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CN-115779698-B - Hollow fiber membrane, preparation method thereof and membrane pulmonary oxygenator

CN115779698BCN 115779698 BCN115779698 BCN 115779698BCN-115779698-B

Abstract

The invention relates to a hollow fiber membrane, a preparation method thereof and a membrane pulmonary oxygenator, wherein the membrane structure of the hollow fiber membrane comprises a porous layer, a compact layer and a microstructure layer from inside to outside; the compact layer is arranged on the porous layer, the microstructure layer is arranged on the compact layer, and the surface of the microstructure layer far away from the compact layer is a rough surface. The surface of the hollow fiber membrane has better anticoagulation effect, longer plasma leakage resisting time and better oxygenation efficiency.

Inventors

  • GAN YU
  • DENG ZHIHUA
  • LI ZHAOMIN

Assignees

  • 创脉医疗科技(上海)有限公司

Dates

Publication Date
20260508
Application Date
20210910

Claims (10)

  1. 1.A hollow fiber membrane, characterized in that the membrane structure of the hollow fiber membrane comprises from inside to outside: A porous layer; A dense layer provided on the porous layer, and The microstructure layer is arranged on the compact layer, and the surface of the microstructure layer far away from the compact layer is a rough surface; The microstructure layer comprises a plurality of protruding portions arranged along a first direction and a second direction, the protruding portions are in a columnar shape, a direction perpendicular to a plane formed by the first direction and the second direction is taken as a third direction, the dimension L 1 of the protruding portions in the first direction is 100-1000 nm, the dimension L 2 of the protruding portions in the second direction is 100-1000 nm, the dimension L 3 of the protruding portions in the third direction is 1800-3200 nm, the distance L 4 between two adjacent protruding portions in the first direction is 100-1000 nm, and the distance L 5 between two adjacent protruding portions in the second direction is 100-1000 nm.
  2. 2. The hollow fiber membrane of claim 1, wherein the porous layer and the dense layer are both functional layers comprising pores; l 3 is 2200-2850 nm; The water contact angle of the outer surface of the microstructure layer is more than 155 degrees, and the rolling angle is less than 10 degrees; The thickness of the compact layer is 0.3-3 mu m; the thickness of the porous layer is 82-90 mu m; The average pore diameter of the holes of the compact layer is 1-200 nm, and the porosity of the compact layer is 5% -35%; the average pore diameter of the pores of the porous layer is 50-2000 nm, and the porosity of the porous layer is 45-75%.
  3. 3. The hollow fiber membrane according to claim 1, wherein the porous layer has a thickness of 70 to 90 μm, the dense layer has a thickness of 0.3 to 3 μm, and L 3 has a thickness of 2300 to 2850nm.
  4. 4. The hollow fiber membrane according to claim 1, wherein the porous layer and the dense layer are functional layers containing pores, wherein the average pore diameter of the pores of the porous layer is 50-2000 nm, the average pore diameter of the pores of the dense layer is 1-200 nm, the porosity of the porous layer is 45-75%, and the porosity of the dense layer is 5-35%.
  5. 5. A method for producing a hollow fiber membrane according to any one of claims 1 to 4, comprising the steps of: Providing a hollow fiber membrane primary product, wherein the hollow fiber membrane primary product comprises the porous layer and the compact layer arranged on the porous layer; and etching the surface of the compact layer to form the microstructure layer to obtain the hollow fiber membrane.
  6. 6. The method according to claim 5, wherein in the step of etching the surface of the dense layer, the etching is performed by a plasma etching method, the processing power is 200 to 1200w, and the processing time is 10 to 60s.
  7. 7. The method of claim 5, wherein the step of providing a hollow fiber membrane precursor comprises the steps of: mixing the raw materials for forming the hollow fiber membrane, and performing extrusion molding to obtain an extrudate; Cooling, phase-separating, cooling and solidifying the extrudate to obtain a nascent hollow fiber membrane; And (3) sequentially drawing, extracting with a diluent and drying the primary hollow fiber membrane to obtain the primary hollow fiber membrane product.
  8. 8. The method according to claim 7, wherein each raw material for forming the hollow fiber membrane comprises polyolefin and a diluent; The polyolefin is selected from one or more of polyethylene, polypropylene and poly-4-methyl-1-pentene, and the diluent is selected from one or more of dioctyl adipate, dioctyl phthalate, isopropyl myristate, dibenzyl ether, dioctyl sebacate, dibutyl phthalate, dibutyl adipate, paraffin oil, sesame oil, dibutyl sebacate, castor oil, glyceryl triacetate, mineral oil and soybean oil.
  9. 9. The method according to claim 7, wherein the step of cooling and solidifying comprises using a bath comprising glyceryl triacetate or water, and/or In the drawing step, the drawing temperature is 30-60 ℃, the drawing multiplying power is 1.2-1.8 times of that of the nascent hollow fiber membrane, and/or In the step of extracting the diluent, the extracting agent is selected from one or more of ethanol, isopropanol, acetone and methanol.
  10. 10. A membrane lung oxygenator comprising the hollow fiber membrane of any one of claims 1-4.

Description

Hollow fiber membrane, preparation method thereof and membrane pulmonary oxygenator Technical Field The invention relates to the technical field of medical instruments, in particular to a hollow fiber membrane, a preparation method thereof and a membrane pulmonary oxygenator. Background In the field of medical appliances, the anticoagulation function of the surface of the product is always the focus of research of various scientific institutions and companies, and the appliance product with better anticoagulation performance can reduce the risk of operation to a great extent. The membrane lung consumable is one of the important parts of the membrane lung oxygenator, plays an important role of artificial lung, plays a role of exchanging oxygen (O 2) and carbon dioxide (CO 2) in blood, and is a hollow fiber membrane prepared from polyolefin materials, and polypropylene and poly-4-methyl-1-pentene materials are commonly used. The hollow fiber membrane has micron or nanometer level pores homogeneously distributed in the wall, and these pores have close relation with the gas exchange rate. In order to provide a membrane lung consumable with a high gas exchange rate and at the same time to be resistant to plasma leakage for a long time, hollow fiber membranes are generally designed as asymmetric structures, in particular, the inner surface in contact with oxygen is designed as a porous layer (support layer) with high porosity, and the outer surface in contact with blood is designed as a dense layer with low porosity. However, the hollow fiber membrane of the simple porous layer and dense layer laminated structure has poor surface anticoagulation effect, and further surface anticoagulation treatment is required. At present, the means of anticoagulation treatment on the surface of a material is mainly surface heparinization treatment, which is one of the most used means of medical instruments, but the method is not suitable for microporous structures and membrane lung consumable materials with high surface permeation resistance requirements, because the heparinization treatment can damage the surface structure, so that the gas flux is reduced or the performance of resisting plasma leakage is weakened. The related literature proposes adding anticoagulant macromolecular material to blend and extrude to prepare anticoagulant hollow fiber membrane, but the additional introduction of anticoagulant component can directly affect the phase separation process of polymer and diluent (solvent), and whether anticoagulant component can effectively move to the outer surface of hollow fiber membrane is unknown, so that the method has certain uncertainty, thereby affecting the oxygenation efficiency of the final hollow fiber membrane. Disclosure of Invention Based on this, it is necessary to provide a hollow fiber membrane, a method for producing the same, and a membrane lung oxygenator. The surface of the hollow fiber membrane has better anticoagulation effect, longer plasma leakage resisting time and better oxygenation efficiency. A hollow fiber membrane, the membrane structure of which comprises, from inside to outside: A porous layer; A dense layer provided on the porous layer, and The microstructure layer is arranged on the compact layer, and the surface, far away from the compact layer, of the microstructure layer is a rough surface. In one embodiment, the microstructure layer includes a plurality of protruding portions arranged along a first direction and a second direction, the first direction and the second direction intersect, and the protruding portions are columnar. In one embodiment, a direction perpendicular to a plane formed by the first direction and the second direction is taken as a third direction, a dimension L 1 of the protruding portion in the first direction is 100-1000 nm, a dimension L 2 of the protruding portion in the second direction is 100-1000 nm, a dimension L 3 of the protruding portion in the third direction is 100-4000 nm, a distance L 4 between two adjacent protruding portions in the first direction is 100-1000 nm, and a distance L 5 between two adjacent protruding portions in the second direction is 100-1000 nm. In one embodiment, L 1 is 400-850 nm, L 2 is 400-850 nm, L 3 is 1000-460 nm, L 4 is 400-850 nm, and L 5 is 500-850 nm. In one embodiment, the thickness of the porous layer is 70-90 μm, the thickness of the dense layer is 0.3-3 μm, and the thickness of the microstructure layer is 0.01-4 μm. In one embodiment, the porous layer and the compact layer are both functional layers containing holes, wherein the average pore diameter of the holes of the porous layer is 50-2000 nm, the average pore diameter of the holes of the compact layer is 1-200 nm, the porosity of the porous layer is 45-75%, and the porosity of the compact layer is 5-35%. In one embodiment, the outer surface of the microstructured layer has a water contact angle greater than 155 degrees and a roll angle less than 10 degrees. T