MOF-based porous liquid modified composite membrane, preparation method and application in ECMO system

Abstract

The invention discloses an MOF-based porous liquid modified composite membrane, a preparation method and an application in an ECMO system, the composite membrane comprises a PMP hollow fiber membrane, Pebax and an MOF-based porous liquid material are doped on the PMP hollow fiber membrane, the Pebax comprises a polyamide-polyether block, the MOF-based porous liquid material is doped on the PMP hollow fiber membrane, the Pebax is doped on the PMP hollow fiber membrane, and the MOF-based porous liquid material is doped on the Pebax. The MOF-based porous liquid material comprises UiO-66 of which the surface is grafted with organic silane. The composite membrane shows excellent CO2 / O2 selective adsorption performance in an ECMO system, and has good blood compatibility and biocompatibility at the same time.

Description

Technical Field

[0001] The present invention relates to a composite membrane modified by MOF-based porous liquid, a preparation method thereof, and an application thereof in an ECMO system, and belongs to the technical field of membranes for ECMO systems. Background Art

[0002] Extracorporeal Membrane Oxygenation (ECMO) is a combination of an artificial lung and an artificial heart, and is a medical first-aid technical device. The most core parts are the membrane lung and the blood pump, which play the roles of an artificial lung and an artificial heart respectively, and can provide short-term cardiopulmonary support for patients with severe cardiopulmonary failure, winning precious time for the rescue of critically ill patients. ECMO support is an auxiliary treatment measure that is currently difficult to replace with other medical technologies, and to a certain extent represents the hospital's rescue level for critically ill patients. According to a research report by Marketsand Markets, Maquet, Medtronic, and LivaNova (the ECMO brand is Sorin) are the top three in the global ECMO equipment market. And for the membrane materials applicable to ECMO, the best in the world currently is Membrana Company, which has now been acquired by 3M Company.

[0003] The gas-blood exchange membrane is the core component of the membrane oxygenator. As a barrier separating blood from the gas phase, it also provides a site for blood oxidation. The structure and distribution of the pores on the surface of the membrane cortex have a very important impact on gas permeability and preventing plasma leakage. Currently, the common core materials of membrane oxygenators include polypropylene (PP) and poly(4-methyl-1-pentene) (PMP). In comparison, PMP has a higher oxygen permeability, and due to its better hydrophobic property, the blood flow resistance during the process is lower, and blood penetration is reduced. However, currently, the global PMP membrane products are monopolized by 3M Company of the United States.

[0004] Poly(4-methyl-1-pentene) (PMP) is a thermoplastic polyolefin with good mechanical stability and thermal stability. PMP also has excellent gas permeability and plasma leakage resistance. Therefore, PMP is an excellent membrane material. However, ECMO has strict requirements for material properties. In addition to having high blood compatibility, it also requires ideal gas-blood exchange performance. In the human body, due to different partial pressures, the transmission rate of CO2 is twice that of O2. In the oxygenator, in order to reduce blood damage, the pressure is even lower than that in the human lung, resulting in the transmission rates of CO2 and O2 in the oxygenator not reaching the ideal state. Therefore, improving the CO2 transmission performance of PMP hollow fiber membranes for ECMO is an urgent problem to be solved.

[0005] In recent years, researchers in various countries have proposed the concept of porous liquids (PLs), which are a new class of porous materials that have the potential to combine the advantages of both solid and liquid adsorbents. Through appropriate design, seemingly contradictory properties, porosity and fluidity, can be combined, featuring rapid mass transfer, strong fluidity, and liquid kinetic stability. Metal-organic frameworks are porous materials with adjustable pore sizes self-assembled from organic ligands and metal sites. The elemental spectrum of MOF materials spans the entire periodic table, exhibiting a wide range of characteristics. Compared with traditional inorganic porous materials, MOFs have a larger specific surface area, higher porosity, and more diverse structures and functions. Therefore, they are widely used in gas adsorption and separation. However, MOFs usually have low stability in the liquid phase and are prone to aggregation, which limits their CO2 adsorption performance in aqueous or organic phases. Therefore, we introduced MOF-based porous liquids to solve these problems. Summary of the Invention

[0006] The object of the present invention is to provide a composite membrane modified with MOF-based porous liquid, a preparation method, and its application in an ECMO system. The composite membrane exhibits excellent CO2 / O2 selective adsorption performance in the ECMO system, and at the same time has good blood compatibility and biocompatibility.

[0007] The technical solution adopted by the present invention is as follows:

[0008] A composite membrane modified with MOF-based porous liquid, the composite membrane includes a PMP hollow fiber membrane, Pebax and an MOF-based porous liquid material are doped on the PMP hollow fiber membrane, the Pebax includes a polyamide-polyether block, and the MOF-based porous liquid material includes UiO-66 grafted with organosilane on the surface.

[0009] The preparation method of the above-mentioned composite membrane modified with MOF-based porous liquid includes the following steps:

[0010] S1. Synthesize UiO-66-OH; mix UiO-66-OH with deionized water, then add organosilane, heat, and after the reaction ends, centrifuge, wash, and dry to obtain UiO-66-OS;

[0011] S2. Disperse UiO-66-OS and a steric hindrance solvent into a solvent, heat to evaporate the solvent to obtain UiO-66-OS porous liquid;

[0012] S3. Disperse the UiO-66-OS porous liquid into a Pebax casting solution to prepare a modified solution, and then immerse the PMP hollow fiber membrane in the above-mentioned modified solution, and dry it after completion to obtain a Pebax / PMP composite membrane.

[0013] Preferably, in the step S1, the specific steps for synthesizing UiO-66-OH are as follows: Dissolve a zirconium precursor and terephthalic acid in a mixture of formic acid and DMF, and stir at room temperature to obtain UiO-66-OH.

[0014] Preferably, the dosage ratios of the zirconium precursor, terephthalic acid, formic acid, and DMF are respectively: (0.8-1.5) g: (0.5-1) g: (3-10) ml: (40-70) ml.

[0015] Preferably, in the step S1, the dosage ratio of UiO-66-OH, deionized water, and organosilane is: (0.01-0.1) g: (40-100) ml: (0.2-0.8) g;

[0016] The heating conditions are: heating in an oil bath, at 60-80 °C, for 20-27 h;

[0017] The drying conditions are: at 60-80 °C, for 22-26 h.

[0018] Preferably, in the step S2, the dosage ratio of UiO-66-OS, a steric hindrance solvent, and a solvent is: (0.02-0.1) g: (0.1-0.3) g: (3-10) ml.

[0019] Preferably, in the step S2, the heating conditions are: heating in an oil bath, at 30-50 °C, for 2-3 d.

[0020] In the step S3, the mass fraction of the Pebax casting solution is 1-5%.

[0021] Preferably, in the step S3, the dosage of the UiO-66-OS porous liquid is 0.1-0.5 g; and the mass ratio of the UiO-66-OS porous liquid to Pebax in the Pebax casting solution is 1: (1-10); the soaking time is 10-50 s.

[0022] The application of the above-mentioned MOF-based porous liquid-modified composite membrane in the ECMO system lies in that the composite membrane is used for the selective adsorption of CO2 / O2.

[0023] A method for improving the blood compatibility and biocompatibility of a membrane used in an ECMO system is to dope Pebax and an MOF-based porous liquid material on the membrane used in the ECMO system. The Pebax includes a polyamide-polyether block, and the MOF-based porous liquid material includes UiO-66 grafted with an organosilane on the surface;

[0024] The membrane used in the ECMO system is a PMP hollow fiber membrane.

[0025] The beneficial effects of the present invention are as follows: The MOF-based porous liquid and Pebax co-modified PMP hollow fiber membrane prepared by the present invention effectively improve the CO2 / O2 selective adsorption performance, and at the same time have good biocompatibility and blood compatibility. In addition, Pebax is composed of a rigid chain segment polyamide (PA) segment that provides mechanical strength and a flexible chain segment polyether (PE) segment that provides gas transmission. In particular, it has a strong selectivity for CO2, further improving the CO2 desorption ability of the PMP hollow fiber membrane; the present invention provides a new idea for the preparation and application of porous liquid material coatings, and has broad application prospects. Description of the Drawings

[0026] Figure 1 It is the infrared spectrum diagram of the PMP original membrane of 3M Company and the modified PMP membrane in Example 3;

[0027] Figure 2 It is the electron microscope diagram of the PMP original membrane of 3M Company and the modified PMP membrane in Example 3;

[0028] Figure 3 It is the gas permeability data diagram of the PMP original membrane of 3M Company and the modified PMP membrane in Example 1;

[0029] Figure 4 It is the gas permeability data diagram of the PMP original membrane of 3M Company and the modified PMP membrane in Example 2;

[0030] Figure 5 It is the gas permeability data diagram of the PMP original membrane of 3M Company and the modified PMP membrane in Example 3;

[0031] Figure 6 It is the gas permeability data diagram of the PMP original membrane of 3M Company and the modified PMP membrane in Example 4;

[0032] Figure 7 It is the gas permeability data diagram of the PMP original membrane of 3M Company and the modified PMP membrane in Example 5;

[0033] Figure 8 It is the CO2 / O2 selectivity data diagram of the PMP original membrane of 3M Company and the modified PMP membrane in Example 3;

[0034] Figure 9 It is the protein adsorption amount data diagram of the PMP original membrane of 3M Company and the modified PMP membrane in Example 3;

[0035] Figure 10 It is the hemolysis rate data diagram of the PMP original membrane of 3M Company and the modified PMP membrane in Example 3;

[0036] Figure 11Graph of the coagulation time data of the original PMP film of 3M Company and the modified PMP film in Example 3;

[0037] Figure 12 Diagram of platelet adhesion of the original PMP film of 3M Company and the modified PMP film in Example 3. Detailed implementation mode

[0038] The present invention will be specifically introduced below in conjunction with the drawings and embodiments.

[0039] The present invention is applied to the field of medical-engineering intersection to improve the CO2 desorption ability of the PMP hollow fiber oxygenation membrane in the ECMO system. Specifically, it relates to a preparation method and application of a highly efficient CO2 desorbing MOF-based porous liquid modified composite membrane for ECMO. The steps of the preparation method are as follows: (1) First, synthesize UiO-66-OH by the hydrothermal method; (2) Then, based on the post-synthesis modification strategy, graft negatively charged organosilane on the MOF matrix as a neck layer; (3) Combine the above UiO-66-OS with a steric solvent through the compatibility principle and steric hindrance effect of similar organic polymer structures to prepare MOF-based porous liquid; (4) Disperse the above porous liquid in the Pebax casting solution and prepare a composite membrane by the dip-coating method. The MOF-based porous liquid for ECMO prepared by the present invention effectively improves the CO2 / O2 selective adsorption performance of the composite membrane, and at the same time has good biocompatibility and blood compatibility. In addition, Pebax is composed of a rigid chain segment polyamide (PA) segment that provides mechanical strength and a flexible chain segment polyether (PE) segment that provides gas transmission, and has a strong selectivity for CO2 in particular, further improving the CO2 desorption ability of the PMP hollow fiber membrane; the present invention provides a new idea for the preparation and application of porous liquid coatings, and has broad application prospects.

[0040] Example 1

[0041] Method for modifying a PMP hollow fiber membrane with an MOF-based porous liquid coating, comprising the following steps:

[0042] (1) Dissolve 1.1 g of the precursor (Zr6O4(OH)4) and 0.7 g of terephthalic acid in a mixture of 5 mL of formic acid and 50 mL of DMF respectively, and then stir at room temperature for 30 min to obtain UiO-66-OH.

[0043] (2) Mix 0.05 g of UiO-66-OH obtained in step (1) with 60 ml of deionized water. After ultrasonic treatment, slowly add 0.5 g of organosilane to the mixture. Then, place the mixed solution in an oil bath at 70 °C and react for 24 h. After the reaction, centrifuge the precipitate at a speed of 8000 r / min. Subsequently, centrifuge and wash with methanol and deionized water in turn for 3 - 5 times. Finally, dry the washed precipitate at 70 °C for 24 h to obtain UiO-66-OS.

[0044] (3) Disperse 0.05 g of UiO-66-OS obtained in step (2) in 5 ml of chloroform and ultrasonicate for 10 min to obtain a solution denoted as solution A. Then, disperse 0.15 g of the steric solvent PDMS (poly(dimethylsiloxane), capped with diglycidyl ether) in 5 ml of chloroform and stir at room temperature for 10 min to obtain a solution denoted as solution B. Subsequently, slowly add solution A to solution B and evaporate the solvent in an oil bath at 35 °C for 2 - 3 days. After evaporation, UiO-66-OS porous liquid is obtained, which is the MOF-based porous liquid.

[0045] (4) Take 0.2 g of the MOF-based porous liquid synthesized in the above steps and disperse it in 10 g of Pebax casting solution. Ultrasonicate for 10 min to make it evenly dispersed to prepare a modified solution, where the mass ratio of the MOF-based porous liquid to Pebax in the Pebax casting solution is 1:1. Cut a 15 - 20 cm PMP membrane and immerse it in the modified solution for 10 s, 20 s, 30 s, 40 s, and 50 s respectively, and then dry it in an oven for 24 h.

[0046] Example 2

[0047] A method for modifying a PMP hollow fiber membrane with a MOF-based porous liquid coating, comprising the following steps:

[0048] (1) Dissolve 1.1 g of the precursor (Zr6O4(OH)4) and 0.7 g of terephthalic acid in a mixture of 5 mL of formic acid and 50 mL of DMF respectively, and then stir at room temperature for 30 min to obtain UiO-66-OH.

[0049] (2) Mix 0.05 g of UiO-66-OH obtained in step (1) with 60 ml of deionized water. After ultrasonic treatment, slowly add 0.5 g of organosilane to the mixture. Then, place the mixed solution in an oil bath at 70 °C and react for 24 h. After the reaction, centrifuge the precipitate at a speed of 8000 r / min. Subsequently, centrifuge and wash with methanol and deionized water in turn for 3 - 5 times. Finally, dry the washed precipitate at 70 °C for 24 h to obtain UiO-66-OS.

[0050] (3) Disperse 0.05 g of UiO-66-OS obtained in step 2 into 5 ml of chloroform and sonicate for 10 min to obtain a solution denoted as solution A; then disperse 0.15 g of the steric solvent PDMS (poly(dimethylsiloxane), terminated with diglycidyl ether) in 5 ml of chloroform as well and stir at room temperature for 10 min to obtain a solution denoted as solution B; subsequently, slowly add solution A to solution B and evaporate the solvent in an oil bath at 35 °C for 2 - 3 days. After evaporation, UiO-66-OS porous liquid is obtained, which is the MOF-based porous liquid.

[0051] (4) Take 0.2 g of the MOF-based porous liquid synthesized in the above step and disperse it in 15 g of Pebax casting solution, sonicate for 10 min to make it disperse evenly, and configure a modified solution. The mass ratio of the MOF-based porous liquid to Pebax in the Pebax casting solution is 2:3; cut a 15 - 20 cm PMP membrane, immerse it in the modified solution for 10 s, 20 s, 30 s, 40 s, and 50 s respectively, and then dry it in an oven for 24 h.

[0052] Example 3

[0053] Method for modifying a PMP hollow fiber membrane with an MOF-based porous liquid coating, comprising the following steps:

[0054] (1) Dissolve 1.1 g of the precursor (Zr6O4(OH)4) and 0.7 g of terephthalic acid in a mixture of 5 mL of formic acid and 50 mL of DMF respectively, and then stir at room temperature for 30 min to obtain UiO-66-OH.

[0055] (2) Take 0.05 g of UiO-66-OH obtained in step 1 and mix it with 60 ml of deionized water. After sonication, slowly add 0.5 g of organosilane to the mixed solution, and then place the mixed solution in an oil bath pot at 70 °C for reaction for 24 h. After the reaction, centrifuge the precipitate at a speed of 8000 r / min, and then centrifuge and wash it with methanol and deionized water in turn for 3 - 5 times. Finally, dry the washed precipitate product at 70 °C for 24 h to obtain UiO-66-OS.

[0056] (3) Disperse 0.05 g of UiO-66-OS obtained in step 2 into 5 ml of chloroform and sonicate for 10 min to obtain a solution denoted as solution A; then disperse 0.15 g of the steric solvent PDMS (poly(dimethylsiloxane), terminated with diglycidyl ether) in 5 ml of chloroform as well and stir at room temperature for 10 min to obtain a solution denoted as solution B; subsequently, slowly add solution A to solution B and evaporate the solvent in an oil bath at 35 °C for 2 - 3 days. After evaporation, UiO-66-OS porous liquid is obtained, which is the MOF-based porous liquid.

[0057] (4) Disperse 0.2 g of the MOF-based porous liquid synthesized in the above steps in 23 g of Pebax casting solution, and ultrasonicate for 10 min to make it evenly dispersed, so as to prepare a modified solution. The mass ratio of the MOF-based porous liquid to Pebax in the Pebax casting solution is about 3:7; Cut a 15-20 cm PMP membrane, immerse it in the modified solution for 10 s, 20 s, 30 s, 40 s and 50 s respectively, and then dry it in an oven for 24 h.

[0058] Example 4

[0059] Method for modifying PMP hollow fiber membrane with MOF-based porous liquid coating, comprising the following steps:

[0060] (1) Dissolve 1.1 g of the precursor (Zr6O4(OH)4) and 0.7 g of terephthalic acid in a mixture of 5 mL of formic acid and 50 mL of DMF respectively, and then stir at room temperature for 30 min to obtain UiO-66-OH.

[0061] (2) Take 0.05 g of UiO-66-OH obtained in step 1 and mix it with 60 ml of deionized water. After ultrasonication, slowly add 0.5 g of organosilane to the mixed solution, and then place the mixed solution in an oil bath at 70 °C for 24 h. After the reaction, centrifuge the precipitate at a speed of 8000 r / min, and then centrifuge and wash it 3-5 times with methanol and deionized water in turn. Finally, dry the washed precipitate at 70 °C for 24 h to obtain UiO-66-OS.

[0062] (3) Disperse 0.05 g of UiO-66-OS obtained in step 2 in 5 ml of chloroform and ultrasonicate for 10 min to obtain a solution denoted as solution A; Then disperse 0.15 g of the steric solvent PDMS (poly(dimethylsiloxane), capped with diglycidyl ether) in 5 ml of chloroform and stir at room temperature for 10 min to obtain a solution denoted as solution B; Subsequently, slowly add solution A to solution B, and evaporate the solvent in an oil bath at 35 °C for 2-3 days. After evaporation, UiO-66-OS porous liquid is obtained, which is the MOF-based porous liquid.

[0063] (4) Take 0.2 g of the MOF-based porous liquid synthesized in the above steps and disperse it in 40 g of Pebax casting solution, and ultrasonicate for 10 min to make it evenly dispersed, so as to prepare a modified solution. The mass ratio of the MOF-based porous liquid to Pebax in the Pebax casting solution is 1:4; Cut a 15-20 cm PMP membrane, immerse it in the modified solution for 10 s, 20 s, 30 s, 40 s and 50 s respectively, and then dry it in an oven for 24 h.

[0064] Example 5

[0065] Method for modifying PMP hollow fiber membrane with MOF-based porous liquid coating, comprising the following steps:

[0066] (1) Dissolve 1.1 g of precursor (Zr6O4(OH)4) and 0.7 g of terephthalic acid in a mixture of 5 mL of formic acid and 50 mL of DMF respectively, and then stir at room temperature for 30 min to obtain UiO-66-OH.

[0067] (2) Take 0.05 g of UiO-66-OH obtained in step 1 and mix it with 60 ml of deionized water. After ultrasonic treatment, slowly add 0.5 g of organosilane to the mixture. Then place the mixed solution in an oil bath at 70 °C and react for 24 h. After the reaction, centrifuge the precipitate at a speed of 8000 r / min, and then centrifuge and wash it with methanol and deionized water in turn for 3 - 5 times. Finally, dry the washed precipitate at 70 °C for 24 h to obtain UiO-66-OS.

[0068] (3) Disperse 0.05 g of UiO-66-OS obtained in step 2 in 5 ml of chloroform and ultrasonicate for 10 min to obtain solution A; then disperse 0.15 g of steric solvent PDMS (poly(dimethylsiloxane), capped with diglycidyl ether) in 5 ml of chloroform and stir at room temperature for 10 min to obtain solution B; then slowly add solution A to solution B and evaporate the solvent in an oil bath at 35 °C for 2 - 3 days. After evaporation, obtain UiO-66-OS porous liquid, which is the MOF-based porous liquid.

[0069] (4) Take 0.2 g of the MOF-based porous liquid synthesized in the above steps and disperse it in 90 g of Pebax casting solution, ultrasonicate for 10 min to make it evenly dispersed, and prepare a modified solution. The mass ratio of the MOF-based porous liquid to Pebax in the Pebax casting solution is 1:9; cut a 15 - 20 cm PMP membrane, immerse it in the modified solution for 10 s, 20 s, 30 s, 40 s and 50 s respectively, and then dry it in an oven for 24 h.

[0070] The infrared analysis results of the original PMP hollow fiber membrane and the modified composite membrane in Example 3 (doping concentration is 30%, coating time is 40 s) are shown in Figure 1 , and the electron microscopy analysis results are shown in Figure 2 , and the gas selectivity test results are shown in Figure 8 , and the protein adsorption amount test results are shown in Figure 9 , and the hemolysis rate test results are shown in Figure 10 , and the coagulation time test results are shown in Figure 11 , and the platelet adhesion test results are shown in Figure 12 . The gas flux test results of the modified composite membranes in Examples 1 - 5 are shown inFigures 3 - 7 。

[0071] From the gas flux test results ( Figures 3 - 7 ) and the gas selectivity test results Figure 8 it can be obtained that at different doping concentrations, with the increase of the coating time, the flux of the modified membrane gradually decreases, and its CO2 / O2 selectivity shows a trend of first increasing and then decreasing. When the doping concentration is 30% and the coating time is 40 s (Example 3), the CO2 / O2 selectivity of the modified membrane is the highest, which is about 15% higher than that of the original membrane; Figure 9 The protein adsorption amount test results show that the protein adsorption amount of the modified membrane is reduced by 40% compared with that of the original membrane; from Figure 10 it can be obtained that the hemolysis rate of the modified membrane is decreased by 28% compared with that of the original membrane; the coagulation time test results Figure 11 show that the coagulation time of the modified membrane is increased by 38% compared with that of the original membrane. From the platelet adhesion Figure 12 , it can be clearly seen that compared with the original membrane, the platelet adhesion amount of the modified membrane is significantly reduced. Therefore, the experiment proves that the MOF-based porous liquid modified PMP hollow fiber membrane of the present invention has high selective adsorption performance for CO2 / O2, excellent oxygenation performance, and good blood compatibility and biocompatibility, is applicable to the ECMO system, and is beneficial to improving the ability of the membrane lung to precipitate CO2 from human blood.

[0072] The above are only the preferred embodiments of the present invention patent. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention patent, several improvements and refinements can still be made, and these improvements and refinements should also be regarded as the protection scope of the present invention patent.

Claims

1. A composite membrane modified by MOF-based porous liquid, characterized in that, The composite membrane described above comprises a PMP hollow fiber membrane, and the PMP hollow fiber membrane is doped with Pebax and an MOF-based porous liquid material. The Pebax includes a polyamide-polyether block, and the MOF-based porous liquid material includes UiO-66 grafted with organosilane on the surface.

2. The preparation method of the MOF-based porous liquid modified composite membrane according to claim 1, characterized in that, It includes the following steps: S1. Synthesize UiO-66-OH; mix UiO-66-OH with deionized water, then add organosilane, heat, and after the reaction ends, centrifuge, wash, and dry to obtain UiO-66-OS; S2. Disperse UiO-66-OS and a steric hindrance solvent in a solvent, heat to evaporate the solvent to obtain UiO-66-OS porous liquid; S3. Disperse the UiO-66-OS porous liquid in a Pebax casting solution to prepare a modified solution, then immerse the PMP hollow fiber membrane in the above modified solution, and dry after completion to obtain a Pebax / PMP composite membrane.

3. The preparation method according to claim 2, characterized in that, In the step S1 described above, the specific steps for synthesizing UiO-66-OH are: dissolve a zirconium precursor and terephthalic acid in a mixture of formic acid and DMF, and stir at room temperature to obtain UiO-66-OH.

4. The preparation method according to claim 3, characterized in that, The dosage ratios of the zirconium precursor, terephthalic acid, formic acid, and DMF are respectively: (0.8 - 1.5) g : (0.5 - 1) g : (3 - 10) ml : (40 - 70) ml.

5. The preparation method according to claim 2, wherein In the step S1 described above, the dosage ratio of UiO-66-OH, deionized water, and organosilane is: (0.01 - 0.1) g : (40 - 100) ml : (0.2 - 0.8) g; The heating conditions are: oil bath heating, 60 - 80 °C, 20 - 27 h; The drying conditions are: 60 - 80 °C, 22 - 26 h.

6. The preparation method according to claim 2, characterized in that, In the step S2 described above, the dosage ratio of UiO-66-OS, the steric hindrance solvent, and the solvent is: (0.02 - 0.1) g : (0.1 - 0.3) g : (3 - 10) ml.

7. The preparation method according to claim 2, characterized in that, In the step S2 described above, the heating conditions are: oil bath heating, 30 - 50 °C, 2 - 3 d; in the step S3, the mass fraction of the Pebax casting solution is 1 - 5%.

8. The preparation method according to claim 2, wherein In the step S3 described above, the dosage of the UiO-66-OS porous liquid is 0.1 - 0.5 g, and the mass ratio of the UiO-66-OS porous liquid to Pebax in the Pebax casting solution is 1 : (1 - 10); the soaking time is 10 - 50 s.

9. Use of the MOF-based porous liquid modified composite membrane according to claim 1 in an ECMO system, characterized in that, The composite membrane is used for the selective adsorption of CO2 / O2.

10. A method for improving the membrane blood compatibility and biocompatibility of an ECMO system, characterized in that, It is a membrane used in an ECMO system doped with Pebax and an MOF-based porous liquid material. The Pebax includes a polyamide-polyether block, and the MOF-based porous liquid material includes UiO-66 grafted with organosilane on the surface; The membrane for the ECMO system is a PMP hollow fiber membrane.

Images