecule, the nano-fiber composite film is double-layer structure: base is nanofiber basement membrane, and surface layer is surface-active separating layer.Preparation method includes: by polyacrylonitrile solution electrostatic spinning, and cold pressing obtains basement membrane；Basement membrane is immersed in the catalysis coagulating bath of catalysis surface cross linking reaction；Crosslinking agent is added in poly-vinyl alcohol solution, after precrosslink, membrane surface is coated in, obtains composite membrane；After surface layer complete cross-linking reaction after, composite membrane through deionized water impregnate to get.Nano-fiber composite film good hydrophilic property of the invention has high osmosis and even aperture distribution, can effectively remove to medium biomolecule while keeping high retention to large biological molecule protein.Nano-fiber composite film of the invention is applied to the fields such as haemodialysis, hemodiafiltration, blood filtering, Separation of Proteins, active biomolecule filtering.

Description

A kind of nano-fiber composite film and preparation method thereof effectively removing medium biomolecule And application
Technical field
The invention belongs to high molecular material composite membrane field, in particular to a kind of nanometer for effectively removing medium biomolecule Composite fiber membrane and its preparation method and application.
Background technique
Acute and chronic kidney trouble is one of the high mortality disease of the mankind in the world.With population in the world aging Development and diabetes, hypertensive patient's number are continuously increased, and the disease incidence of the disease also increases sharply in recent years.According to system Meter, there are about 3,010,000 people to suffer from end-stage renal disease (ESRD) in the whole world, and is just increased with every year about 6%~7% rate.Mesh Preceding research thinks that its pathogenesis is that the toxic solute i.e. uremic toxins that should largely remove by kidney are remained in internal. When the concentration of uremic toxins in blood is above standard range, toxic side effects just occur and cause acute and chronic kidney trouble.Base In the existing medical condition of the mankind, two kinds for the treatment of methods can extend patient's service life i.e. kidney organ's transplanting and dialysis treatment.Kidney transplant Postoperative patient's survival rate with higher, but its limitation for suffering from donor organ critical shortage.Therefore, most Patients with renal failure need dialysis treatment, haemodialysis also becomes for a kind of important clinical treatment renal disease patient Method.The principle of haemodialysis is exactly plain and extra by the convection current for fenestra of dialysing, diffusion, sieving actoion removing septicemia Moisture and prevent the necessary loss of proteins of the mankind, so that blood be made to be purified.
Due to during dialysis, effect depends on dialysis film properties, therefore the preparation of high performance hemodialysis membrane Become the critical issue for improving therapeutic quality, extending patient's service life with research.High-performance hemodialysis membrane should include (1) height Permeability；(2) high selection permeability；(3) good biocompatibility.Wherein: high osmosis ensure that over the course for the treatment of Dialytic efficiency；High selection permeability be require dialysis membrane remove as far as possible small-molecular-weight and intermediate molecular weight toxin it is same When, macromolecular benefit materials in human body can be retained to greatest extent；Good biocompatibility requirement hemodialysis membrane is not easy to inhale Attached protein is not easy blood coagulation etc., can carry out safely treating in this way and not generate new complication.
First generation hemodialysis membrane is the hemodialysis membrane prepared by cellulose and its derivates material in the prior art, Since its raw material is easy to get, cheap and small molecule removal rate can satisfy clinical requirement.But due to the spy of material itself Property and structure, with low-permeability, pure water ultrafiltration rate is 0.12~55.69mL/m2HmmHg is pure at 0.1Mpa Water flux is about 0.09~41.76L/m2·h[Kee C M,Idris A 2010Sep.Purif.Technol 75 102- 113], and molecular cut off about 2000Da, can hardly centering molecular weight toxins remove, therefore which limit its development prospects.
For the removal for improving dialysis permeability of the membrane and centering molecular weight toxins, more and more researchs were concentrated in recent years Synthesizing polymeric material and it is modified to prepare high flux hemodialysis film.Utilize the high flux hemodialysis with more large aperture Film removes middle molecule toxins.However the dialysis membrane of currently available technology preparation, mainly prepared by phase inversion one-pass molding Plate membrane or hollow-fibre membrane, one-pass molding make surface apertures finely regulating difficulty to which throughout curve is lower, it is difficult to simultaneous Caring for should have high retention to have high removing to intermediate molecular weight toxin simultaneously to protein macromolecule.In Publication No. CN In the Chinese invention patent of 101422706A, describe a kind of with the hydrophilic blending polyvinylidene fluoride hollow fiber membrane of improvement Preparation method, vinylidene fluoride film after modified is 80L/m in pure water flux2When h, bovine serum albumin rejection is 80%, when flux reaches 150L/m2When h, 72% is reduced to the rejection of bovine serum albumin.In Publication No. CN In the Chinese invention patent of 102961977A, a kind of preparation method of polylactic acid hollow fiber dialysis membrane is described, preparation gathers Lactic acid dialysis membrane pure water ultrafiltration rate about 100mL/m2HmmHg, that is, 75L/m2H is about 30% to middle-molecular-weihydroxyethyl removal rate, right Macro-molecular protein rejection is about 90%.After polyether sulfone dialysis membrane is by polyvinylpyrrolidone and acidification carbon nano-tube modification Flux by 7.14L/m2H is increased to 72.2L/m2H is also increased to 28.4% by 1.5% to the removal rate of middle-molecular-weihydroxyethyl, Simultaneously to the rejection of high molecular weight protein be about 90% [Irfan M, Idris A, Yusof N M, Khairuddin N F M, Akhmal H 2014J.Membr.Sci 467 73-84].The permeability of the Hemodialysis Membrane Material of prior art preparation, selection Permeability (especially low to the removal rate of intermediate molecular weight) still needs to be further increased, and needs to develop high throughput and to medium Biomolecule has the new and effective dialysis membrane specifically removed.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of nanofiber for effectively removing medium biomolecule is compound Film and its preparation method and application, dialysis membrane permeability is low in the prior art and is guaranteeing to retain macromolecular height for invention solution Centering molecular weight toxins removal rate low problem while rate.
A kind of nano-fiber composite film effectively removing medium biomolecule of the invention, the nano-fiber composite film are Double-layer structure: base is nanofiber basement membrane, and surface layer is surface-active separating layer.
The nanofiber basement membrane with a thickness of 20~50 μm, the surface-active separating layer of coating with a thickness of 300~ 900nm。
The nano-fiber composite film is 0.65~0.85 to the screening efficiency of medium biomolecule, and dialysis clearance rate is 45 ~50%.
The medium biomolecule is molecular weight between the parathyroid hormone of 6~60kDa, β2-microglobulin, leucocyte At least one of interleukin iL-1 β and Tumor necrosis factor TNF-R.
The molecular weight of the parathyroid hormone is 9.5kDa；The molecular weight of β2-microglobulin is 11.8kDa, leucocyte The molecular weight of interleukin iL-1 β is 17kDa；The molecular weight of Tumor necrosis factor TNF-R is between 6~60kDa.
A kind of preparation method of nano-fiber composite film effectively removing medium biomolecule of the invention, comprising:
(1) by polyacrylonitrile solution electrostatic spinning, nano fibrous membrane is obtained, is cold-pressed, obtains basement membrane；
(2) basement membrane in step (1) is immersed in the catalysis coagulating bath of catalysis surface cross linking reaction, prevents from being seeped under surface layer In basement membrane；
(3) crosslinking agent is added in poly-vinyl alcohol solution, after 15~30min of precrosslink, by the basement membrane in step (2) from It is catalyzed in coagulating bath and takes out and be coated in its surface, obtain the composite membrane with surface-active separating layer；
(4) composite membrane in step (3) is continued to complete into 3~15h of cross-linking reaction, deionized water is impregnated, and the double-deck knot is obtained The nano-fiber composite film for effectively removing medium biomolecule of structure；Screening system of the nano-fiber composite film to medium biomolecule Number is 0.65~0.85, and dialysis clearance rate is 45~50%.
Polyacrylonitrile weight average molecular weight is 100,000~150,000 in the step (1).
Polyacrylonitrile solution concentration is mass fraction 6~12%, solvent N, N- dimethyl formyl in the step (1) Amine.
The condition of electrostatic spinning in the step (1) are as follows: voltage is 16~24kV, and it is 15~20 μ L/ that solution, which promotes rate, Min, environment composition atmosphere be open wide or closed three-dimensional system (relative humidity therein regulates and controls 30~70%, temperature 20~50 DEG C), receiving distance is 15~30cm, receives 500~1000r/min of drum rotation speed.
The pressure being cold-pressed in the step (1) is 5~10Mpa, and the time is 30~90s.
Coagulating bath is the boric acid solution of 0.5~0.8M in the step (2).
Crosslinking agent is glutaraldehyde in the step (3)；Additional amount is the molar ratio of glutaraldehyde and polyvinyl alcohol repetitive unit It is 0.1~0.3.
Poly-vinyl alcohol solution concentration is mass fraction 1.0~2.5% in the step (3), and solvent is deionized water, poly- second Enol weight average molecular weight is 120,000~180,000.
It is applied in the step (3) and is coated by coating-reaction method.
Deionized water soaking time is 24~72h in the step (4)；Deionized water impregnates removal coagulating bath and unreacted Crosslinking agent.
The pure water contact angle of nano-fiber composite film is 55~65 ° in the step (4), and the pure water under 0.1Mpa pressure is logical Amount is 250~400L/m2H, the screening efficiency to small molecule are 0.95~0.99, and dialysis clearance rate is 80~90%, simultaneously It is 0.01~0.05 to macromolecular screening efficiency, dialysis rejection is 98.5~99.5%.The test method of these performance indicators Referring to document: 452 390-399 of Gao A, Liu F, Xue L 2014J.Membr.Sci.
The small molecule is urea；Macromolecular is proteins Bovine albumin.
The nano-fiber composite film for effectively removing medium biomolecule is applied to haemodialysis, haemodialysis is filtered Cross, blood filtering, Separation of Proteins, active biomolecule filtering etc. fields.
Polyacrylonitrile solution electrostatic spinning is obtained nano fibrous membrane and carries out cold pressing to it as composite membrane by the present invention Basement membrane；Above-mentioned basement membrane is immersed in the coagulating bath of catalysis surface cross linking reaction；Then crosslinking agent warp is added in poly-vinyl alcohol solution Membrane surface is coated in by coating-reaction method after precrosslink reaction；Finally above-mentioned composite membrane is completed to hand at room temperature Removal coagulating bath is impregnated through deionized water after connection reaction and unreacted crosslinking agent, the nanofiber for obtaining double-layer structure are compound Film.Nano-fiber composite film good hydrophilic property made from this method has high osmosis and even aperture distribution, to biological big point Sub- protein keeps to effectively remove medium biomolecule while high retention.
Beneficial effect
(1) nano-fiber composite film produced by the present invention shows high osmosis, the pure water flux under 0.1Mpa pressure For 250~400L/m2·h；
(2) pore-size distribution of nano-fiber composite film produced by the present invention traditional dialysis membrane one-time formed compared with the prior art It is relatively narrow, medium biomolecule can be effectively removed while keeping high retention to large biological molecule protein, small molecule is urinated The screening efficiency of element is 0.95~0.99, and dialysis clearance rate is 80~90%, the screening to medium biomolecule β2-microglobulin Coefficient is 0.65~0.85, and dialysis clearance rate is 45~50%, while being to high molecular weight protein bovine serum albumin screening efficiency 0.01~0.05, dialysis rejection is 98.5~99.5%；
(3) nano-fiber composite film produced by the present invention can be applied to haemodialysis, hemodiafiltration, blood filtering, The fields such as Separation of Proteins, active biomolecule filtering.
Detailed description of the invention
Fig. 1 is nano-fiber composite film profile scanning electron microscope in embodiment 2；
Fig. 2 is nano-fiber composite film surface scan electron microscope in embodiment 2.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Range.
Embodiment 1
(1) polyacrylonitrile that weight average molecular weight is 120,000 N,N-dimethylformamide 6h is dissolved at 50 DEG C to be configured to The homogeneous solution that mass fraction is 8%, electrostatic spinning voltage are 18kV, and it is 16 μ L/min, relative humidity that solution, which promotes rate, 40%, 35 DEG C of environment temperature, receiving distance is 20cm, receives drum rotation speed 800r/min, carries out electrostatic spinning, preparation to solution Polyacrylonitrile nanofiber film thickness out is 50 μm.
It (2) with pressure is at room temperature 5Mpa by the polyacrylonitrile nanofiber film prepared, the time is that 60s is cold-pressed As basement membrane, and immerse in the coagulating bath of the boric acid solution containing 0.8M of catalysis surface cross linking reaction.
(3) it is 160,000 polyvinyl alcohol by weight average molecular weight, is configured to the aqueous solution that solution concentration is mass fraction 2%, Glutaraldehyde is added and carries out precrosslink reaction, the ratio of glutaraldehyde and polyvinyl alcohol repetitive unit is 0.2, and the precrosslink reaction time is 18min is coated in membrane surface, obtains composite membrane, nano-fiber composite film continues to complete cross-linking reaction in room temperature after precrosslink Time is 6h, and deionized water impregnates 48h, removes coagulating bath and unreacted crosslinking agent.
(4) nano-fiber composite film obtained pure water permeation flux, screening efficiency and dialysis performance is carried out to assess.Specifically Operating condition is as follows: pure water flux is calculated after 30min precompressed under 0.1Mpa pressure.Screening efficiency is compound by calculating Film calculates the rejection of solute under 0.1Mpa pressure, and solution concentration is respectively as follows: the β 2- of 1.5mg/mL urea, 0.4mg/mL The bovine serum albumin of microglobulin and 1.0mg/mL.Dialysis-effect passes through the removing or retention of composite membrane solute after the 4h that dialyses Rate show that simulated solution is the bovine serum albumen solution of 1.5mg/mL urea, the β2-microglobulin of 0.4mg/mL and 1.0mg/mL, Dialyzate is deionized water, and simulation flow velocity is 200mL/min, dialysate flow rate 500mL/min.
Pure water flux of the nano fibrous membrane under 0.1Mpa pressure is 360L/m2H, to the screening system of small molecule urea Number is 0.98, and dialysis clearance rate is 88%, and the screening efficiency to medium biomolecule β2-microglobulin is 0.8, clearance rate of dialysing It is 48%, while is 0.05 to high molecular weight protein bovine serum albumin screening efficiency, dialysis rejection is 98.6%.
Embodiment 2
(1) polyacrylonitrile that weight average molecular weight is 120,000 N,N-dimethylformamide 6h is dissolved at 50 DEG C to be configured to The homogeneous solution that mass fraction is 8%, electrostatic spinning voltage are 18kV, and it is 16 μ L/min, relative humidity that solution, which promotes rate, 40%, 35 DEG C of environment temperature, receiving distance is 20cm, receives drum rotation speed 800r/min, carries out electrostatic spinning, preparation to solution Polyacrylonitrile nanofiber film thickness out is 50 μm.
It (2) with pressure is at room temperature 5Mpa by the polyacrylonitrile nanofiber film prepared, the time is that 60s is cold-pressed As basement membrane, and immerse in the coagulating bath of the boric acid solution containing 0.8M of catalysis surface cross linking reaction.
(3) it is 160,000 polyvinyl alcohol by weight average molecular weight, is configured to the aqueous solution that solution concentration is mass fraction 2%, Glutaraldehyde is added and carries out precrosslink reaction, the ratio of glutaraldehyde and polyvinyl alcohol repetitive unit is 0.25, and the precrosslink reaction time is 18min is coated in membrane surface, obtains composite membrane, nano-fiber composite film continues to complete cross-linking reaction in room temperature after precrosslink Time is 6h, and deionized water impregnates 48h, removes coagulating bath and unreacted crosslinking agent.The cross-section morphology of nano-fiber composite film See Fig. 1；Surface topography is shown in Fig. 2.
(4) nano-fiber composite film obtained pure water permeation flux, screening efficiency and dialysis performance is carried out to assess.Specifically Operating condition is as follows: pure water flux is calculated after 30min precompressed under 0.1Mpa pressure.Screening efficiency is compound by calculating Film calculates the rejection of solute under 0.1Mpa pressure, and solution concentration is respectively as follows: the β 2- of 1.5mg/mL urea, 0.4mg/mL The bovine serum albumin of microglobulin and 1.0mg/mL.Dialysis-effect passes through the removing or retention of composite membrane solute after the 4h that dialyses Rate show that simulated solution is the bovine serum albumen solution of 1.5mg/mL urea, the β2-microglobulin of 0.4mg/mL and 1.0mg/mL, Dialyzate is deionized water, and simulation flow velocity is 200mL/min, dialysate flow rate 500mL/min.
Pure water flux of the nano fibrous membrane under 0.1Mpa pressure is 290L/m2H, to the screening system of small molecule urea Number is 0.96, and dialysis clearance rate is 83%, and the screening efficiency to medium biomolecule β2-microglobulin is 0.75, and dialysis is removed Rate is 46%, while being 0.04 to high molecular weight protein bovine serum albumin screening efficiency, and dialysis rejection is 98.8%.
Embodiment 3
(1) polyacrylonitrile that weight average molecular weight is 120,000 N,N-dimethylformamide 6h is dissolved at 50 DEG C to be configured to The homogeneous solution that mass fraction is 8%, electrostatic spinning voltage are 18kV, and it is 16 μ L/min, relative humidity that solution, which promotes rate, 40%, 35 DEG C of environment temperature, receiving distance is 20cm, receives drum rotation speed 800r/min, carries out electrostatic spinning, preparation to solution Polyacrylonitrile nanofiber film thickness out is 50 μm.
It (2) with pressure is at room temperature 5Mpa by the polyacrylonitrile nanofiber film prepared, the time is that 60s is cold-pressed As basement membrane, and immerse in the coagulating bath of the boric acid solution containing 0.8M of catalysis surface cross linking reaction.
(3) it is 160,000 polyvinyl alcohol by weight average molecular weight, is configured to the aqueous solution that solution concentration is mass fraction 2%, Glutaraldehyde is added and carries out precrosslink reaction, the ratio of glutaraldehyde and polyvinyl alcohol repetitive unit is 0.3, and the precrosslink reaction time is It is coated in membrane surface after 18min precrosslink, obtains composite membrane, nano-fiber composite film is when room temperature continues to complete cross-linking reaction Between be 6h, deionized water impregnates 48h, removes coagulating bath and unreacted crosslinking agent.
(4) nano-fiber composite film obtained pure water permeation flux, screening efficiency and dialysis performance is carried out to assess.Specifically Operating condition is as follows: pure water flux is calculated after 30min precompressed under 0.1Mpa pressure.Screening efficiency is compound by calculating Film calculates the rejection of solute under 0.1Mpa pressure, and solution concentration is respectively as follows: the β 2- of 1.5mg/mL urea, 0.4mg/mL The bovine serum albumin of microglobulin and 1.0mg/mL.Dialysis-effect passes through the removing or retention of composite membrane solute after the 4h that dialyses Rate show that simulated solution is the bovine serum albumen solution of 1.5mg/mL urea, the β2-microglobulin of 0.4mg/mL and 1.0mg/mL, Dialyzate is deionized water, and simulation flow velocity is 200mL/min, dialysate flow rate 500mL/min.
Pure water flux of the nano fibrous membrane under 0.1Mpa pressure is 265L/m2H, to the screening system of small molecule urea Number is 0.95, and dialysis clearance rate is 81%, and the screening efficiency to medium biomolecule β2-microglobulin is 0.70, and dialysis is removed Rate is 46%, while being 0.02 to high molecular weight protein bovine serum albumin screening efficiency, and dialysis rejection is 99.3%.
Embodiment 4
(1) polyacrylonitrile that weight average molecular weight is 120,000 N,N-dimethylformamide 6h is dissolved at 50 DEG C to be configured to The homogeneous solution that mass fraction is 8%, electrostatic spinning voltage are 18kV, and it is 16 μ L/min, relative humidity that solution, which promotes rate, 40%, 35 DEG C of environment temperature, receiving distance is 20cm, receives drum rotation speed 800r/min, carries out electrostatic spinning, preparation to solution Polyacrylonitrile nanofiber film thickness out is 50 μm.
It (2) with pressure is at room temperature 5Mpa by the polyacrylonitrile nanofiber film prepared, the time is that 60s is cold-pressed As basement membrane, and immerse in the coagulating bath of the boric acid solution containing 0.8M of catalysis surface cross linking reaction.
It (3) is 160,000 polyvinyl alcohol by weight average molecular weight, being configured to solution concentration is the water-soluble of mass fraction 2.5% The ratio of liquid, addition glutaraldehyde progress precrosslink reaction, glutaraldehyde and polyvinyl alcohol repetitive unit is 0.2, the precrosslink reaction time To be coated in membrane surface after 18min precrosslink, composite membrane is obtained, nano-fiber composite film continues to complete cross-linking reaction in room temperature Time is 6h, and deionized water impregnates 48h, removes coagulating bath and unreacted crosslinking agent.
(4) nano-fiber composite film obtained pure water permeation flux, screening efficiency and dialysis performance is carried out to assess.Specifically Operating condition is as follows: pure water flux is calculated after 30min precompressed under 0.1Mpa pressure.Screening efficiency is compound by calculating Film calculates the rejection of solute under 0.1Mpa pressure, and solution concentration is respectively as follows: the β 2- of 1.5mg/mL urea, 0.4mg/mL The bovine serum albumin of microglobulin and 1.0mg/mL.Dialysis-effect passes through the removing or retention of composite membrane solute after the 4h that dialyses Rate show that simulated solution is the bovine serum albumen solution of 1.5mg/mL urea, the β2-microglobulin of 0.4mg/mL and 1.0mg/mL, Dialyzate is deionized water, and simulation flow velocity is 200mL/min, dialysate flow rate 500mL/min.
Pure water flux of the nano fibrous membrane under 0.1Mpa pressure is 320L/m2H, to the screening system of small molecule urea Number is 0.97, and dialysis clearance rate is 86%, and the screening efficiency to medium biomolecule β2-microglobulin is 0.78, and dialysis is removed Rate is 47%, while being 0.04 to high molecular weight protein bovine serum albumin screening efficiency, and dialysis rejection is 98.7%.
Embodiment 5
(1) polyacrylonitrile that weight average molecular weight is 120,000 N,N-dimethylformamide 6h is dissolved at 50 DEG C to be configured to The homogeneous solution that mass fraction is 8%, electrostatic spinning voltage are 18kV, and it is 16 μ L/min, relative humidity that solution, which promotes rate, 40%, 35 DEG C of environment temperature, receiving distance is 20cm, receives drum rotation speed 800r/min, carries out electrostatic spinning, preparation to solution Polyacrylonitrile nanofiber film thickness out is 50 μm.
It (2) with pressure is at room temperature 5Mpa by the polyacrylonitrile nanofiber film prepared, the time is that 60s is cold-pressed As basement membrane, and immerse in the coagulating bath of the boric acid solution containing 0.8M of catalysis surface cross linking reaction.
It (3) is 160,000 polyvinyl alcohol by weight average molecular weight, being configured to solution concentration is the water-soluble of mass fraction 2.5% The ratio of liquid, addition glutaraldehyde progress precrosslink reaction, glutaraldehyde and polyvinyl alcohol repetitive unit is 0.3, the precrosslink reaction time To be coated in membrane surface after 18min precrosslink, composite membrane is obtained, nano-fiber composite film continues to complete cross-linking reaction in room temperature Time is 6h, and deionized water impregnates 48h, removes coagulating bath and unreacted crosslinking agent.
(4) nano-fiber composite film obtained pure water permeation flux, screening efficiency and dialysis performance is carried out to assess.Specifically Operating condition is as follows: pure water flux is calculated after 30min precompressed under 0.1Mpa pressure.Screening efficiency is compound by calculating Film calculates the rejection of solute under 0.1Mpa pressure, and solution concentration is respectively as follows: the β 2- of 1.5mg/mL urea, 0.4mg/mL The bovine serum albumin of microglobulin and 1.0mg/mL.Dialysis-effect passes through the removing or retention of composite membrane solute after the 4h that dialyses Rate show that simulated solution is the bovine serum albumen solution of 1.5mg/mL urea, the β2-microglobulin of 0.4mg/mL and 1.0mg/mL, Dialyzate is deionized water, and simulation flow velocity is 200mL/min, dialysate flow rate 500mL/min.
Pure water flux of the nano fibrous membrane under 0.1Mpa pressure is 250L/m2H, to the screening system of small molecule urea Number is 0.95, and dialysis clearance rate is 80%, and the screening efficiency to medium biomolecule β2-microglobulin is 0.68, and dialysis is removed Rate is 45%, while being 0.01 to high molecular weight protein bovine serum albumin screening efficiency, and dialysis rejection is 99.4%.

Claims (9)

1. a kind of nano-fiber composite film for effectively removing medium biomolecule, which is characterized in that the nano-fiber composite film For double-layer structure: base is nanofiber basement membrane, and surface layer is surface-active separating layer；Preparation method includes: that polyacrylonitrile is molten Liquid electrostatic spinning obtains nano fibrous membrane and carries out being cold-pressed the basement membrane as composite membrane to it；Above-mentioned basement membrane is immersed into catalysis surface layer In the coagulating bath of cross-linking reaction；Then crosslinking agent is added in poly-vinyl alcohol solution and passes through coating-reaction after precrosslink is reacted Method is coated in membrane surface；It finally completes after cross-linking reaction the above-mentioned composite membrane to impregnate removal through deionized water at room temperature solidifying Gu bath and unreacted crosslinking agent, obtain the nano-fiber composite film of double-layer structure；Wherein, the condition of electrostatic spinning are as follows: voltage For 16~24kV, it is 15~20 μ L/min that solution, which promotes rate, and envionmental humidity is 30~70%, 20~50 DEG C of temperature, is connect Receiving distance is 15~30cm, receives 500~1000r/min of drum rotation speed；The pressure of cold pressing be 5~10Mpa, the time be 30~ 90s。
2. a kind of nano-fiber composite film for effectively removing medium biomolecule according to claim 1, which is characterized in that The nanofiber basement membrane with a thickness of 20~50 μm, the surface-active separating layer of coating is with a thickness of 300~900nm.
3. a kind of nano-fiber composite film for effectively removing medium biomolecule according to claim 1, which is characterized in that The medium biomolecule is molecular weight between the parathyroid hormone of 6~60kDa, β2-microglobulin, interleukins iL-1 At least one of β and Tumor necrosis factor TNF-R.
4. a kind of preparation method for the nano-fiber composite film for effectively removing medium biomolecule, comprising:
(1) by polyacrylonitrile solution electrostatic spinning, nano fibrous membrane is obtained, is cold-pressed, obtains basement membrane；Wherein, the item of electrostatic spinning Part are as follows: voltage is 16~24kV, and it is 15~20 μ L/min that solution, which promotes rate, and envionmental humidity is 30~70%, temperature 20 ~50 DEG C, receiving distance is 15~30cm, receives 500~1000r/min of drum rotation speed；The pressure of cold pressing is 5~10Mpa, when Between be 30~90s；
(2) basement membrane in step (1) is immersed in the catalysis coagulating bath of catalysis surface cross linking reaction, prevents from being seeped into basement membrane under surface layer In；
(3) crosslinking agent is added in poly-vinyl alcohol solution, after 15~30min of precrosslink, by the basement membrane in step (2) from catalysis Its surface is taken out and be coated in coagulating bath, obtains the composite membrane with surface-active separating layer；
(4) composite membrane in step (3) is continued into 3~15h of cross-linking reaction, deionized water is impregnated, and the effective of double-layer structure is obtained Remove the nano-fiber composite film of medium biomolecule；Nano-fiber composite film is 0.65 to the screening efficiency of medium biomolecule ~0.85, dialysis clearance rate is 45~50%.
5. a kind of preparation method of nano-fiber composite film for effectively removing medium biomolecule according to claim 4, It is characterized in that, polyacrylonitrile solution concentration is mass fraction 6~12%, solvent N, N- dimethyl methyl in the step (1) Amide.
6. a kind of preparation method of nano-fiber composite film for effectively removing medium biomolecule according to claim 4, It is characterized in that, coagulating bath is the boric acid solution of 0.5~0.8M in the step (2).
7. a kind of preparation method of nano-fiber composite film for effectively removing medium biomolecule according to claim 4, It is characterized in that, poly-vinyl alcohol solution concentration is mass fraction 1.0~2.5% in the step (3), solvent is deionized water； Crosslinking agent is glutaraldehyde, and the molar ratio of glutaraldehyde and polyvinyl alcohol repetitive unit is 0.1~0.3.
8. a kind of preparation method of nano-fiber composite film for effectively removing medium biomolecule according to claim 4, It is characterized in that, the pure water contact angle of nano-fiber composite film is 55~65 ° in the step (4), it is pure under 0.1Mpa pressure Water flux is 250~400L/m2H, the screening efficiency to small molecule are 0.95~0.99, and dialysis clearance rate is 80~90%, It is simultaneously 0.01~0.05 to macromolecular screening efficiency, dialysis rejection is 98.5~99.5%.
9. one kind effectively removes the application of the nano-fiber composite film of medium biomolecule, feature as described in claim 1 It is, is applied to haemodialysis, hemodiafiltration, blood filtering, Separation of Proteins or active biomolecule filtration art.
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