CN103877634B - A kind of hemodialyzer and haemodialysis equipment - Google Patents

A kind of hemodialyzer and haemodialysis equipment Download PDF

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Publication number
CN103877634B
CN103877634B CN201410083974.0A CN201410083974A CN103877634B CN 103877634 B CN103877634 B CN 103877634B CN 201410083974 A CN201410083974 A CN 201410083974A CN 103877634 B CN103877634 B CN 103877634B
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polyether sulfone
weight portion
dialysis solution
hemodialyzer
hollow fibre
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CN103877634A (en
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韩全
张恒
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Guangdong ace Medical Technology Co Ltd
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SHIJIAZHUANG DAAI MEDICAL INSTRUMENT SCIENCE & TECHNOLOGY Co Ltd
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61MDEVICES 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
    • A61M1/00Suction or pumping devices for medical purposes; Devices for carrying-off, for treatment of, or for carrying-over, body-liquids; Drainage systems
    • A61M1/14Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis
    • A61M1/16Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis with membranes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08Hollow fibre membranes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • B01D71/66Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68Polysulfones; Polyethersulfones

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  • Health & Medical Sciences (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Urology & Nephrology (AREA)
  • Chemical & Material Sciences (AREA)
  • Anesthesiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • Engineering & Computer Science (AREA)
  • Emergency Medicine (AREA)
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  • Hematology (AREA)
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  • Vascular Medicine (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Artificial Filaments (AREA)
  • External Artificial Organs (AREA)

Abstract

A kind of hemodialyzer and haemodialysis equipment, this hemodialyzer includes: shell, the fibre bundle being made up of doughnut fiber tube, end cap, packaging plastic, annular water conservancy diversion distribution rings, dialysis solution entrance, dialysis solution outlet, blood entry port and blood outlet;Annular water conservancy diversion distribution rings is positioned at the position just dialysis solution entrance and/or dialysis solution exported, annular one end of water conservancy diversion distribution rings is connected with the end of shell, the other end of annular water conservancy diversion distribution rings along shell be longitudinally oriented with its just to dialysis solution entrance or the inclination of dialysis solution Way out;Doughnut fiber tube adopts polyether sulphone hollow fibre film to prepare, and the spinning solution of polyether sulphone hollow fibre film comprises: the part by weight modified PES Blend of 250-650,20-400 part by weight of hydrophilic molecular compound, 1-90 weight portion nano modification hydroxy dioxetane titanium mixture and 20-120 weight portion alcohols solvent。The hemodialyzer of the present invention improves contact area and the clearance of dialysis solution and cellosilk tube-surface, has higher clearance and ultrafiltrate coefficient。

Description

A kind of hemodialyzer and haemodialysis equipment
Technical field
The invention belongs to technical field of medical instruments, be specifically related to a kind of hemodialyzer and haemodialysis equipment。
Background technology
Hemodialyzer is mainly used in carry out hemodialysis and blood filtration when kidney diseases。The structure of existing hemodialyzer specifically includes that shell, the fibre bundle being made up of fiber fiber tube, packaging plastic, end cap, dialysis solution entrance, dialysis solution exports, blood entry port, blood exports and is positioned at the blocking solution plate at dialysis solution entrance and exit place, wherein fibre bundle loads in shell, dialysis solution entrance is positioned at one end of shell with blood outlet, and dialysis solution outlet and blood entry port are positioned at the other end of shell, fibre bundle two ends packaging plastic seals, blocking solution plate lays respectively at shell two and rectifies dialysis solution entrance and dialysis solution exit and parallel with shell, to prevent dialysis solution from when being directly entered dialysate chamber, fibre bundle is caused damage。
When using above-mentioned hemodialyzer to carry out hemodialysis, concentration polarization phenomenon easily occur, dialysis solution is less with the contact area of cellosilk tube-surface, and clearance is relatively low, and fiber fiber tube wire broken rate is higher。
It addition, the dialyzer most important part that is hemodialyzer, dialysis membrane material is the key factor affecting effects of hemodialysis in treating。At present, clinical conventional dialyzer can be divided three classes: 1, the cellulose membrane of unmodified;2, modified or regenerated cellulose film;3, synthesis film。This three classes dialyzer all has bigger difference in biocompatibility, Water permeability, uremic toxins's removing etc.。Removing solute and ultrafiltration are two major functions of dialyser, and clearance rate and ultrafiltrate coefficient are the key indexs evaluating dialyzer quality。The transmission characteristic of film determines the clearance rate of solute and the clearance to liquid。Conventional small-molecule substance (such as carbamide, creatinine) and medium molecular substance (such as vitamin B12, B2M) are as the index evaluating clearance of dialyzer。
The surface nature of film determines characteristic and the degree of the interphase interaction of blood and film, including the absorption of protein, the formation of thrombosis, complement activation and immunoreation etc.。Desirable biocompatible membrane should be very close to the blood vessel endothelium performance of human body, avirulence, no antigen, not activating complement, leukocyte and mononuclear cell, and the release of the acellular factor has excellent biocompatibility, on blood coagulation system also without impact。Dialyzer is as a kind of allosome material, all the time human vas endotheliocyte it is different from, contact with blood, inevitably cause the reaction of body, high flux, efficiently, there is the Main way that preferably biocompatibility, hydrophilic and clearance will be dialyzer development from now on。
Polyether sulphone hollow fibre film is used as the dialyzer of hemodialyzer due to the performance (clearance rate as Middle molecule solute is higher) of its excellence, but the biocompatibility of the polyether sulphone hollow fibre film produced at present and blood compatibility, hydrophilic, smoothness and clearance are relatively low。
Therefore, how structure and the dialysis membrane material of hemodialyzer is improved, to reduce concentration polarization phenomenon, improve contact area and the clearance of dialysis solution and cellosilk tube-surface, reduce fiber fiber tube wire broken rate, make dialyzer have good biocompatibility and blood compatibility, hydrophilic and a smoothness simultaneously, and there is higher clearance and ultrafiltrate coefficient becomes the emphasis of research at present。
Summary of the invention
For the problems referred to above, it is an object of the present invention to provide a kind of hemodialyzer, this hemodialyzer arranges the annular water conservancy diversion distribution rings with certain angle of inclination in the side dialysis solution path of shell, considerably reduce concentration polarization phenomenon, it is effectively improved contact area and the clearance of dialysis solution and cellosilk tube-surface, and reduce fiber fiber tube wire broken rate, the doughnut fiber tube of this hemodialyzer adopts modified polyether sulphone hollow fibre film to prepare simultaneously, there is good biocompatibility and blood compatibility, hydrophilic and smoothness, and there is higher clearance and ultrafiltrate coefficient。
A kind of haemodialysis equipment of offer is provided。
For reaching above-mentioned purpose, the present invention provides a kind of hemodialyzer, comprising: shell, the fibre bundle being made up of doughnut fiber tube, end cap, packaging plastic, annular water conservancy diversion distribution rings, dialysis solution entrance, dialysis solution outlet, blood entry port and blood outlet;Wherein, described annular water conservancy diversion distribution rings is positioned at the position just described dialysis solution entrance and/or dialysis solution exported, described annular one end of water conservancy diversion distribution rings is connected with the end of described shell, the other end of described annular water conservancy diversion distribution rings towards with its just to dialysis solution entrance or the inclination of dialysis solution Way out;
Wherein, described doughnut fiber tube adopts polyether sulphone hollow fibre film to prepare, and the spinning solution of described polyether sulphone hollow fibre film comprises:
The modified polyether sulfone blends of 250-650 weight portion;
The hydrophilic molecule compound of 20-400 weight portion;
The nano modification hydroxy dioxetane titanium mixture of 1-90 weight portion;And
The alcohols solvent of 20-120 weight portion,
Wherein, described modified polyether sulfone blends comprises polyether sulfone, polyvinylpyrrolidone, sodium hydroxide and sodium peroxydisulfate, and described nano modification hydroxy dioxetane titanium mixture comprises nano-water soluble titanium dioxide and alcohol。
Preferably, described annular water conservancy diversion distribution rings is 2-6 ° relative to the angle of the fore-and-aft tilt of described shell, it is preferable that 4 °;
Preferably, the diameter of described annular water conservancy diversion distribution rings is 53-55mm, it is preferable that 54mm;
Preferably, the width of described annular water conservancy diversion distribution rings less than with its just to dialysis solution entrance or dialysis solution outlet along the longitudinal width of shell;
Preferably, the width of described annular water conservancy diversion distribution rings is 7-9mm, it is preferable that 8mm。
Preferably, the spinning solution of described polyether sulphone hollow fibre film comprises:
The modified polyether sulfone blends of 250-450 weight portion;
The hydrophilic molecule compound of 50-150 weight portion;
The nano modification hydroxy dioxetane titanium mixture of 10-90 weight portion;And
The alcohols solvent of 50-100 weight portion。
Preferably, described modified polyether sulfone blends comprises the sodium peroxydisulfate of the polyether sulfone of 850-980 weight portion, the polyvinylpyrrolidone of 20-150 weight portion, the sodium hydroxide of 0.01-1 weight portion and 0.1-1 weight portion;
Preferably, described modified polyether sulfone blends comprises the sodium peroxydisulfate of the polyether sulfone of 900-980 weight portion, the polyvinylpyrrolidone of 20-100 weight portion, the sodium hydroxide of 0.05-0.1 weight portion and 0.5-1 weight portion;
Polyvinylpyrrolidone in described modified polyether sulfone blends is preferably PVP k15, polyvinylpyrrolidone k30 or polyvinylpyrrolidone k90, and described polyether sulfone is preferably polyether sulfone P-3500 or polyether sulfone E6020。
Preferably, described nano modification hydroxy dioxetane titanium mixture comprises nano-water soluble titanium dioxide and ethylene glycol;
Preferably, described nano modification hydroxy dioxetane titanium mixture comprises the water-soluble titanium dioxide of 100-800 weight portion and the ethylene glycol of 600-980 weight portion;
Preferably, described nano modification hydroxy dioxetane titanium mixture comprises the water-soluble titanium dioxide of 200-400 weight portion and the ethylene glycol of 600-900 weight portion;
Preferably, the particle diameter of described water-soluble titanium dioxide is 1-10nm;
Preferably, described hydrophilic molecule compound is polyvinylpyrrolidone or Polyethylene Glycol;Preferably, described hydrophilic molecule compound is PVP k15, polyvinylpyrrolidone k30, polyvinylpyrrolidone k90 or molecular weight is the Polyethylene Glycol of 2000;
Preferably, described alcohols solvent is Polyethylene Glycol or glycerol, it is preferable that molecular weight is the Polyethylene Glycol of 2000。
Preferably, the preparation method of described modified polyether sulfone blends includes:
Polyether sulfone, polyvinylpyrrolidone, sodium hydroxide and sodium peroxydisulfate are mixed; and under 95-120 DEG C of preferred 100-110 DEG C of nitrogen protection, mix certain time; mix 30-120 minute preferably 60-90 minute, cross-linking reaction occurs, prepares modified polyether sulfone blends。
Preferably, the preparation method of described modified hydroxyl titanium dioxide mixture includes:
Nano-water soluble titanium dioxide is mixed with alcohol, at 20-60 DEG C of preferred 40-50 DEG C of stirred under nitrogen atmosphere, stirs 10-60 minute and preferably obtain modified hydroxyl titanium dioxide mixture after 20-40 minute。
Preferably, the preparation method of described polyether sulphone hollow fibre film comprises the following steps:
Add modified polyether sulfone blends, hydrophilic molecule compound, nano modification hydroxy dioxetane titanium mixture and alcohols solvent in organic solvent; dry-wet method is adopted to stir under nitrogen protection and prepare spinning liquid; spinning liquid is carried out ripening; and extruded by spinneret; by air section, then pass through pure water coagulating bath and prepare polyether sulphone hollow fibre film;
Preferably, the preparation method of described polyether sulphone hollow fibre film comprises the following steps: add modified polyether sulfone blends in organic solvent, hydrophilic molecule compound, nano modification hydroxy dioxetane titanium mixture and alcohols solvent, dry-wet method is adopted within 4-24 hour, preferably within 12-24 hour, to obtain spinning liquid at 55-100 DEG C of preferred 60-85 DEG C of stirred under nitrogen atmosphere, by spinning liquid ripening 12-72 hour, preferred 24-36 hour, and extruded by spinneret, and by the air section of the preferred 300-500mm of 1-800mm, then with the speed of 6-15 m/min preferred 6-9 m/min by pure water coagulating bath, dry and prepare polyether sulphone hollow fibre film。
Preferably, described organic solvent is dimethyl acetylamide, dimethylformamide or dimethyl sulfoxide。
The present invention further provides a kind of haemodialysis equipment comprising above-mentioned hemodialyzer。
Compared with prior art, the invention have the advantages that
One compared with the hemodialyzer being provided with blocking solution plate (parallel with shell), the present invention by arranging the annular water conservancy diversion distribution rings with certain angle of inclination in the side dialysis solution path of hemodialyzer, dialysis solution in dialysis procedure is flowed along the tangential direction of hollow fibre filament tube outer surface, considerably reduce concentration polarization phenomenon, it is effectively improved the contact area of dialysis solution and cellosilk tube-surface, the effect of dialysis solution turbulent flow can be reached simultaneously, expand disperse effect, improve clearance;When additionally the hemodialyzer of the present invention is more beneficial for preventing dialysis solution to be directly entered dialysate chamber by arranging annular water conservancy diversion distribution rings, fibre bundle is caused damage, reduction fiber fiber tube wire broken rate;
Two, the doughnut fiber tube of the hemodialyzer of the present invention adopts modified polyether sulphone hollow fibre film to prepare, relative to unmodified polyether sulphone hollow fibre film, the present invention has outstanding biocompatibility and blood compatibility by polyether sulfone and nano titanium oxide are modified the modified poly (ether-sulfone) hollow-fibre membrane of preparation, and avirulence, no antigen, not activating complement, leukocyte and mononuclear cell, the release of the acellular factor, on blood coagulation system also without impact;
Three, relative to unmodified polyether sulphone hollow fibre film, the surface roughness of the modified poly (ether-sulfone) hollow-fibre membrane in the hemodialyzer of the present invention substantially reduces, considerably reduce its impact on blood, blood residuals is less, significantly reduce complement activation and blood resistance, and there is higher hydrophilic and bigger water flux;
Four, relative to unmodified polyether sulphone hollow fibre film, modified poly (ether-sulfone) hollow-fibre membrane in the hemodialyzer of the present invention has higher clearance and ultrafiltrate coefficient, it is QB=200ml/min in test condition, QD=500ml/min, when TMP=1000mmHg, the clearance of carbamide, creatinine, phosphate and vitamin B is respectively reached 210ml/min, 190ml/min, 170ml/min and 180ml/min, and ultrafiltrate coefficient reaches 200ml/kpa.h;It addition, each component content in blood after the hemodialyzer dialysis that after adopting the hemodialyzer hemodialysis 15 minutes of the modified poly (ether-sulfone) doughnut film preparation of the present invention, the level etc. of blood middle leukocytes, platelet count and complement C 3, C5a is superior under the same terms to adopt unmodified polyether sulphone hollow fibre film to make;
Five, the modified poly (ether-sulfone) hollow-fibre membrane in the hemodialyzer of the present invention has higher chemical stability, it is possible to sterilizations such as gamma-rays, oxirane and steam, material glass temperature is 200 degrees Celsius。
Accompanying drawing explanation
Hereinafter, describe embodiment of the present invention in detail in conjunction with accompanying drawing, wherein:
Fig. 1 is partial appearance and the profile of the hemodialyzer of the present invention, illustrated therein is the hemodialyzer profile at dialysis solution entrance side;
Fig. 2 is the profile of the hemodialyzer of the present invention;
Fig. 3 is the hemodialyzer top view at dialysis solution entrance side of the present invention;
Fig. 4 is the hemodialyzer amplification profile at dialysis solution entrance side of the present invention;
Fig. 5 is that the hemodialyzer of the present invention flows to top view at the dialysis solution of dialysis solution intake section;
Fig. 6 is the hemodialyzer dialysis solution flow graph at dialysis solution intake section of the present invention;
Fig. 7 illustrates the configuration of surface of the modified poly (ether-sulfone) hollow-fibre membrane of the present invention;
Fig. 8 illustrates the configuration of surface of unmodified polyether sulphone hollow fibre film in prior art;
Fig. 9 illustrates the smoothness Electronic Speculum figure of the modified poly (ether-sulfone) hollow-fibre membrane of the present invention;
Figure 10 illustrates the smoothness Electronic Speculum figure of unmodified polyether sulphone hollow fibre film in prior art;
Figure 11 illustrates the structure Electronic Speculum figure of the modified poly (ether-sulfone) hollow-fibre membrane of the present invention;
Figure 12 illustrates the view that the modified poly (ether-sulfone) hollow-fibre membrane of the present invention contacts with water;
Figure 13 illustrates the view that in prior art, unmodified polyether sulphone hollow fibre film contacts with water。
Description of reference numerals
1 shell
2 doughnut fiber tubes
3 dialysis solution outlets
6 end caps
7 packaging plastics
8 annular water conservancy diversion distribution rings
The dialysis solution runner of 9 shells
10 dialysis solution entrances
11 blood outlets
12 blood entry port
Detailed description of the invention
Referring to specific embodiment, the present invention is described。It will be appreciated by those skilled in the art that these embodiments are merely to illustrate the present invention, its scope not limited the present invention in any way。
Reagent material etc. used in following embodiment, if no special instructions, is commercially available purchase product。
Shown in Fig. 4, hemodialyzer provided by the invention includes shell 1, the fibre bundle being made up of doughnut fiber tube 2, end cap 6, packaging plastic 7, annular water conservancy diversion distribution rings 8, dialysis solution entrance 10, dialysis solution outlet 3, blood entry port 12 and blood outlet 11。Wherein, fibre bundle is filled in shell 1, dialysis solution entrance 10 is positioned at one end of shell 1 with blood outlet 11, and dialysis solution outlet 3 and blood entry port 12 are positioned at the other end of shell 1, the edge of end cap 6 is fixed on by packaging plastic 7 in fibre bundle two ends, end cap 6 is positioned at the two ends of shell 1, makes the doughnut fiber tube 2 of fibre bundle be internally formed the blood access of sealing, and doughnut fiber tube 2 is outside forms dialysis solution path with shell 1。
Annular water conservancy diversion distribution rings 8 is in the form of a ring (as shown in Figure 3), in the side dialysis solution path of hemodialyzer, and it is positioned at the position that just dialysis solution entrance 10 and/or dialysis solution are exported 3, described annular one end of water conservancy diversion distribution rings 8 is connected with the end of shell 1, annular water conservancy diversion distribution rings 8 the other end along shell 1 be longitudinally oriented with its just to dialysis solution entrance 10 or dialysis solution export 3 directions tilt, namely annular water conservancy diversion distribution rings 8 tilt certain angle α (as shown in Figure 6) relative to shell 1。After the hemodialyzer of the present invention arranges annular water conservancy diversion distribution rings 8, the flow direction of dialysis solution is as shown in Figures 5 and 6, after dialysis solution enters dialysis solution entrance 10, touch annular water conservancy diversion distribution rings 8, and the region between annular water conservancy diversion distribution rings 8 and dialysis solution runner 9 is full of, then dialysis solution flows to the direction of fluid sealant 7 along the direction of annular water conservancy diversion distribution rings 8, so that dialysis solution contacts with doughnut fiber tube 2 at a certain angle, and flows to dialysis solution and exports 3 directions。It is so designed that, dialysis solution can be guided in dialysis procedure to flow along doughnut fiber tube 2 outer surface tangential direction, thus considerably reducing concentration polarization phenomenon, it is effectively improved the contact area of dialysis solution and hollow fibre filament tube-surface, the effect of dialysis solution turbulent flow can be reached simultaneously, expand disperse effect, improve clearance, and desirably prevent when dialysis solution is directly entered dialysate chamber, fibre bundle to be caused damage, reduce fiber fiber tube wire broken rate。
In the hemodialyzer of the present invention, the angle [alpha] that annular water conservancy diversion distribution rings 8 tilts relative to shell 1 is 2-6 °, it is preferable that 4 °。If inclination angle is excessive, will cause that dialysis solution can not smooth and easy be distributed, increase the resistance of dialysis solution, cause that in dialysis solution import, local current are disorderly;If inclination angle is too small, does not reach and concentration polarization phenomenon is greatly lowered, improve contact area and the clearance of dialysis solution and cellosilk tube-surface, and reduce the effect of fiber fiber tube wire broken rate。
Preferably, the diameter of annular water conservancy diversion distribution rings 8 is 53-55mm, it is preferable that 54mm;Width is 7-9mm, it is preferable that 8mm;
Preferably, the width of described annular water conservancy diversion distribution rings 8 less than with its just to dialysis solution entrance 10 or dialysis solution outlet 3 along the width of shell 1 longitudinal direction。
In the hemodialyzer of the present invention, the internal diameter of doughnut fiber tube 2 is 150-400 μm, and thickness is 15-60 μm, and the inwall of doughnut fiber tube 2 has the micropore of 1-5nm。The fibre bundle filled in shell 1 accounts for the 55%-85% of hemodialyzer cumulative volume, additionally also dependent on the size of practical application housing 1, select the packed density of fibre bundle, the area of preferred fibre bundle is 0.8-3.0 square metre, the blood room volume formed by doughnut fiber tube 2 is 30-120ml, the preferred 12000-35000 root of quantity of the doughnut fiber tube 2 filled in shell 1, the preferred 300mm of length of doughnut fiber tube 2, in fibre bundle, the total surface area of all doughnut fiber tubes 2 is 0.6-4.0 square metre。
Packaging plastic 7 can be material conventional in prior art, includes but not limited to polyurethane or poly-imido resin, it is preferable that polyurethane resin, and the thickness of packaging plastic 7 is 5-20mm。
The shape of shell 1 can be the shape that this area is conventional, preferably drum shape of the present invention, the preferred 30-48mm of internal diameter of cylinder-like shell。It addition, the size of shell can be determined according to practical situation。
Doughnut fiber tube 2 in the hemodialyzer of the present invention adopts modified polyether sulphone hollow fibre film to prepare, and is below the preparation embodiment of the modified polyether sulphone hollow fibre film of the present invention。
Embodiment 1The preparation of polyether sulphone hollow fibre film 1
1, the preparation of each composition:
Hydroxy dioxetane titanium mixture: mixed with 700g ethylene glycol by 1-10 nanometer of 300g water-soluble titanium dioxide, obtains hydroxy dioxetane titanium mixture at 45 DEG C of stirred under nitrogen atmosphere after 30 minutes。
Modified polyether sulfone blends: 900g polyether sulfone P-3500,100g polyvinylpyrrolidone k90,0.05g sodium hydroxide and 0.5g sodium peroxydisulfate are mixed; and mix 35 minutes under 95 DEG C of nitrogen protections; make each component generation cross-linking reaction, prepare modified polyether sulfone blends。
2, the preparation of polyether sulphone hollow fibre film:
Dimethyl sulfoxide adds 300g modified polyether sulfone blends, 90g polyvinylpyrrolidone k90,30g nano modification hydroxy dioxetane titanium mixture and 70g Polyethylene Glycol (2000); dry-wet method is adopted within 24 hours, to obtain spinning liquid at 60 DEG C of stirred under nitrogen atmosphere; after spinning liquid ripening 12 hours; extruded by spinneret; and by after the air section of 320mm, with the speed of 6 ms/min by pure water coagulating bath, dry prepare polyether sulphone hollow fibre film 1。
Embodiment 2The preparation of polyether sulphone hollow fibre film 2
1, the preparation of each composition:
Hydroxy dioxetane titanium mixture: mixed with 745g ethylene glycol by 1-10 nanometer of 255g water-soluble titanium dioxide, obtains hydroxy dioxetane titanium mixture at 45 DEG C of stirred under nitrogen atmosphere after 30 minutes。
Modified polyether sulfone blends: 980g polyether sulfone P-3500,20g polyvinylpyrrolidone k90,0.08g sodium hydroxide and 0.8g sodium peroxydisulfate are mixed; and mix 60 minutes under 100 DEG C of nitrogen protections; make each component generation cross-linking reaction, prepare modified polyether sulfone blends。
2, the preparation of polyether sulphone hollow fibre film:
Acetic acid dimethylamide adds 280g modified polyether sulfone blends, 70g polyvinylpyrrolidone k90,20g nano modification hydroxy dioxetane titanium mixture and 90g Polyethylene Glycol (1800); dry-wet method is adopted within 24 hours, to obtain spinning liquid at 60 DEG C of stirred under nitrogen atmosphere; after spinning liquid ripening 12 hours; extruded by spinneret; and by after the air section of 400mm, with the speed of 9 ms/min by pure water coagulating bath, dry prepare polyether sulphone hollow fibre film 2。
Embodiment 3The preparation of polyether sulphone hollow fibre film 3
1, the preparation of each composition:
Hydroxy dioxetane titanium mixture: mixed with 800g ethylene glycol by 1-10 nanometer of 200g water-soluble titanium dioxide, obtains hydroxy dioxetane titanium mixture at 50 DEG C of stirred under nitrogen atmosphere after 30 minutes。
Modified polyether sulfone blends: 950g polyether sulfone P-3500,50g polyvinylpyrrolidone k90,0.05g sodium hydroxide and 0.8g sodium peroxydisulfate are mixed; and mix 30 minutes under 95 DEG C of nitrogen protections; make each component generation cross-linking reaction, prepare modified polyether sulfone blends。
2, the preparation of polyether sulphone hollow fibre film:
Dimethyl sulfoxide adds 320g modified polyether sulfone blends, 120g polyvinylpyrrolidone k90,80g nano modification hydroxy dioxetane titanium mixture and 50g Polyethylene Glycol (2000); dry-wet method is adopted within 8 hours, to obtain spinning liquid at 80 DEG C of stirred under nitrogen atmosphere; after spinning liquid ripening 24 hours; extruded by spinneret; and by after the air section of 500mm, with the speed of 6.5 ms/min by pure water coagulating bath, dry prepare polyether sulphone hollow fibre film 3。
Embodiment 4The preparation of polyether sulphone hollow fibre film 4
1, the preparation of each composition:
Hydroxy dioxetane titanium mixture: mixed with 750g ethylene glycol by 1-10 nanometer of 250g water-soluble titanium dioxide, obtains hydroxy dioxetane titanium mixture at 40 DEG C of stirred under nitrogen atmosphere after 30 minutes。
Modified polyether sulfone blends: 960g polyether sulfone P-3500,40g polyvinylpyrrolidone k90,0.08g sodium hydroxide and 0.8g sodium peroxydisulfate are mixed; and mix 45 minutes under 95 DEG C of nitrogen protections; make each component generation cross-linking reaction, prepare modified polyether sulfone blends。
2, the preparation of polyether sulphone hollow fibre film:
Dimethyl sulfoxide adds 400g modified polyether sulfone blends, 60g polyvinylpyrrolidone k90,90g nano modification hydroxy dioxetane titanium mixture and 50g Polyethylene Glycol (2000); dry-wet method is adopted within 24 hours, to obtain spinning liquid at 80 DEG C of stirred under nitrogen atmosphere; after spinning liquid ripening 24 hours; extruded by spinneret; and by after the air section of 450mm, with the speed of 8 ms/min by pure water coagulating bath, dry prepare polyether sulphone hollow fibre film 4。
Embodiment 5The preparation of polyether sulphone hollow fibre film 5
1, the preparation of each composition:
Hydroxy dioxetane titanium mixture: mixed with 780g ethylene glycol by 1-10 nanometer of 220g water-soluble titanium dioxide, obtains hydroxy dioxetane titanium mixture at 45 DEG C of stirred under nitrogen atmosphere after 30 minutes。
Modified polyether sulfone blends: 910g polyether sulfone P-3500,90g polyvinylpyrrolidone k90,0.09g sodium hydroxide and 0.6g sodium peroxydisulfate are mixed; and mix 40 minutes under 110 DEG C of nitrogen protections; make each component generation cross-linking reaction, prepare modified polyether sulfone blends。
2, the preparation of polyether sulphone hollow fibre film:
Dimethyl sulfoxide adds 430g modified polyether sulfone blends, 50g Polyethylene Glycol (2000), 80g nano modification hydroxy dioxetane titanium mixture and 50g Polyethylene Glycol (2000); dry-wet method is adopted within 24 hours, to obtain spinning liquid at 80 DEG C of stirred under nitrogen atmosphere; after spinning liquid ripening 24 hours; extruded by spinneret; and by after the air section of 400mm, with the speed of 6.5 ms/min by pure water coagulating bath, dry prepare polyether sulphone hollow fibre film 5。
Embodiment 6The preparation of polyether sulphone hollow fibre film 6
1, the preparation of each composition:
Hydroxy dioxetane titanium mixture: mixed with 770g ethylene glycol by 1-10 nanometer of 230g water-soluble titanium dioxide, obtains hydroxy dioxetane titanium mixture at 45 DEG C of stirred under nitrogen atmosphere after 35 minutes。
Modified polyether sulfone blends: 920g polyether sulfone P-3500,80g polyvinylpyrrolidone k30,0.08g sodium hydroxide and 0.8g sodium peroxydisulfate are mixed; and mix 50 minutes under 120 DEG C of nitrogen protections; make each component generation cross-linking reaction, prepare modified polyether sulfone blends。
2, the preparation of polyether sulphone hollow fibre film:
Dimethyl sulfoxide adds 310g modified polyether sulfone blends, 80g polyvinylpyrrolidone k90,55g nano modification hydroxy dioxetane titanium mixture and 80g Polyethylene Glycol (2000); dry-wet method is adopted within 24 hours, to obtain spinning liquid at 65 DEG C of stirred under nitrogen atmosphere; after spinning liquid ripening 24 hours; extruded by spinneret; and by after the air section of 400mm, with the speed of 6.5 ms/min by pure water coagulating bath, dry prepare polyether sulphone hollow fibre film 6。
Embodiment 7The preparation of polyether sulphone hollow fibre film 7
1, the preparation of each composition:
Hydroxy dioxetane titanium mixture: mixed with 760g ethylene glycol by 1-10 nanometer of 240g water-soluble titanium dioxide, obtains hydroxy dioxetane titanium mixture at 45 DEG C of stirred under nitrogen atmosphere after 30 minutes。
Modified polyether sulfone blends: 910g polyether sulfone P-3500,90g PVP k15,0.05g sodium hydroxide and 0.8g sodium peroxydisulfate are mixed; and mix 60 minutes under 98 DEG C of nitrogen protections; make each component generation cross-linking reaction, prepare modified polyether sulfone blends。
2, the preparation of polyether sulphone hollow fibre film:
Dimethyl sulfoxide adds 250g modified polyether sulfone blends, 150g polyvinylpyrrolidone k90,70g nano modification hydroxy dioxetane titanium mixture and 50g glycerol; dry-wet method is adopted within 18 hours, to obtain spinning liquid at 80 DEG C of stirred under nitrogen atmosphere; after spinning liquid ripening 36 hours; extruded by spinneret; and by after the air section of 400mm, with the speed of 7 ms/min by pure water coagulating bath, dry prepare polyether sulphone hollow fibre film 7。
Embodiment 8The preparation of polyether sulphone hollow fibre film 8
1, the preparation of each composition:
Hydroxy dioxetane titanium mixture: mixed with 740g ethylene glycol by 1-10 nanometer of 260g water-soluble titanium dioxide, obtains hydroxy dioxetane titanium mixture at 45 DEG C of stirred under nitrogen atmosphere after 30 minutes。
Modified polyether sulfone blends: 940g polyether sulfone P-3500,60g polyvinylpyrrolidone k30,0.05g sodium hydroxide and 0.8g sodium peroxydisulfate are mixed; and mix 90 minutes under 95 DEG C of nitrogen protections; make each component generation cross-linking reaction, prepare modified polyether sulfone blends。
2, the preparation of polyether sulphone hollow fibre film:
Dimethyl sulfoxide adds 320g modified polyether sulfone blends, 70g Polyethylene Glycol (2000), 50g nano modification hydroxy dioxetane titanium mixture and 80g glycerol; dry-wet method is adopted within 18 hours, to obtain spinning liquid at 65 DEG C of stirred under nitrogen atmosphere; after spinning liquid ripening 36 hours; extruded by spinneret; and by after the air section of 350mm, with the speed of 8 ms/min by pure water coagulating bath, dry prepare polyether sulphone hollow fibre film 8。
Embodiment 9The preparation of polyether sulphone hollow fibre film 9
1, the preparation of each composition:
Hydroxy dioxetane titanium mixture: mixed with 720g ethylene glycol by 1-10 nanometer of 280g water-soluble titanium dioxide, obtains hydroxy dioxetane titanium mixture at 40 DEG C of stirred under nitrogen atmosphere after 30 minutes。
Modified polyether sulfone blends: 930g polyether sulfone P-3500,70g polyvinylpyrrolidone k30,0.08g sodium hydroxide and 0.5g sodium peroxydisulfate are mixed; and mix 110 minutes under 95 DEG C of nitrogen protections; make each component generation cross-linking reaction, prepare modified polyether sulfone blends。
2, the preparation of polyether sulphone hollow fibre film:
Dimethyl sulfoxide adds 280g modified polyether sulfone blends, 90g polyvinylpyrrolidone k30,60g nano modification hydroxy dioxetane titanium mixture and 50g Polyethylene Glycol (2000); dry-wet method is adopted within 18 hours, to obtain spinning liquid at 60 DEG C of stirred under nitrogen atmosphere; after spinning liquid ripening 36 hours; extruded by spinneret; and by after the air section of 350mm, with the speed of 6.5 ms/min by pure water coagulating bath, dry prepare polyether sulphone hollow fibre film 9。
Embodiment 10The preparation of polyether sulphone hollow fibre film 10
1, the preparation of each composition:
Hydroxy dioxetane titanium mixture: mixed with 690g ethylene glycol by 1-10 nanometer of 310g water-soluble titanium dioxide, obtains hydroxy dioxetane titanium mixture at 45 DEG C of stirred under nitrogen atmosphere after 30 minutes。
Modified polyether sulfone blends: 980g polyether sulfone P-3500,20g polyvinylpyrrolidone k30,0.05g sodium hydroxide and 0.8g sodium peroxydisulfate are mixed; and mix 40 minutes under 100 DEG C of nitrogen protections; make each component generation cross-linking reaction, prepare modified polyether sulfone blends。
2, the preparation of polyether sulphone hollow fibre film:
Dimethyl sulfoxide adds 450g modified polyether sulfone blends, 60g Polyethylene Glycol (2000), 30g nano modification hydroxy dioxetane titanium mixture and 90g Polyethylene Glycol (2000); dry-wet method is adopted within 18 hours, to obtain spinning liquid at 65 DEG C of stirred under nitrogen atmosphere; after spinning liquid ripening 36 hours; extruded by spinneret; and by after the air section of 350mm, with the speed of 6.5 ms/min by pure water coagulating bath, dry prepare polyether sulphone hollow fibre film 10。
Embodiment 11The preparation of polyether sulphone hollow fibre film 11
1, the preparation of each composition:
Hydroxy dioxetane titanium mixture: mixed with 600g ethylene glycol by 1-10 nanometer of 400g water-soluble titanium dioxide, obtains hydroxy dioxetane titanium mixture at 45 DEG C of stirred under nitrogen atmosphere after 30 minutes。
Modified polyether sulfone blends: 930g polyether sulfone E6020,70g polyvinylpyrrolidone k30,0.05g sodium hydroxide and 0.8g sodium peroxydisulfate are mixed; and mix 60 minutes under 120 DEG C of nitrogen protections; make each component generation cross-linking reaction, prepare modified polyether sulfone blends。
2, the preparation of polyether sulphone hollow fibre film:
Dimethyl sulfoxide adds 340g modified polyether sulfone blends, 90g polyvinylpyrrolidone k30,20g nano modification hydroxy dioxetane titanium mixture and 100g Polyethylene Glycol (2000); dry-wet method is adopted within 24 hours, to obtain spinning liquid at 70 DEG C of stirred under nitrogen atmosphere; after spinning liquid ripening 36 hours; extruded by spinneret; and by after the air section of 400mm, with the speed of 7 ms/min by pure water coagulating bath, dry prepare polyether sulphone hollow fibre film 11。
Embodiment 12The preparation of polyether sulphone hollow fibre film 12
1, the preparation of each composition:
Hydroxy dioxetane titanium mixture: mixed with 620g ethylene glycol by 1-10 nanometer of 380g water-soluble titanium dioxide, obtains hydroxy dioxetane titanium mixture at 45 DEG C of stirred under nitrogen atmosphere after 30 minutes。
Modified polyether sulfone blends: 920g polyether sulfone E6020,80g polyvinylpyrrolidone k30,0.08g sodium hydroxide and 0.9g sodium peroxydisulfate are mixed; and mix 90 minutes under 120 DEG C of nitrogen protections; make each component generation cross-linking reaction, prepare modified polyether sulfone blends。
2, the preparation of polyether sulphone hollow fibre film:
Dimethyl sulfoxide adds 370g modified polyether sulfone blends, 50g polyvinylpyrrolidone k30,40g nano modification hydroxy dioxetane titanium mixture and 80g Polyethylene Glycol (2000); dry-wet method is adopted within 18 hours, to obtain spinning liquid at 70 DEG C of stirred under nitrogen atmosphere; after spinning liquid ripening 24 hours; extruded by spinneret; and by after the air section of 400mm, with the speed of 6.5 ms/min by pure water coagulating bath, dry prepare polyether sulphone hollow fibre film 12。
Embodiment 13The preparation of polyether sulphone hollow fibre film 13
1, the preparation of each composition:
Hydroxy dioxetane titanium mixture: mixed with 650g ethylene glycol by 1-10 nanometer of 350g water-soluble titanium dioxide, obtains hydroxy dioxetane titanium mixture at 50 DEG C of stirred under nitrogen atmosphere after 30 minutes。
Modified polyether sulfone blends: 920g polyether sulfone E6020,80g PVP k15,0.05g sodium hydroxide and 0.8g sodium peroxydisulfate are mixed; and mix 45 minutes under 110 DEG C of nitrogen protections; make each component generation cross-linking reaction, prepare modified polyether sulfone blends。
2, the preparation of polyether sulphone hollow fibre film:
Dimethyl sulfoxide adds 280g modified polyether sulfone blends, 80g PVP k15,20g nano modification hydroxy dioxetane titanium mixture and 100g Polyethylene Glycol (2000); dry-wet method is adopted within 18 hours, to obtain spinning liquid at 70 DEG C of stirred under nitrogen atmosphere; after spinning liquid ripening 24 hours; extruded by spinneret; and by after the air section of 400mm, with the speed of 8 ms/min by pure water coagulating bath, dry prepare polyether sulphone hollow fibre film 13。
Embodiment 14The preparation of polyether sulphone hollow fibre film 14
1, the preparation of each composition:
Hydroxy dioxetane titanium mixture: mixed with 670g ethylene glycol by 1-10 nanometer of 330g water-soluble titanium dioxide, obtains hydroxy dioxetane titanium mixture at 45 DEG C of stirred under nitrogen atmosphere after 30 minutes。
Modified polyether sulfone blends: 930g polyether sulfone E6020,70g PVP k15,0.08g sodium hydroxide and 0.8g sodium peroxydisulfate are mixed; and mix 90 minutes under 100 DEG C of nitrogen protections; make each component generation cross-linking reaction, prepare modified polyether sulfone blends。
2, the preparation of polyether sulphone hollow fibre film:
Dimethyl sulfoxide adds 300g modified polyether sulfone blends, 70g PVP k15,50g nano modification hydroxy dioxetane titanium mixture and 70g Polyethylene Glycol (2000); dry-wet method is adopted within 18 hours, to obtain spinning liquid at 70 DEG C of stirred under nitrogen atmosphere; after spinning liquid ripening 24 hours; extruded by spinneret; and by after the air section of 400mm, with the speed of 6.5 ms/min by pure water coagulating bath, dry prepare polyether sulphone hollow fibre film 14。
Embodiment 15The preparation of polyether sulphone hollow fibre film 15
1, the preparation of each composition:
Hydroxy dioxetane titanium mixture: mixed with 645g ethylene glycol by 1-10 nanometer of 355g water-soluble titanium dioxide, obtains hydroxy dioxetane titanium mixture at 45 DEG C of stirred under nitrogen atmosphere after 30 minutes。
Modified polyether sulfone blends: 980g polyether sulfone E6020,20g polyvinylpyrrolidone k90,0.05g sodium hydroxide and 0.9g sodium peroxydisulfate are mixed; and mix 120 minutes under 95 DEG C of nitrogen protections; make each component generation cross-linking reaction, prepare modified polyether sulfone blends。
2, the preparation of polyether sulphone hollow fibre film:
Dimethyl sulfoxide adds 280g modified polyether sulfone blends, 150g polyvinylpyrrolidone k90,30g nano modification hydroxy dioxetane titanium mixture and 80g Polyethylene Glycol (2000); dry-wet method is adopted within 18 hours, to obtain spinning liquid at 70 DEG C of stirred under nitrogen atmosphere; after spinning liquid ripening 24 hours; extruded by spinneret; and by after the air section of 400mm, with the speed of 7 ms/min by pure water coagulating bath, dry prepare polyether sulphone hollow fibre film 15。
Embodiment 16The preparation of polyether sulphone hollow fibre film 16
1, the preparation of each composition:
Hydroxy dioxetane titanium mixture: mixed with 610g ethylene glycol by 1-10 nanometer of 390g water-soluble titanium dioxide, obtains hydroxy dioxetane titanium mixture at 45 DEG C of stirred under nitrogen atmosphere after 30 minutes。
Modified polyether sulfone blends: 950g polyether sulfone E6020,50g polyvinylpyrrolidone k90,0.08g sodium hydroxide and 0.4g sodium peroxydisulfate are mixed; and mix 30 minutes under 95 DEG C of nitrogen protections; make each component generation cross-linking reaction, prepare modified polyether sulfone blends。
2, the preparation of polyether sulphone hollow fibre film:
Dimethyl sulfoxide adds 250g modified polyether sulfone blends, 150g polyvinylpyrrolidone k90,40g nano modification hydroxy dioxetane titanium mixture and 60g Polyethylene Glycol (2000); dry-wet method is adopted within 18 hours, to obtain spinning liquid at 70 DEG C of stirred under nitrogen atmosphere; after spinning liquid ripening 36 hours; extruded by spinneret; and by after the air section of 400mm, with the speed of 6.5 ms/min by pure water coagulating bath, dry prepare polyether sulphone hollow fibre film 16。
Embodiment 17The preparation of polyether sulphone hollow fibre film 17
1, the preparation of each composition:
Hydroxy dioxetane titanium mixture: mixed with 775g ethylene glycol by 1-10 nanometer of 225g water-soluble titanium dioxide, obtains hydroxy dioxetane titanium mixture at 45 DEG C of stirred under nitrogen atmosphere after 30 minutes。
Modified polyether sulfone blends: 970g polyether sulfone E6020,30g polyvinylpyrrolidone k90,0.05g sodium hydroxide and 0.8g sodium peroxydisulfate are mixed; and mix 45 minutes under 95 DEG C of nitrogen protections; make each component generation cross-linking reaction, prepare modified polyether sulfone blends。
2, the preparation of polyether sulphone hollow fibre film:
Dimethyl sulfoxide adds 280g modified polyether sulfone blends, 120g polyvinylpyrrolidone k90,60g nano modification hydroxy dioxetane titanium mixture and 70g Polyethylene Glycol (2000); dry-wet method is adopted within 18 hours, to obtain spinning liquid at 65 DEG C of stirred under nitrogen atmosphere; after spinning liquid ripening 36 hours; extruded by spinneret; and by after the air section of 400mm, with the speed of 6.5 ms/min by pure water coagulating bath, dry prepare polyether sulphone hollow fibre film 17。
Embodiment 18The preparation of polyether sulphone hollow fibre film 18
1, the preparation of each composition:
Hydroxy dioxetane titanium mixture: mixed with 755g ethylene glycol by 1-10 nanometer of 245g water-soluble titanium dioxide, obtains hydroxy dioxetane titanium mixture at 45 DEG C of stirred under nitrogen atmosphere after 20 minutes。
Modified polyether sulfone blends: 940g polyether sulfone E6020,60g polyvinylpyrrolidone k90,0.08g sodium hydroxide and 0.8g sodium peroxydisulfate are mixed; and mix 90 minutes under 95 DEG C of nitrogen protections; make each component generation cross-linking reaction, prepare modified polyether sulfone blends。
2, the preparation of polyether sulphone hollow fibre film:
Dimethyl sulfoxide adds 380g modified polyether sulfone blends, 50g polyvinylpyrrolidone k90,90g nano modification hydroxy dioxetane titanium mixture and 50g Polyethylene Glycol (2000); dry-wet method is adopted within 18 hours, to obtain spinning liquid at 65 DEG C of stirred under nitrogen atmosphere; after spinning liquid ripening 36 hours; extruded by spinneret; and by after the air section of 400mm, with the speed of 6.5 ms/min by pure water coagulating bath, dry prepare polyether sulphone hollow fibre film 18。
Embodiment 19The preparation of polyether sulphone hollow fibre film 19
1, the preparation of each composition:
Hydroxy dioxetane titanium mixture: mixed with 900g ethylene glycol by 1-10 nanometer of 100g water-soluble titanium dioxide, obtains hydroxy dioxetane titanium mixture at 20 DEG C of stirred under nitrogen atmosphere after 60 minutes。
Modified polyether sulfone blends: 910g polyether sulfone E6020,150g polyvinylpyrrolidone k90,0.01g sodium hydroxide and 0.1g sodium peroxydisulfate are mixed; and mix 30 minutes under 95 DEG C of nitrogen protections; make each component generation cross-linking reaction, prepare modified polyether sulfone blends。
2, the preparation of polyether sulphone hollow fibre film:
Dimethyl sulfoxide adds 370g modified polyether sulfone blends, 400g polyvinylpyrrolidone k90,60g nano modification hydroxy dioxetane titanium mixture and 20g Polyethylene Glycol (2000); dry-wet method is adopted within 12 hours, to obtain spinning liquid at 55 DEG C of stirred under nitrogen atmosphere; after spinning liquid ripening 36 hours; extruded by spinneret; and by after the air section of 300mm, with the speed of 6.5 ms/min by pure water coagulating bath, dry prepare polyether sulphone hollow fibre film 19。
Embodiment 20The preparation of polyether sulphone hollow fibre film 20
1, the preparation of each composition:
Hydroxy dioxetane titanium mixture: mixed with 670g ethylene glycol by 1-10 nanometer of 800g water-soluble titanium dioxide, obtains hydroxy dioxetane titanium mixture at 40 DEG C of stirred under nitrogen atmosphere after 10 minutes。
Modified polyether sulfone blends: 850g polyether sulfone E6020,60g polyvinylpyrrolidone k90,1g sodium hydroxide and 0.5g sodium peroxydisulfate are mixed; and mix 45 minutes under 100 DEG C of nitrogen protections; make each component generation cross-linking reaction, prepare modified polyether sulfone blends。
2, the preparation of polyether sulphone hollow fibre film:
Dimethyl sulfoxide adds 650g modified polyether sulfone blends, 150g polyvinylpyrrolidone k90,10g nano modification hydroxy dioxetane titanium mixture and 80g Polyethylene Glycol (2000); dry-wet method is adopted within 4 hours, to obtain spinning liquid at 85 DEG C of stirred under nitrogen atmosphere; after spinning liquid ripening 72 hours; extruded by spinneret; and by after the air section of 1mm, with the speed of 6.5 ms/min by pure water coagulating bath, dry prepare polyether sulphone hollow fibre film 20。
Embodiment 21The preparation of polyether sulphone hollow fibre film 21
1, the preparation of each composition:
Hydroxy dioxetane titanium mixture: mixed with 980g ethylene glycol by 1-10 nanometer of 390g water-soluble titanium dioxide, obtains hydroxy dioxetane titanium mixture at 60 DEG C of stirred under nitrogen atmosphere after 40 minutes。
Modified polyether sulfone blends: 950g polyether sulfone E6020,80g polyvinylpyrrolidone k90,0.1g sodium hydroxide and 1g sodium peroxydisulfate are mixed; and mix 90 minutes under 95 DEG C of nitrogen protections; make each component generation cross-linking reaction, prepare modified polyether sulfone blends。
2, the preparation of polyether sulphone hollow fibre film:
Dimethyl sulfoxide adds 430g modified polyether sulfone blends, 20g polyvinylpyrrolidone k90,1g nano modification hydroxy dioxetane titanium mixture and 120g Polyethylene Glycol (2000); dry-wet method is adopted within 18 hours, to obtain spinning liquid at 100 DEG C of stirred under nitrogen atmosphere; after spinning liquid ripening 30 hours; extruded by spinneret; and by after the air section of 800mm, with the speed of 15 ms/min by pure water coagulating bath, dry prepare polyether sulphone hollow fibre film 21。
Comparative exampleThe preparation of unmodified polyether sulphone hollow fibre film
Dimethylformamide adds 220g polyether sulfone and 120g Polyethylene Glycol (400); dry-wet method is adopted within 8 hours, to obtain spinning liquid at 72 DEG C of stirred under nitrogen atmosphere; after spinning liquid ripening 24 hours; extruded by spinneret; and by after the air section of 400mm, with the speed of 12 ms/min by pure water coagulating bath, dry prepare unmodified polyether sulphone hollow fibre film。
Test case 1Film surface roughness and smoothness test
Test one: adopt 3D surface microscope (Toshiba's 3-D view Metering measuring table stereomicroscope, TM3000), respectively the unmodified polyether sulphone hollow fibre film of preparation in the modified poly (ether-sulfone) hollow-fibre membrane of the embodiment of the present invention 1 preparation and comparative example is carried out configuration of surface test, as shown in Figures 7 and 8, the parameter that test obtains is as shown in table 1 for the configuration of surface figure that test obtains。
Test two: being respectively adopted the scanning electron microscope JSM-6510 scanning electron microscope of JEOL (Japan) and the unmodified polyether sulphone hollow fibre film of preparation in the modified poly (ether-sulfone) hollow-fibre membrane of the embodiment of the present invention 1 preparation and comparative example is carried out smoothness test, the picture that scanning obtains is as shown in FIG. 9 and 10。
The modified poly (ether-sulfone) hollow-fibre membrane of table 1 present invention is with the roughness ratio of unmodified polyether sulphone hollow fibre film relatively
As seen from Table 1, in the same or analogous situation of surface area, the roughness Ra of modified poly (ether-sulfone) hollow-fibre membrane of the present invention, Rq and Rmax are respectively less than the respective value of unmodified polyether sulphone hollow fibre film。This also can find out from Fig. 7 and Fig. 8, relative to unmodified polyether sulphone hollow fibre film, the surface roughness of modified poly (ether-sulfone) hollow-fibre membrane prepared by the present invention substantially reduces, thus considerably reducing its impact on blood, significantly reduces complement activation and blood resistance。
The smoothness Electronic Speculum figure of unmodified polyether sulphone hollow fibre film in the modified poly (ether-sulfone) hollow-fibre membrane of Fig. 9 and Figure 10 respectively present invention and comparative example, from Fig. 9 and Figure 10 it can also be seen that the surface flatness of the modified poly (ether-sulfone) hollow-fibre membrane of the present invention is apparently higher than the surface flatness of unmodified polyether sulphone hollow fibre film。
Test case 2Each comparison of ingredients after hemodialysis
Being respectively adopted in the modified poly (ether-sulfone) hollow-fibre membrane of the embodiment of the present invention 1 preparation and comparative example the unmodified polyether sulphone hollow fibre film of preparation prepares hemodialyzer under the same conditions (membrane area is 1.4m2, film internal diameter is 220 μm), then it is respectively adopted two kinds of hemodialyzers and blood is dialysed, after dialysing 15 minutes, according to the detection method of regulation in GB YY0053-2008, GB/T16886.1 and GB/T16886.4, each component content in test blood, test result is as shown in table 2。
Table 2 adopt the hemodialyzer of the modified fibre film preparation of the present invention with adopt the hemodialyzer of unmodified fibers film preparation in comparative example and dialyse 15 minutes after in blood each component content compare
As seen from Table 2, adopt the present invention modified poly (ether-sulfone) doughnut film preparation hemodialyzer hemodialysis 15 minutes after blood middle leukocytes, platelet count, complement C 3, C5a level be below after the hemodialyzer dialysis adopting unmodified polyether sulphone hollow fibre film to make in blood the content of corresponding composition。
Test case 3Membrane structure Electronic Speculum figure
Adopt scanning electron microscope (the JSM-6510 scanning electron microscope of Japan JEOL) that the modified poly (ether-sulfone) hollow-fibre membrane of the embodiment of the present invention 1 preparation is carried out structural scan (test condition: HFW90.13 μm, WD10.9mm, HV20.0kv, fine vacuum, amplify 1500 times), the picture that scanning obtains is as shown in figure 11。
Figure 11 illustrates the structure chart of the modified poly (ether-sulfone) hollow-fibre membrane of the present invention, as shown in figure 11, the modified poly (ether-sulfone) hollow-fibre membrane smooth surface of the present invention, even structure, there is the micropore of 1-5nm。
Test case 4Clearance is tested
Being respectively adopted in the modified poly (ether-sulfone) hollow-fibre membrane of the embodiment of the present invention 1 preparation and comparative example the unmodified polyether sulphone hollow fibre film of preparation prepares hemodialyzer under the same conditions (membrane area is 1.4m2Film internal diameter is 220 μm), then according to the detection method of regulation in GB YY0053-2008, GB/T16886.1 and GB/T16886.4, respectively the clearance of two kinds of hemodialyzers is tested (test condition: QB=200ml/min, QD=500ml/min, TMP=1000mmHg), test result is as shown in table 3。
The modified poly (ether-sulfone) hollow-fibre membrane of table 3 present invention compares with the clearance of unmodified polyether sulphone hollow fibre film
As seen from Table 3, adopt the hemodialyzer of modified poly (ether-sulfone) doughnut film preparation of the present invention at QB=200ml/min, QD=500ml/min, when TMP=1000mmHg, to carbamide, creatinine, the clearance of phosphate and vitamin B respectively reaches 210ml/min, 190ml/min, 170ml/min and 180ml/min, ultrafiltrate coefficient reaches 200ml/kpa.h, it is above the respective value of the hemodialyzer adopting unmodified polyether sulphone hollow fibre film to prepare, show that the hemodialyzer adopting the modified poly (ether-sulfone) doughnut film preparation of the present invention has preferably clearance and ultrafiltrate coefficient。
Test case 5Hydrophilic is tested
Adopt optical contact angle instrument (Sweden Attensionthetalite), respectively the unmodified polyether sulphone hollow fibre film of preparation in the modified poly (ether-sulfone) hollow-fibre membrane of the embodiment of the present invention 1 preparation and comparative example is carried out hydrophilic test。
Figure 12 and Figure 13 respectively illustrates the view that the modified poly (ether-sulfone) hollow-fibre membrane of the present invention contacts with water with unmodified polyether sulphone hollow fibre film。As shown in Figure 12 and Figure 13, the modified poly (ether-sulfone) hollow-fibre membrane of the present invention contact with water after left and right contact angle respectively 53.1 °, 52.6 °, the left and right contact angle after adopting unmodified polyether sulphone hollow fibre film to contact with water respectively 67.0 °, 65.9 °。Thus illustrating, relative to unmodified polyether sulphone hollow fibre film, the modified poly (ether-sulfone) hollow-fibre membrane of the present invention has good hydrophilic。
Specific description of embodiments of the present invention above is not limiting as the present invention, and those skilled in the art can make various change or deformation according to the present invention, without departing from the spirit of the present invention, all should belong to scope of the following claims of the present invention。

Claims (23)

1. a hemodialyzer, comprising: shell, the fibre bundle being made up of doughnut fiber tube, end cap, packaging plastic, annular water conservancy diversion distribution rings, dialysis solution entrance, dialysis solution outlet, blood entry port and blood outlet;Wherein, described annular water conservancy diversion distribution rings is positioned at the position just described dialysis solution entrance and/or dialysis solution exported, described annular one end of water conservancy diversion distribution rings is connected with the end of described shell, the other end of described annular water conservancy diversion distribution rings towards with its just to dialysis solution entrance or the inclination of dialysis solution Way out;
Wherein, described doughnut fiber tube adopts polyether sulphone hollow fibre film to prepare, and the spinning solution of described polyether sulphone hollow fibre film comprises:
The modified polyether sulfone blends of 250-650 weight portion;
The hydrophilic molecule compound of 20-400 weight portion;
The nano modification hydroxy dioxetane titanium mixture of 1-90 weight portion;And
The alcohols solvent of 20-120 weight portion,
Wherein, described modified polyether sulfone blends comprises polyether sulfone, polyvinylpyrrolidone, sodium hydroxide and sodium peroxydisulfate, and described nano modification hydroxy dioxetane titanium mixture comprises nano-water soluble titanium dioxide and alcohol。
2. hemodialyzer according to claim 1, it is characterised in that described annular water conservancy diversion distribution rings is 2-6 ° relative to the angle of the fore-and-aft tilt of described shell;
The diameter of described annular water conservancy diversion distribution rings is 53-55mm;
The width of described annular water conservancy diversion distribution rings less than with its just to dialysis solution entrance or dialysis solution outlet along the longitudinal width of shell;
The width of described annular water conservancy diversion distribution rings is 7-9mm。
3. hemodialyzer according to claim 1 and 2, it is characterised in that described annular water conservancy diversion distribution rings is 4 ° relative to the angle of the fore-and-aft tilt of described shell;
The diameter of described annular water conservancy diversion distribution rings is 54mm;
The width of described annular water conservancy diversion distribution rings is 8mm。
4. hemodialyzer according to claim 1 and 2, it is characterised in that the spinning solution of described polyether sulphone hollow fibre film comprises:
The modified polyether sulfone blends of 250-450 weight portion;
The hydrophilic molecule compound of 50-150 weight portion;
The nano modification hydroxy dioxetane titanium mixture of 10-90 weight portion;And
The alcohols solvent of 50-100 weight portion。
5. hemodialyzer according to claim 1 and 2, it is characterized in that, described modified polyether sulfone blends comprises the sodium peroxydisulfate of the polyether sulfone of 850-980 weight portion, the polyvinylpyrrolidone of 20-150 weight portion, the sodium hydroxide of 0.01-1 weight portion and 0.1-1 weight portion;
Polyvinylpyrrolidone in described modified polyether sulfone blends is PVP k15, polyvinylpyrrolidone k30 or polyvinylpyrrolidone k90, and described polyether sulfone is polyether sulfone P-3500 or polyether sulfone E6020。
6. hemodialyzer according to claim 5, it is characterized in that, described modified polyether sulfone blends comprises the sodium peroxydisulfate of the polyether sulfone of 900-980 weight portion, the polyvinylpyrrolidone of 20-100 weight portion, the sodium hydroxide of 0.05-0.1 weight portion and 0.5-1 weight portion。
7. hemodialyzer according to claim 1 and 2, it is characterised in that described nano modification hydroxy dioxetane titanium mixture comprises nano-water soluble titanium dioxide and ethylene glycol。
8. hemodialyzer according to claim 7, it is characterised in that comprise the water-soluble titanium dioxide of 100-800 weight portion and the ethylene glycol of 600-980 weight portion in described nano modification hydroxy dioxetane titanium mixture。
9. hemodialyzer according to claim 7, it is characterised in that comprise the water-soluble titanium dioxide of 200-400 weight portion and the ethylene glycol of 600-900 weight portion in described nano modification hydroxy dioxetane titanium mixture。
10. hemodialyzer according to claim 7, it is characterised in that the particle diameter of described water-soluble titanium dioxide is 1-10nm。
11. hemodialyzer according to claim 1 and 2, it is characterised in that described hydrophilic molecule compound is polyvinylpyrrolidone or Polyethylene Glycol。
12. hemodialyzer according to claim 1 and 2, it is characterised in that described hydrophilic molecule compound is PVP k15, polyvinylpyrrolidone k30, polyvinylpyrrolidone k90 or molecular weight is the Polyethylene Glycol of 2000。
13. hemodialyzer according to claim 1 and 2, it is characterised in that described alcohols solvent is Polyethylene Glycol or glycerol。
14. hemodialyzer according to claim 13, it is characterised in that described alcohols solvent is molecular weight is the Polyethylene Glycol of 2000。
15. hemodialyzer according to claim 1 and 2, it is characterised in that the preparation method of described modified polyether sulfone blends includes:
Polyether sulfone, polyvinylpyrrolidone, sodium hydroxide and sodium peroxydisulfate are mixed, and mixes 30-120 minute under 95-120 DEG C of nitrogen protection, cross-linking reaction occurs, prepares modified polyether sulfone blends。
16. hemodialyzer according to claim 15, it is characterised in that the preparation method of described modified polyether sulfone blends includes:
Polyether sulfone, polyvinylpyrrolidone, sodium hydroxide and sodium peroxydisulfate are mixed, and mixes 60-90 minute under 100-110 DEG C of nitrogen protection, cross-linking reaction occurs, prepares modified polyether sulfone blends。
17. hemodialyzer according to claim 1 and 2, it is characterised in that the preparation method of described modified hydroxyl titanium dioxide mixture includes:
Nano-water soluble titanium dioxide is mixed with alcohol, obtains modified hydroxyl titanium dioxide mixture at 20-60 DEG C of stirred under nitrogen atmosphere after 10-60 minute。
18. hemodialyzer according to claim 17, it is characterised in that the preparation method of described modified hydroxyl titanium dioxide mixture includes:
Nano-water soluble titanium dioxide is mixed with alcohol, obtains modified hydroxyl titanium dioxide mixture at 40-50 DEG C of stirred under nitrogen atmosphere after 20-40 minute。
19. hemodialyzer according to claim 1, it is characterised in that the preparation method of described polyether sulphone hollow fibre film comprises the following steps:
Add modified polyether sulfone blends, hydrophilic molecule compound, nano modification hydroxy dioxetane titanium mixture and alcohols solvent in organic solvent; dry-wet method is adopted to stir under nitrogen protection and prepare spinning liquid; spinning liquid is carried out ripening; and extruded by spinneret; by air section, then pass through pure water coagulating bath and prepare polyether sulphone hollow fibre film。
20. hemodialyzer according to claim 19, it is characterised in that the preparation method of described polyether sulphone hollow fibre film comprises the following steps:
Add modified polyether sulfone blends, hydrophilic molecule compound, nano modification hydroxy dioxetane titanium mixture and alcohols solvent in organic solvent; dry-wet method is adopted within 4-24 hour, to obtain spinning liquid at 55-100 DEG C of stirred under nitrogen atmosphere; by spinning liquid ripening 12-72 hour; and extruded by spinneret; and by the air section of 1-800mm, then with the speed of 6-15 m/min by pure water coagulating bath, dry prepare polyether sulphone hollow fibre film。
21. hemodialyzer according to claim 20, it is characterised in that the preparation method of described polyether sulphone hollow fibre film comprises the following steps:
Add modified polyether sulfone blends, hydrophilic molecule compound, nano modification hydroxy dioxetane titanium mixture and alcohols solvent in organic solvent; dry-wet method is adopted within 12-24 hour, to obtain spinning liquid at 60-85 DEG C of stirred under nitrogen atmosphere; by spinning liquid ripening 24-36 hour; and extruded by spinneret; and by the air section of 300-500mm, then with the speed of 6-9 m/min by pure water coagulating bath, dry prepare polyether sulphone hollow fibre film。
22. the hemodialyzer according to any one of claim 19-21, it is characterised in that described organic solvent is dimethyl acetylamide, dimethylformamide or dimethyl sulfoxide。
23. a haemodialysis equipment, it comprises the hemodialyzer according to any one of claim 1-22。
CN201410083974.0A 2014-03-10 2014-03-10 A kind of hemodialyzer and haemodialysis equipment Active CN103877634B (en)

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CN104906972A (en) * 2015-05-20 2015-09-16 苏州市贝克生物科技有限公司 Nano-grade titanium dioxide/polyether hemodialysis membrane and preparation method thereof
CN107929838B (en) * 2017-11-15 2020-12-25 青岛市市立医院 Hemodialysis device for nephrology department
CN108042864A (en) * 2017-12-23 2018-05-18 玉林市玉州区万通华信科技服务部 A kind of blood dialysis solution manufacture modified resin absorber being easily installed with temperature control
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