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
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- 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
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- anticoagulant
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- 229920002492 poly(sulfone) Polymers 0.000 title claims abstract description 151
- 238000001631 haemodialysis Methods 0.000 title claims abstract description 99
- 230000000322 hemodialysis Effects 0.000 title claims abstract description 94
- 239000012528 membrane Substances 0.000 title claims abstract description 75
- 239000003146 anticoagulant agent Substances 0.000 title claims abstract description 61
- 229940127219 anticoagulant drug Drugs 0.000 title claims abstract description 61
- 230000002459 sustained effect Effects 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 239000000843 powder Substances 0.000 claims abstract description 37
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 16
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000005253 cladding Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 102
- 238000006243 chemical reaction Methods 0.000 claims description 50
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 39
- 229920000858 Cyclodextrin Polymers 0.000 claims description 38
- 239000001116 FEMA 4028 Substances 0.000 claims description 38
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical group OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 38
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 38
- 229960004853 betadex Drugs 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 102000007625 Hirudins Human genes 0.000 claims description 29
- 108010007267 Hirudins Proteins 0.000 claims description 29
- WQPDUTSPKFMPDP-OUMQNGNKSA-N hirudin Chemical compound C([C@@H](C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N1[C@@H](CCC1)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](CC=1C=CC(OS(O)(=O)=O)=CC=1)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CCC(N)=O)C(O)=O)NC(=O)[C@H](CC(O)=O)NC(=O)CNC(=O)[C@H](CC(O)=O)NC(=O)[C@H](CC(N)=O)NC(=O)[C@H](CC=1NC=NC=1)NC(=O)[C@H](CO)NC(=O)[C@H](CCC(N)=O)NC(=O)[C@H]1N(CCC1)C(=O)[C@H](CCCCN)NC(=O)[C@H]1N(CCC1)C(=O)[C@@H](NC(=O)CNC(=O)[C@H](CCC(O)=O)NC(=O)CNC(=O)[C@@H](NC(=O)[C@@H](NC(=O)[C@H]1NC(=O)[C@H](CCC(N)=O)NC(=O)[C@H](CC(N)=O)NC(=O)[C@H](CCCCN)NC(=O)[C@H](CCC(O)=O)NC(=O)CNC(=O)[C@H](CC(O)=O)NC(=O)[C@H](CO)NC(=O)CNC(=O)[C@H](CC(C)C)NC(=O)[C@H]([C@@H](C)CC)NC(=O)[C@@H]2CSSC[C@@H](C(=O)N[C@@H](CCC(O)=O)C(=O)NCC(=O)N[C@@H](CO)C(=O)N[C@@H](CC(N)=O)C(=O)N[C@H](C(=O)N[C@H](C(NCC(=O)N[C@@H](CCC(N)=O)C(=O)NCC(=O)N[C@@H](CC(N)=O)C(=O)N[C@@H](CCCCN)C(=O)N2)=O)CSSC1)C(C)C)NC(=O)[C@H](CC(C)C)NC(=O)[C@H]1NC(=O)[C@H](CC(C)C)NC(=O)[C@H](CC(N)=O)NC(=O)[C@H](CCC(N)=O)NC(=O)CNC(=O)[C@H](CO)NC(=O)[C@H](CCC(O)=O)NC(=O)[C@H]([C@@H](C)O)NC(=O)[C@@H](NC(=O)[C@H](CC(O)=O)NC(=O)[C@@H](NC(=O)[C@H](CC=2C=CC(O)=CC=2)NC(=O)[C@@H](NC(=O)[C@@H](N)C(C)C)C(C)C)[C@@H](C)O)CSSC1)C(C)C)[C@@H](C)O)[C@@H](C)O)C1=CC=CC=C1 WQPDUTSPKFMPDP-OUMQNGNKSA-N 0.000 claims description 29
- 229940006607 hirudin Drugs 0.000 claims description 29
- 230000004048 modification Effects 0.000 claims description 27
- 238000012986 modification Methods 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- HTTJABKRGRZYRN-UHFFFAOYSA-N Heparin Chemical compound OC1C(NC(=O)C)C(O)OC(COS(O)(=O)=O)C1OC1C(OS(O)(=O)=O)C(O)C(OC2C(C(OS(O)(=O)=O)C(OC3C(C(O)C(O)C(O3)C(O)=O)OS(O)(=O)=O)C(CO)O2)NS(O)(=O)=O)C(C(O)=O)O1 HTTJABKRGRZYRN-UHFFFAOYSA-N 0.000 claims description 23
- 229960002897 heparin Drugs 0.000 claims description 23
- 229920000669 heparin Polymers 0.000 claims description 23
- 230000004888 barrier function Effects 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 15
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 230000010355 oscillation Effects 0.000 claims description 11
- 238000005266 casting Methods 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 239000002504 physiological saline solution Substances 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 5
- 238000007711 solidification Methods 0.000 claims description 5
- 230000008023 solidification Effects 0.000 claims description 5
- 230000000977 initiatory effect Effects 0.000 claims description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- CTXUTPWZJZHRJC-UHFFFAOYSA-N 1-ethenylpyrrole Chemical class C=CN1C=CC=C1 CTXUTPWZJZHRJC-UHFFFAOYSA-N 0.000 claims 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical class CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims 1
- 210000004369 blood Anatomy 0.000 abstract description 13
- 239000008280 blood Substances 0.000 abstract description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 abstract description 3
- 230000010148 water-pollination Effects 0.000 abstract description 3
- 230000007704 transition Effects 0.000 abstract description 2
- 238000000502 dialysis Methods 0.000 description 13
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 11
- 238000004090 dissolution Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000007853 buffer solution Substances 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 9
- 229920002678 cellulose Polymers 0.000 description 8
- 239000001913 cellulose Substances 0.000 description 8
- 238000005119 centrifugation Methods 0.000 description 8
- 210000004185 liver Anatomy 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 3
- 102000004506 Blood Proteins Human genes 0.000 description 3
- 108010017384 Blood Proteins Proteins 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000004154 complement system Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000035479 physiological effects, processes and functions Effects 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 125000001174 sulfone group Chemical group 0.000 description 3
- 241000545744 Hirudinea Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NNJVILVZKWQKPM-UHFFFAOYSA-N Lidocaine Chemical compound CCN(CC)CC(=O)NC1=C(C)C=CC=C1C NNJVILVZKWQKPM-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 208000001647 Renal Insufficiency Diseases 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000021736 acetylation Effects 0.000 description 2
- 238000006640 acetylation reaction Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 201000006370 kidney failure Diseases 0.000 description 2
- 229960004194 lidocaine Drugs 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011709 vitamin E Substances 0.000 description 2
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- WXQDFOGZIYLEGP-UHFFFAOYSA-N C(C(C)C)#N.C(C(C)C)#N.[N] Chemical compound C(C(C)C)#N.C(C(C)C)#N.[N] WXQDFOGZIYLEGP-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 206010020772 Hypertension Diseases 0.000 description 1
- CJKRXEBLWJVYJD-UHFFFAOYSA-N N,N'-diethylethylenediamine Chemical compound CCNCCNCC CJKRXEBLWJVYJD-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 208000007536 Thrombosis Diseases 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000002429 anti-coagulating effect Effects 0.000 description 1
- 102000015736 beta 2-Microglobulin Human genes 0.000 description 1
- 108010081355 beta 2-Microglobulin Proteins 0.000 description 1
- 230000023555 blood coagulation Effects 0.000 description 1
- 210000001772 blood platelet Anatomy 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 208000020832 chronic kidney disease Diseases 0.000 description 1
- 208000022831 chronic renal failure syndrome Diseases 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 210000003714 granulocyte Anatomy 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000001631 hypertensive effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 210000001616 monocyte Anatomy 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- -1 polyethylene pyrrole Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
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.
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| EP3710806B1 (en) * | 2017-11-15 | 2024-08-28 | 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 | A kind of method for preparing nano lignin balls from corn stover |
| 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 |
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| 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 |
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