CN117339407A - Anticoagulation hemodialysis device and preparation method and application thereof - Google Patents
Anticoagulation hemodialysis device and preparation method and application thereof Download PDFInfo
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- CN117339407A CN117339407A CN202311221922.0A CN202311221922A CN117339407A CN 117339407 A CN117339407 A CN 117339407A CN 202311221922 A CN202311221922 A CN 202311221922A CN 117339407 A CN117339407 A CN 117339407A
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- anticoagulation
- hollow fiber
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- silk
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- 238000001631 haemodialysis Methods 0.000 title claims abstract description 109
- 230000000322 hemodialysis Effects 0.000 title claims abstract description 109
- 230000010100 anticoagulation Effects 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 98
- 239000012510 hollow fiber Substances 0.000 claims abstract description 79
- 239000012528 membrane Substances 0.000 claims abstract description 69
- 229920000642 polymer Polymers 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000008280 blood Substances 0.000 claims abstract description 30
- 210000004369 blood Anatomy 0.000 claims abstract description 30
- 230000008569 process Effects 0.000 claims abstract description 24
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 17
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 238000000502 dialysis Methods 0.000 claims abstract description 14
- 150000002433 hydrophilic molecules Chemical class 0.000 claims abstract description 14
- 150000003457 sulfones Chemical class 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000002166 wet spinning Methods 0.000 claims abstract description 6
- 238000000746 purification Methods 0.000 claims abstract description 4
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 70
- 239000008213 purified water Substances 0.000 claims description 43
- 238000003756 stirring Methods 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 25
- 238000005520 cutting process Methods 0.000 claims description 24
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 22
- 239000004695 Polyether sulfone Substances 0.000 claims description 22
- 230000001112 coagulating effect Effects 0.000 claims description 22
- 230000004907 flux Effects 0.000 claims description 22
- 229920006393 polyether sulfone Polymers 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000011049 filling Methods 0.000 claims description 12
- 239000003292 glue Substances 0.000 claims description 12
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- 239000003146 anticoagulant agent Substances 0.000 claims description 10
- 229940127219 anticoagulant drug Drugs 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 150000005846 sugar alcohols Polymers 0.000 claims description 8
- 229920002873 Polyethylenimine Polymers 0.000 claims description 7
- 150000008064 anhydrides Chemical class 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- ZSZRUEAFVQITHH-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 2-(trimethylazaniumyl)ethyl phosphate Chemical compound CC(=C)C(=O)OCCOP([O-])(=O)OCC[N+](C)(C)C ZSZRUEAFVQITHH-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 4
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 108010010803 Gelatin Proteins 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
- 239000008273 gelatin Substances 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 claims description 2
- 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 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 229920000669 heparin Polymers 0.000 claims description 2
- 229960002897 heparin Drugs 0.000 claims description 2
- 229920002674 hyaluronan Polymers 0.000 claims description 2
- 229960003160 hyaluronic acid Drugs 0.000 claims description 2
- 150000003951 lactams Chemical class 0.000 claims description 2
- 230000002572 peristaltic effect Effects 0.000 claims description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000003373 anti-fouling effect Effects 0.000 abstract description 3
- 230000015271 coagulation Effects 0.000 abstract description 3
- 238000005345 coagulation Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 108090000623 proteins and genes Proteins 0.000 abstract description 3
- 102000004169 proteins and genes Human genes 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000007711 solidification Methods 0.000 abstract 1
- 230000008023 solidification Effects 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 description 52
- 239000000243 solution Substances 0.000 description 44
- 238000010438 heat treatment Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- 238000002329 infrared spectrum Methods 0.000 description 14
- 230000023555 blood coagulation Effects 0.000 description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 12
- 239000011575 calcium Substances 0.000 description 12
- 229910052791 calcium Inorganic materials 0.000 description 12
- 238000011084 recovery Methods 0.000 description 12
- 230000006872 improvement Effects 0.000 description 11
- 238000011068 loading method Methods 0.000 description 10
- 238000010907 mechanical stirring Methods 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- 238000005191 phase separation Methods 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 8
- 238000007872 degassing Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 238000009987 spinning Methods 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 210000003734 kidney Anatomy 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 208000017169 kidney disease Diseases 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 238000002054 transplantation Methods 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- -1 methacrylic acylated hyaluronic acid Chemical class 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M1/00—Suction or pumping devices for medical purposes; Devices for carrying-off, for treatment of, or for carrying-over, body-liquids; Drainage systems
- A61M1/14—Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis
- A61M1/16—Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis with membranes
- A61M1/1621—Constructional aspects thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
- B01D69/087—Details relating to the spinning process
- B01D69/088—Co-extrusion; Co-spinning
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/36—Introduction of specific chemical groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/60—Co-casting; Co-extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/40—Fibre reinforced membranes
Landscapes
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Chemical & Material Sciences (AREA)
- Urology & Nephrology (AREA)
- Heart & Thoracic Surgery (AREA)
- Hematology (AREA)
- Anesthesiology (AREA)
- Biomedical Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Vascular Medicine (AREA)
- Emergency Medicine (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- External Artificial Organs (AREA)
Abstract
The invention relates to the technical field of blood purification, and particularly discloses an anticoagulation hemodialyzer and a preparation method and application thereof, wherein the anticoagulation hemodialyzer mainly comprises a dialyzer shell, a dialysis membrane, an end cover, an O-shaped ring and a protective cap, the dialysis membrane is an anticoagulation hollow fiber membrane, the anticoagulation hollow fiber membrane is prepared by taking a sulfone polymer, an amino-containing compound and an auxiliary agent as main raw materials, firstly, carrying out wet spinning and solidification to form a membrane, and then, carrying out treatment by a hydrophilic compound containing carbon-carbon double bonds and a catalyst, wherein the wet spinning process comprises the steps of coextruding silk liquid and core liquid, the silk liquid takes the sulfone polymer, the amino-containing compound and the auxiliary agent as main raw materials, and the core liquid takes a high-molecular polymer solution containing double bonds and ester bonds as the main raw materials; the anticoagulation hemodialysis device prepared by the invention can permanently anticoagulate, can reduce protein adsorption in the use process, increase the anti-fouling performance of the product, reduce or avoid the coagulation condition of the product, and is easy for industrial production.
Description
Technical Field
The invention relates to the technical field of blood purification, in particular to an anticoagulant hemodialysis device and a preparation method and application thereof.
Background
At present, hollow fiber membranes are applied to the fields of gas treatment, liquid treatment and the like, and related industries are various, and mainly comprise chemical engineering, pharmacy, medical equipment, biological engineering technology and the like. The medical device is mainly applied to hemodialysis, and there are three methods for treating a patient suffering from kidney disease, peritoneal dialysis, hemodialysis and kidney transplantation. In 2022, the hemodialysis patients in China are about 83 ten thousand, and the market scale can reach 259 hundred million yuan. Due to cost and kidney source limitations, only less than 5% of kidney disease patients recover from kidney transplantation, and the remainder of patients can only sustain life by dialysis. As the range of hemodialysis treatment diseases continues to expand, the demand for hemodialysis equipment increases.
Polyethersulfone and polysulfone are important raw materials of a dialysis membrane, the dialysis membrane is a core technology of a hemodialysis device, and the quality of the dialysis membrane directly determines the quality of the hemodialysis device and the safety and efficiency of the dialysis process. The surface of the conventional hollow fiber membrane is inert and hydrophobic, so that proteins in blood are easily adsorbed, membrane pollution is caused, and water flux is reduced; in addition, different patients need to add different amounts of anticoagulant when hemodialysis is performed, which sometimes results in the situation that the hemodialysis machine hangs blood.
In the prior art, the dialysis membrane is often modified by adopting methods such as blending, grafting and the like so as to improve the hydrophilia, anticoagulation and anti-fouling properties of the dialysis membrane. The modified hollow fiber membrane prepared by the blending method is easy to fall off in use, and influences the use effect and the service life; the grafting modification is to combine the organic matters containing the required active functional groups on the surface of the membrane through covalent bonds, hydrogen bonds and other modes by grafting reaction, wherein the covalent bond modification mode has strong binding force and high stability, but the preparation process is more complex and the cost is high; the hydrogen bond modification mode has weak binding force, is easy to fall off, and is not easy to realize industrial production.
Disclosure of Invention
Based on this, the object of the present invention is to provide an anticoagulant hemodialysis machine and a method for its preparation and application, which address the deficiencies of the prior art.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides an anticoagulation hemodialysis device, which comprises a dialyzer shell, a dialysis membrane, an end cover, an O-shaped ring and a protective cap, and is characterized in that the dialysis membrane is an anticoagulation hollow fiber membrane; the anticoagulation hollow fiber membrane is prepared by taking a sulfone polymer, an amino-containing compound and an auxiliary agent as main raw materials through wet spinning and solidifying to form a film, and then treating the film through a hydrophilic compound containing carbon-carbon double bonds and a catalyst, wherein the wet spinning process comprises the steps of co-extrusion of silk liquid and core liquid;
the silk liquid comprises the following components in mass: 16-24 parts of sulfone polymer, 2-7 parts of amino-containing compound, 3-8 parts of auxiliary agent and 61-80 parts of solvent;
the core liquid comprises the following components in mass: the content of the high polymer solution containing double bonds and ester bonds is 50-90 parts, the content of the solvent is 9-45 parts, and the content of the alkaline substance is 1-5 parts;
the sulfone polymer comprises polysulfone or polyether sulfone; the amino-containing compound comprises one or more of methacryloylated gelatin, methacryloylated hyaluronic acid, methacryloylated heparin and polyethyleneimine; the alkaline substance comprises one or more of sodium bicarbonate, potassium hydroxide and sodium hydroxide.
As a further improvement of the invention, the anticoagulation hollow fiber membrane has hydrophilicity, the contact angle of the anticoagulation hollow fiber membrane is 35-15 degrees, the surface pore diameter is less than or equal to 2.5 mu m, and the water flux is 89-93mL (calculated by 50mmHg and 200 mL/min).
The invention also provides a preparation method of the anticoagulation hemodialysis device, which comprises the following steps:
s1, preparing silk liquid
Adding an auxiliary agent and a solvent into a reaction container, stirring and dissolving, adding a sulfone polymer, stirring until the sulfone polymer is completely dissolved, adding an amino-containing compound, stirring until the amino-containing compound is completely dissolved, cooling, vacuumizing, exhausting bubbles, and continuously stirring until bubbles are completely discharged to obtain a silk solution;
s2, preparing core liquid
Adding a polyalcohol substance and purified water into a reaction vessel, dissolving, adding double bond-containing anhydride, reacting for 1-3h at 40-60 ℃ to obtain a high polymer solution containing double bonds and ester bonds, adding a solvent and an alkaline substance, and uniformly mixing to obtain core liquid;
s3 preparation hemodialysis ware
The silk liquid prepared in the step S1 and the core liquid prepared in the step S2 are extruded together to form hollow fiber silk, the hollow fiber silk is separated into films through a coagulating bath phase, and then the films are manufactured into a hemodialysis device through a post-treatment process; the hemodialysis device comprises a blood chamber and a dialysate chamber, wherein the blood chamber comprises a hollow fiber membrane inner layer, and the dialysate chamber comprises a hollow fiber membrane outer layer;
s4 preparation anticoagulation hemodialysis ware
S4-1, adding a catalyst and purified water into a reaction container, stirring and dissolving, adding a hydrophilic compound containing carbon-carbon double bonds, and fully stirring and dissolving to obtain a solution to be reacted;
and S4-2, pumping the to-be-reacted liquid into a blood chamber of the hemodialysis machine prepared in the step S3 through a peristaltic pump, treating the to-be-reacted liquid for 1-4 hours, and then washing with water and drying with microwaves to obtain an anticoagulation hollow fiber membrane, and further obtaining the anticoagulation hemodialysis machine.
As a further improvement of the invention, the temperature of cooling in S1 is 45-55 ℃; the temperature of the microwave drying in the step S5 is 40-90 ℃.
As a further improvement of the invention, the auxiliary agent in the S1 comprises one or more of polyethylene glycol and polyvinylpyrrolidone.
Preferably, the auxiliary agent in S1 is polyvinylpyrrolidone.
As a further improvement of the invention, the polyalcohol in the S2 comprises one or more of polyvinyl alcohol and polyethylene glycol, and the addition amount of the polyalcohol accounts for 0.1-2% of the purified water.
Preferably, the polyalcohol in S2 is polyvinyl alcohol.
As a further improvement of the invention, the double bond-containing anhydride in the S2 comprises one or more of acrylic anhydride and methacrylic anhydride, and the double bond-containing anhydride is added in an amount of 0.2-12% of the purified water.
Preferably, the double bond containing anhydride in S2 is methacrylic anhydride.
As a further improvement of the invention, the solvent in S1 and S2 comprises one or more of N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide, dimethylacetamide and purified water;
preferably, the solvent in S1 and S2 is dimethylacetamide.
As a further improvement of the invention, the post-treatment process in the step S3 comprises the steps of drying, wire collecting, wire cutting, sintering, glue filling, cutting and cover mounting; when the silk liquid and the core liquid are extruded together, the pressure of the silk liquid is 500-850kpa, and the pressure of the core liquid is 0.5-1.5kpa.
As a further improvement of the invention, the catalyst in the S4-1 comprises one or more of ammonium persulfate and potassium persulfate, and the catalyst is added in an amount of 0.1-2% of the purified water.
Preferably, the catalyst in S4-1 is potassium persulfate.
As a further improvement of the invention, the hydrophilic functional group of the hydrophilic compound containing carbon-carbon double bond in S4-1 comprises one or more of sulfonic acid group, hydroxyl group, carboxyl group, lactam and phosphate group; the hydrophilic compound containing carbon-carbon double bonds comprises one or more of 2-acrylamide-2-methylpropanesulfonic acid, 2-methacryloyloxyethyl phosphorylcholine and N-vinyl pyrrolidone; the hydrophilic compound containing carbon-carbon double bond accounts for 1-20% of the purified water.
The invention also provides application of the anticoagulation hemodialysis device in the field of blood purification.
The beneficial effects of the invention are as follows:
1. the hollow fiber membrane prepared by the invention has the advantages that the durable anticoagulation effect is provided for the hollow fiber membrane on the basis of maintaining the original aperture, meanwhile, the hydrophilicity of the hollow fiber membrane is increased, the protein adsorption can be reduced, the anti-fouling performance of the product is improved, and the coagulation condition of the product is reduced or avoided in the actual use process.
2. The invention adopts hydroxyl in polyalcohol substances and anhydride containing double bonds to react to generate high polymer solution containing double bonds and ester bonds, which can increase the hydrophilicity of hollow fiber membranes, and the core liquid is formed after solvent and alkaline substances are added.
3. The silk liquid of the invention is blended with amino-containing compounds to provide reactive groups amino for synthesizing high molecular polymers with network structures.
4. The invention adopts the amino group in amino-containing compound in silk liquid and unreacted double bond-containing anhydride in core liquid to react, so as to generate high molecular polymer containing carbon-carbon double bond and amide bond; under the action of heating and alkaline substances, the double bonds of the high molecular polymer containing double bonds and ester bonds in the core liquid and the double bonds of the high molecular polymer containing carbon-carbon double bonds and amide bonds in the filament liquid react to generate the high molecular polymer containing amide bonds and amino groups, thereby providing the high molecular polymer with reactive groups for the grafting reaction of the hollow fiber membrane.
5. The invention adopts carbon-carbon double bond of hydrophilic compound containing carbon-carbon double bond and amino group of high molecular polymer containing amide bond and amino group in the inner wall of hollow fiber membrane, and makes them produce addition reaction under the action of heating and catalyst to form stable chemical bond, so that it is firm in combination, and not easy to fall off, and can effectively reduce the risk of coagulation of hemodialysis equipment in the course of actual use, and can reduce economic loss or body injury for patient.
6. The invention has the advantages of low-cost and easily-obtained reaction raw materials, mild reaction conditions, short reaction time and firm combination.
7. The anticoagulation hemodialysis device, the preparation method and the application thereof provided by the invention have the advantages that the contact angle of the prepared anticoagulation hollow fiber membrane is 35-15 degrees, the surface aperture is less than or equal to 2.5 mu m, the water flux is 89-93mL (calculated by 50mmHg and 200 mL/min), and the anticoagulation effect is obvious.
8. According to the anticoagulation hemodialyzer, the preparation method and the application thereof, the prepared anticoagulation hollow fiber membrane has hydrophilicity, the water flux is 89-93mL (calculated by 50mmHg and 200 mL/min) after water flux test, the anticoagulation effect is obvious through the blood coagulation and calcium recovery experiment, the used equipment is simple, the operation is simple, convenient and safe, the experiment period is short, the treatment process is mature, and the industrial production is easy.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram showing the overall structure of a hemodialyzer prepared in accordance with the present invention.
FIG. 2 is a cross-sectional view of the hemodialyzer of FIG. 1 taken along the A-A direction, made in accordance with the present invention.
FIG. 3 is a schematic cross-sectional view of the hemodialysis machine of FIG. 1 taken along the direction B-B, made in accordance with the present invention.
FIG. 4 is a reaction equation of the present invention.
Fig. 5 is a contact angle test chart of comparative example 1.
Fig. 6 is a graph of the contact angle test of example 1.
FIG. 7 is a scanning electron microscope test chart of comparative example 1.
Fig. 8 is a scanning electron microscope test chart of example 1.
FIG. 9 is an infrared spectrum of comparative example 1 and example 1.
FIG. 10 is a graph showing the results of the calcium-recalcification test of comparative example 1 and example 1.
Description of the embodiments
The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
S1, preparing silk liquid
Adding 6 parts of polyvinylpyrrolidone and 74 parts of dimethylacetamide into a reaction vessel with mechanical stirring, wherein the dissolution speed is set to 30rpm, the dissolution temperature is set to 85 ℃, and the dissolution is carried out for 4 hours; then 16 parts of polyethersulfone is added, and heating, stirring and dissolution are continued for 6 hours; adding 4 parts of polyethylenimine, and continuously heating, stirring and dissolving for 3 hours; after complete dissolution, cooling to 50 ℃, and using a vacuum system to remove bubbles from the polyether sulfone mixed solution, wherein the bubble removal time is 10 hours, so as to obtain silk solution;
s2, preparing core liquid
Adding 1 part of polyvinyl alcohol and 90 parts of purified water into a reaction vessel with a stirring device, and dissolving for 1h at a dissolving rotating speed of 20 rpm; 9 parts of methacrylic anhydride is added after dissolution, and the mixture is reacted for 2 hours at 50 ℃ to obtain a high polymer containing double bonds and ester bonds; and adding dimethylacetamide and sodium hydroxide, wherein the ratio of the dimethylacetamide to the sodium hydroxide to the high polymer solution containing double bonds and ester bonds is 38:2:60, stirring and dissolving uniformly, and degassing for 1h to obtain core liquid;
s3 preparation hemodialysis ware
Respectively extruding silk liquid and core liquid at 50 ℃ through a spinneret under the pressure of 500kpa and 0.8kpa to form hollow fiber silk, immersing the hollow fiber silk leaving the spinneret into a coagulating bath after passing through an air gap of 2s, and performing phase separation in the coagulating bath to form a film, thus obtaining an initial hollow fiber membrane; collecting an initial hollow fiber membrane, and performing processes of drying, wire collecting, wire cutting, sintering, glue filling, cutting and cover loading to obtain the hemodialysis device;
s4 preparation anticoagulation hemodialysis ware
1.5 parts of potassium persulfate is dissolved in 93.5 parts of purified water, and 5 parts of 2-acrylamide-2-methylpropanesulfonic acid is added at the temperature of 5 ℃ of the potassium persulfate solution, so that the solution is completely dissolved to obtain a solution to be reacted; at 50 ℃, the liquid to be reacted is circulated in a blood chamber of the hemodialysis machine for 2 hours to obtain a modified hemodialysis machine; and circularly cleaning the blood chamber and the dialysate chamber of the modified hemodialysis device by using purified water at 80 ℃ for 15min, and drying by microwaves at 80 ℃ to obtain the anticoagulation hemodialysis device.
S5 test
And (3) carrying out contact angle, scanning electron microscope, infrared spectrum, blood coagulation and calcium recovery experimental test and water flux test on the anticoagulation hemodialysis device prepared in the step (S4).
Example 2
S1, preparing silk liquid
5 parts of polyvinylpyrrolidone, 1 part of purified water and 74 parts of dimethyl sulfoxide are added into a reaction vessel with mechanical stirring, the dissolution speed is set to 30rpm, the dissolution temperature is set to 80 ℃, and the dissolution is carried out for 3 hours; then 16 parts of polyethersulfone is added, and the mixture is continuously heated, stirred and dissolved for 5 hours; adding 4 parts of polyethylenimine, and continuously heating, stirring and dissolving for 2 hours; after complete dissolution, cooling to 48 ℃, and using a vacuum system to remove bubbles from the polyether sulfone mixed solution, wherein the bubble removal time is 9 hours, so as to obtain silk solution;
s2, preparing core liquid
Adding 1 part of polyethylene glycol and 90 parts of purified water into a reaction vessel with a stirring device, and dissolving for 1h at a dissolving rotating speed of 20 rpm; 9 parts of methacrylic anhydride is added after dissolution, and the mixture reacts for 1.5 hours at 50 ℃ to obtain a high polymer containing double bonds and ester bonds; adding dimethylacetamide and potassium hydroxide, wherein the proportion of the dimethylacetamide, the potassium hydroxide and the high polymer solution containing double bonds and ester bonds is 38:2:60, stirring and dissolving uniformly, and degassing for 1h to obtain core liquid;
s3 preparation hemodialysis ware
Respectively extruding silk liquid and core liquid at 50 ℃ through a spinneret under the pressure of 500kpa and 0.8kpa to form hollow fiber silk, immersing the hollow fiber silk leaving the spinneret into a coagulating bath after passing through an air gap of 1.5s, and carrying out phase separation in the coagulating bath to form a film, thus obtaining an initial hollow fiber membrane; collecting an initial hollow fiber membrane, and performing processes of drying, wire collecting, wire cutting, sintering, glue filling, cutting and cover loading to obtain the hemodialysis device;
s4 preparation anticoagulation hemodialysis ware
1.5 parts of ammonium persulfate is dissolved in 93.5 parts of purified water, and 5 parts of 2-methacryloyloxyethyl phosphorylcholine is added at the temperature of 7 ℃ of the ammonium persulfate solution, so that the solution is completely dissolved, and a solution to be reacted is obtained; at 50 ℃, the liquid to be reacted is circulated in a blood chamber of the hemodialysis machine for 2 hours to obtain a modified hemodialysis machine; and circularly cleaning the blood chamber and the dialysate chamber of the modified hemodialysis device by using purified water at 75 ℃ for 20min, and drying by microwaves at 50 ℃ to obtain the anticoagulation hemodialysis device.
S5 test
And (3) carrying out contact angle, scanning electron microscope, infrared spectrum, blood coagulation and calcium recovery experimental test and water flux test on the anticoagulation hemodialysis device prepared in the step (S4).
Example 3
S1, preparing silk liquid
Adding 6 parts of polyethylene glycol and 74 parts of N, N-dimethylformamide into a reaction vessel with mechanical stirring, wherein the dissolution speed is set to 30rpm, the dissolution temperature is set to 85 ℃, and the dissolution is carried out for 4 hours; then 16 parts of polyethersulfone is added, and heating, stirring and dissolution are continued for 5 hours; adding 4 parts of polyethylenimine, and continuously heating, stirring and dissolving for 2 hours; after complete dissolution, cooling to 52 ℃, and using a vacuum system to remove bubbles from the polyether sulfone mixed solution, wherein the bubble removal time is 10 hours, so as to obtain silk solution;
s2, preparing core liquid
Adding 1 part of polyvinyl alcohol and 94 parts of purified water into a reaction vessel with a stirring device, and dissolving for 1h at a dissolving rotating speed of 20 rpm; after dissolution, adding 5 parts of acrylic anhydride, and reacting for 2 hours at 50 ℃ to obtain a high molecular polymer containing double bonds and ester bonds; adding N, N-dimethylformamide and sodium bicarbonate, wherein the proportion of the N, N-dimethylformamide, the sodium bicarbonate and the high polymer solution containing double bonds and ester bonds is 38:4:58, stirring and dissolving uniformly, and degassing for 1h to obtain core liquid;
s3 preparation hemodialysis ware
Respectively extruding silk liquid and core liquid at 50 ℃ through a spinneret under the pressure of 500kpa and 0.8kpa to form hollow fiber silk, immersing the hollow fiber silk leaving the spinneret into a coagulating bath after passing through an air gap of 1s, and performing phase separation in the coagulating bath to form a film, thus obtaining an initial hollow fiber membrane; collecting an initial hollow fiber membrane, and performing processes of drying, wire collecting, wire cutting, sintering, glue filling, cutting and cover loading to obtain the hemodialysis device;
s4 preparation anticoagulation hemodialysis ware
1.5 parts of potassium persulfate is dissolved in 83.5 parts of purified water, 15 parts of N-vinyl pyrrolidone is added at the temperature of 10 ℃ of the potassium persulfate solution, and the solution is completely dissolved to obtain a solution to be reacted; at 50 ℃, the liquid to be reacted is circulated in a blood chamber of the hemodialysis machine for 3 hours to obtain a modified hemodialysis machine; and circularly cleaning the blood chamber and the dialysate chamber of the modified hemodialysis device by using purified water at 70 ℃ for 30min, and drying by microwaves at 75 ℃ to obtain the anticoagulation hemodialysis device.
S5 test
And (3) carrying out contact angle, scanning electron microscope, infrared spectrum, blood coagulation and calcium recovery experimental test and water flux test on the anticoagulation hemodialysis device prepared in the step (S4).
Example 4
S1, preparing silk liquid
Adding 4 parts of polyvinylpyrrolidone and 74 parts of dimethylacetamide into a reaction vessel with mechanical stirring, wherein the dissolution speed is set to 30rpm, the dissolution temperature is set to 80 ℃, and the dissolution is carried out for 4 hours; then adding 20 parts of polyethersulfone, and continuing heating, stirring and dissolving for 8 hours; adding 2 parts of methacryloylated gelatin, and continuously heating, stirring and dissolving for 3 hours; after complete dissolution, cooling to 45 ℃, and using a vacuum system to remove bubbles from the polyether sulfone mixed solution, wherein the bubble removal time is 12 hours, so as to obtain silk solution;
s2, preparing core liquid
Adding 1 part of polyvinyl alcohol and 92 parts of purified water into a reaction vessel with a stirring device, and dissolving for 1h at a dissolving rotating speed of 20 rpm; 7 parts of methacrylic anhydride is added after dissolution, and the mixture reacts for 2 hours at 50 ℃ to obtain a high polymer containing double bonds and ester bonds; the ratio of dimethylacetamide, potassium bicarbonate and high molecular polymer solution containing double bonds and ester bonds is 38:4:58, stirring and dissolving uniformly, and degassing for 1h to obtain core liquid;
s3 preparation hemodialysis ware
Respectively extruding silk liquid and core liquid at 50 ℃ through a spinneret under the pressure of 500kpa and 0.8kpa to form hollow fiber silk, immersing the hollow fiber silk leaving the spinneret into a coagulating bath after passing through an air gap of 1.5s, and carrying out phase separation in the coagulating bath to form a film, thus obtaining an initial hollow fiber membrane; collecting an initial hollow fiber membrane, and performing processes of drying, wire collecting, wire cutting, sintering, glue filling, cutting and cover loading to obtain the hemodialysis device;
s4 preparation anticoagulation hemodialysis ware
Dissolving 1.5 parts of potassium persulfate in 94.5 parts of purified water, and adding 4 parts of 2-acrylamide-2-methylpropanesulfonic acid at the temperature of 8 ℃ to obtain a solution to be reacted; at 50 ℃, the liquid to be reacted is circulated in a blood chamber of the hemodialysis machine for 2 hours to obtain a modified hemodialysis machine; and circularly cleaning the blood chamber and the dialysate chamber of the modified hemodialysis device by purified water at 85 ℃ for 13min, and drying by microwaves at 70 ℃ to obtain the anticoagulation hemodialysis device.
S5 test
And (3) carrying out contact angle, scanning electron microscope, infrared spectrum, blood coagulation and calcium recovery experimental test and water flux test on the anticoagulation hemodialysis device prepared in the step (S4).
Example 5
S1, preparing silk liquid
Adding 5 parts of polyethylene glycol and 72 parts of N-methylpyrrolidone into a reaction vessel with mechanical stirring, wherein the dissolution speed is set to 30rpm, the dissolution temperature is set to 80 ℃, and the dissolution is carried out for 4 hours; then adding 18 parts of polyethersulfone, and continuing heating, stirring and dissolving for 6 hours; adding 5 parts of methacrylic acylated hyaluronic acid, and continuously heating, stirring and dissolving for 2 hours; after complete dissolution, cooling to 55 ℃, and using a vacuum system to remove bubbles from the polyether sulfone mixed solution, wherein the bubble removal time is 9 hours, so as to obtain silk solution;
s2, preparing core liquid
Adding 1 part of polyvinyl alcohol and 95 parts of purified water into a reaction vessel with a stirring device, and dissolving for 1h at a dissolving rotating speed of 20 rpm; after dissolution, adding 4 parts of methacrylic anhydride, and reacting for 1.5 hours at 50 ℃ to obtain a high polymer containing double bonds and ester bonds; adding N-methyl pyrrolidone and potassium hydroxide, wherein the proportion of the N-methyl pyrrolidone, sodium hydroxide and the high polymer solution containing double bonds and ester bonds is 38:2:60, stirring and dissolving uniformly, and degassing for 1h to obtain core liquid;
s3 preparation hemodialysis ware
Respectively extruding silk liquid and core liquid at 50 ℃ through a spinneret under the pressure of 500kpa and 0.8kpa to form hollow fiber silk, immersing the hollow fiber silk leaving the spinneret into a coagulating bath after passing through an air gap of 1s, and performing phase separation in the coagulating bath to form a film, thus obtaining an initial hollow fiber membrane; collecting an initial hollow fiber membrane, and performing processes of drying, wire collecting, wire cutting, sintering, glue filling, cutting and cover loading to obtain the hemodialysis device;
s4 preparation anticoagulation hemodialysis ware
1.5 parts of potassium persulfate is dissolved in 88.5 parts of purified water, 10 parts of 2-acrylamide-2-methylpropanesulfonic acid is added at the temperature of 12 ℃ of the potassium persulfate solution, and the solution is completely dissolved to obtain a solution to be reacted; at 50 ℃, the liquid to be reacted is circulated in a blood chamber of the hemodialysis machine for 3 hours to obtain a modified hemodialysis machine; and circularly cleaning the blood chamber and the dialysate chamber of the modified hemodialysis device by using purified water at 80 ℃ for 20min, and drying by microwaves at 72 ℃ to obtain the anticoagulation hemodialysis device.
S5 test
And (3) carrying out contact angle, scanning electron microscope, infrared spectrum, blood coagulation and calcium recovery experimental test and water flux test on the anticoagulation hemodialysis device prepared in the step (S4).
Example 6
S1, preparing silk liquid
Adding 3 parts of polyethylene glycol, 2 parts of purified water and 71 parts of dimethylacetamide into a reaction vessel with mechanical stirring, wherein the dissolution speed is set to 30rpm, the dissolution temperature is set to 80 ℃, and the dissolution is carried out for 3 hours; then 22 parts of polyethersulfone is added, and heating, stirring and dissolution are continued for 7 hours; adding 2 parts of polyethylenimine, and continuously heating, stirring and dissolving for 2 hours; after complete dissolution, cooling to 50 ℃, and using a vacuum system to remove bubbles from the polyether sulfone mixed solution, wherein the bubble removal time is 9 hours, so as to obtain silk solution;
s2, preparing core liquid
Adding 0.5 part of polyvinyl alcohol and 98.5 parts of purified water into a reaction vessel with a stirring device, and dissolving for 1h at a dissolving rotating speed of 20 rpm; after dissolution, adding 1 part of acrylic anhydride, and reacting for 1.5 hours at 50 ℃ to obtain a high molecular polymer containing double bonds and ester bonds; adding dimethylacetamide and sodium hydroxide, wherein the proportion of the dimethylacetamide, the sodium hydroxide and the high polymer solution containing double bonds and ester bonds is 38:2:60, stirring and dissolving uniformly, and degassing for 1h to obtain core liquid;
s3 preparation hemodialysis ware
Respectively extruding silk liquid and core liquid at 50 ℃ through a spinneret under the pressure of 500kpa and 0.8kpa to form hollow fiber silk, immersing the hollow fiber silk leaving the spinneret into a coagulating bath after passing through an air gap of 0.8s, and carrying out phase separation in the coagulating bath to form a film, thus obtaining an initial hollow fiber membrane; collecting an initial hollow fiber membrane, and performing processes of drying, wire collecting, wire cutting, sintering, glue filling, cutting and cover loading to obtain the hemodialysis device;
s4 preparation anticoagulation hemodialysis ware
1 part of ammonium persulfate is dissolved in 89 parts of purified water, 10 parts of N-vinyl pyrrolidone is added at the temperature of 10 ℃ of the ammonium persulfate solution, and the solution is completely dissolved to obtain a solution to be reacted; at 50 ℃, the liquid to be reacted is circulated in a blood chamber of the hemodialysis machine for 3 hours to obtain a modified hemodialysis machine; and (3) circularly cleaning the blood chamber and the dialysate chamber of the modified hemodialysis device by using purified water at 90 ℃ for 10min, and performing microwave drying at 76 ℃ to obtain the anticoagulation hemodialysis device.
S5 test
And (3) carrying out contact angle, scanning electron microscope, infrared spectrum, blood coagulation and calcium recovery experimental test and water flux test on the anticoagulation hemodialysis device prepared in the step (S4).
Example 7
S1, preparing silk liquid
Adding 4 parts of polyethylene glycol, 1 part of water and 73 parts of dimethylacetamide into a reaction vessel with mechanical stirring, wherein the dissolution speed is set to 30rpm, the dissolution temperature is set to 80 ℃, and the dissolution is carried out for 4 hours; then adding 18 parts of polysulfone, and continuing heating, stirring and dissolving for 6 hours; adding 4 parts of polyethylenimine, and continuously heating, stirring and dissolving for 3 hours; after complete dissolution, cooling to 52 ℃, and using a vacuum system to remove bubbles from the polyether sulfone mixed solution, wherein the bubble removal time is 11 hours, so as to obtain silk solution;
s2, preparing core liquid
Adding 1.5 parts of polyvinyl alcohol and 95 parts of purified water into a reaction vessel with a stirring device, and dissolving for 1h at a dissolving rotating speed of 20 rpm; after dissolution, adding 3.5 parts of methacrylic anhydride, and reacting for 2 hours at 50 ℃ to obtain a high molecular polymer containing double bonds and ester bonds; adding dimethylacetamide and sodium bicarbonate, wherein the proportion of the dimethylacetamide, the sodium bicarbonate and the high polymer solution containing double bonds and ester bonds is 38:4:58, stirring and dissolving uniformly, and degassing for 1h to obtain core liquid;
s3 preparation hemodialysis ware
Respectively extruding silk liquid and core liquid at 50 ℃ through a spinneret under the pressure of 500kpa and 0.8kpa to form hollow fiber silk, immersing the hollow fiber silk leaving the spinneret into a coagulating bath after passing through an air gap of 2s, and performing phase separation in the coagulating bath to form a film, thus obtaining an initial hollow fiber membrane; collecting an initial hollow fiber membrane, and performing processes of drying, wire collecting, wire cutting, sintering, glue filling, cutting and cover loading to obtain the hemodialysis device;
s4 preparation anticoagulation hemodialysis ware
1.5 parts of potassium persulfate is dissolved in 93.5 parts of purified water, 5 parts of 2-methacryloyloxyethyl phosphorylcholine is added under ice cooling at the temperature of 15 ℃ of the potassium persulfate solution, and the solution is completely dissolved to obtain a solution to be reacted; at 50 ℃, the liquid to be reacted is circulated in a blood chamber of the hemodialysis machine for 2 hours to obtain a modified hemodialysis machine; and circularly cleaning the blood chamber and the dialysate chamber of the modified hemodialysis device by using purified water at 85 ℃ for 15min, and performing microwave drying at 82 ℃ to obtain the anticoagulation hemodialysis device.
S5 test
And (3) carrying out contact angle, scanning electron microscope, infrared spectrum, blood coagulation and calcium recovery experimental test and water flux test on the anticoagulation hemodialysis device prepared in the step (S4).
Comparative example 1
S1, preparing silk liquid
Adding 6 parts of polyethylene glycol and 78 parts of dimethylacetamide into a reaction vessel with mechanical stirring, wherein the dissolution speed is set to 30rpm, the dissolution temperature is set to 85 ℃, and the dissolution is carried out for 4 hours; then 16 parts of polyethersulfone is added, and heating, stirring and dissolution are continued for 7 hours; after complete dissolution, cooling to 50 ℃, and using a vacuum system to remove bubbles from the polyether sulfone mixed solution, wherein the bubble removal time is 9 hours, so as to obtain silk solution;
s2, preparing core liquid
Dimethylacetamide and purified water were mixed according to 40:60, uniformly mixing to obtain core liquid;
s3 preparation hemodialysis ware
Under 480kpa and 0.7kpa pressure, extruding silk liquid and core liquid at a certain temperature through a spinning nozzle together to form hollow fiber silk, immersing the hollow fiber silk leaving the spinning nozzle into a coagulating bath after passing through an air gap of 2s, and performing phase separation in the coagulating bath to form a film, thus obtaining an initial hollow fiber membrane; collecting an initial hollow fiber membrane, and performing processes of drying, wire collecting, wire cutting, sintering, glue filling, cutting and cover loading to obtain the hemodialysis device; the hemodialysis machine 1 was obtained by circulating and washing the blood chamber and the dialysate chamber of the hemodialysis machine with purified water at 80 ℃ for 15min and microwave drying at 80 ℃.
S4 test
And (3) carrying out contact angle, scanning electron microscope, infrared spectrum, blood coagulation and calcium recovery experimental test and water flux test on the hemodialysis device 1 prepared in the step (S3).
Comparative example 2
S1, preparing silk liquid
8 parts of polyvinylpyrrolidone and 76 parts of dimethylacetamide are added into a reaction vessel with mechanical stirring, the dissolution speed is set to 30rpm, the dissolution temperature is set to 85 ℃, and the dissolution is carried out for 6 hours; then 16 parts of polyethersulfone is added, and heating and stirring are continued for dissolution for 6 hours; after complete dissolution, cooling to 48 ℃, and using a vacuum system to remove bubbles from the polyether sulfone mixed solution, wherein the bubble removal time is 15 hours, so as to obtain silk solution;
s2, preparing core liquid
Dimethylacetamide and purified water were purified according to 42:58, uniformly mixing to obtain core liquid;
s3 preparation hemodialysis ware
Under 480kpa and 0.7kpa pressure, extruding silk liquid and core liquid at a certain temperature through a spinning nozzle together to form hollow fiber silk, immersing the hollow fiber silk leaving the spinning nozzle into a coagulating bath after passing through an air gap of 1.5s, and performing phase separation in the coagulating bath to form a film, thus obtaining an initial hollow fiber membrane; collecting an initial hollow fiber membrane, and performing processes of drying, wire collecting, wire cutting, sintering, glue filling, cutting and cover loading to obtain the hemodialysis device; the hemodialysis machine 2 is obtained by circulating and cleaning the blood chamber and the dialysate chamber of the hemodialysis machine with purified water at 70 ℃ for 30min and microwave drying at 50 ℃.
S4 test
And (3) carrying out contact angle, scanning electron microscope, infrared spectrum, blood coagulation and calcium recovery experimental test and water flux test on the hemodialysis device 2 prepared in the step (S3).
Comparative example 3
S1, preparing silk liquid
5 parts of polyvinylpyrrolidone, 1 part of water and 76 parts of dimethylacetamide are added into a reaction vessel with mechanical stirring, the dissolution speed is set to 30rpm, the dissolution temperature is set to 80 ℃, and the dissolution is carried out for 4 hours; then adding 18 parts of polyethersulfone, and continuing heating, stirring and dissolving for 7 hours; after complete dissolution, cooling to 52 ℃, and using a vacuum system to remove bubbles from the polyether sulfone mixed solution for 9 hours to obtain silk solution;
s2, preparing core liquid
Dimethylacetamide and purified water were purified according to 35:65, uniformly mixing to obtain core liquid;
s3 preparation hemodialysis ware
Under 480kpa and 0.7kpa pressure, extruding silk liquid and core liquid at a certain temperature through a spinning nozzle together to form hollow fiber silk, immersing the hollow fiber silk leaving the spinning nozzle into a coagulating bath after passing through an air gap of 1s, and carrying out phase separation in the coagulating bath to form a film, thus obtaining an initial hollow fiber membrane; collecting an initial hollow fiber membrane, and performing processes of drying, wire collecting, wire cutting, sintering, glue filling, cutting and cover loading to obtain the hemodialysis device; the hemodialysis machine 3 is obtained by circulating and washing the blood chamber and the dialysate chamber of the hemodialysis machine with purified water at 90 ℃ for 10min and microwave drying at 75 ℃.
S4 test
And (3) carrying out contact angle, scanning electron microscope, infrared spectrum, blood coagulation and calcium recovery experimental test and water flux test on the hemodialysis device 3 prepared in the step (S3).
TABLE 1 Water flux test results
Examples 1 to 7 and comparative examples 1 to 3 were subjected to "contact angle, scanning electron microscope, infrared spectrum, blood clotting and recalcification test and water flux test". The water flux test results are shown in table 1, and the contact angle, scanning electron microscope, infrared spectrum and blood coagulation and calcium recovery experimental test are illustrated in the figure of the best embodiment 1.
Taking 50mmHg and 200ml/min as an example, the water flux can reflect the ultrafiltration capacity of the blood dialyzer, the ultrafiltration capacity of the anticoagulation hemodialysis device provided by the invention is obviously enhanced, and the water flux is 89-93ml, which is shown in table 1.
The contact angle of the hollow fiber membranes of comparative examples 1-3 ranged from 45-50, see FIG. 5; examples 1-7 anticoagulation hollow fiber membranes had contact angles ranging from 15 to 35 °, and examples 1-7 decreased from 45.519 ° of comparative example 1 to 15.067 °, demonstrating that anticoagulation hollow fiber membranes have good hydrophilicity, see fig. 6.
The pore diameters of the surfaces of the hollow fiber membranes of comparative examples 1 to 3 are less than or equal to 2.1 μm, as shown in FIG. 7; the surface pore diameters of the anticoagulation hollow fiber membranes of examples 1-7 were not more than 2.5. Mu.m, the surface pore diameters were kept substantially unchanged and slightly increased, and the water flux of the hemodialyzer was also slightly increased, as shown in FIG. 8.
Infrared spectrum shows that the hollow fiber membranes of comparative examples 1-3 are at 1728cm -1 No vibrational peak of-c=o bond at 1038cm -1 The anticoagulation hollow fiber membranes of examples 1-7 were at 1728cm without a vibrational peak of the-C-N-bond -1 And 1038cm -1 There are vibrational peaks of-c=o bond and-C-N-bond, respectively, indicating that the hydrophilic compound containing carbon-carbon double bond has reacted successfully, see fig. 9.
The hollow fiber membranes of comparative examples 1 to 3 have no remarkable anticoagulation effect, and the hollow fiber membranes of examples 1 to 7 have anticoagulation effect and are superior to those of comparative examples 1 to 3, see fig. 10; the reaction equation of the present invention is shown in FIG. 4.
It should be understood that the foregoing detailed description of the present invention is provided for illustration only and is not limited to the technical solutions described in the embodiments of the present invention, and those skilled in the art should understand that the present invention may be modified or substituted for the same technical effects; as long as the use requirement is met, the invention is within the protection scope of the invention.
Finally, it is further noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
The foregoing is a description of embodiments of the present application, and it should be noted that, for those skilled in the art, several improvements and modifications can be made without departing from the principles of the embodiments of the present application, and these improvements and modifications are also considered as the protection scope of the present application.
Claims (10)
1. An anticoagulation hemodialysis device mainly comprises a dialyzer shell, a dialysis membrane, an end cover, an O-shaped ring and a protective cap, and is characterized in that the dialysis membrane is an anticoagulation hollow fiber membrane; the anticoagulation hollow fiber membrane is prepared by taking a sulfone polymer, an amino-containing compound and an auxiliary agent as main raw materials through wet spinning and solidifying to form a film, and then treating the film through a hydrophilic compound containing carbon-carbon double bonds and a catalyst, wherein the wet spinning process comprises the steps of co-extrusion of silk liquid and core liquid;
the silk liquid comprises the following components in mass: 16-24 parts of sulfone polymer, 2-7 parts of amino-containing compound, 3-8 parts of auxiliary agent and 61-80 parts of solvent;
the core liquid comprises the following components in mass: the content of the high polymer solution containing double bonds and ester bonds is 50-90 parts, the content of the solvent is 9-45 parts, and the content of the alkaline substance is 1-5 parts;
the sulfone polymer comprises polysulfone or polyether sulfone; the amino-containing compound comprises one or more of methacryloylated gelatin, methacryloylated hyaluronic acid, methacryloylated heparin and polyethyleneimine; the hydrophilic compound containing carbon-carbon double bonds comprises one or more of 2-acrylamide-2-methylpropanesulfonic acid, 2-methacryloyloxyethyl phosphorylcholine and N-vinyl pyrrolidone.
2. The anticoagulation hemodialyzer according to claim 1, wherein the anticoagulation hollow fiber membrane has hydrophilicity, the contact angle of the anticoagulation hollow fiber membrane is 35-15 °, the surface pore diameter is less than or equal to 2.5 μm, and the water flux is 89-93mL.
3. A method for preparing an anticoagulant hemodialyzer according to any one of claims 1 to 2, characterized by comprising the steps of:
s1, preparing silk liquid
Adding an auxiliary agent and a solvent into a reaction container, stirring and dissolving, adding a sulfone polymer, stirring until the sulfone polymer is completely dissolved, adding an amino-containing compound, stirring until the amino-containing compound is completely dissolved, cooling at 45-55 ℃, vacuumizing, and exhausting bubbles, and continuously stirring until bubbles are completely discharged to obtain a silk solution;
s2, preparing core liquid
Adding a polyalcohol substance and purified water into a reaction vessel, dissolving, adding double bond-containing anhydride, reacting for 1-3h at 40-60 ℃ to obtain a high polymer solution containing double bonds and ester bonds, adding a solvent and an alkaline substance, and uniformly mixing to obtain core liquid;
s3 preparation hemodialysis ware
The silk liquid prepared in the step S1 and the core liquid prepared in the step S2 are extruded together to form hollow fiber silk, the hollow fiber silk is separated into films through a coagulating bath phase, and then the films are manufactured into a hemodialysis device through a post-treatment process; the hemodialysis device comprises a blood chamber and a dialysate chamber, and the inner cavity of the hollow fiber membrane forms the blood chamber;
s4 preparation anticoagulation hemodialysis ware
S4-1, adding a catalyst and purified water into a reaction container, stirring and dissolving, adding a hydrophilic compound containing carbon-carbon double bonds, and fully stirring and dissolving to obtain a solution to be reacted;
and S4-2, pumping the to-be-reacted liquid into a blood chamber of the hemodialysis machine prepared in the step S3 through a peristaltic pump, treating the to-be-reacted liquid for 1-4 hours, washing with water, and drying with microwaves at 40-90 ℃ to obtain an anticoagulation hollow fiber membrane, and further obtaining the anticoagulation hemodialysis machine.
4. The method for preparing an anticoagulant hemodialysis machine according to claim 3, wherein the auxiliary agent in S1 comprises one or more of polyethylene glycol and polyvinylpyrrolidone.
5. The method for preparing an anticoagulant hemodialysis machine according to claim 3, wherein the polyalcohol substance in the S2 comprises one or more of polyvinyl alcohol and polyethylene glycol, and the addition amount of the polyalcohol substance is 0.1-2% of the purified water; the alkaline substance comprises one or more of sodium bicarbonate, potassium hydroxide and sodium hydroxide.
6. The method for producing an anticoagulated hemodialyzer according to claim 3, wherein the double bond-containing acid anhydride in S2 comprises one or more of acrylic anhydride and methacrylic anhydride, and the double bond-containing acid anhydride is added in an amount of 0.2 to 12% of the purified water.
7. The method for preparing an anticoagulant hemodialyzer according to claim 3, wherein the solvent in S1 and S2 comprises one or more of N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide, dimethylacetamide, purified water; the catalyst in the S4-1 comprises one or more of ammonium persulfate and potassium persulfate, and the added amount of the catalyst accounts for 0.1-2% of the purified water.
8. The method for preparing an anticoagulant hemodialysis machine according to claim 3, wherein the post-treatment process in S3 comprises drying, wire collecting, wire cutting, sintering, glue filling, cutting and capping; when the silk liquid and the core liquid are extruded together, the pressure of the silk liquid is 500-850kpa, and the pressure of the core liquid is 0.5-1.5kpa.
9. The method for preparing an anticoagulant hemodialyzer according to any one of claims 4 to 8, wherein the hydrophilic functional group of the hydrophilic compound containing a carbon-carbon double bond in S4-1 includes one or more of a sulfonic acid group, a hydroxyl group, a carboxyl group, a lactam, a phosphate group; the hydrophilic compound containing carbon-carbon double bonds comprises one or more of 2-acrylamide-2-methylpropanesulfonic acid, 2-methacryloyloxyethyl phosphorylcholine and N-vinyl pyrrolidone; the hydrophilic compound containing carbon-carbon double bond accounts for 1-20% of the purified water.
10. Use of an anticoagulant hemodialysis machine according to any one of claims 1-2 in the field of blood purification.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311221922.0A CN117339407A (en) | 2023-09-21 | 2023-09-21 | Anticoagulation hemodialysis device and preparation method and application thereof |
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| CN202311221922.0A CN117339407A (en) | 2023-09-21 | 2023-09-21 | Anticoagulation hemodialysis device and preparation method and application thereof |
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| CN117339407A true CN117339407A (en) | 2024-01-05 |
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| CN202311221922.0A Pending CN117339407A (en) | 2023-09-21 | 2023-09-21 | Anticoagulation hemodialysis device and preparation method and application thereof |
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