CN106943898B - A kind of surface can be sustained the preparation method of anticoagulant polysulfones hemodialysis membrane - Google Patents
A kind of surface can be sustained the preparation method of anticoagulant polysulfones hemodialysis membrane Download PDFInfo
- Publication number
- CN106943898B CN106943898B CN201710222393.4A CN201710222393A CN106943898B CN 106943898 B CN106943898 B CN 106943898B CN 201710222393 A CN201710222393 A CN 201710222393A CN 106943898 B CN106943898 B CN 106943898B
- Authority
- CN
- China
- Prior art keywords
- polysulfones
- hemodialysis
- solution
- anticoagulant
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- 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
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- 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
- 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
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- External Artificial Organs (AREA)
- Medicinal Preparation (AREA)
Abstract
The present invention provides the preparation methods that a kind of surface can be sustained anticoagulant polysulfones hemodialysis membrane, it is fixed glycidyl methacrylate (GMA) in polysulfones hemodialysis film surface first with Raolical polymerizable, construct epoxy group transition zone, again based on this, it is reacted by glycidol ether and cladding powder is grafted to polysulfones (PSf) micropore film surface, cladding powder can coat anti-coagulants, so that preparation can be sustained anticoagulant polysulfones hemodialysis membrane.The hydrophily that prepared surface can be sustained anticoagulant polysulfones hemodialysis membrane significantly improves, blood reduces through resistance.Meanwhile the anticoagulant stability and slow release, the side effect for reducing haemodialysis of polysulfones hemodialysis film are further increased, for the exploitation and application of polysulfones hemodialysis membrane, with high value.
Description
Technical field
The invention belongs to biological medical polymer material and hemodialysis technology field, be related to a kind of surface can be sustained it is anticoagulant
The preparation method of polysulfones hemodialysis membrane.
Background technique
Haemodialysis is by blood samples of patients and dialyzate while to introduce dialysis machine according to Gibbs-Donman membrane equilibrium principle
It is interior, when they flow separately through dialysis membrane two sides, cross-film movement is made by the solute and water of dialysis membrane and carries out mass exchange,
Some of them harmful substance is removed using mechanism such as disperse, convection current, ultrafiltration, absorption, purifies blood, reaches the mesh for the treatment of disease
, its mostly important and mature application is in the treatment of renal failure (renal failure) patient.Due to adding for mankind's aging
Weight, diabetes and hypertensive patient increase, and Chronic Renal Failure Patients number is in rising trend, and the demand to haemodialyser is continuous
Increase.In hemodialysis system, the core element for playing centrifugation is the hemodialysis membrane (abbreviation directly contacted with blood
Hemodialysis film), hemodialysis permeability of the membrane can decide the effect for the treatment of with surface property, also determine the space of Future Development.
First generation hemodialysis film is cuprophan membrane, and cuprophan membrane is a kind of regenerated cellulose, the property and cellulose family on surface seemingly,
Due to the hydroxyl of high-content, with very strong polarity and good wetability, and due to the presence of surface great amount of hydroxy group, cuprophan membrane
Internal complement system can be activated and generate other physiological reactions, such as oligoleukocythemia, this poses be modified to cellulose
Requirement.In order to improve the blood compatibility of cellulose membrane, needs to replace the hydroxyl of part, mainly there are following three kinds of sides
Method: acetylation, lignocaine and phenylating.Cellulose acetate film is that the product after acetylation is carried out to cellulose, due to hydroxyl
The hydrophobicity of the reduction of base, film surface increases, this makes it that can adsorb more plasma proteins in dialysis procedure.Acetate fiber
Plain film is unsymmetric structure, has broader pore-size distribution, and it is certain that this has molecular weight also greater than the molecule of 5000 Da
Permeability.The dialysis membrane being prepared after cellulose is etherified with diethyl ethylene diamine is called hemophan membrane.Hemophan membrane has
More good blood compatibility will not induce the activation of complement system, while lignocaine makes surface still and has centainly
Hydrophily, reduce the absorption of plasma protein.The method that others improve cellulose membrane surface biocompatible is included in table
Face coats PEG or vitamin E (VE) etc..Especially film surface passes through VEAfter coating, blood monocytes and granulocyte
Activation and migration are greatly inhibited.
Due to the rapid development of polymer science, diversified macromolecule member material is developed and is used to produce,
The various aspects of life.For cellulose or modified cellulosic materials, the type and structure of high molecular material are synthesized
More, processing is more convenient, and is easy to obtain required property by modification.Polyacrylonitrile is the first for dialysis membrane
High molecular material is synthesized, but the film being prepared by its homopolymer usually has big pore structure.Polymethyl methacrylate
Dialysis membrane most began to use early in 1977, due to its high-throughput property, was also applied to blood filtration, hemodiafiltration etc.
On new treatment.The film is much larger than cellulose membrane to the through-rate of intermediate molecular weight and water, maintains fine to albumin
Interception capacity.During dialysis, β2-microglobulin can be removed partially by vacuum distillation by the effect of absorption.Currently, poly- first
Base methyl acrylate dialysis membrane is mainly that Toray is generated and applied.Polyether sulphone is that a kind of main chain contains aromatic ring, sulfuryl
With the high performance engineering plastics of aryl oxide key etc., there is extraordinary thermally and chemically stability, can be penetrated by steam, β or γ
Line disinfection, and apparent variation is not generated to the chemical structure on surface.Meanwhile this kind of material has certain blood compatibility,
It is not easy to cause complement system activation, it is also less to the excitation of leucocyte.Polyether sulphone has stronger hydrophobicity, with polyethylene pyrrole
The blending of pyrrolidone is the general method of modifying of polyether sulphone dialysis membrane production, such as Gambro, Fresenius and Membrana public affairs
Take charge of the polysulfones or polyether sulfone dialysis membrane of production.Unlike above-mentioned synthesis high molecular material, ethylene-vinyl alcohol copolymer
It is a kind of with fine hydrophilic polymer, so the blood compatibility that its dialysis membrane has been shown.
Current hemodialysis membrane material is mainly petroleum based polyalcohol, and there are poor biocompatibilities, easy blood coagulation and at high cost
The problems such as.Polysulfones (PSf) is to contain alkyl-SO in molecular backbone2The thermoplastic resin of chain link, have abrasion-resistant, high temperature resistant,
The advantages that mechanical strength is big.PSf has preferable biocompatibility relative to other membrane materials, therefore is widely used in haemodialysis
The preparation of membrane material.However, polysulfones (PSf) microporous barrier is hydrophobic material, surface is easy the blood such as adsorbed proteins, blood platelet
Ingredient is starched, the formation of thrombus is eventually led to.How PSf dialysis film surface blood compatibility is improved, which solves.
Summary of the invention
Goal of the invention: in order to overcome the above deficiency, the present invention, which provides a kind of surface, can be sustained anticoagulant polysulfones hemodialysis membrane
Preparation method.
Technical solution: in order to overcome the deficiencies in the prior art, the present invention provides a kind of surface can be sustained it is anticoagulant
The preparation method of polysulfones hemodialysis membrane, comprising the following steps:
Step (1): dried polysulfones (PSf) particle and polyethylene glycol oxide (PEO) 3:1 in mass ratio are dissolved in
In N-Methyl pyrrolidone (NMP), casting solution is obtained；Then casting solution is cast to glass plate surface, with scraper knifing, shape
At preformed film sample；Preformed film sample is immersed in room temperature water bath again, solidification obtains polysulfones (PSf) microporous barrier；
Step (2): will be based on mass component, 5.5-7.5 parts of vinyltriethoxysilane (VTES), 7.5-9.5 parts of N-
Vinyl pyrrolidone (NVP) and 4.1-6.1 parts of glycidyl methacrylate (GMA) are added continuously to 200 parts of tricresyl phosphates
In ethyl ester (TEP), it is stirred at room temperature 0.5 hour；Reaction temperature is then quickly ramped up to 80 DEG C, 0.16-0.36 parts of initiators are added
Initiation reaction obtains P (VP-VTES-GMA)/TEP solution；P (the VP-VTES-GMA)/TEP solution is diluted with isometric water
And after stirring, polysulfones obtained in step (1) (PSf) microporous barrier is added and impregnates 0.5-1.5h, and the citric acid at 50-90 DEG C
8-14h is reacted in solution, obtains the polysulfones hemodialysis film of surface epoxy group modification；
Step (3): will be based on mass component, 0.1-0.3 parts of cladding powders are dissolved in NaOH solution, are adjusted with hydrochloric acid anti-
System PH to 12 is answered, reaction 10-14 hours is stirred at room temperature；It is slow added into epoxy group modification in surface obtained in step (2)
Polysulfones hemodialysis film, reacted 0.5-2 hours under the conditions of 30-80 DEG C, obtain surface-coated powder modification polysulfones hemodialysis film；
Step (4): the surface-coated powder modification polysulfones hemodialysis film that step (3) obtains is immersed in anti-coagulants solution,
Oscillation treatment 8-12 hours under the conditions of 37 DEG C, anticoagulant polysulfones hemodialysis membrane can be sustained by obtaining the surface.
Surface of the present invention can be sustained the preparation method of anticoagulant polysulfones hemodialysis membrane, first with free radical polymerization
Reaction is fixed glycidyl methacrylate (GMA) in polysulfones hemodialysis film surface, building epoxy group transition zone, then as
Basis is reacted by glycidol ether cladding powder being grafted to polysulfones (PSf) micropore film surface, and cladding powder can coat anti-
Solidifying agent, so that preparation can be sustained anticoagulant polysulfones hemodialysis membrane.Prepared surface can be sustained anticoagulant polysulfones hemodialysis membrane
Hydrophily significantly improves, blood reduces through resistance.Meanwhile further increasing the anticoagulant stability and sustained release of polysulfones hemodialysis film
Property, the side effect that reduces haemodialysis there is high value for the exploitation and application of polysulfones hemodialysis membrane.
Further, above-mentioned surface can be sustained the preparation method of anticoagulant polysulfones hemodialysis membrane, and the step (1) obtains
The shape of polysulfones microporous barrier is plate membrane or hollow-fibre membrane.PS membrane can be selected according to different, and adaptability is good.
Further, above-mentioned surface can be sustained the preparation method of anticoagulant polysulfones hemodialysis membrane, the anti-coagulants solution
By based on mass component, 1-2 parts of anti-coagulants are dissolved in 40-60 parts of physiological saline and are prepared.Anti-coagulants is in physiological saline
(NaCl, 0.9 wt.%) keeps good bioactivity.
Further, above-mentioned surface can be sustained the preparation method of anticoagulant polysulfones hemodialysis membrane, and the anti-coagulants is water
The one or both mixture of leech element, heparin.The anti-coagulants is the mixture of hirudin, heparin or both, anticoagulant effect
It is good.
Further, above-mentioned surface can be sustained the preparation method of anticoagulant polysulfones hemodialysis membrane, and the hirudin is logical
It crosses and Hementaria officianalis element ontology is centrifuged to extraction under 2000-4000rpm revolving speed.Hirudin source is wide, easy to use.
Further, above-mentioned surface can be sustained the preparation method of anticoagulant polysulfones hemodialysis membrane, and the initiator is even
Nitrogen bis-isobutyronitrile (AIBN).Azodiisobutyronitrile is oil-soluble azo initiator, and it is first order reaction that initiator for reaction, which is stablized,
There is no side reaction, and reacts easily controllable.
Further, above-mentioned surface can be sustained the preparation method of anticoagulant polysulfones hemodialysis membrane, and the cladding powder is
Beta-cyclodextrin powder.Prepared beta-cyclodextrin PS membrane has excellent cladding characteristic, and cladding host molecule is beta-cyclodextrin,
Guest molecule is hirudin, heparin or both mixture.By interaction of hydrogen bond, beta-cyclodextrin can coat hirudin, liver
Element or both mixture, so that preparation can be sustained anticoagulant polysulfones hemodialysis membrane.By interaction of hydrogen bond, by hirudin, liver
Element or both blend is embedded in beta-cyclodextrin Cage molecules inner cavity, with improve hirudin or heparin molecule anticoagulant stability and
Slow release, so that preparation can be sustained anticoagulant polysulfones hemodialysis membrane.
Further, above-mentioned surface can be sustained the preparation method of anticoagulant polysulfones hemodialysis membrane, and the initiator causes
Reaction stirring under the conditions of nitrogen protection carries out reaction 18-24 hours.Reaction safety is high under the conditions of nitrogen protection.
Further, above-mentioned surface can be sustained the preparation method of anticoagulant polysulfones hemodialysis membrane, and the NaOH solution is
20% NaOH solution；The concentration of the citric acid solution is 1 wt.%.Beta-cyclodextrin powder uniform dissolution is molten in 20%NaOH
In liquid, it can prevent beta-cyclodextrin powder from reuniting in polysulfones film surface, guarantee the uniform packet of film surface hirudin or heparin molecule
It covers and slow release effect.
Further, above-mentioned surface can be sustained the preparation method of anticoagulant polysulfones hemodialysis membrane, the polysulfones particle and
For polyethylene glycol oxide by being dried, drying temperature is 40-100 DEG C, and drying time is 1-24 hours.It can subtract after drying process
Few influence of the traces of moisture to film forming defect guarantees that the surface of preparation can be sustained anticoagulant polysulfones hemodialysis membrane quality.
The utility model has the advantages that compared with prior art, the invention has the following advantages that the present invention utilizes Subjective and Objective molecule phase interaction
With anticoagulant coating can be sustained by preparing.First with Raolical polymerizable in polysulfones micropore film surface fixed ring oxygen groups；It is logical
Glycidol ether reaction is crossed by grafted by beta cyclodextrin to polysulfones micropore film surface.The PS membrane of prepared beta-cyclodextrin modified,
By interaction of hydrogen bond, hirudin, heparin or both mixture are embedded in beta-cyclodextrin Cage molecules inner cavity, to improve water
The anticoagulant stability and slow release of leech element or heparin molecule.Prepared surface can be sustained the hydrophilic of anticoagulant polysulfones hemodialysis membrane
Property significantly improve, blood through resistance reduce.Meanwhile it further increasing the anticoagulant stability of polysulfones hemodialysis film and slow release, subtracting
The side effect of few haemodialysis has high value for the exploitation and application of polysulfones hemodialysis membrane.
Specific embodiment
Below will be by several specific embodiments, the present invention is furture elucidated, these embodiments simply to illustrate that problem,
It is not a kind of limitation.
Embodiment 1:
18 grams of polysulfones (PSf) particles of drying process (drying temperature is 60 DEG C, and drying time is 8 hours), 6 grams are gathered
Ethylene oxide (PEO) is dissolved in 76 milliliters of N-Methyl pyrrolidones (NMP), is obtained casting solution, is then cast to casting solution
Glass plate surface, with scraper knifing.Finally preformed film sample is immersed in room temperature water bath, solidification obtains polysulfones
(PSf) microporous barrier；It is molten that VTES (5.5 grams), NVP (7.5 grams) and GMA (4.1 grams) are added continuously to 200 grams of TEP
In agent, it is stirred at room temperature 0.5 hour.Reaction temperature is then quickly ramped up to 80 DEG C, is then dissolved in 0.16 gram of AIBN above-mentioned molten
In liquid.The reaction of completion in 20 hours is stirred under the conditions of nitrogen protection, finally obtains P (VP-VTES-GMA)/TEP solution.By vacuum
It is molten that polysulfones (PSf) microporous barrier after drying is immersed in above-mentioned P (VP-VTES-GMA)/TEP after being diluted and stirred with isometric water
1 hour in liquid, and 10h is reacted in the citric acid solution at 70 DEG C, prepares the polysulfones film surface of epoxy group modification；It will
0.1 gram of beta-cyclodextrin powder is dissolved in 40 milliliter of 20% NaOH solution, and reaction 12 hours is stirred at room temperature.Later by the table of preparation
The polysulfones hemodialysis film (mm of 100 mm × 100) of face ring oxygen groups modification is slowly put into above-mentioned solution, is at the uniform velocity vibrated, and adjust
PH to 12 reacts 1 hour under the conditions of 50 DEG C.At the end of reaction is fast, PH=7.2 are adjusted with PBS buffer solution, sample mould is soaked
It steeps in distilled water 18 hours, obtains the polysulfones hemodialysis film of surface beta-cyclodextrin modified；2.0g Hementaria officianalis element bulk powder is molten
Solution is in 40 milliliters of physiological saline, and then under 2000rpm revolving speed, centrifugation 10min prepares hirudin solution.It takes respectively above-mentioned
20 milliliters of centrifugate, surface beta-cyclodextrin modified polysulfones hemodialysis film (mm of 50 mm × 50) is dissolved in above-mentioned hirudin solution
In, the oscillation treatment 10 hours under the conditions of 37 DEG C, hirudin anticoagulant polysulfones hemodialysis membrane can be sustained by finally obtaining surface.
Embodiment 2:
By 18 grams of polysulfones (PSf) particles of drying process (drying temperature is 100 DEG C, and drying time is 1 hour), 6 grams
Polyethylene glycol oxide (PEO) is dissolved in 76 milliliters of N-Methyl pyrrolidones (NMP), obtains casting solution, then casting solution is cast
To glass plate surface, with scraper knifing.Finally preformed film sample is immersed in room temperature water bath, solidification obtains polysulfones
(PSf) microporous barrier；It is molten that VTES (6.5 grams), NVP (8.5 grams) and GMA (5.1 grams) are added continuously to 200 grams of TEP
In agent, it is stirred at room temperature 0.5 hour.Reaction temperature is then quickly ramped up to 80 DEG C, is then dissolved in 0.26 gram of AIBN above-mentioned molten
In liquid.The reaction of completion in 20 hours is stirred under the conditions of nitrogen protection, finally obtains P (VP-VTES-GMA)/TEP solution.It will preparation
Polysulfones (PSf) microporous barrier be immersed in it is above-mentioned diluted and stirred with isometric water after P (VP-VTES-GMA)/TEP solution in
1.5 hours, and 8h is reacted in the citric acid solution at 50 DEG C, prepare the polysulfones film surface of epoxy group modification；By 0.2 gram
Beta-cyclodextrin powder is dissolved in 40 milliliter of 20% NaOH solution, and reaction 10 hours is stirred at room temperature.Later by the surface loop of preparation
Oxygen groups modification polysulfones hemodialysis film (mm of 100 mm × 100) be slowly put into above-mentioned solution, at the uniform velocity vibrate, and adjust PH to
12, it is reacted 2 hours under the conditions of 30 DEG C.At the end of reaction is fast, PH=7.2 are adjusted with PBS buffer solution, sample mould is dipped into
18 hours in distilled water, the polysulfones hemodialysis film of surface beta-cyclodextrin modified is obtained；2.0g Hementaria officianalis element bulk powder is dissolved in
In 50 milliliters of physiological saline, then under 3000rpm revolving speed, centrifugation 10min prepares hirudin solution.Above-mentioned centrifugation is taken respectively
20 milliliters of liquid, surface beta-cyclodextrin modified polysulfones hemodialysis film (mm of 50 mm × 50) is dissolved in above-mentioned hirudin solution,
Oscillation treatment 12 hours under the conditions of 37 DEG C, hirudin anticoagulant polysulfones hemodialysis membrane can be sustained by finally obtaining surface.
Embodiment 3:
By 18 grams of polysulfones (PSf) particles of drying process (drying temperature is 40 DEG C, and drying time is 24 hours), 6 grams
Polyethylene glycol oxide (PEO) is dissolved in 76 milliliters of N-Methyl pyrrolidones (NMP), obtains casting solution, then casting solution is cast
To glass plate surface, with scraper knifing.Finally preformed film sample is immersed in room temperature water bath, solidification obtains polysulfones
(PSf) microporous barrier；It is molten that VTES (7.5 grams), NVP (9.5 grams) and GMA (6.1 grams) are added continuously to 200 grams of TEP
In agent, it is stirred at room temperature 0.5 hour.Reaction temperature is then quickly ramped up to 80 DEG C, is then dissolved in 0.36 gram of AIBN above-mentioned molten
In liquid.The reaction of completion in 20 hours is stirred under the conditions of nitrogen protection, finally obtains P (VP-VTES-GMA)/TEP solution.It will preparation
Polysulfones (PSf) microporous barrier be immersed in it is above-mentioned diluted and stirred with isometric water after P (VP-VTES-GMA)/TEP solution in
0.5 hour, and 14h is reacted in the citric acid solution at 90 DEG C, prepare the polysulfones film surface of epoxy group modification；By 0.3
Gram beta-cyclodextrin powder is dissolved in 40 milliliter of 20% NaOH solution, and reaction 14 hours is stirred at room temperature.Later by the surface of preparation
The polysulfones hemodialysis film (mm of 100 mm × 100) of epoxy group modification is slowly put into above-mentioned solution, is at the uniform velocity vibrated, and adjust PH
To 12, reacted 0.5 hour under the conditions of 80 DEG C.At the end of reaction is fast, PH=7.2 are adjusted with PBS buffer solution, sample mould is soaked
It steeps in distilled water 18 hours, obtains the polysulfones hemodialysis film of surface beta-cyclodextrin modified；2.0g Hementaria officianalis element bulk powder is molten
Solution is in 60 milliliters of physiological saline, and then under 4000rpm revolving speed, centrifugation 10min prepares hirudin solution.It takes respectively above-mentioned
20 milliliters of centrifugate, surface beta-cyclodextrin modified polysulfones hemodialysis film (mm of 50 mm × 50) is dissolved in above-mentioned hirudin solution
In, the oscillation treatment 8 hours under the conditions of 37 DEG C, hirudin anticoagulant polysulfones hemodialysis membrane can be sustained by finally obtaining surface.
Embodiment 4:
VTES (5.5 grams), NVP (7.5 grams) and GMA (4.1 grams) are added continuously in 200 grams of TEP solvents,
It is stirred at room temperature 0.5 hour.Reaction temperature is then quickly ramped up to 80 DEG C, then in the above solution by 0.16 gram of AIBN dissolution.
The reaction of completion in 20 hours is stirred under the conditions of nitrogen protection, finally obtains P (VP-VTES-GMA)/TEP solution.Embodiment 1 is made
Standby polysulfones (PSf) microporous barrier is immersed in above-mentioned P (VP-VTES-GMA)/TEP solution after being diluted and stirred with isometric water
1 hour, and 10h is reacted in the citric acid solution at 70 DEG C, prepare the polysulfones film surface of epoxy group modification；By 0.1 gram
Beta-cyclodextrin powder is dissolved in 40 milliliter of 20% NaOH solution, and reaction 12 hours is stirred at room temperature.Later by the surface loop of preparation
Oxygen groups modification polysulfones hemodialysis film (mm of 100 mm × 100) be slowly put into above-mentioned solution, at the uniform velocity vibrate, and adjust PH to
12, it is reacted 1 hour under the conditions of 50 DEG C.At the end of reaction is fast, PH=7.2 are adjusted with PBS buffer solution, sample mould is dipped into
18 hours in distilled water, the polysulfones hemodialysis film of surface beta-cyclodextrin modified is obtained；2.0g heparin powder is dissolved in 40 milliliters of physiology
In salt water, heparin solution is prepared.20 milliliters of above-mentioned centrifugate is taken respectively, by surface beta-cyclodextrin modified polysulfones hemodialysis film (50
The mm of mm × 50) it is dissolved in above-mentioned heparin solution, the oscillation treatment 10 hours under the conditions of 37 DEG C, finally obtaining surface can be sustained
Anticoagulant heparin polysulfones hemodialysis membrane.
Embodiment 5:
VTES (6.5 grams), NVP (8.5 grams) and GMA (5.1 grams) are added continuously in 200 grams of TEP solvents,
It is stirred at room temperature 0.5 hour.Reaction temperature is then quickly ramped up to 80 DEG C, then in the above solution by 0.26 gram of AIBN dissolution.
The reaction of completion in 20 hours is stirred under the conditions of nitrogen protection, finally obtains P (VP-VTES-GMA)/TEP solution.Embodiment 2 is made
Standby polysulfones (PSf) microporous barrier is immersed in above-mentioned P (VP-VTES-GMA)/TEP solution after being diluted and stirred with isometric water
1 hour, and 10h is reacted in the citric acid solution at 70 DEG C, prepare the polysulfones film surface of epoxy group modification；By 0.2 gram
Beta-cyclodextrin powder is dissolved in 40 milliliter of 20% NaOH solution, and reaction 12 hours is stirred at room temperature.Later by the surface loop of preparation
Oxygen groups modification polysulfones hemodialysis film (mm of 100 mm × 100) be slowly put into above-mentioned solution, at the uniform velocity vibrate, and adjust PH to
12, it is reacted 1 hour under the conditions of 50 DEG C.At the end of reaction is fast, PH=7.2 are adjusted with PBS buffer solution, sample mould is dipped into
18 hours in distilled water, the polysulfones hemodialysis film of surface beta-cyclodextrin modified is obtained；2.0g heparin powder is dissolved in 50 milliliters of physiology
In salt water, heparin solution is prepared.20 milliliters of above-mentioned centrifugate is taken respectively, by surface beta-cyclodextrin modified polysulfones hemodialysis film (50
The mm of mm × 50) it is dissolved in above-mentioned heparin solution, the oscillation treatment 10 hours under the conditions of 37 DEG C, finally obtaining surface can be sustained
Anticoagulant heparin polysulfones hemodialysis membrane.
Embodiment 6:
VTES (7.5 grams), NVP (9.5 grams) and GMA (6.1 grams) are added continuously in 200 grams of TEP solvents,
It is stirred at room temperature 0.5 hour.Reaction temperature is then quickly ramped up to 80 DEG C, then in the above solution by 0.36 gram of AIBN dissolution.
The reaction of completion in 20 hours is stirred under the conditions of nitrogen protection, finally obtains P (VP-VTES-GMA)/TEP solution.Embodiment 3 is made
Standby polysulfones (PSf) microporous barrier is immersed in above-mentioned P (VP-VTES-GMA)/TEP solution after being diluted and stirred with isometric water
1 hour, and 10h is reacted in the citric acid solution at 70 DEG C, prepare the polysulfones film surface of epoxy group modification；By 0.3 gram
Beta-cyclodextrin powder is dissolved in 40 milliliter of 20% NaOH solution, and reaction 12 hours is stirred at room temperature.Later by the surface loop of preparation
Oxygen groups modification polysulfones hemodialysis film (mm of 100 mm × 100) be slowly put into above-mentioned solution, at the uniform velocity vibrate, and adjust PH to
12, it is reacted 1 hour under the conditions of 50 DEG C.At the end of reaction is fast, PH=7.2 are adjusted with PBS buffer solution, sample mould is dipped into
18 hours in distilled water, the polysulfones hemodialysis film of surface beta-cyclodextrin modified is obtained；2.0g heparin powder is dissolved in 60 milliliters of physiology
In salt water, heparin solution is prepared.20 milliliters of above-mentioned centrifugate is taken respectively, by surface beta-cyclodextrin modified polysulfones hemodialysis film (50
The mm of mm × 50) it is dissolved in above-mentioned heparin solution, the oscillation treatment 10 hours under the conditions of 37 DEG C, finally obtaining surface can be sustained
Anticoagulant heparin polysulfones hemodialysis membrane.
Embodiment 7:
VTES (5.5 grams), NVP (7.5 grams) and GMA (4.1 grams) are added continuously in 200 grams of TEP solvents,
It is stirred at room temperature 0.5 hour.Reaction temperature is then quickly ramped up to 80 DEG C, then in the above solution by 0.16 gram of AIBN dissolution.
The reaction of completion in 24 hours is stirred under the conditions of nitrogen protection, finally obtains P (VP-VTES-GMA)/TEP solution.Embodiment 1 is made
Standby polysulfones (PSf) microporous barrier is immersed in above-mentioned P (VP-VTES-GMA)/TEP solution after being diluted and stirred with isometric water
1 hour, and 10h is reacted in the citric acid solution at 70 DEG C, prepare the polysulfones film surface of epoxy group modification；By 0.1 gram
Beta-cyclodextrin powder is dissolved in 40 milliliter of 20% NaOH solution, and reaction 12 hours is stirred at room temperature.Later by the surface loop of preparation
Oxygen groups modification polysulfones hemodialysis film (mm of 100 mm × 100) be slowly put into above-mentioned solution, at the uniform velocity vibrate, and adjust PH to
12, it is reacted 1 hour under the conditions of 50 DEG C.At the end of reaction is fast, PH=7.2 are adjusted with PBS buffer solution, sample mould is dipped into
18 hours in distilled water, the polysulfones hemodialysis film of surface beta-cyclodextrin modified is obtained；1.0g Hementaria officianalis element bulk powder and 1 gram of liver
Plain powder mixed dissolution is in 40 milliliters of physiological saline, then under 2000rpm revolving speed, centrifugation 10min prepare hirudin and
Heparin solution.20 milliliters of above-mentioned centrifugate is taken respectively, surface beta-cyclodextrin modified polysulfones hemodialysis film (mm of 50 mm × 50) is molten
Solution is in above-mentioned hirudin solution, and the oscillation treatment 10 hours under the conditions of 37 DEG C, hirudin and liver can be sustained by finally obtaining surface
Element mixes anticoagulant polysulfones hemodialysis membrane.
Embodiment 8:
VTES (6.5 grams), NVP (8.5 grams) and GMA (5.1 grams) are added continuously in 200 grams of TEP solvents,
It is stirred at room temperature 0.5 hour.Reaction temperature is then quickly ramped up to 80 DEG C, then in the above solution by 0.26 gram of AIBN dissolution.
The reaction of completion in 20 hours is stirred under the conditions of nitrogen protection, finally obtains P (VP-VTES-GMA)/TEP solution.Embodiment 2 is made
Standby polysulfones (PSf) microporous barrier is immersed in above-mentioned P (VP-VTES-GMA)/TEP solution after being diluted and stirred with isometric water
1 hour, and 10h is reacted in the citric acid solution at 70 DEG C, prepare the polysulfones film surface of epoxy group modification；By 0.2 gram
Beta-cyclodextrin powder is dissolved in 40 milliliter of 20% NaOH solution, and reaction 12 hours is stirred at room temperature.Later by the surface loop of preparation
Oxygen groups modification polysulfones hemodialysis film (mm of 100 mm × 100) be slowly put into above-mentioned solution, at the uniform velocity vibrate, and adjust PH to
12, it is reacted 1 hour under the conditions of 50 DEG C.At the end of reaction is fast, PH=7.2 are adjusted with PBS buffer solution, sample mould is dipped into
18 hours in distilled water, the polysulfones hemodialysis film of surface beta-cyclodextrin modified is obtained；1.0g Hementaria officianalis element bulk powder and 1 gram of liver
Plain powder mixed dissolution is in 50 milliliters of physiological saline, then under 3000rpm revolving speed, centrifugation 10min prepare hirudin and
Heparin solution.20 milliliters of above-mentioned centrifugate is taken respectively, surface beta-cyclodextrin modified polysulfones hemodialysis film (mm of 50 mm × 50) is molten
Solution is in above-mentioned hirudin solution, and the oscillation treatment 10 hours under the conditions of 37 DEG C, hirudin and liver can be sustained by finally obtaining surface
Element mixes anticoagulant polysulfones hemodialysis membrane.
Embodiment 9:
VTES (7.5 grams), NVP (9.5 grams) and GMA (6.1 grams) are added continuously in 200 grams of TEP solvents,
It is stirred at room temperature 0.5 hour.Reaction temperature is then quickly ramped up to 80 DEG C, then in the above solution by 0.36 gram of AIBN dissolution.
The reaction of completion in 18 hours is stirred under the conditions of nitrogen protection, finally obtains P (VP-VTES-GMA)/TEP solution.Embodiment 3 is made
Standby polysulfones (PSf) microporous barrier is immersed in above-mentioned P (VP-VTES-GMA)/TEP solution after being diluted and stirred with isometric water
1 hour, and 10h is reacted in the citric acid solution at 70 DEG C, prepare the polysulfones film surface of epoxy group modification；By 0.3 gram
Beta-cyclodextrin powder is dissolved in 40 milliliter of 20% NaOH solution, and reaction 12 hours is stirred at room temperature.Later by the surface loop of preparation
Oxygen groups modification polysulfones hemodialysis film (mm of 100 mm × 100) be slowly put into above-mentioned solution, at the uniform velocity vibrate, and adjust PH to
12, it is reacted 1 hour under the conditions of 50 DEG C.At the end of reaction is fast, PH=7.2 are adjusted with PBS buffer solution, sample mould is dipped into
18 hours in distilled water, the polysulfones hemodialysis film of surface beta-cyclodextrin modified is obtained；1.0g Hementaria officianalis element bulk powder and 1 gram of liver
Plain powder mixed dissolution is in 60 milliliters of physiological saline, then under 4000rpm revolving speed, centrifugation 10min prepare hirudin and
Heparin solution.20 milliliters of above-mentioned centrifugate is taken respectively, surface beta-cyclodextrin modified polysulfones hemodialysis film (mm of 50 mm × 50) is molten
Solution is in above-mentioned hirudin solution, and the oscillation treatment 10 hours under the conditions of 37 DEG C, hirudin and liver can be sustained by finally obtaining surface
Element mixes anticoagulant polysulfones hemodialysis membrane.
Above-described embodiment is not for limitation of the invention, and the present invention is not limited only to above-described embodiment, as long as meeting
The present invention claims all belong to the scope of protection of the present invention.
Claims (9)
1. the preparation method that a kind of surface can be sustained anticoagulant polysulfones hemodialysis membrane, it is characterised in that: the following steps are included:
Step (1): dried polysulfones particle and polyethylene glycol oxide 3:1 in mass ratio are dissolved in N-Methyl pyrrolidone
In, obtain casting solution；Then casting solution is cast to glass plate surface, with scraper knifing, forms preformed film sample；Again will
Preformed film sample is immersed in room temperature water bath, and solidification obtains polysulfones microporous barrier；
Step (2): will be based on mass component, 5.5-7.5 parts of vinyltriethoxysilane, 7.5-9.5 parts of N- vinyl pyrroles
Alkanone and 4.1-6.1 parts of glycidyl methacrylate are added continuously in 200 parts of triethyl phosphates, and it is small to be stirred at room temperature 0.5
When；Reaction temperature is then risen to 80 DEG C, 0.16-0.36 parts of initiator initiation reactions are added, obtain P (VP-VTES-GMA)/
TEP solution；After P (the VP-VTES-GMA)/TEP solution is diluted and stirred with isometric water, it is added obtained in step (1)
Polysulfones microporous barrier impregnates 0.5-1.5h, and reacts 8-14h in the citric acid solution at 50-90 DEG C, obtains surface epoxy group
The polysulfones hemodialysis film of modification；
Step (3): will be based on mass component, 0.1-0.3 parts of cladding powders are dissolved in NaOH solution, and reaction 10- is stirred at room temperature
14 hours；The polysulfones hemodialysis film for adding epoxy group modification in surface obtained in step (2), reacts under the conditions of 30-80 DEG C
0.5-2 hours, obtain the polysulfones hemodialysis film of surface-coated powder modification；
Step (4): the surface-coated powder modification polysulfones hemodialysis film that step (3) obtains is immersed in anti-coagulants solution, 37
Oscillation treatment 8-12 hours under the conditions of DEG C, anticoagulant polysulfones hemodialysis membrane can be sustained by obtaining the surface.
2. the preparation method that surface according to claim 1 can be sustained anticoagulant polysulfones hemodialysis membrane, it is characterised in that: institute
Anti-coagulants solution is stated by based on mass component, 1-2 parts of anti-coagulants are dissolved in 40-60 parts of physiological saline and are prepared.
3. the preparation method that surface according to claim 2 can be sustained anticoagulant polysulfones hemodialysis membrane, it is characterised in that: institute
State the one or both mixture that anti-coagulants is hirudin, heparin.
4. the preparation method that surface according to claim 3 can be sustained anticoagulant polysulfones hemodialysis membrane, it is characterised in that: institute
Stating hirudin is by the way that Hementaria officianalis element ontology to be centrifuged to extraction under 2000-4000rpm revolving speed.
5. the preparation method that surface according to claim 1 can be sustained anticoagulant polysulfones hemodialysis membrane, it is characterised in that: institute
Stating initiator is azodiisobutyronitrile.
6. the preparation method that surface according to claim 1 can be sustained anticoagulant polysulfones hemodialysis membrane, it is characterised in that: institute
Stating cladding powder is beta-cyclodextrin powder.
7. the preparation method that surface according to claim 1 can be sustained anticoagulant polysulfones hemodialysis membrane, it is characterised in that: institute
State initiator initiation reaction stirred under the conditions of nitrogen protection carry out reaction 18-24 hours.
8. the preparation method that surface according to claim 1 can be sustained anticoagulant polysulfones hemodialysis membrane, it is characterised in that: institute
State the NaOH solution that NaOH solution is 20%；The concentration of the citric acid solution is 1 wt.%.
9. the preparation method that surface according to claim 1 can be sustained anticoagulant polysulfones hemodialysis membrane, it is characterised in that: institute
Stating and being dried drying temperature is 40-100 DEG C, and drying time is 1-24 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710222393.4A CN106943898B (en) | 2017-04-07 | 2017-04-07 | A kind of surface can be sustained the preparation method of anticoagulant polysulfones hemodialysis membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710222393.4A CN106943898B (en) | 2017-04-07 | 2017-04-07 | A kind of surface can be sustained the preparation method of anticoagulant polysulfones hemodialysis membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106943898A CN106943898A (en) | 2017-07-14 |
| CN106943898B true CN106943898B (en) | 2019-08-02 |
Family
ID=59474177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710222393.4A Active CN106943898B (en) | 2017-04-07 | 2017-04-07 | A kind of surface can be sustained the preparation method of anticoagulant polysulfones hemodialysis membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106943898B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107737534A (en) * | 2017-10-27 | 2018-02-27 | 广州青岭医疗器械有限公司 | A kind of polyester anticoagulation hemodialysis membrane and preparation method thereof |
| WO2019096598A1 (en) * | 2017-11-15 | 2019-05-23 | Radiometer Medical Aps | Heparin-based blood sampler without platelet activation |
| EP3680005A1 (en) * | 2019-01-10 | 2020-07-15 | Gambro Lundia AB | Membrane with immobilized anticoagulant and process for producing same |
| CN110721602B (en) * | 2019-10-09 | 2020-10-16 | 天津工业大学 | Vitamin B6Hyperbranched polymer modified polymer membrane and preparation method and application thereof |
| CN113072714B (en) * | 2021-04-02 | 2022-07-29 | 齐鲁工业大学 | Method for preparing nano lignin balls from corn straws |
| CN114307668B (en) * | 2021-12-01 | 2023-09-22 | 佛山市南海区苏科大环境研究院 | PGMA (pgmA) copolymer microsphere-polyethyleneimine coating modified polymer film and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6456034B2 (en) * | 2014-04-04 | 2019-01-23 | 旭化成メディカル株式会社 | Hollow fiber membrane for blood treatment |
| CN105311974B (en) * | 2014-07-31 | 2018-11-13 | 中国科学院大连化学物理研究所 | One kind having highly blood coagulation resistant performance hemodialysis membrane and preparation method thereof |
| CN106466562B (en) * | 2015-08-21 | 2018-10-23 | 江苏朗生生命科技有限公司 | The preparation method of anticoagulation hemodialysis membrane |
-
2017
- 2017-04-07 CN CN201710222393.4A patent/CN106943898B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106943898A (en) | 2017-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106943898B (en) | A kind of surface can be sustained the preparation method of anticoagulant polysulfones hemodialysis membrane | |
| Azhar et al. | Cellulose acetate-polyvinyl alcohol blend hemodialysis membranes integrated with dialysis performance and high biocompatibility | |
| Li et al. | Modification of polyethersulfone hemodialysis membrane by blending citric acid grafted polyurethane and its anticoagulant activity | |
| Ma et al. | Toward highly blood compatible hemodialysis membranes via blending with heparin-mimicking polyurethane: Study in vitro and in vivo | |
| Amiji | Permeability and blood compatibility properties of chitosan-poly (ethylene oxide) blend membranes for haemodialysis | |
| KR100525604B1 (en) | Application of sulfone, ketone and ester containing polyalkyl ether units to medical materials | |
| Ishihara et al. | Improvement of blood compatibility on cellulose dialysis membrane. III. Synthesis and performance of water‐soluble cellulose grafted with phospholipid polymer as coating material on cellulose dialysis membrane | |
| Teotia et al. | Bifunctional polysulfone-chitosan composite hollow fiber membrane for bioartificial liver | |
| CN107088370A (en) | Dialysis membrane and its production method | |
| Yin et al. | Hemocompatible polyethersulfone/polyurethane composite membrane for high‐performance antifouling and antithrombotic dialyzer | |
| CN103301759B (en) | A kind of hollow polysulfone fiber dialysis membrane and manufacture method thereof | |
| Modi et al. | Extracellular matrix-coated polyethersulfone-TPGS hollow fiber membranes showing improved biocompatibility and uremic toxins removal for bioartificial kidney application | |
| WO2010133612A1 (en) | Membranes having improved performance | |
| CN104984664A (en) | Method for preparing amino acid modified polyether sulfone hematodialysis membrane | |
| Liu et al. | Heparin reduced dialysis through a facile anti-coagulant coating on flat and hollow fiber membranes | |
| CN105521715B (en) | A kind of blending polyvinylidene fluoride hollow fiber membrane and preparation method thereof | |
| Zheng et al. | In vitro hemocompatibility and hemodialysis performance of hydrophilic ionic liquid grafted polyethersulfone hollow fiber membranes | |
| CN103285431A (en) | Anticoagulation fibroin material and preparation method | |
| Zaman et al. | Recent advancement challenges with synthesis of biocompatible hemodialysis membranes | |
| Wang et al. | Enhanced hemocompatibility of flat and hollow fiber membranes via a heparin free surface crosslinking strategy | |
| Su et al. | Polyethersulfone hollow fiber membranes for hemodialysis | |
| CN105268331A (en) | PVDF separating membrane with good blood compatibility and preparation method thereof | |
| CN106466562B (en) | The preparation method of anticoagulation hemodialysis membrane | |
| Song et al. | A novel anticoagulant affinity membrane for enhanced hemocompatibility and bilirubin removal | |
| Ye et al. | Design of functional hollow fiber membranes modified with phospholipid polymers for application in total hemopurification system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |