CN114749032A - PMP hollow fiber membrane and preparation method and application thereof - Google Patents

PMP hollow fiber membrane and preparation method and application thereof Download PDF

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CN114749032A
CN114749032A CN202210387117.4A CN202210387117A CN114749032A CN 114749032 A CN114749032 A CN 114749032A CN 202210387117 A CN202210387117 A CN 202210387117A CN 114749032 A CN114749032 A CN 114749032A
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pmp
fiber membrane
hollow fiber
antioxidant
layer
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CN114749032B (en
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张思佳
谢毅
刘向卿
王秋君
张毅
朱伟琪
王雅晴
王波
张迪
李昭进
王欢
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Hebei University of Science and Technology
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D69/08—Hollow fibre membranes
    • 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
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
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    • 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
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/30—Cross-linking
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    • B01D2323/39—Electrospinning
    • B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract

The invention discloses a PMP hollow fiber membrane and a preparation method and application thereof. According to the PMP hollow fiber membrane provided by the invention, the first antioxidant layer, the PMP layer and the second antioxidant layer are arranged in sequence from inside to outside, and the three layers are matched with each other, so that the antioxidant performance of the PMP hollow fiber membrane can be obviously improved. When the porous anti-oxidation film is used for the blood oxygenation film in the ECMO system, the first anti-oxidation layer and the second anti-oxidation layer which are in porous structures can effectively prevent the PMP layer from being oxidized, and the gas permeability of the PMP layer is not influenced; the PMP layer is used as a blood oxygen exchange layer, can effectively prevent blood plasma from permeating, and prolongs the service life of the blood oxygen film.

Description

PMP hollow fiber membrane and preparation method and application thereof
Technical Field
The invention relates to a technical method of a high-molecular separation membrane, in particular to a PMP hollow fiber membrane, a preparation method and application thereof.
Background
The poly 4-methyl-1-pentene (PMP) hollow fiber membrane is a novel membrane technology product formed by crossing a functional fiber material and a separation membrane technology, is also a novel membrane technology product with the fastest development, the largest scale and the highest output value in the separation membrane field, is widely applied to the fields of water treatment, food industry, biological fermentation and the like, particularly in the medical field, and is mainly applied to blood oxygenation membranes in an extracorporeal membrane lung oxygenator (ECMO) system for hemodialysis in kidney diseases and treating patients with severe cardiopulmonary respiratory failure.
PMP hollow fiber membrane is a tubular structure, has a new fiber type membrane with self-supporting function, and is the most important channel for ECMO to absorb oxygen and remove carbon dioxide. PMP hollow fiber membrane combines the advantages of solid silica gel membrane and single-layer microporous hollow fiber membrane, and is recognized as the most promising blood oxygenation membrane. Although the PMP hollow fiber membrane has the characteristics of high gas permeability coefficient, low dissolution, plasma permeation prevention and the like, most of the conventional PMP hollow fiber membranes have the defect of easy oxidation.
Disclosure of Invention
In view of this, the present invention provides a PMP hollow fiber membrane, a method for preparing the same, and applications thereof, wherein the PMP hollow fiber membrane can significantly improve the oxidation resistance of the PMP hollow fiber membrane by a specific three-layer structure arrangement manner.
In order to achieve the purpose of the invention, the embodiment of the invention adopts the following technical scheme:
a PMP hollow fiber membrane has a porous structure and sequentially comprises a first antioxidation layer, a PMP layer and a second antioxidation layer from inside to outside.
According to the PMP hollow fiber membrane provided by the invention, the first antioxidant layer, the PMP layer and the second antioxidant layer are arranged in sequence from inside to outside, and the three layers are matched with each other, so that the antioxidant performance of the PMP hollow fiber membrane can be obviously improved. When the porous structure is used for the blood oxygenation membrane in the ECMO system, the first anti-oxidation layer and the second anti-oxidation layer which have porous structures can effectively prevent the PMP layer from being oxidized, and the gas permeability of the PMP layer is not influenced; the PMP layer is used as a blood oxygen exchange layer, can effectively prevent blood plasma from permeating, and prolongs the service life of the blood oxygen film.
Optionally, the first anti-oxidation layer contains phosphite;
the PMP layer contains PMP resin.
Optionally, the second oxidation resistant layer comprises a phosphite.
By further limiting the components of each layer, the oxidation resistance and mechanical properties of the PMP hollow fiber membrane can be further improved. If the raw materials of each layer are replaced, the blood oxygen exchange, mechanical property or anticoagulation property of the PMP hollow fiber membrane can be greatly reduced.
Optionally, the second antioxidation layer further contains polycarboxylic betaine and sodium alginate.
By further introducing polycarboxylic betaine and sodium alginate into the second antioxidant layer, the polycarboxylic betaine and the sodium alginate are mutually crosslinked to form a net structure, and the phosphite ester and the net structure are mixed into a whole and mutually matched, platelet adhesion and aggregation can be effectively inhibited, thrombosis can be prevented, an anticoagulant function is realized, and the biocompatibility and the biological pollution resistance of the PMP hollow fiber membrane are improved.
The invention also provides a preparation method of the PMP hollow fiber membrane, which comprises the following steps:
step one, preparation of spinning solution
First antioxidant spinning solution: uniformly mixing phosphite ester powder, a pore-forming agent and a diluent to obtain a first antioxidant spinning solution for later use;
PMP spin solution: dissolving PMP resin in a diluent to obtain PMP spinning solution for later use;
second antioxidant spinning solution: phosphite powder, a pore-forming agent and SrCl2Dissolving in diluent to obtain second anti-oxidation spinning solution for later use;
step two, coaxial electrostatic spinning: respectively spraying the first antioxidant spinning solution, the PMP spinning solution and the second antioxidant spinning solution to a receiving device through three coaxial spinning nozzles with different diameters, and cooling to obtain phosphite ester-pore forming agent/PMP/phosphite ester-pore forming agent-SrCl2The coaxial composite fiber membrane of (3).
The preparation method of the PMP hollow fiber membrane provided by the invention can obviously improve the oxidation resistance, toughness and mechanical property of the PMP hollow fiber membrane by limiting the components in each spinning solution and combining a coaxial electrostatic spinning method, the whole preparation process is easy to control, and continuous and stable production can be realized.
In addition, the thickness, porosity and pore size distribution of each layer in the PMP hollow fiber membrane can be adjusted according to actual needs, such as the amount of each raw material and parameters of electrostatic spinning: the thickness of each layer can reach nanometer level or micron level, the porosity can reach 20-70%, the average pore diameter can reach 0.5-1.0nm or 0.2-0.6 μm, etc., the thickness of the first antioxidation layer can be controlled at 100-150nm, the thickness of the PMP layer can be controlled at 100-200nm, the thickness of the second antioxidation layer can be controlled at 100-180nm, etc.
Optionally, the content of the phosphite ester in the first antioxidant spinning solution is 10 wt% -25 wt%, and the content of the pore-forming agent is 5 wt% -10 wt%;
the PMP spinning solution contains 5-25 wt% of PMP resin;
the phosphite ester content in the second antioxidant spinning solution is 5-20 wt%, the pore-forming agent content is 5-10 wt%, and SrCl2The content is 5wt percent to 15wt percent.
Optionally, the PMP spinning solution further contains a pore-forming agent, and the content of the pore-forming agent is less than or equal to 15 wt%.
By limiting the content of phosphite ester and pore-forming agent (preferably polyethylene glycol (PEG) which is easily soluble in water) with environmental protection and stability in the first antioxidant spinning solution, the upper limit of the processing temperature in the preparation process can be obviously improved, the PMP layer can be prevented from being oxidized in the electrostatic spinning process, and the stable preparation of the PMP hollow fiber membrane with the sandwich structure can be ensured. Because the PMP resin has high porosity, even if pore-forming agents are omitted from PMP spinning solution, the finally prepared PMP hollow fiber membrane still has excellent blood oxygen exchange function; by adding the pore-foaming agent into the PMP spinning solution and limiting the contents of the PMP resin and the pore-foaming agent, the gas permeability of the PMP layer can be further improved so as to meet the application requirement of high porosity in practical application. The antioxidant function, the mechanical property and the gas permeability of the PMP hollow fiber membrane can be further improved by limiting the raw materials and the consumption of the raw materials in the second antioxidant layer.
If the raw materials in the spinning solutions are finely adjusted within the above-mentioned limited range, PMP hollow fiber membranes having a sandwich structure can be prepared, but if the raw materials in the spinning solutions are greatly varied, for example, if the adjustment range within the above-mentioned limited range exceeds 5%, the viscosity of the system is increased or too low due to too high or too low concentration of the raw materials in the spinning solutions, so that the coaxial electrostatic spinning process cannot form a filamentous structure, and a stable sandwich structure cannot be formed.
Optionally, the phosphite ester in both the first and second antioxidant spinning solutions is phosphite ester powder.
Optionally, the pore-forming agent is polyethylene glycol (PEG), preferably, the molecular weight of the polyethylene glycol is 8600-10500.
Optionally, the diluent is any one of N, N-Dimethylacetamide (DMA), N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP), acetone, Tetrahydrofuran (THF), and acetic acid.
Optionally, in the coaxial electrostatic spinning step, the voltage between the three coaxial spinning nozzles with different diameters and the receiving device is 10-30kV, and the receiving distance (the distance between the three coaxial spinning nozzles with different diameters and the receiving device) is 5-20 cm;
In the coaxial electrostatic spinning step, the feeding speeds of the first antioxidant spinning solution, the PMP spinning solution and the second antioxidant spinning solution are all 5-20 mL/h; in the coaxial electrospinning step, the rotation speed of the receiving device is 150-600 rpm.
By further limiting each parameter of the coaxial electrostatic spinning step, the binding force between each layer in the prepared PMP hollow fiber membrane can be obviously improved, a stable sandwich structure is realized, and the comprehensive performances of oxidation resistance, mechanical property, anticoagulation property and the like of the PMP hollow fiber membrane are further improved.
Optionally, the preparation method of the PMP hollow fiber membrane further includes adding the phosphite ester-porogen/PMP/phosphite ester-porogen-SrCl2And (3) after cooling, swelling the coaxial composite fiber membrane in water to obtain the PMP hollow fiber membrane.
By mixing phosphite-porogen/PMP/phosphite-porogen-SrCl2The coaxial composite fiber membrane swells in water, and water-soluble pore-forming agent and SrCl in the coaxial composite fiber membrane can be used2And the like are dissolved in water to form the PMP hollow fiber membrane with uniform pore size distribution.
Alternatively, the cooling may be performed by air cooling or cooling in a coagulation bath, such as a water bath, a brine bath, or the like.
Optionally, the preparation method of the PMP hollow fiber membrane further includes adding the phosphite-porogen/PMP/phosphite-porogen-SrCl2After cooling the coaxial composite fiber membrane, crosslinking the coaxial composite fiber membrane in a crosslinking solution to obtain the PMP hollow fiber membrane;
the crosslinking solution is prepared by mixing 2-5g/L polycarboxylic betaine aqueous solution and 5-10g/L sodium alginate aqueous solution in equal volume.
Optionally, the crosslinking temperature is 40-50 ℃, and the time is 5-6 h.
By further reacting phosphite-porogen/PMP/phosphite-porogen-SrCl2After the coaxial composite fiber membrane is cooled, the coaxial composite fiber membrane is crosslinked in specific crosslinking liquid, sodium alginate and polycarboxylic betaine can be introduced into a second antioxidant layer, the sodium alginate and the polycarboxylic betaine can be mutually wound and embedded, meanwhile, the polycarboxylic betaine and a pore-forming agent polyethylene glycol are subjected to physical crosslinking, and Na in the sodium alginate+With SrCl2Sr in2+Ion exchange is carried out, and then a net structure is formed on the surface of the second antioxidation layer, so that the platelet adhesion and aggregation can be effectively inhibited, the thrombosis can be prevented, the anticoagulation function is realized, and the biocompatibility and the biological pollution resistance are good. Thereby remarkably improving the oxidation resistance, anticoagulation, gas transmittance and mechanical properties of the PMP hollow fiber membrane.
In addition, phosphite-porogen/PMP/phosphite-porogen SrCl2The coaxial composite fiber membrane can be crosslinked in the crosslinking solution, and simultaneously, the water-soluble pore-foaming agent and SrCl in the coaxial composite fiber membrane2And the like are dissolved in water to form the PMP hollow fiber membrane with uniformly distributed pore diameters.
Optionally, the ratio of the length of the coaxial composite fiber membrane to the volume of the crosslinking liquid is 1cm (1.5-2.5) mL.
The invention also provides application of the PMP hollow fiber membrane or the PMP hollow fiber membrane prepared by the preparation method of the PMP hollow fiber membrane in an ECMO system.
Drawings
FIG. 1 is a schematic structural view of a cross section of a PMP hollow fiber membrane prepared in example 1 of the present invention;
FIG. 2 is a pore size distribution diagram of a PMP hollow fiber membrane prepared in example 1 of the present invention;
fig. 3 is an SEM image of a PMP hollow fiber membrane prepared in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Most of the conventional PMP hollow fiber membranes are composed of a PMP base layer and a coating layer on the surface of the base layer (for reducing the leakage of the hollow fiber membrane), or are composed of a single layer with gradually reduced pore diameter from the center to the surface (gradient pores), but all have the defect of poor oxidation resistance. In the prior art, the antioxidant is mostly added into a coating layer or a single layer aiming at the defect, but the antioxidant effect is not outstanding.
According to the invention, the anti-oxidation performance of the PMP hollow fiber membrane can be obviously improved by arranging the sandwich structure of the first anti-oxidation layer, the PMP layer and the second anti-oxidation layer from inside to outside and mutually matching the three layers. If the first antioxidant layer and the PMP layer are mixed to form a layer, the PMP layer and the second antioxidant layer are mixed to form a layer, or the first antioxidant layer, the PMP layer and the second antioxidant layer are mixed to form a layer, the antioxidant performance of the finally prepared PMP hollow fiber membrane is obviously reduced, and the use requirement of the blood oxygenation membrane in an ECMO system cannot be met. The anti-oxidation layer which is formed by mixing the existing materials and has a porous structure and an anti-oxidation function can be used as the first anti-oxidation layer and the second anti-oxidation layer, and the realization of the technical effect is not influenced. However, the inventors have intensively studied and found that when the first antioxidant layer is defined as phosphite, the PMP layer is defined as PMP resin, and the second antioxidant layer is defined as phosphite, the finally obtained PMP hollow fiber membrane has the best antioxidant effect and the excellent anti-leakage effect.
The pore-forming agent may be selected from those conventionally used in the art, such as polyethylene glycol.
The hollow inner diameter, the thickness of each layer, the porosity and the like of the PMP hollow fiber membrane can be adjusted according to actual needs so as to meet different use requirements.
As a further improvement of the PMP hollow fiber membrane described above, polycarboxylic betaine and sodium alginate may also be added to the second antioxidant layer. Sodium alginate and polycarboxylic betaine can be mutually wound and embedded, and further a net structure is formed on the surface of the second antioxidant layer, so that the oxidation resistance is improved, the adhesion and aggregation of platelets can be effectively inhibited, the thrombosis is prevented, the anticoagulation function is realized, and the biocompatibility and the biological pollution resistance are good.
Most of the existing preparation methods of PMP hollow fiber membranes adopt a dry molding or melt extrusion mode, but the two methods are difficult to control and the pore size is difficult to adjust, so that the quality of the prepared PMP hollow fiber membrane is unstable, and the use requirement of the blood oxygen composite membrane cannot be met. Therefore, the inventors tried a coaxial electrospinning method, and although the pore diameter of the conventional coaxial electrospinning method is easy to control according to different requirements, the prepared PMP hollow fiber membrane still has the defects of poor oxidation resistance and low mechanical strength. The inventor finds that the PMP hollow fiber membrane with a sandwich structure prepared by adopting the spinning solution with the following specific components and combining a coaxial electrostatic spinning mode has excellent oxidation resistance and mechanical strength, and the prepared PMP hollow fiber membrane has stable quality and easy pore size adjustment and can realize continuous production. Specifically, the preparation method of the PMP hollow fiber membrane by adopting coaxial electrostatic spinning comprises the following steps:
Step one, preparation of spinning solution
First antioxidant spinning solution: uniformly mixing phosphite ester powder, a pore-forming agent and a diluent, and stirring for 2-3 hours to obtain a first antioxidant spinning solution for later use;
PMP spin solution: dissolving PMP resin and a pore-forming agent in a diluent, and stirring for 2-3h to obtain PMP spinning solution for later use;
second antioxidant spinning solution: phosphite powder, a pore-forming agent and SrCl2Dissolving in diluent, and stirring for 2-3h to obtain second antioxidant spinning solution for later use;
step two, coaxial electrostatic spinning: respectively spraying the first antioxidant spinning solution, the PMP spinning solution and the second antioxidant spinning solution to a spinning joint through three spinning nozzles with the same shaft and different diametersThe device is collected to obtain phosphite ester-pore-forming agent/PMP/phosphite ester-pore-forming agent-SrCl2(from inside to outside) coaxial composite fiber membranes;
pore-forming: cooling the coaxial composite fiber membrane to room temperature, swelling in water or crosslinking in a crosslinking agent, and adding water-soluble pore-forming agents PEG and SrCl2And dissolving in water or a crosslinking agent to obtain the PMP hollow fiber membrane.
The PMP hollow fiber membrane with the sandwich structure prepared by adopting the coaxial electrostatic spinning mode can obviously improve the oxidation resistance, the gas transmittance and the mechanical property of the PMP hollow fiber membrane, the whole preparation process is easy to control, the pore size is easy to regulate and control, and the continuous and stable production can be realized.
Wherein, the concentration of each substance in each spinning solution can be adjusted according to actual conditions and requirements, and the diluent can be any one of the diluents which are conventional in the industry, such as DMA, DMF, NMP, acetone, THF, acetic acid and the like. When the content of the phosphite ester in the first antioxidant spinning solution is 10-25 wt%, the content of the pore-forming agent is 5-10 wt%; the PMP spinning solution contains 5-25 wt% of PMP resin and 0-15 wt% of pore-forming agent; the second antioxidant spinning solution contains 5-20 wt% of phosphite ester, 5-10 wt% of pore-forming agent and SrCl2When the content is 5-15 wt%, the PMP hollow fiber membrane prepared by the preparation method has the most stable quality and the most excellent comprehensive performances such as oxidation resistance, anticoagulation resistance and the like.
The voltage between the three spinning nozzles and the receiving device is further limited to be 10-30kV, and the receiving distance is 5-20 cm; the feeding speeds of the first antioxidant spinning solution, the PMP spinning solution and the second antioxidant spinning solution are all 5-20 mL/h; the rotation speed of the receiving device is 150-600rpm, so that the parameters are matched with each other, and the stability of the sandwich structure of the prepared PMP hollow fiber membrane can be obviously improved.
Further, the phosphite-porogen/PMP/phosphite-porogen-SrCl prepared as described above may be used 2The coaxial composite fiber membrane is crosslinked in a crosslinking solution, and the preparation method of the crosslinking solution comprises the following steps: mixing 2-5g/L polycarboxylic betaine aqueous solution and 5-10g/L alginic acidMixing the sodium water solution with equal volume, and stirring for 0.5-1.0 hr to remove bubbles.
By mixing the above phosphite-porogen/PMP/phosphite-porogen-SrCl2Second antioxidation layer (phosphite-porogen-SrCl) in the coaxial composite fiber membrane of (2)2) Crosslinking is carried out, i.e. by Na in sodium alginate+With SrCl2Sr in2+And ion exchange is carried out, so that the mutually wound and embedded polycarboxylic betaine and sodium alginate can enter the second antioxidant layer, and the polycarboxylic betaine and the sodium alginate are matched with a pore-forming agent to form a net structure on the surface of the second antioxidant layer, so that the adhesion and aggregation of platelets can be effectively inhibited, thrombosis can be prevented, an anticoagulation function is realized, and the polycarboxylic betaine and sodium alginate biological anticoagulant composite material has good biocompatibility and biological pollution resistance.
If the combination of the substances in the second antioxidant layer of the PMP hollow fiber membrane obtained in the cross-linking step is unstable, and when the PMP hollow fiber membrane is applied to an ECMO system in the later period, plasma macromolecular substances such as albumin with affinity can be combined with polycarboxylic betaine to cause the polycarboxylic betaine to fall off, so that the service life of the PMP hollow fiber membrane is greatly reduced, and the application risk of the PMP hollow fiber membrane is increased. If the crosslinking between the substances in the second antioxidant layer is too tight and firm, the carboxylic acid betaine can lose activity, and the anticoagulant effect of the PMP hollow fiber membrane is obviously reduced. Therefore, the cross-linking step directly affects the use safety, the service life and the anticoagulation function of the PMP hollow fiber membrane, and how to successfully cross-link is the key for the successful preparation of the PMP hollow fiber membrane.
The inventor finds that by limiting the concentration of each raw material in each crosslinking solution and limiting each parameter in the electrostatic spinning step, the direct bonding force of each layer in the coaxial composite fiber membrane of phosphite ester-pore forming agent/PMP/phosphite ester-pore forming agent-SrCl 2 can be controlled in a proper range, the concentration of each raw material in the subsequent crosslinking solution is controlled in a combined manner, and the parameters are matched with each other, so that the bonding force between each layer in the PMP hollow fiber membrane, particularly between each substance in the second antioxidant layer can be controlled in a proper range, the comprehensive performances of anticoagulation, oxidation resistance and the like of the PMP hollow fiber membrane can be obviously improved, the stable preparation of the PMP hollow fiber membrane can be realized, and the industrial popularization is facilitated.
If the concentration of the polycarboxylic betaine in the crosslinking solution is too high or too low, the anticoagulation effect is too strong, abnormal bleeding occurs, or the anticoagulation effect cannot be achieved; if the concentration of sodium alginate is too high or too low, a crosslinked solution can form a suspension, subsequent crosslinking is not uniform, the performance of the PMP hollow fiber membrane is not uniform, or due to insufficient concentration of divalent sodium ions, polycarboxylic betaine cannot be crosslinked on the surface or is not firmly fixed, and the expected anticoagulation effect cannot be achieved.
Optionally, the temperature and time of crosslinking are adjusted according to actual requirements.
For comparison, the molecular weight of the polyvinyl alcohol (PEG) as the pore-forming agent used in the following examples and comparative examples is 8600-10500.
Example 1
This example provides a PMP hollow fiber membrane, which is prepared as follows:
(1) preparation of spinning solution
Uniformly mixing DMF (dimethyl formamide) and PEG (polyethylene glycol) in a first antioxidant spinning solution, adding phosphite ester powder, magnetically stirring for 3 hours at the temperature of not more than 40 ℃ to obtain a first antioxidant spinning solution, and standing for later use; wherein, the content of phosphite ester is 10 wt%, and the content of PEG is 8 wt%;
PMP spinning solution, dissolving PMP resin in PEG and DMF, magnetically stirring for 3h at the temperature of not more than 40 ℃ to obtain PMP spinning solution, and standing for later use; the content of PMP resin is 25 wt%, and the content of PEG is 15 wt%
Second antioxidant spinning solution is prepared by mixing phosphite powder and SrCl2Dissolving in mixed solution of PEG and DMF, magnetically stirring at 40 deg.C for 3 hr to obtain second antioxidant spinning solution, and standing; phosphite content of 5 wt%, PEG content of 10 wt%, SrCl2The content was 15 wt%.
(2) Coaxial electrostatic spinning
Mixing the first antioxidant spinning solution, PMP spinning solution and second antioxidant spinning solutionInjecting the solution into 3 injectors respectively, enabling the feeding speed of each spinning solution entering each injector to be 15mL/h, connecting the injectors and spinning needles, adopting coaxial needles as the three spinning needles, selecting a receiving device, setting the spinning voltage between the spinning needles and the receiving device to be 20kV, the distance to be 5cm, and the rotating speed of the receiving device to be 150rpm, and preparing to obtain phosphite ester-PEG/PMP-PEG/phosphite ester-PEG-SrCl2The coaxial composite fiber membrane of (3).
(3) Preparation of crosslinking solution
Mixing 3g/L polycarboxylic acid betaine aqueous solution and 8g/L sodium alginate aqueous solution in equal volume, mixing for 1h under magnetic stirring to obtain a cross-linking solution, and standing for later use;
(4) cross-linking
And (2) taking the coaxial composite fiber membrane obtained in the coaxial electrostatic spinning step, sealing two ends of the coaxial composite fiber membrane, immersing the coaxial composite fiber membrane into the crosslinking solution, then placing the coaxial composite fiber membrane into a constant-temperature water tank at 50 ℃ for oscillation for 5.5 hours to perform ion exchange reaction, taking out the coaxial composite fiber membrane after the reaction is finished, and drying the coaxial composite fiber membrane to obtain the PMP hollow fiber membrane, wherein the ratio of the length of the coaxial composite fiber membrane to the volume of the crosslinking solution is 1cm:2.5 mL.
Fig. 1 is a schematic cross-sectional view of the PMP hollow fiber membrane having a sandwich-like structure, the middle of which is a hollow structure, and then a first antioxidant layer, a PMP layer, and a second antioxidant layer in this order. Due to PEG and SrCl which are easily dissolved in water during the crosslinking process 2And the like are basically dissolved in the crosslinking solution, and a pore structure is formed in each layer, so that the first anti-oxidation layer is basically formed by phosphite ester, the PMP layer is basically formed by PMP resin, and the second anti-oxidation layer is basically formed by phosphite ester, polycarboxylic acid betaine and sodium alginate.
Example 2
This example provides a PMP hollow fiber membrane, which is prepared as follows:
(1) preparation of spinning solution
Uniformly mixing DMF (dimethyl formamide) and PEG (polyethylene glycol) in a first antioxidant spinning solution, adding phosphite ester powder, magnetically stirring for 3 hours at the temperature of not more than 40 ℃ to obtain a first antioxidant spinning solution, and standing for later use; wherein, the content of phosphite ester is 25 wt%, and the content of PEG is 10 wt%;
PMP spinning solution, dissolving PMP resin in PEG and DMF, magnetically stirring for 3h at the temperature of not more than 40 ℃ to obtain PMP spinning solution, and standing for later use; the content of PMP resin is 10 wt%, and the content of PEG is 10 wt%
A second antioxidant spinning solution, phosphite powder and SrCl2Dissolving in mixed solution of PEG and DMF, magnetically stirring at 40 deg.C for 3 hr to obtain second antioxidant spinning solution, and standing; 20% by weight of phosphite, 5% by weight of PEG, SrCl 2The content was 5 wt%.
(2) Coaxial electrostatic spinning
Respectively injecting the first antioxidant spinning solution, the PMP spinning solution and the second antioxidant spinning solution into 3 injectors, wherein the feeding speed of each spinning solution entering each injector is 20mL/h, connecting the injectors and spinning needles, adopting coaxial needles as the three spinning needles, selecting a receiving device, setting the spinning voltage between the spinning needles and the receiving device to be 10kV, the distance to be 10cm and the rotating speed of the receiving device to be 600rpm, and preparing to obtain phosphite ester-PEG/PMP-PEG/phosphite ester-PEG-SrCl2The coaxial composite fiber membrane of (3).
(3) Preparation of crosslinking solution
Mixing 2g/L polycarboxylic acid betaine aqueous solution and 5g/L sodium alginate aqueous solution in equal volume, mixing for 1h under magnetic stirring to obtain a cross-linking solution, and standing for later use;
(4) cross-linking
And (2) taking the coaxial composite fiber membrane obtained in the coaxial electrostatic spinning step, sealing two ends of the coaxial composite fiber membrane, immersing the coaxial composite fiber membrane into the crosslinking solution, then placing the coaxial composite fiber membrane into a 45-DEG C constant-temperature water tank, oscillating for 5 hours to perform an ion exchange reaction until the reaction is finished, taking out and drying to obtain the PMP hollow fiber membrane, wherein the ratio of the length of the coaxial composite fiber membrane to the volume of the crosslinking solution is 1cm:1.5 mL.
Example 3
This example provides a PMP hollow fiber membrane, which is prepared as follows:
(1) preparation of spinning solution
Uniformly mixing DMF (dimethyl formamide) and PEG (polyethylene glycol) in a first antioxidant spinning solution, adding phosphite ester powder, magnetically stirring for 3 hours at the temperature of not more than 40 ℃ to obtain a first antioxidant spinning solution, and standing for later use; wherein, the content of the phosphite ester is 15 wt%, and the content of the PEG is 5 wt%;
PMP spinning solution, dissolving PMP resin in PEG and DMF, magnetically stirring for 3h at the temperature of not more than 40 ℃ to obtain PMP spinning solution, and standing for later use; PMP resin content of 5 wt%, PEG content of 5 wt%
A second antioxidant spinning solution, phosphite powder and SrCl2Dissolving in mixed solution of PEG and DMF, magnetically stirring at 40 deg.C for 3 hr to obtain second antioxidant spinning solution, and standing; phosphite content of 12 wt.%, PEG content of 7 wt.%, SrCl2The content was 10 wt%.
(2) Coaxial electrostatic spinning
Respectively injecting the first antioxidant spinning solution, the PMP spinning solution and the second antioxidant spinning solution into 3 injectors, wherein the feeding speed of each spinning solution entering each injector is 5mL/h, connecting the injectors and spinning needles, selecting a receiving device by using coaxial needles as the three spinning needles, setting the spinning voltage between the spinning needle and the receiving device to be 30kV, the distance to be 20cm, and the rotating speed of the receiving device to be 300rpm, and preparing to obtain phosphite ester-PEG/PMP-PEG/phosphite ester-PEG-SrCl 2The coaxial composite fiber membrane of (3).
(3) Preparation of crosslinking solution
Mixing 5g/L polycarboxylic acid betaine aqueous solution and 10g/L sodium alginate aqueous solution in equal volume, mixing for 1h under magnetic stirring to obtain a cross-linking solution, and standing for later use;
(4) cross-linking
And (2) taking the coaxial composite fiber membrane obtained in the coaxial electrostatic spinning step, sealing two ends of the coaxial composite fiber membrane, immersing the coaxial composite fiber membrane into the crosslinking solution, then placing the coaxial composite fiber membrane into a constant-temperature water tank at 40 ℃ for oscillation for 6 hours to perform ion exchange reaction, taking out the coaxial composite fiber membrane after the reaction is finished, and drying the coaxial composite fiber membrane to obtain the PMP hollow fiber membrane, wherein the ratio of the length of the coaxial composite fiber membrane to the volume of the crosslinking solution is 1cm:2 mL.
Example 4
The PMP hollow fiber membrane and the preparation method thereof provided in this example are similar to those of example 1, except that PEG is omitted from the PMP spinning solution.
Example 5
The PMP hollow fiber membrane and the preparation method thereof provided in this example are similar to those of example 1, except that the voltage between the spinning nozzle and the receiving device in the coaxial electrospinning step is different, and the voltage between the spinning nozzle and the receiving device in this example is 32 kV.
Example 6
The PMP hollow fiber membrane and the preparation method thereof provided in this example are similar to those of example 1, except that the rotation speed of the receiving device in the coaxial electrospinning step is different, and the rotation speed of the receiving device in this example is 140 rpm.
Example 7
The PMP hollow fiber membrane and the preparation method thereof provided in this example are similar to those of example 1, except that the concentration of the polycarboxylic acid betaine aqueous solution in the step of preparing the cross-linking solution is different, and the concentration of the polycarboxylic acid betaine aqueous solution in the step of preparing the cross-linking solution in this example is 7 g/L.
The PMP hollow fiber membranes prepared in the above examples 2 to 7 all had a sandwich-like structure, with the hollow structure at the center, followed by the first antioxidant layer, the PMP layer, and the second antioxidant layer in this order. The first antioxidation layer is basically composed of phosphite ester, the PMP layer is basically composed of PMP resin, and the second antioxidation layer is basically composed of phosphite ester, polycarboxylic betaine and sodium alginate.
Example 8
The PMP hollow fiber membrane and the preparation method thereof provided in this example are similar to example 1, except that the preparation of the cross-linking solution and the cross-linking step are omitted in this example, and the phosphite-PEG/PMP-PEG/phosphite-PEG-SrCl is swollen2The raw material which is easily dissolved in water is removed from the coaxial composite fiber membrane. The specific swelling method is as follows:
phosphite ester-PEG/PMP-PEG/phosphite ester-PEG-SrCl prepared by coaxial electrostatic spinning2The coaxial composite fiber membrane is immersed in water at the temperature of 35-45 ℃ for 6 hours, taken out and dried to obtain the PMP hollow fiber membrane.
The PMP hollow fiber membrane prepared in this example had a sandwich-like structure with the hollow structure at the center, followed by a first antioxidant layer, a PMP layer, and a second antioxidant layer in this order. The first antioxidant layer is substantially composed of phosphite, the PMP layer is substantially composed of PMP resin, and the second antioxidant layer is substantially composed of phosphite.
Comparative example 1
The present comparative example provides a PMP hollow fiber membrane, which was prepared as follows:
(1) preparation of spinning solution
Uniformly mixing DMF (dimethyl formamide) and PEG (polyethylene glycol), adding phosphite ester powder, magnetically stirring for 3 hours at the temperature of not more than 40 ℃ to obtain an antioxidant spinning solution, and standing for later use; wherein, the content of phosphite ester is 15 wt%, and the content of PEG is 18 wt%;
PMP spinning solution, dissolving PMP resin in PEG and DMF, magnetically stirring for 3h at the temperature of not more than 40 ℃ to obtain PMP spinning solution, and standing for later use; the content of PMP resin is 25 wt%, and the content of PEG is 15 wt%;
(2) coaxial electrostatic spinning
And (2) injecting the antioxidant spinning solution and PMP spinning solution into 2 injectors respectively, enabling the feeding speed of each spinning solution entering each injector to be 15mL/h, connecting the injectors and spinning needles, adopting coaxial needles for the two spinning needles, selecting a receiving device, setting the spinning voltage between the spinning needles and the receiving device to be 20kV, the distance between the spinning needles and the receiving device to be 5cm, and setting the rotating speed of the receiving device to be 150rpm, and preparing the phosphite ester-PEG/PMP-PEG coaxial composite fiber membrane.
(3) Swelling of the particles
And (3) immersing the phosphite ester-PEG/PMP-PEG coaxial composite fiber membrane prepared by coaxial electrostatic spinning into water at 35-45 ℃ for 6 hours, taking out, and drying to obtain the PMP hollow fiber membrane. Wherein the ratio of the length of the coaxial composite fiber membrane to the volume of the crosslinking liquid is 1cm:2.5 mL.
The PMP hollow fiber membrane prepared in this comparative example had a hollow structure at the center and then an antioxidation layer and a PMP layer in this order from the inside out. The oxidation resistant layer is substantially composed of phosphite and the PMP layer is substantially composed of PMP resin.
Comparative example 2
The present comparative example provides a PMP hollow fiber membrane, which was prepared as follows:
(1) preparation of spinning solution
DMF and PEG were mixed well, and then phosphite powder, PMP resin and SrCl were added2Magnetically stirring for 3h under the condition that the temperature is controlled not to exceed 40 ℃ to obtain spinning solution, and standing for later use; wherein the content of phosphite ester is 15 wt%, the content of PEG is 33 wt%, the content of PMP resin is 25 wt%, SrCl2The content was 15 wt%.
(2) Coaxial electrostatic spinning
Injecting the spinning solution into an injector at the speed of 15mL/h, connecting the injector and a spinning needle, selecting a receiving device, setting the spinning voltage between the spinning needle and the receiving device to be 20kV, the distance to the spinning needle to be 5cm, and the rotating speed of the receiving device to be 150rpm, and preparing phosphite ester-PEG-PMP-SrCl 2The composite fiber membrane of (3).
(3) Preparation of crosslinking solution
Mixing 3g/L polycarboxylic acid betaine aqueous solution and 8g/L sodium alginate aqueous solution in equal volume, mixing for 1h under magnetic stirring to obtain a cross-linking solution, and standing for later use;
(4) cross-linking
And (2) taking the composite fiber membrane obtained in the coaxial electrostatic spinning step, sealing two ends of the composite fiber membrane, immersing the composite fiber membrane into the crosslinking solution, then placing the composite fiber membrane into a constant-temperature water tank at 50 ℃ for oscillation for 5.5 hours to perform ion exchange reaction, taking out the composite fiber membrane and drying the composite fiber membrane after the reaction is finished, thus obtaining the PMP hollow fiber membrane, wherein the ratio of the length of the coaxial composite fiber membrane to the volume of the crosslinking solution is 1cm:2.5 mL.
The PMP hollow fiber membrane prepared by this comparative example is a hollow circle center structure, and is essentially composed of phosphite, PMP resin, polycarboxylic acid betaine, and sodium alginate.
Comparative example 3
The present comparative example provides a PMP hollow fiber membrane, which was prepared as follows:
(1) preparation of spinning solution
PMP spinning solution, dissolving PMP resin in PEG and DMF, magnetically stirring for 3h at the temperature of not more than 40 ℃ to obtain PMP spinning solution, and standing for later use; the content of PMP resin is 25 wt%, and the content of PEG is 15 wt%
Antioxidant spinning solution is prepared by mixing phosphite powder and SrCl2Dissolving in mixed solution of PEG and DMF, magnetically stirring at 40 deg.C for 3 hr to obtain antioxidant spinning solution, and standing; phosphite content of 5 wt%, PEG content of 10 wt%, SrCl2The content was 15 wt%.
(2) Coaxial electrostatic spinning
Respectively injecting the PMP spinning solution and the antioxidant spinning solution into 2 injectors, enabling the feeding speed of each spinning solution entering each injector to be 15mL/h, connecting the injectors and spinning needle heads, adopting coaxial needle heads for the two spinning needle heads, selecting a receiving device, setting the spinning voltage between the spinning needle heads and the receiving device to be 20kV, enabling the distance to be 5cm, enabling the rotating speed of the receiving device to be 150rpm, and preparing to obtain PMP-PEG/phosphite ester-PEG-SrCl2The coaxial composite fiber membrane of (1).
(3) Preparation of crosslinking solution
Mixing 3g/L polycarboxylic acid betaine aqueous solution and 8g/L sodium alginate aqueous solution in equal volume, mixing for 1h under magnetic stirring to obtain a cross-linked solution, and standing for later use;
(4) cross-linking
And (2) taking the coaxial composite fiber membrane obtained in the coaxial electrostatic spinning step, sealing two ends of the coaxial composite fiber membrane, immersing the coaxial composite fiber membrane into the crosslinking solution, then placing the coaxial composite fiber membrane into a constant-temperature water tank at 50 ℃ for oscillation for 5.5 hours to perform ion exchange reaction, taking out the coaxial composite fiber membrane after the reaction is finished, and drying the coaxial composite fiber membrane to obtain the PMP hollow fiber membrane, wherein the ratio of the length of the coaxial composite fiber membrane to the volume of the crosslinking solution is 1cm:2.5 mL.
The PMP hollow fiber membrane prepared by the comparative example has a hollow structure and sequentially comprises a PMP layer and an oxidation resistant layer from inside to outside, wherein the PMP layer is basically composed of PMP resin, and the oxidation resistant layer is basically composed of phosphite ester, polycarboxylic acid betaine and sodium alginate.
Experimental example 1
The PMP hollow fiber membrane prepared in example 1 was subjected to Scanning Electron Microscopy (SEM) and pore size distribution tests, respectively, and the specific test results are shown in fig. 2 to 3.
And (4) SEM test: the PMP hollow fiber membrane was subjected to gold spraying, and then placed in an electron microscope chamber to be observed under vacuum, with a scanning voltage of 20.0kV, and fig. 3 is an SEM image magnified 10K times, and it can be seen from fig. 3 that the PMP hollow fiber membrane exhibits a pore-like cross structure.
And (3) testing pore size distribution: PMP hollow fiber membranes were immersed in an immersion liquid of absolute ethanol using a pore size tester, and then pressure was applied between the center and the outside thereof to form a pressure difference (about 3.6X 10)-1MPa) to overcome the surface tension of the impregnation liquid in the pore channels, and driving the impregnation liquid through the pore channels of the membrane by pressure difference to obtain a pore size distribution diagram, as can be seen from fig. 2, the pore size of the PMP hollow fiber membrane prepared in example 1 is concentrated between 0.2 nm and 1.0nm, which indicates that the pore size distribution of the PMP hollow fiber membrane is uniform, and the degree of recombination between layers is high.
Experimental example 2
The PMP hollow fiber membranes prepared in the examples and comparative examples were respectively tested for mechanical properties, anticoagulation properties, and oxidation resistance, and the specific test results are shown in tables 1 to 3 below.
The mechanical property test method comprises the following steps: 10 samples to be tested with the length of 200mm are taken, 1 sample is inserted into a holder at room temperature (23-25 ℃), pre-tension is applied, the sample is tightened, a universal testing machine is started, the tensile speed is set to be 200mm/min, the fracture tensile determination is carried out according to the standard testing method of ASTM D-638, each sample is tested for 1 time, the average value of the 10 samples is taken, and the mechanical strength is represented by the average elongation at break.
Elongation at break of single PMP hollow fiber:
Figure BDA0003594117870000181
in the formula:
Eielongation at break of the individual PMP hollow fibers;
Li-the single PMP hollow fiber has a stretched length in millimeters (mm);
L0-initial length of single PMP hollow fiber in millimeters (mm).
Average elongation at break:
Figure BDA0003594117870000182
in the formula:
Figure BDA0003594117870000183
-average elongation at break;
Eielongation at break of the individual PMP hollow fibers;
n is the number of trials.
And (3) testing anticoagulant performance: 1.8mL of healthy human blood (for men, blood sampling after 12h of fasting) is selected and put into 0.2mL of sodium citrate aqueous solution (10wt percent), and the blood plasma is prepared after uniform mixing. Putting the plasma into a sample tube, putting a PMP hollow fiber membrane (the length is 100mm) to be tested into the sample tube, sealing, then incubating for 30min in water bath at 37 ℃ (so as to ensure that the test is carried out under the strip without edge leakage), irradiating at the wavelength of 660nm, measuring the turbidity of the plasma in the blood coagulation process through the change of the light intensity of scattered light (the light intensity is gradually increased along with the formation process of blood clots in the sample until the blood clots are completely coagulated and no longer changed), and calculating the prothrombin time through a standard curve (a blood coagulation curve), and reflecting the anticoagulation performance by the Prothrombin Time (PT).
Wherein the standard of the healthy human body is medical diagnosis without diseases, the systolic pressure of the healthy human body is 125-135mmHg, and the diastolic pressure of the healthy human body is 80-90 mmHg.
And (3) testing the oxidation resistance: the method is characterized in that a DPPH (diphenyl picryl phenylhydrazine) free radical scavenging method is selected to measure the clearance rate of free radicals of a tested sample, so that the oxidation resistance of the tested sample is indirectly obtained, and the specific test method is as follows:
cutting 25mg of a sample to be detected, putting the sample to be detected in 4mL of distilled water, fully stirring the solution to be detected to be completely dissolved to obtain an aqueous solution containing the sample to be detected, measuring 0.2mL of the aqueous solution containing the sample to be detected, uniformly mixing the aqueous solution with 7.2mL of PPH ethanol solution (0.1mmol/L), incubating the mixture at room temperature (23-25 ℃) in the dark for 60min, and respectively reading the absorbance (marked as A) of the solution at 517nmSample(s)) And absorbance of DPPH in ethanol (denoted A)DPPH) Each group was tested 3 times, averaged, and DPPH radical scavenging capacity was calculated using the following formula:
Figure BDA0003594117870000191
TABLE 1 mechanical Property results
Figure BDA0003594117870000192
TABLE 2 anticoagulant Effect test results
Figure BDA0003594117870000193
TABLE 3 Oxidation resistance test results
Figure BDA0003594117870000194
As can be seen from the data in the above table, compared with the existing PMP hollow fiber membrane, the PMP hollow fiber membrane provided by the present invention forms a porous sandwich structure by sequentially disposing the first antioxidant layer, the PMP layer and the second antioxidant layer from inside to outside, and the three layers cooperate with each other, so that the PMP hollow fiber membrane has more excellent antioxidant, anticoagulant and mechanical properties.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. The PMP hollow fiber membrane is characterized by having a porous structure and sequentially comprising a first antioxidation layer, a PMP layer and a second antioxidation layer from inside to outside.
2. The PMP hollow fiber membrane of claim 1, wherein the first oxidation resistant layer comprises a phosphite; and/or
The PMP layer contains PMP resin.
3. The PMP hollow fiber membrane of claim 1 or 2, characterized in that the second antioxidant layer contains a phosphite.
4. The PMP hollow fiber membrane of claim 3, wherein the second antioxidant layer further comprises polycarboxylic acid betaine and sodium alginate.
5. The process for the preparation of a PMP hollow fiber membrane according to any one of claims 1 to 4, characterized in that it comprises the following steps:
step one, preparation of spinning solution:
first antioxidant spinning solution: uniformly mixing phosphite ester, a pore-forming agent and a diluent to obtain a first antioxidant spinning solution for later use;
PMP spinning solution: dissolving PMP resin in a diluent to obtain PMP spinning solution for later use;
second antioxidant spinning solution: phosphite ester, a pore-forming agent and SrCl2Dissolving in diluent to obtain second anti-oxidation spinning solution for later use;
step two, coaxial electrostatic spinning: mixing the first antioxidant spinning solutionThe PMP spinning solution and the second anti-oxidation spinning solution are respectively sprayed to a receiving device through three spinning nozzles with different coaxial diameters to obtain phosphite ester-pore-forming agent/PMP/phosphite ester-pore-forming agent-SrCl2The coaxial composite fiber membrane of (1).
6. The preparation method of the PMP hollow fiber membrane according to claim 5, wherein the first antioxidant spinning solution contains 10 wt% to 25 wt% of phosphite ester and 5 wt% to 10 wt% of pore-forming agent; and/or
In the PMP spinning solution, the content of PMP resin is 5-25 wt%; and/or
In the second antioxidant spinning solution, the phosphite ester content is 5-20 wt%, the pore-forming agent content is 5-10 wt%, and SrCl2The content is 5 wt% -15 wt%.
7. The PMP hollow fiber membrane preparation method of claim 5, wherein in the coaxial electrospinning step, the voltage between the three spinning nozzles and the receiving device is 10-30kV, and the receiving distance is 5-20 cm; and/or
In the coaxial electrostatic spinning step, the feeding speeds of the first antioxidant spinning solution, the PMP spinning solution and the second antioxidant spinning solution are all 5-20 mL/h; the rotation speed of the receiving device is 150-600 rpm.
8. The method for preparing PMP hollow fiber membrane according to any one of claims 5 to 7, further comprising submitting the phosphite-porogen/PMP/phosphite-porogen-SrCl2Swelling the coaxial composite fiber membrane in water to obtain the PMP hollow fiber membrane.
9. The method for preparing PMP hollow fiber membrane according to any one of claims 5 to 7, further comprising submitting the phosphite-porogen/PMP/phosphite-porogen-SrCl2Crosslinking the coaxial composite fiber membrane in a crosslinking solution to obtain the PMP hollow fiber membraneA step of;
the crosslinking solution is prepared by mixing 2-5g/L polycarboxylic betaine aqueous solution and 5-10g/L sodium alginate aqueous solution in equal volume.
10. Use of the PMP hollow fiber membrane of any one of claims 1 to 4 or of the PMP hollow fiber membrane prepared by the process for its preparation of any one of claims 5 to 9 in an ECMO system.
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