CN-119793217-B - Fluorine surface modified hollow fiber membrane material and preparation method thereof

Abstract

The invention provides a fluorine surface modified hollow fiber membrane material, a preparation method and application thereof, in particular to a fluorine surface modified hollow fiber membrane which is prepared by the preparation method, comprising the following steps of 1, preparing a casting solution containing polyolefin materials and diluents; step 2, preparing a hollow fiber membrane silk precursor by a film casting solution through a spinning process, step 3, sequentially passing the hollow fiber membrane silk precursor through an air gap, a cooling tank and a solvent exchange tank to obtain a semi-finished membrane with the diluent removed, wherein the cooling liquid in the cooling tank is perfluoropolyether and dihydroxyperfluoro polyether, and step 4, drying the semi-finished membrane to obtain the fluorine surface modified hollow fiber membrane. The invention utilizes the cooling link in the spinning process, finishes the cooling of the hollow fiber membrane at a higher speed, carries out fluorine modification on the hollow fiber membrane, forms a chemical functional group containing fluorine, and powerfully improves the biocompatibility of the hollow fiber membrane.

Inventors

• JIA WEI
• GAO MING
• PENG JINGJUN
• WANG YU
• PENG XIAOQUAN
• HUANG LINJIE
• YU XUEFENG

Assignees

• 深圳高性能医疗器械国家研究院有限公司
• 中国科学院深圳先进技术研究院

Dates

Publication Date

20260505

Application Date

20241218

Claims (15)

1. 1. A method for preparing a fluorine surface modified hollow fiber membrane, which is characterized by comprising the following steps: step 1, preparing a casting solution containing polyolefin materials and diluents; step 2, preparing a hollow fiber membrane silk precursor from the membrane casting solution through a silk spraying process; Step 3, sequentially passing the hollow fiber membrane wire precursor through an air gap, a cooling tank and a solvent exchange tank to obtain a semi-finished membrane after the diluent is removed, wherein the cooling liquid in the cooling tank is at least one of perfluoropolyether and dihydroxy perfluoropolyether; step 4, drying the semi-finished membrane to obtain a hollow fiber membrane with a fluorine surface modified; The polyolefin material is selected from poly 4-methyl-1-pentene or polypropylene; the diluent is at least one selected from dioctyl oxalate, glyceryl triacetate, dibutyl phthalate and dioctyl phthalate; in the step3, an extractant is arranged in the solvent exchange tank, and the diluent is removed through extraction of the extractant.
2. 2. The method of claim 1, wherein the polyolefin material is present in the casting solution in an amount of 20 wt% to 50% wt% and the diluent is present in an amount of 50% wt% to 80% wt%.
3. 3. The method according to claim 1, wherein in step 2, the spinning process is a process of extruding and spinning the casting solution through a spinneret to form hollow fibers, and the difference between the outer diameter of the spinneret and the inner diameter of the spinneret is 5 μm to 500 μm.
4. 4. The method according to claim 3, wherein the difference between the outer diameter of the spinneret and the inner diameter of the spinneret is 150 μm to 500 μm.
5. 5. The method according to claim 3, wherein the spinneret has an inner diameter of 50 μm to 500 μm and an outer diameter of 100 μm to 1000 μm.
6. 6. The method according to claim 3, wherein the spinneret has an inner diameter of 100 μm to 300 μm and an outer diameter of 200 μm to 800 μm.
7. 7. The method according to claim 1, wherein the air gap is at least one selected from the group consisting of air, nitrogen and carbon dioxide, and the air gap is 10 mm to 500 mm.
8. 8. The method of claim 7, wherein the air gap is 50 mm to 300 mm.
9. 9. The process according to claim 3, wherein the extrusion spinning speed is 20 m to 300 m per minute.
10. 10. The method of claim 9, wherein the extrusion spinning speed is 20 m/min to 100 m/min.
11. 11. The method of claim 1, wherein the cooling fluid in the cooling bath is at a temperature of 25 ℃ to 65 ℃.
12. 12. The method of claim 11, wherein the cooling fluid in the cooling bath is at a temperature of 30 ℃ to 60 ℃.
13. 13. The method according to claim 1, wherein the extractant is at least one selected from the group consisting of ethanol, isopropanol, N dimethylformamide, ethyl acetate, amyl acetate, methylene chloride and ethylene glycol butyl ether.
14. 14. The method of claim 12, wherein the extraction time in the solvent exchange tank is 10h to 100 h.
15. 15. The fluorine surface-modified hollow fiber membrane produced by the production method according to any one of claims 1 to 14.

Description

Fluorine surface modified hollow fiber membrane material and preparation method thereof Technical Field The invention relates to the technical field of material surface modification, in particular to a fluorine surface modified hollow fiber membrane material and a preparation method thereof Background The membrane oxygenator is also called membrane artificial lung, is a disposable artificial device capable of blood gas exchange, is mainly used for extracorporeal circulation support in critical emergency rescue or disease treatment process, and is a core part of the current external membrane pulmonary oxygenation (ECMO) equipment, mechanical perfusion equipment and donor organ mechanical perfusion protection equipment. When the system is in operation, blood of a patient flows outside the hollow fiber membrane, oxygen is injected into the membrane, and carbon dioxide in the blood and oxygen in the membrane wires are replaced in a pressure difference mode, so that the gas exchange function of the lung is realized. The membrane material is required to have good air permeability and long-acting water repellency, so that the requirement of continuous operation for weeks or even months in clinic is met. Thus, for membrane oxygenators, the most critical component is the hollow fiber membrane material, the properties of which determine the performance of the oxygenator. In addition, since the membrane material is in direct contact with blood, excellent blood compatibility is also required for the membrane material used. EP2295132A1 proposes a strategy for the preparation of antithrombotic extracorporeal blood circuits and their components, including hollow fiber membranes, blood tubes and filters, and their use in the relevant directions of hemofiltration, hemodialysis, hemodiafiltration, hemoconcentration, blood oxygenation, etc., wherein the use of anticoagulants can be avoided. The hollow fiber membrane defined in this document contains fluorine-containing macromolecules by a blending process. In order to achieve the effect of reducing thrombosis, a large amount of such fluorine-containing macromolecules must be used. CN113316481a proposes a dialyzer for fluorine-containing hollow fiber membranes, and the hollow fiber membranes defined in the document contain fluorine-containing macromolecules through a blending process, and a large number of fluorine-containing macromolecules are required to be used in order to achieve a certain biocompatibility improving effect. However, for the thermal spinning process of the hollow fiber membrane, the membrane degradation is easily caused in the membrane forming process by blending a large amount of fluorine-containing macromolecules into the membrane casting solution to improve the membrane biocompatibility, which is not beneficial to the continuous production of the membrane. Disclosure of Invention Aiming at the problems existing in the prior art, the invention aims to provide a preparation technology for improving a hollow fiber membrane by adjusting a cooling process, and the hollow fiber membrane with a fluorine surface modified is obtained by fully utilizing a coolant in the preparation process of the hollow fiber membrane. The invention aims to improve the process of preparing a hollow fiber membrane by a Thermal Induced Phase Separation (TIPS) method by using a cooling liquid, and fluorine element is added to the surface of the hollow fiber membrane under the action of the fluorine-containing cooling liquid, so that fluorine-containing related chemical groups are formed on the surface of the fiber membrane. The first aspect of the present invention provides a method for producing a fluorine surface-modified hollow fiber membrane, the method comprising the steps of: step 1, preparing a casting solution containing polyolefin materials and diluents; step 2, preparing a hollow fiber membrane silk precursor from the membrane casting solution through a silk spraying process; Step 3, sequentially passing the hollow fiber membrane wire precursor through an air gap, a cooling tank and a solvent exchange tank to obtain a semi-finished membrane after the diluent is removed, wherein the cooling liquid in the cooling tank is at least one of perfluoropolyether and dihydroxy perfluoropolyether; And step 4, drying the semi-finished membrane to obtain the fluorine surface modified hollow fiber membrane. Further, the content of the polyolefin material in the casting film liquid is 20-50 wt%, and the content of the diluent is 50-80 wt%. Further, the polyolefin material is selected from poly 4-methyl-1-pentene, polypropylene. Further, the diluent is at least one selected from dioctyl oxalate, glyceryl triacetate, dibutyl phthalate and dioctyl phthalate. In step 2, the spinning process is to extrude and spin the casting solution through a spinneret to form hollow fibers, wherein the difference between the outer diameter of the spinneret and the inner diameter of the spinneret is 5-500 μm